CN103483743A - PVC (polyvinyl chloride) heat shrinking film and preparation method thereof - Google Patents
PVC (polyvinyl chloride) heat shrinking film and preparation method thereof Download PDFInfo
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- CN103483743A CN103483743A CN201310453418.3A CN201310453418A CN103483743A CN 103483743 A CN103483743 A CN 103483743A CN 201310453418 A CN201310453418 A CN 201310453418A CN 103483743 A CN103483743 A CN 103483743A
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- pvc
- shrinkable film
- pvc heat
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92009—Measured parameter
- B29C2948/92114—Dimensions
- B29C2948/92152—Thickness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92323—Location or phase of measurement
- B29C2948/92428—Calibration, after-treatment, or cooling zone
Abstract
The invention discloses a PVC heat shrinking film which is prepared by raw materials in parts by weight as follows: 90-100 parts of PVC resin, 1-5 parts of an assistant, 2-5 parts of a lubricating agent, 1-3 parts of a plasticizer and 2-5 parts of an antioxidant. The invention further discloses a preparation method of the PVC heat shrinkage film. The PVC heat shrinkage film obtained by adopting the preparation method has better transparency compared with a common PVC heat shrinkage film, and is uniform in shrinkage, high in shrink rate and environment-friendly; and the preparation method is simple and easy to operate, and can realize large-scale production.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of PVC heat-shrinkable film and preparation method thereof.
Background technology
PVC heat-shrinkable film system with ethylene process polyvinyl chloride resin, with tens kinds of auxiliary materials, mix after the secondary inflations form, be characterized in that good, the easy contraction of transparency, intensity are high, shrinking percentage can need to freely be adjusted according to the user, workable.Although current whole some defect that has made up traditional technology of the PVC heat-shrinkable film of preparation, the PVC product obtained need to improve at aspect of performance, so requires study and prepare for the PVC heat-shrinkable film that various performance perameters all meet high request.
Summary of the invention
Goal of the invention: for the problems referred to above, first purpose of the present invention is to provide a kind of good toughness and PVC heat-shrinkable film transparent, environmental protection.Second purpose of the present invention is to provide the preparation method of this shrink film.
Technical scheme: in order solving the problems of the technologies described above, to the invention provides a kind of PVC heat-shrinkable film, mainly to be made by following raw material by weight: 90 ~ 100 parts of polyvinyl chloride resins, 1 ~ 5 part of auxiliary agent, 2 ~ 5 parts of lubricants, 1 ~ 3 part, softening agent, 2 ~ 5 parts, oxidation inhibitor.
Described polyvinyl chloride resin is SG-5.SG-5 buys in Shandong Bo Hui remittance paper industrial limited company.
Wherein, auxiliary agent is HANKINS NCP-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 to the sticking power of base material.Because its unique chemical structure HANKINS*NCP/2 has hydrolysis, frost resistance and the hydrophobicity of height.Significantly improve glossiness and transparency after emulsion film forming, significant ductility and Restoration, strengthen glue-line elasticity and force of cohesion, strengthened snappiness and elasticity, excellent moist cohesive strength and dryness bond strength, improved stripping strength, the sticking power of the sticky base of difficulty is being shown to raising, good high temperature performance, strengthen the film formation at low temp performance, greatly improve the low temperature resistant of polymkeric substance, anti-freezing property.
Described lubricant is a kind of in ethylene bis stearamide, glyceryl monostearate, stearyl alcohol or stearic acid.
Described softening agent is hexanodioic acid fat.
Described oxidation inhibitor is ESC-1010 oxidation inhibitor.
The preparation method of PVC heat-shrinkable film comprises the following steps:
1) take the raw material of above-mentioned parts by weight;
2) add polyvinyl chloride resin, auxiliary agent, lubricant, softening agent, oxidation inhibitor and stir 5 ~ 10min with 160 ~ 220rpm rotating speed in reactor at 70 ~ 80 ℃;
3) reactor temperature is increased to 280 ~ 300 ℃, Pressure Drop, to 90pa, reacts with this understanding 1 ~ 3h and obtains polymer melt, then the polymer melt of preparation is extruded, pelletizing, drying, obtains the PVC polyester slice;
4) above-mentioned PVC polyester slice is melt extruded, die head slab, slab spooling, two-way stretch, cooling and shaping, detect thickness, rolling, cutting and rewinding, packing, finished product.
