WO2019075775A1 - 一种适用于生产线自动快速包装的热收缩膜 - Google Patents

一种适用于生产线自动快速包装的热收缩膜 Download PDF

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WO2019075775A1
WO2019075775A1 PCT/CN2017/108349 CN2017108349W WO2019075775A1 WO 2019075775 A1 WO2019075775 A1 WO 2019075775A1 CN 2017108349 W CN2017108349 W CN 2017108349W WO 2019075775 A1 WO2019075775 A1 WO 2019075775A1
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layer
barrier
production line
pop
shrinkable film
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PCT/CN2017/108349
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English (en)
French (fr)
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宋建新
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江阴升辉包装材料有限公司
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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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2307/308—Heat stability
    • 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
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/02—Open containers
    • B32B2439/06—Bags, sacks, sachets

Definitions

  • the invention relates to the technical field of heat shrinkable film, in particular to a heat shrinkable film suitable for automatic fast packaging of a production line.
  • Shrink film is widely used in the packaging of various products such as food, medicine, disinfection tableware, cultural and sports articles, craft gifts, printed matter, hardware and plastic products, telephones, electronic appliances, etc., especially in the combination of irregular physical goods or commodities (In terms of packaging, it can not only meet the functions of moisture-proof, dust-proof, touch-proof, transparent display, but also increase the attractiveness of the product. It can also be used to replace various types of paper boxes.
  • the traditional shrink bag packaging method is inefficient and cannot be automatically packaged online.
  • Cid patent document CN106739356 discloses a multi-layer co-extruded shrink film comprising a heat seal layer on the inner surface of the coextruded shrink film and an anti-mechanical damage layer on the outer surface, and a barrier intermediate between the heat seal layer and the anti-mechanical damage layer
  • the barrier intermediate layer comprises at least one layer of an ethylene-vinyl alcohol copolymer barrier core layer and at least one layer inner layer respectively disposed on both sides of the barrier core layer, and a secondary outer layer is disposed between the secondary inner layer and the anti-mechanical damage layer.
  • the secondary outer layer is connected to the mechanically damaged layer and the secondary inner layer on the surface of the barrier intermediate layer by an adhesive resin layer;
  • the heat seal layer is made of polyethylene;
  • the secondary inner layer is made of polyamide or polyethylene.
  • the technical problems solved by the invention are as follows: 1. The heat sealing performance of the film - low temperature heat sealing and high heat sealing strength; 2. film moving performance - better film flatness, flexibility; 3. film shrinkage performance - Higher heat shrinkage rate.
  • the invention 1) blown film 2) printing - bag making 3) manual packaging 4) vacuum sealing 5) heat shrinking - packaging finished product.
  • the invention 1) blown film 2) printing - slitting 3) automatic packaging on the machine - cutting - vacuum sealing - heat shrinking - packaging finished products, greatly improving packaging efficiency, reducing operational processes and steps, reducing product contamination risk.
  • the invention has the excellent performance and high barrier of the shrink bag, high strength, good heat sealing performance, and Excellent escape performance, suitable for fully automatic online packaging.
  • a heat shrinkable film suitable for automatic rapid packaging of a production line comprising a surface layer on the outer surface, a heat seal layer on the inner surface, and a barrier layer disposed between the skin layer and the heat seal layer;
  • the barrier layer comprises a layer of an ethylene-vinyl alcohol copolymer (EVOH) barrier intermediate layer, and the EVOH barrier intermediate layer is provided with a barrier layer protective layer on at least one side thereof, and the barrier layer protective layer is a polyamide ( a PA layer; the surface layer is a PA layer or a polyester (PET) layer;
  • the heat seal layer is a POP layer or a metallocene linear low density polyethylene (mLLDPE) layer, and an ultra low density polyethylene (ULDPE) a layer, a layer of Surlyn resin layer, or a blended layer of POP and mLLDPE;
  • the surface layer and the barrier layer, the barrier layer and the heat seal layer are respectively connected by a bonding resin (abbreviated
  • the polyester (PET) a general term for a polymer obtained by polycondensation of a polyhydric alcohol and a polybasic acid, mainly refers to polyethylene terephthalate. Choose from equipolymers, EASTMAN, Dufor C series, GN series, FX series, etc.
