CN103483784B - A kind of Flame-retardant PET heat-shrinkable film and preparation method thereof - Google Patents
A kind of Flame-retardant PET heat-shrinkable film and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 32
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229920006257 Heat-shrinkable film Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims description 17
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000004806 packaging method and process Methods 0.000 claims abstract description 11
- 239000004902 Softening Agent Substances 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical group CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 20
- 229920000728 polyester Polymers 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 230000002269 spontaneous effect Effects 0.000 abstract description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 37
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 7
- 229920002799 BoPET Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 229920001634 Copolyester Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 2
- 229920006300 shrink film Polymers 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- FDSYTWVNUJTPMA-UHFFFAOYSA-N 2-[3,9-bis(carboxymethyl)-3,6,9,15-tetrazabicyclo[9.3.1]pentadeca-1(15),11,13-trien-6-yl]acetic acid Chemical compound C1N(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC2=CC=CC1=N2 FDSYTWVNUJTPMA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- -1 HANKINSNCP-2 Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 150000007520 diprotic acids Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Landscapes
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a kind of Flame-retardant PET heat-shrinkable film, make primarily of following raw material by weight: PET resin 80 ~ 90 parts, environment friendly flame retardant 5 ~ 10 parts, auxiliary agent 1 ~ 5 part, lubricant 2 ~ 5 parts, 1 ~ 3 part, softening agent.Flame-retardant PET heat-shrinkable film prepared by the present invention, not only has high tensile strength, shrinkage is strong, but also possess anti-flaming function, be suitable for the outer packaging of electronic product, can prevent the heatings such as electronic product from causing the generation of spontaneous combustion, stop the generation of fire.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of Flame-retardant PET heat-shrinkable film and preparation method thereof.
Background technology
PET resin forms line style homopolymerization polyester by dibasic alcohol (ethylene glycol, EG) and diprotic acid (terephthalic acid, TPA) polycondensation, and copolyester is the polyester with alcohol or sour modification, has PETG, PCTG and PCTA and degradable copolyester.
PET film is the comprehensive packaging film of a kind of Performance comparision.Its transparency is good, glossy; There is good resistance to air loss and fragrance protectiveness; Moistureproofness is medium, and rate of perviousness declines at low temperatures.The good mechanical performance of PET film, its obdurability is best in all thermoplasticss, tensile strength and resistance to impact shock more much higher than general film; And very power is good, dimensional stabilizing, is suitable for the secondary processing such as printing, paper bag.PET film also has excellent heat-resisting, winter hardiness and good chemical proofing and oil-proofness.But its not resistance to highly basic; Easy static electrification, does not still have the method for suitable anti-electrostatic, therefore should arouse attention when for packaging powdered article.
PET film is specifically applied to high-performance shrink film, has the large final shrinking percentage of dry 70%, can be made into the packaging of complex configuration container, have high plastic uptake power, high-clarity, high gloss, low haze, is easy to printing, difficult drop-off, the advantage that during storage, natural shrinking rate is low, is applied to beverage bottle, food and change.Wherein the PETG film of two-way stretch is applicable to the high-quality base material of high-grade packaging, printing, electronic apparatus, dressing of cable, insulating material and various industrial circle.Unilateral stretching PET, heat-shrinkable film are applicable to various canned, the external application such as polyester bottles, various containers label.
In life, we sometimes keep away the generations such as unavoidable fire, and also do not have the correlative study about the PET heat-shrinkable film having flame retardant effect and report at present.
Summary of the invention
Goal of the invention: for the problems referred to above, first object of the present invention be to provide a kind of good toughness, transparent, can Flame-retardant PET heat-shrinkable film.Second object of the present invention is to provide the preparation method of this shrink film.
Technical scheme: in order to solve the problems of the technologies described above, the invention provides a kind of Flame-retardant PET heat-shrinkable film, make primarily of following raw material by weight: PET resin 80 ~ 90 parts, environment friendly flame retardant 5 ~ 10 parts, auxiliary agent 1 ~ 5 part, lubricant 2 ~ 5 parts, 1 ~ 3 part, softening agent.