Described to melt extrude temperature be 275 ~ 280 ℃, and described two-way stretch temperature is 110 ~ 116 ℃, and described detect thickness is 45 ~ 50 μ m.
Beneficial effect: the PVC heat-shrinkable film that the present invention obtains by above-mentioned preparation method, the transparency is good higher than common PVC heat-shrinkable film, and contraction is even and shrinking percentage is high, is environmentally friendly shrink film.Preparation method of the present invention is simple, easy to operate, can realize scale operation.This PVC heat-shrinkable film can be for food, electronics, machinery industry.
Embodiment
According to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand, the described concrete material proportion of embodiment is only for the present invention is described, and should also can not limit the present invention described in detail in claims.
Embodiment 1
PVC heat-shrinkable film of the present invention, mainly made by following raw material: 90 parts of the SG-5 of Shandong Bo Hui, 1 part of HANKINS NCP-2,2 parts of ethylene bis stearamides, 1 part, hexanodioic acid fat, 2 parts, ESC-1010 oxidation inhibitor by weight.
Take the raw material of above-mentioned parts by weight; Add SG-5, HANKINS NCP-2, ethylene bis stearamide, hexanodioic acid fat, ESC-1010 oxidation inhibitor and stir 5min with the 160rpm rotating speed in reactor at 70 ℃; Reactor temperature is increased to 280 ℃, and Pressure Drop, to 90pa, reacts with this understanding 1h and obtains polymer melt, then the polymer melt of preparation is extruded, pelletizing, drying, obtains the PVC polyester slice; By above-mentioned PVC polyester slice melt extrude, die head slab, slab spooling, two-way stretch, cooling and shaping, detect thickness, rolling, cutting and rewinding, packing, finished product.Described to melt extrude temperature be 275 ℃, and described two-way stretch temperature is 110 ℃, and described detect thickness is 45 μ m.
The performance perameter measuring result:
Embodiment 2
PVC heat-shrinkable film of the present invention, mainly made by following raw material: 100 parts of the SG-5 of Shandong Bo Hui, 5 parts of HANKINS NCP-2,5 parts of glyceryl monostearates, 3 parts, hexanodioic acid fat, 5 parts, ESC-1010 oxidation inhibitor by weight.
Take the raw material of above-mentioned parts by weight; Add SG-5, HANKINS NCP-2, glyceryl monostearate, hexanodioic acid fat, ESC-1010 oxidation inhibitor and stir 10min with the 220rpm rotating speed in reactor at 80 ℃; Reactor temperature is increased to 300 ℃, and Pressure Drop, to 90pa, reacts with this understanding 3h and obtains polymer melt, then the polymer melt of preparation is extruded, pelletizing, drying, obtains the PVC polyester slice; By above-mentioned PVC polyester slice melt extrude, die head slab, slab spooling, two-way stretch, cooling and shaping, detect thickness, rolling, cutting and rewinding, packing, finished product.Described to melt extrude temperature be 280 ℃, and described two-way stretch temperature is 116 ℃, and described detect thickness is 50 μ m.
The performance perameter measuring result:
Embodiment 3
PVC heat-shrinkable film of the present invention, mainly made by following raw material: 95 parts of the SG-5 of Shandong Bo Hui, 3 parts of HANKINS NCP-2,3 parts of stearyl alcohol, 2 parts, hexanodioic acid fat, 3 parts, ESC-1010 oxidation inhibitor by weight.
Take the raw material of above-mentioned parts by weight; Add SG-5, HANKINS NCP-2, stearyl alcohol, hexanodioic acid fat, ESC-1010 oxidation inhibitor and stir 7min with the 195rpm rotating speed in reactor at 75 ℃; Reactor temperature is increased to 295 ℃, and Pressure Drop, to 90pa, reacts with this understanding 2h and obtains polymer melt, then the polymer melt of preparation is extruded, pelletizing, drying, obtains the PVC polyester slice; By above-mentioned PVC polyester slice melt extrude, die head slab, slab spooling, two-way stretch, cooling and shaping, detect thickness, rolling, cutting and rewinding, packing, finished product.Described to melt extrude temperature be 277 ℃, and described two-way stretch temperature is 113 ℃, and described detect thickness is 47 μ m.