  • the Surlyn resin is a copolymer produced by DuPont DuPont in the United States using a unique production process and is a partial or total neutralization of a high pressure radically polymerized ethylene-methacrylic acid copolymer.
  • the POP is a vinyl polymer grafted polyether polyol, commonly known as "Polyether Polyol” (Polyether Polyol), which is a polyether (POP), which is an in-situ polymerization of ethylene and octene using a metallocene catalyst.
  • Thermoplastic elastomer Available in SABIC, Exxonmobil, DOW grade COHERE 8380, COHERE 8185, 9061, 9071, 9182, KC8852G, VP8770G1, 1881G, 1850G, etc.
  • the metallocene linear low density polyethylene is a linear copolymer of ethylene and an olefin having a narrow distribution molecular weight obtained by coordination polymerization using a metallocene compound as a catalyst.
  • PRIME, Exxonmobil, DOW grades 1018MF, 2018KB, 1012HJ, SP 1520, etc. can be selected.
  • a structural layer is disposed between the surface layer and the barrier layer, and the structural layer is selected from the group consisting of a polyethylene (PE) layer, an ethylene-vinyl acetate copolymer (EVA) layer, a POP layer, and a PP layer.
  • PE polyethylene
  • EVA ethylene-vinyl acetate copolymer
  • POP ethylene-vinyl acetate copolymer
  • PP PP layer
  • the PE is a lower density ( ⁇ 0.91 g/cm 3 ) PE. Exxonmobil, DuPont, DOW grades 701, 705, 3165, 3129, 1881, 1850, etc. can be selected.
  • a secondary inner layer is further disposed between the heat seal layer and the barrier layer, and the secondary inner layer is selected from the group consisting of A blended layer of one or both of a polyethylene (PE) layer, an ethylene-vinyl acetate copolymer (EVA) layer, and a POP layer, wherein the secondary inner layer and the barrier layer are joined by a bonding resin.
  • PE polyethylene
  • EVA ethylene-vinyl acetate copolymer
  • the surface layer PA layer is composed of PA6, copolymerized PA and amorphous PA, and the mass percentage of the amorphous PA in the resin is 10 to 30% (more preferably 20%), and the mass percentage of the copolymerized PA is 10 to 60% (more preferably 10%).
  • the resin of the PA layer of the barrier layer protective layer is composed of PA6, copolymerized PA and amorphous PA, and the mass percentage of the amorphous PA in the resin of the PA layer is not more than 40%.
  • the PA, the copolymerized PA, and the amorphous PA have a relative viscosity of 3.5-4.17 and a density of 1.12-1.19 g/cm 3 .
  • the heat seal layer is a blended layer of POP and mLLDPE, wherein the content of POP in the heat seal layer is 30-90% (more preferably 50%).
  • the number of film layers of the heat shrinkable film suitable for automatic fast packaging of the production line is 4 to 11 layers.
  • the heat shrinkable film suitable for automatic fast packaging of the production line has a total thickness of 40 to 100 um (preferably 75 um).
  • the surface layer accounts for 5-15% of the total thickness
  • the barrier layer accounts for 4-10% of the total thickness
  • the heat seal layer accounts for 18-35% of the total thickness
  • the structural layer accounts for 30-50% of the total thickness.
  • the heat shrinkable film has a longitudinal/lateral shrinkage ratio of 20-45 (90 ° C), an elongation of 80-180, a surface tension of 36-40 dyne, a heat-sealing temperature of 80-90 ° C, and a melting point of 90- 220 ° C.
  • the heat seal layer further comprises an opening agent
  • the outer layer further comprises a slip agent
  • the heat shrinkable film includes a surface layer (PA), a structural layer (PE), and a barrier layer (PA/EVOH/PA, including an EVOH barrier intermediate layer and both sides, from the outside to the inside.
  • the barrier layer is a PA layer) and a heat seal layer (POP+mLLDPE).
  • the surface layer, the structural layer, the barrier layer and the heat seal layer are respectively connected by a bonding resin (Tie).
  • the specific membrane structure is: PA/Tie/PE/Tie/PA/EVOH/PA/Tie/POP+mLLDPE;
  • the PA in the surface layer and the middle layer are all blended with PA6, copolymerized PA and amorphous PA.