Described environment friendly flame retardant is the one in TDE, brominated epoxy resin or brominated Polystyrene.TDE 80108010 does not belong to polybromodiphenyl ether, absolutely not generation PBDD or PBDF in burning; The relative molecular weight of 8010 is 971; Bromine content 82%, and the brominated amount of DBDPO is quite (83%), therefore flame retardant properties is basically identical; First fusing point 345 DEG C, thermostability is DBDPO(305 DEG C comparatively) high; Its photostabilization and the feature of not easily dialysis are all better than DBDPO, and the most valuable is that its fire-retardant plastics can reclaim use, and this is the feature not available for many bromide fire retardants.8010 industrial goods are the white crystalline powder of mean particle size 3 μm, unrestricted flow, micronizing, easily disperse in modifying plastics, and plastics color freely.And industrialization cost and DBDPO are suitable, it is the ideal substitute of DBDPO.As addition type bromide fire retardant, 8010 use procedure also need with stibnide with the use of, mixing ratio is identical with DBDPO/ stibnide ratio; Compare with DBDPO, 8010 engineering plastics being more suitable for high-temperature sticky characteristic.
Described lubricant is the one in Zinic stearas, ethylene bis stearamide, inspissated wax or butyl stearate.
Described softening agent is dibutyl phthalate.
Wherein, auxiliary agent is HANKINSNCP-2.HANKINS*NCP/2 is a kind of nonvolatile, low viscous polymeric additive.Product is environmentally friendly additive, colorless and odorless, can be used for vinegar third, pure third and benzene emulsion in, to give outstanding viscosity and the sticking power to base material.Chemical structure HANKINS*NCP/2 due to its uniqueness has hydrolysis highly, frost resistance and hydrophobicity.Significantly improve the glossiness after emulsion film forming and transparency, significant ductility and Restoration, strengthen the elasticity of glue-line and force of cohesion, enhance snappiness and elasticity, excellent moist cohesive strength and dryness bond strength, improve stripping strength, sticking power difficulty being glued to base shows raising, good high temperature performance, strengthen film formation at low temp performance, greatly improve the low temperature resistant of polymkeric substance, anti-freezing property.
The preparation method of described Flame-retardant PET heat-shrinkable film, comprises the following steps:
1) raw material of above-mentioned parts by weight is taken;
2) 75 ~ 85 DEG C add in reactor PET resin, environment friendly flame retardant, auxiliary agent, lubricant, softening agent and with 150 ~ 200rpm rotating speed stir 10 ~ 20min;
3) reactor temperature is increased to 290 ~ 300 DEG C, Pressure Drop to below 90pa, react 2 ~ 3h with this understanding and obtain polymer melt, then the polymer melt of preparation is extruded, pelletizing, drying, obtain PET polyester slice;
4) above-mentioned PET polyester slice is melt extruded, die head slab, slab spooling, two-way stretch, cooling and shaping, detect thickness, rolling, cutting and rewinding, packaging, finished product.
Described to melt extrude temperature be 285 ~ 290 DEG C, and described two-way stretch temperature is 112 ~ 117 DEG C, and described detect thickness is 35 ~ 45 μm.
Beneficial effect: Flame-retardant PET heat-shrinkable film prepared by the present invention, not only there is high tensile strength, shrinkage is strong, but also possess anti-flaming function, be suitable for the outer packaging of electronic product, can prevent the heatings such as electronic product from causing the generation of spontaneous combustion, stop the generation of fire.
Embodiment
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, the concrete material proportion described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
Embodiment 1
A kind of Flame-retardant PET heat-shrinkable film, makes primarily of following raw material: PET resin 80 parts, TDE 5 parts, HANKINSNCP-21 part, Zinic stearas 2 parts, dibutyl phthalate 1 part by weight.