The performance perameter measuring result:
Embodiment 4
PVC heat-shrinkable film of the present invention, mainly made by following raw material: 96 parts of the SG-5 of Shandong Bo Hui, 4 parts of HANKINS NCP-2,4 parts of stearic acid, 3 parts, hexanodioic acid fat, 4 parts, ESC-1010 oxidation inhibitor by weight.
Take the raw material of above-mentioned parts by weight; At 77 ℃ toward the SG-5, the HANKINS NCP-2 that add in reactor, stearic acid, hexanodioic acid fat, ESC-1010 oxidation inhibitor and stir 7min with the 168rpm rotating speed; Reactor temperature is increased to 290 ℃, and Pressure Drop, to 90pa, reacts with this understanding 2.5h and obtains polymer melt, then the polymer melt of preparation is extruded, pelletizing, drying, obtains the PVC polyester slice; By above-mentioned PVC polyester slice melt extrude, die head slab, slab spooling, two-way stretch, cooling and shaping, detect thickness, rolling, cutting and rewinding, packing, finished product.Described to melt extrude temperature be 278 ℃, and described two-way stretch temperature is 115 ℃, and described detect thickness is 48 μ m.
The performance perameter measuring result:
Claims (8)
1. a PVC heat-shrinkable film, is characterized in that, mainly by following raw material, made by weight: 90 ~ 100 parts of polyvinyl chloride resins, 1 ~ 5 part of auxiliary agent, 2 ~ 5 parts of lubricants, 1 ~ 3 part, softening agent, 2 ~ 5 parts, oxidation inhibitor.
2. PVC heat-shrinkable film according to claim 1, is characterized in that, described polyvinyl chloride resin is SG-5.
3. PVC heat-shrinkable film according to claim 1, is characterized in that, described auxiliary agent is HANKINS NCP-2.
4. PVC heat-shrinkable film according to claim 1, is characterized in that, described lubricant is a kind of in ethylene bis stearamide, glyceryl monostearate, stearyl alcohol or stearic acid.
5. PVC heat-shrinkable film according to claim 1, is characterized in that, described softening agent is hexanodioic acid fat.
6. PVC heat-shrinkable film according to claim 1, is characterized in that, described oxidation inhibitor is ESC-1010 oxidation inhibitor.
7. the preparation method of PVC heat-shrinkable film claimed in claim 1, is characterized in that, comprises the following steps:
1) take the raw material of above-mentioned parts by weight;
2) add polyvinyl chloride resin, auxiliary agent, lubricant, softening agent, oxidation inhibitor and stir 5 ~ 10min with 160 ~ 220rpm rotating speed in reactor at 70 ~ 80 ℃;
3) reactor temperature is increased to 280 ~ 300 ℃, Pressure Drop, to 90pa, reacts with this understanding 1 ~ 3h and obtains polymer melt, then the polymer melt of preparation is extruded, pelletizing, drying, obtains the PVC polyester slice;
4) above-mentioned PVC polyester slice is melt extruded, die head slab, slab spooling, two-way stretch, cooling and shaping, detect thickness, rolling, cutting and rewinding, packing, finished product.
8. the preparation method of PVC heat-shrinkable film according to claim 7, is characterized in that, described to melt extrude temperature be 275 ~ 280 ℃, and described two-way stretch temperature is 110 ~ 116 ℃, and described detect thickness is 45 ~ 50 μ m.