  • the mass percentage of copolymerized PA in the resin of the PA layer is 10%, the content of POP in the heat seal layer is 90%, and the total thickness of the film. It is 75um.
  • the heat shrinkable film is selected from the outside to the specific film structure:
  • the specific film structure of the heat shrinkable film is:
  • a production process of a heat shrinkable film suitable for automatic fast packaging of a production line as described above comprising the steps of:
  • the heating temperature of the PA resin forming the protective layer of the barrier layer is 255 to 265 ° C
  • the temperature of the cooling water in the cooling water quenching and setting step is 5 to 15 ° C.
  • the heating temperature of the POP and PE of the heat seal layer is 220 to 230 °C.
  • the method specifically includes the following steps:
  • the S1 co-extruded film is extruded from top to bottom by water cooling to achieve film cooling and control of crystal formation to facilitate the orientation of the molecular segments and reduce the haze of the film.
  • the water-cooling treatment water temperature in S1 is 5 to 15 ° C, and the flow rate is 20 to 35 L/min.
  • the preheating temperature in S2 is 30 to 80 ° C; the inflation ratio of the secondary inflation is 1.5 to 4, and the traction ratio is 2.5 to 3.0.
  • the inflation ratio and the draw ratio of the secondary inflation match the crystallinity of the coextruded film in S1. If the inflation ratio and the traction ratio are too large, the bubble is unstable, and the film is prone to wrinkles; if it is too small, the shrinkage of the finished product is less than 30%, which does not meet the requirements of the finished packaging.
  • the setting temperature in S3 is 30 to 70 °C.
  • the stereotyping effect of the three bubbles can effectively inhibit the free shrinkage of the ordinary shrink film during storage (the natural solution orientation of the molecular chain at the storage environment temperature).
  • the water-cooling treatment water temperature in S1 is 10 ° C, and the flow rate is 20 to 30 L/min.
  • the preheating temperature in S2 was 75 ° C; the inflation ratio of the secondary inflation was 3.0, and the draw ratio was 3.0.
  • the setting temperature in S3 is 60 °C.
  • heat sealing material In order to improve the anti-pollution heat sealing ability and heat sealing heat-bonding strength of the material, POP, ULDPE, SURLYN and other materials are used in the heat sealing layer; the heat sealing layer adopts a density of about 0.9 g/cm 3 PE heat seal layer, or sarin heat seal layer. It has excellent low temperature heat sealability and high efficiency anti-pollution heat sealing performance.
  • the unsealing temperature is 10-20 ° C lower than conventional materials.
  • the heat seal strength rise rate In addition to the low seal temperature, it is also necessary to increase the heat seal strength rise rate, that is, the heat seal strength is increased more in the same temperature range.
  • low-melting materials have a lower sealing temperature, but their heat-sealing strength is correspondingly weak.
  • the insufficient heat-sealing strength may cause heat sealing problems.
  • increasing the heat seal strength is a major point to be solved in the application of such automatic packaging line.
  • the invention achieves the coordination of the low sealing temperature and the high heat sealing strength by the auxiliary heat sealing by the heat sealing layer and the secondary inner layer.
  • film flatness through the choice of structural layer material to control the softness of the film, the use of lower density ⁇ 0.91g / cm 3 PE, or softer materials such as EVA used in the structural layer, making it better Film flatness, softness.
  • Shrinkage properties of the film on the one hand, controlled by the process conditions, on the other hand, controlled by materials, especially the PA layer material will limit the shrinkage rate of the film, select the slower PA material, increase the proportion of the copolymerized nylon, add Amorphous nylon or the like to increase the shrinkage rate of the film.
  • the novel heat shrinkable film of the invention has the excellent performance and high barrier possession of the shrink bag, high strength, good heat sealing performance, and excellent passenger performance, and is suitable for fully automatic online packaging, and the invention will change the packaging method of the shrink bag. And packaging efficiency.
  • Example 1 is a schematic cross-sectional structural view of a heat shrinkable film in Example 1.
  • the heat shrinkable film comprises, in order from the outside to the inside, a surface layer 1 (PA), a structural layer 2 (PE), a barrier layer 3 (PA/EVOH/PA, including an EVOH barrier intermediate layer 31 and barrier layer protective layers 32 on both sides). It is a PA layer), a heat seal layer 4 (POP+mLLDPE).