The preparation method of Flame-retardant PET heat-shrinkable film, comprises the following steps: the raw material taking above-mentioned parts by weight;
In reactor, add PET resin, TDE, HANKINSNCP-2, Zinic stearas, dibutyl phthalate at 75 DEG C, and stir 10min with 150rpm rotating speed; Reactor temperature is increased to 290 DEG C, Pressure Drop to below 90pa, react 2 ~ 3h with this understanding and obtain polymer melt, then the polymer melt of preparation is extruded, pelletizing, drying, obtain PET polyester slice; Above-mentioned PET polyester slice is melt extruded, die head slab, slab spooling, two-way stretch, cooling and shaping, detect thickness, rolling, cutting and rewinding, packaging, finished product.Melt extruding temperature is 285 DEG C, and two-way stretch temperature is 112 DEG C, and detect thickness is 35 μm.Performance perameter measuring result:
Embodiment 2
A kind of Flame-retardant PET heat-shrinkable film, makes primarily of following raw material: PET resin 90 parts, brominated epoxy resin 10 parts, HANKINSNCP-25 part, ethylene bis stearamide 5 parts, dibutyl phthalate 3 parts by weight.
The preparation method of Flame-retardant PET heat-shrinkable film, comprises the following steps: the raw material taking above-mentioned parts by weight; In reactor, add PET resin, brominated epoxy resin, HANKINSNCP-2, ethylene bis stearamide, dibutyl phthalate at 85 DEG C, and stir 20min with 200rpm rotating speed; Reactor temperature is increased to 300 DEG C, Pressure Drop to below 90pa, with this understanding react 3h obtain polymer melt, then the polymer melt of preparation is extruded, pelletizing, drying, obtain PET polyester slice; Above-mentioned PET polyester slice is melt extruded, die head slab, slab spooling, two-way stretch, cooling and shaping, detect thickness, rolling, cutting and rewinding, packaging, finished product.Melt extruding temperature is 290 DEG C, and two-way stretch temperature is 117 DEG C, and detect thickness is 45 μm.Performance perameter measuring result:
Embodiment 3
A kind of Flame-retardant PET heat-shrinkable film, makes primarily of following raw material: PET resin 85 parts, brominated Polystyrene 7 parts, HANKINSNCP-23 part, inspissated wax 3 parts, dibutyl phthalate 2 parts by weight.
The preparation method of Flame-retardant PET heat-shrinkable film, comprises the following steps: the raw material taking above-mentioned parts by weight; In reactor, add PET resin, brominated Polystyrene, HANKINSNCP-2, inspissated wax, dibutyl phthalate at 80 DEG C, and stir 15min with 180rpm rotating speed; Reactor temperature is increased to 295 DEG C, Pressure Drop to below 90pa, with this understanding react 2.5h obtain polymer melt, then the polymer melt of preparation is extruded, pelletizing, drying, obtain PET polyester slice; Above-mentioned PET polyester slice is melt extruded, die head slab, slab spooling, two-way stretch, cooling and shaping, detect thickness, rolling, cutting and rewinding, packaging, finished product.Melt extruding temperature is 287 DEG C, and two-way stretch temperature is 115 DEG C, and detect thickness is 40 μm.
Performance perameter measuring result:
Embodiment 4
A kind of Flame-retardant PET heat-shrinkable film, makes primarily of following raw material: PET resin 87 parts, TDE 8 parts, HANKINSNCP-24 part, Zinic stearas, stearic acid 4 parts, dibutyl phthalate 2 parts by weight.The preparation method of described Flame-retardant PET heat-shrinkable film, comprises the following steps: the raw material taking above-mentioned parts by weight; In reactor, add PET resin, TDE, HANKINSNCP-2, stearic acid, dibutyl phthalate at 77 DEG C, and stir 13min with 155rpm rotating speed; Reactor temperature is increased to 297 DEG C, Pressure Drop to below 90pa, with this understanding react 2.5h obtain polymer melt, then the polymer melt of preparation is extruded, pelletizing, drying, obtain PET polyester slice; Above-mentioned PET polyester slice is melt extruded, die head slab, slab spooling, two-way stretch, cooling and shaping, detect thickness, rolling, cutting and rewinding, packaging, finished product.Melt extruding temperature is 288 DEG C, and two-way stretch temperature is 113 DEG C, and detect thickness is 36 μm.Performance perameter measuring result:
Claims (3)
1. a Flame-retardant PET heat-shrinkable film, it is characterized in that, make primarily of following raw material by weight: PET resin 80 ~ 90 parts, environment friendly flame retardant 5 ~ 10 parts, auxiliary agent 1 ~ 5 part, lubricant 2 ~ 5 parts, 1 ~ 3 part, softening agent, described environment friendly flame retardant is the one in TDE, brominated epoxy resin or brominated Polystyrene, described lubricant is the one in Zinic stearas, ethylene bis stearamide, inspissated wax or butyl stearate, described softening agent is dibutyl phthalate, and described auxiliary agent is HANKINSNCP-2.