Priority Applications (1)
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| CN201310453418.3A CN103483743B (en) | 2013-09-29 | 2013-09-29 | A kind of PVC heat-shrinkable film and preparation method thereof |
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| CN201310453418.3A CN103483743B (en) | 2013-09-29 | 2013-09-29 | A kind of PVC heat-shrinkable film and preparation method thereof |
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| CN103483743A true CN103483743A (en) | 2014-01-01 |
| CN103483743B CN103483743B (en) | 2016-03-16 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104194237A (en) * | 2014-08-18 | 2014-12-10 | 苏州市盛百威包装设备有限公司 | Polyisoprene composite winding film material and preparation method thereof |
| CN104212088A (en) * | 2014-08-06 | 2014-12-17 | 吴永 | Toxic-free thermal-shrinking thin film |
| CN104672715A (en) * | 2015-03-06 | 2015-06-03 | 苏州市景荣科技有限公司 | Environment-friendly antistatic agent for PVC (polyvinyl chloride) sole and preparation method of antistatic agent |
| CN106147063A (en) * | 2015-03-25 | 2016-11-23 | 温州瑞禾实业有限公司 | PVC heat shrink films |
| CN106188935A (en) * | 2016-07-08 | 2016-12-07 | 安徽致达包装有限公司 | A kind of production technology of the PVC heat shrink films packaging bag for tobacco smoke |
| CN106280110A (en) * | 2016-08-25 | 2017-01-04 | 太仓市鸿运包装材料有限公司 | A kind of antistatic PVC heat shrink films and preparation method thereof |
| CN106280109A (en) * | 2016-08-25 | 2017-01-04 | 太仓市鸿运包装材料有限公司 | A kind of uvioresistant PVC heat shrink films and preparation method thereof |
| CN106751228A (en) * | 2017-02-05 | 2017-05-31 | 山东中塑泰富科技有限公司 | A kind of PVC heat shrink films |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101463170A (en) * | 2008-12-31 | 2009-06-24 | 宿迁市彩塑包装有限公司 | Broad width polychloroethylene contraction film, and production facility and manufacturing process thereof |
| US20120141761A1 (en) * | 2009-08-12 | 2012-06-07 | Guenther Deiringer | Vinyl Chloride Polymer Film and Method for Producing Same |
-
2013
- 2013-09-29 CN CN201310453418.3A patent/CN103483743B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101463170A (en) * | 2008-12-31 | 2009-06-24 | 宿迁市彩塑包装有限公司 | Broad width polychloroethylene contraction film, and production facility and manufacturing process thereof |
| US20120141761A1 (en) * | 2009-08-12 | 2012-06-07 | Guenther Deiringer | Vinyl Chloride Polymer Film and Method for Producing Same |
Non-Patent Citations (2)
| Title |
|---|
| 周祥兴: ""PVC热收缩薄膜的新进展"", 《塑料包装》, vol. 13, no. 2, 30 May 2003 (2003-05-30), pages 38 - 40 * |
| 杨丽庭: "《聚氯乙烯改性及配方》", 30 November 2011, article ""第一节 聚氯乙烯热收缩膜"", pages: 185-188 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104212088A (en) * | 2014-08-06 | 2014-12-17 | 吴永 | Toxic-free thermal-shrinking thin film |
| CN104194237A (en) * | 2014-08-18 | 2014-12-10 | 苏州市盛百威包装设备有限公司 | Polyisoprene composite winding film material and preparation method thereof |
| CN104194237B (en) * | 2014-08-18 | 2016-08-24 | 苏州市盛百威包装设备有限公司 | A kind of polyisoprene composite winding membrane material and preparation method thereof |
| CN104672715A (en) * | 2015-03-06 | 2015-06-03 | 苏州市景荣科技有限公司 | Environment-friendly antistatic agent for PVC (polyvinyl chloride) sole and preparation method of antistatic agent |
| CN106147063A (en) * | 2015-03-25 | 2016-11-23 | 温州瑞禾实业有限公司 | PVC heat shrink films |
| CN106188935A (en) * | 2016-07-08 | 2016-12-07 | 安徽致达包装有限公司 | A kind of production technology of the PVC heat shrink films packaging bag for tobacco smoke |
| CN106280110A (en) * | 2016-08-25 | 2017-01-04 | 太仓市鸿运包装材料有限公司 | A kind of antistatic PVC heat shrink films and preparation method thereof |
| CN106280109A (en) * | 2016-08-25 | 2017-01-04 | 太仓市鸿运包装材料有限公司 | A kind of uvioresistant PVC heat shrink films and preparation method thereof |
| CN106751228A (en) * | 2017-02-05 | 2017-05-31 | 山东中塑泰富科技有限公司 | A kind of PVC heat shrink films |
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| CN103483743B (en) | 2016-03-16 |
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Effective date of registration: 20160204 Address after: 215431 Taicang City, Jiangsu province Liuhe Town, the new village gate Applicant after: Ji Xiangbao (Taicang) material science and Technology Development Co., Ltd. Address before: Shuangfeng town Suzhou city Jiangsu province 215400 Phoenix Road Taicang City, No. 999 Applicant before: Taicang Hongyun Package Materials Co., Ltd. |
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