  • the surface layer 1, the structural layer 2, the barrier layer 3, and the heat seal layer 4 are connected by an adhesive resin 5 (Tie), respectively.
  • the specific membrane structure is: PA/Tie/PE/Tie/PA/EVOH/PA/Tie/POP+mLLDPE;
  • the PA of the surface layer 1 and the middle two layers are all blended with PA6, copolymerized PA and amorphous PA.
  • the mass percentage of copolymerized PA in the resin of the PA layer is 10%, the content of the POP of the heat seal layer is 90%, and the total thickness of the film. It is 75um.
  • PE is a lower density ( ⁇ 0.91 g/cm 3 ) PE.
  • the production process includes the following steps:
  • S1 The raw material is placed in an extruder and co-extruded to obtain a membrane tube, and the membrane tube is cooled; the water-cooling treatment water temperature in S1 is 10 ° C, and the flow rate is 20 to 30 L/min.
  • S3 The film obtained by the second inflation is drawn to the shaping mechanism, and is again heated to the setting temperature to shape the film, and the multi-layer co-extruded shrink film is finished.
  • the setting temperature in S3 is 60 °C.
  • the metallocene material mLLDPE was added to the heat seal layer, and the difference from Example 1 was that the content of the heat seal layer POP was 85%, 70%, and 50%, respectively.
  • the mass percentages of the copolymerized PA in the resin of the surface layer and the middle two layers of PA and PA layers were 20%, 30%, 40%, and 50%, respectively.
  • the inflation ratio of the secondary inflation in S2 is 2.0-4.5, and the traction ratio is 3.0-3.5.
  • the specific membrane structure is: PA/Tie/PE/Tie/PA/EVOH/PA/Tie/PE.
  • the specific membrane structure is: PA/Tie/PE/Tie/PA/EVOH/PA/Tie/POP.
  • Comparative Example 1-2 The production process steps of Comparative Example 1-2 were the same as in Example 1, and the PA of the surface layer and the middle two layers were both PA6.
  • Examples 1-5 and Comparative Example 1-2 Low-temperature heat-sealing property data (take heat-sealing temperature point values of 90 ° C, 100 ° C, 110 ° C, 120 ° C, 130 ° C, 140 ° C) are shown in Table 1 below, Example 1 The 90 °C shrinkage % of 8 and Comparative Example 1-2 are shown in Table 2 below:
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Comparative example 1 Comparative example 2 MD 36.75 37.50 41.00 44.13 45.38 30.65 31.50 TD 36.65 37.50 37.88 42.75 43.88 30.55 30.85
  • Example 6 Example 7
  • Example 8 MD 45.4 45.8 46.45 TD 44.12 44.57 45.53
  • Example 5/6/7/8 It can be seen from Example 5/6/7/8 that the heat shrinkage rate of the film can be increased by increasing the proportion of the copolymerized PA. This is mainly due to the more random segments that can be oriented in the copolymerized PA.