2. the preparation method of Flame-retardant PET heat-shrinkable film according to claim 1, is characterized in that, comprise the following steps:
1) raw material of above-mentioned parts by weight is taken;
2) 75 ~ 85 DEG C add in reactor PET resin, environment friendly flame retardant, auxiliary agent, lubricant, softening agent and with 150 ~ 200rpm rotating speed stir 10 ~ 20min;
3) reactor temperature is increased to 290 ~ 300 DEG C, Pressure Drop to below 90Pa, react 2 ~ 3h with this understanding and obtain polymer melt, then the polymer melt of preparation is extruded, pelletizing, drying, obtain PET polyester slice;
4) above-mentioned PET polyester slice is melt extruded, die head slab, slab spooling, two-way stretch, cooling and shaping, detect thickness, rolling, cutting and rewinding, packaging, finished product.
3. the preparation method of Flame-retardant PET heat-shrinkable film according to claim 2, is characterized in that, described in melt extrude temperature be 285 ~ 290 DEG C, described two-way stretch temperature is 112 ~ 117 DEG C, and described detect thickness is 35 ~ 45 μm.
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| CN104231571B (en) * | 2014-09-23 | 2016-08-24 | 苏州圣谱拉新材料科技有限公司 | Anti-flaming thermal-insulation film and preparation method thereof |
| CN106280303A (en) * | 2016-08-10 | 2017-01-04 | 安徽省宁国天成电工有限公司 | A kind of heater polyethylene terephthalate membrane material |
| CN106009556A (en) * | 2016-08-10 | 2016-10-12 | 安徽省宁国天成电工有限公司 | Polyethylene glycol terephthalate plastic film used for heating cable |
| CN106398133A (en) * | 2016-08-25 | 2017-02-15 | 太仓市鸿运包装材料有限公司 | Antistatic PET heat shrinkable film and preparation method thereof |
| CN106398132A (en) * | 2016-08-25 | 2017-02-15 | 太仓市鸿运包装材料有限公司 | Anti-ultraviolet PET heat shrinkable film and preparation method thereof |
| CN106398139A (en) * | 2016-09-28 | 2017-02-15 | 东莞市金顺包装材料有限公司 | Preparation method of sterilizing PET (Polyethylene Terephthalate) plastic |
| CN106349549B (en) * | 2016-11-03 | 2018-08-28 | 连云港雨虹篷布制品有限公司 | A kind of fire-retardant heat shrinkable package film and preparation method thereof |
| CN107556634A (en) * | 2017-08-31 | 2018-01-09 | 无锡英普林纳米科技有限公司 | A kind of environment-friendly type nano compressive film |
| CN108641310A (en) * | 2018-05-04 | 2018-10-12 | 宁国市千洪电子有限公司 | A kind of fire-retardant heat shrink films and manufacturing method |
| CN111793334B (en) * | 2020-08-18 | 2023-01-10 | 圆创享(苏州)新材料技术有限公司 | PET film and preparation method thereof |
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| CN101076556A (en) * | 2004-12-07 | 2007-11-21 | 伊斯曼化学公司 | Void-containing polyester shrink film with improved density retention |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6623821B1 (en) * | 1995-03-31 | 2003-09-23 | E. I. Du Pont De Nemours And Company | Heat-shrinkable, heat-sealable polyester film for packaging |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101076556A (en) * | 2004-12-07 | 2007-11-21 | 伊斯曼化学公司 | Void-containing polyester shrink film with improved density retention |
Non-Patent Citations (1)
| Title |
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| "聚酯热收缩薄膜";尹鸿梅等;《聚酯工业》;20011231;第14卷(第6期);第1-4、26页 * |
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