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Abstract

一种适用于生产线自动快速包装的热收缩膜，包括位于外表面的表层（1），位于内表面的热封层（4），和设置在表层（1）和热封层（4）之间的阻隔层（3）；阻隔层（3）包括一层EVOH阻隔中间层（31），EVOH阻隔中间层（31）至少一侧设有一层阻隔层保护层（32），阻隔层保护层（32）为PA层；表层（1）为PA层；热封层（4）为POP层或mLLDPE层、ULDPE层、Surlyn树脂层中的一种，或POP和mLLDPE的共混层；表层（1）和阻隔层（3）、阻隔层（3）和热封层（4）之间分别通过粘接树脂（5）连接。该热收缩膜具有高阻隔，高强度，热封性能好，同时具有优良的走机性能，适用于全自动在线包装，改变了收缩袋的包装方式及包装效率。

Description

一种适用于生产线自动快速包装的热收缩膜 技术领域
本发明涉及热收缩膜技术领域，具体地说，是一种适用于生产线自动快速包装的热收缩膜。
背景技术
收缩膜广泛应用于食品、药品、消毒餐具、文体用品、工艺礼品、印刷品、五金塑料制品、电话、电子电器等等各种产品的外包装，尤其是在不规则形体物品或商品的组合式(集束)包装方面，既能满足商品的防潮防尘、防触摸偷换、透明展示等功能，又能增加产品外观吸引力，也可用于代替各类纸盒。传统的收缩袋包装方式效率较低，无法实现在线自动包装。
中国专利文献CN106739356公开了一种多层共挤收缩膜，包括位于共挤收缩膜内表面的热封层和外表面的抗机械损伤层，热封层和抗机械损伤层之间设置有阻隔中间层，阻隔中间层包含至少一层乙烯-乙烯醇共聚物阻隔芯层和分别设置在阻隔芯层两侧的至少一层次内层，次内层与抗机械损伤层之间设置有次外层，次外层与抗机械损伤层以及位于阻隔中间层表面的次内层之间分别通过粘接树脂层连接；热封层的材质为聚乙烯；次内层的材质为聚酰胺或聚乙烯。但是关于一种适用于生产线自动快速包装的热收缩膜目前还未见报道。
发明内容
本发明的目的在于克服现有技术中存在的缺陷，提供一种适用于生产线自动快速包装的热收缩膜。
本发明解决的技术问题在于：1.薄膜的热封性能-低温热封且热封强度要高；2.薄膜的走机性能-较好的薄膜平整度，柔软性；3.薄膜的收缩性能-较高的热收缩率。
原有技术：1)吹膜2)印刷-制袋3)人工包装4)抽真空封口5)热收缩-包装成品。而本发明：1)吹膜2)印刷-分切3)上机自动包装-切割-抽真空封口-热收缩-包装成品，大大提高包装效率，减少操作流程与步骤，降低产品的污染风险。本发明具有收缩袋所拥有的优异性能高阻隔，高强度，热封性能好，同时具有 优良的走机性能，适用于全自动在线包装。
本发明的第一方面，提供一种适用于生产线自动快速包装的热收缩膜，包括位于外表面的表层，位于内表面的热封层，和设置在表层和热封层之间的阻隔层；所述的阻隔层包括一层乙烯-乙烯醇共聚物(EVOH)阻隔中间层，所述的EVOH阻隔中间层至少一侧设有一层阻隔层保护层，所述的阻隔层保护层为聚酰胺(PA)层；所述的表层为PA层或聚酯(PET)层；所述的热封层为POP层或茂金属线型低密度聚乙烯(mLLDPE)层、超低密度聚乙烯(ULDPE)层、Surlyn树脂层中的一种，或POP和mLLDPE的共混层；所述的表层和阻隔层、阻隔层和热封层之间分别通过粘接树脂(简称Tie)连接。
所述的聚酯(PET)，由多元醇和多元酸缩聚而得的聚合物总称，主要指聚对苯二甲酸乙二酯。可选择equipolymers，EASTMAN，Dufor牌号C系列，GN系列，FX系列等。
所述的Surlyn树脂是杜邦美国杜邦公司利用独特的生产工艺聚合而成，是由高压自由基聚合的乙烯-甲基丙烯酸共聚物经部分或全部中和而制成的一种共聚物。
所述的POP是乙烯基聚合物接枝聚醚多元醇，俗称“聚合物多元醇”(Polyether Polyol)，简称聚醚(POP)，是采用茂金属催化剂的乙烯和辛烯实现原位聚合的热塑性弹性体。可选择SABIC，Exxonmobil，DOW牌号COHERE 8380，COHERE8185，9061，9071，9182，KC8852G，VP8770G1，1881G，1850G等。
所述的茂金属线型低密度聚乙烯(metallocene linear low density polyethylene，简称mLLDPE)用茂金属化合物做催化剂，经配位聚合得到的具有窄分布分子量的乙烯和物-烯烃的线型共聚物。可选择PRIME，Exxonmobil，DOW牌号1018MF，2018KB，1012HJ，SP 1520等。
优选的，所述的表层和阻隔层之间设有结构层，所述的结构层为选自聚乙烯(PE)层、乙烯-醋酸乙烯共聚物(EVA)层、POP层、PP层中的一种或两种的共混层，所述的结构层与表层、阻隔层之间分别通过粘接树脂连接。更优选的，所述的PE为较低密度(≤0.91g/cm3)的PE。可选择Exxonmobil，DuPont，DOW牌号701，705，3165，3129，1881，1850等。
优选的，所述的热封层和阻隔层之间还设有次内层，所述的次内层为选自 聚乙烯(PE)层、乙烯-醋酸乙烯共聚物(EVA)层、POP层中的一种或两种的共混层，所述的次内层与阻隔层之间通过粘接树脂连接。
优选的，所述的表层PA层由PA6、共聚PA和无定型PA共混而成，树脂中无定型PA的质量百分比为10～30％(更优选为20％)，共聚PA的质量百分比为10～60％(更优选为10％)。
优选的，所述的阻隔层保护层的PA层的树脂由PA6、共聚PA和无定型PA共混而成，PA层的树脂中无定型PA的质量百分比不大于40％。
优选的，所述的PA、共聚PA、无定型PA的相对粘度3.5-4.17，密度1.12-1.19g/cm3。
优选的，所述的热封层为POP和mLLDPE的共混层，其中热封层中POP的含量为30-90％(更优选为50％)。
优选的，所述的适用于生产线自动快速包装的热收缩膜的膜层数为4～11层。
优选的，所述的适用于生产线自动快速包装的热收缩膜的总厚度为40～100um(优选75um)。其中表层占总厚度的5-15％，阻隔层占总厚度的4-10％，热封层占总厚度的18-35％，结构层占总厚度的30-50％。
优选的，所述的热收缩膜：纵向/横向收缩率20-45(90℃)，伸长率80-180，表面张力36-40达因，热起封温度80-90℃，熔点90-220℃。
优选的，所述的热封层中还包括开口剂，外表层还包括爽滑剂。
在本发明的一个优选实施方式中，所述的热收缩膜由外至内依次包括表层(PA)、结构层(PE)、阻隔层(PA/EVOH/PA，包括EVOH阻隔中间层和两侧的阻隔层保护层为PA层)、热封层(POP+mLLDPE)。所述的表层、结构层、阻隔层和热封层之间分别通过粘接树脂(Tie)连接。
具体膜结构为：PA/Tie/PE/Tie/PA/EVOH/PA/Tie/POP+mLLDPE；
其中表层和中间两层的PA均采用PA6、共聚PA和无定型PA共混而成，PA层的树脂中共聚PA的质量百分比为10％，热封层POP的含量为90％，薄膜总厚度为75um。
在本发明的其他优选实施方式中，所述的热收缩膜由外至内具体的膜结构选自：
PA/Tie/PA/EVOH/PA/Tie/POP；
PA/Tie/PA/EVOH/PA/Tie/POP+mLLDPE；
PA/Tie/PE/Tie/EVOH/PA/Tie/mLLDPE；
PA/Tie/EVA/Tie/EVOH/PA/Tie/mLLDPE；
PA/Tie/EVOH/PA/Tie/POP；
PA/Tie/EVOH/PA/Tie/mLLDPE；
PA/Tie/EVOH/PA/Tie/POP+mLLDPE；
PA/Tie/EVA/Tie/PA/EVOH/PA/Tie/POP；
PA/Tie/EVA/Tie/PA/EVOH/PA/Tie/mLLDPE；
PA/Tie/EVA/Tie/PA/EVOH/PA/Tie/POP+mLLDPE；
PET/Tie/PE/Tie/PA/EVOH/PA/Tie/PE；
PET/Tie/PE/Tie/PA/EVOH/PA/Tie/POP；
PET/Tie/PE/Tie/PA/EVOH/PA/Tie/mLLDPE；
PET/Tie/PE/Tie/PA/EVOH/PA/Tie/POP+mLLDPE；
PET/Tie/PP/Tie/PA/EVOH/PA/Tie/PE；
PET/Tie/PP/Tie/PA/EVOH/PA/Tie/POP；
PET/Tie/PP/Tie/PA/EVOH/PA/Tie/mLLDPE；
PET/Tie/PP/Tie/PA/EVOH/PA/Tie/POP+mLLDPE；
PET/Tie/EVA/Tie/PA/EVOH/PA/Tie/PE；
PET/Tie/EVA/Tie/PA/EVOH/PA/Tie/POP；
PET/Tie/EVA/Tie/PA/EVOH/PA/Tie/mLLDPE；
PET/Tie/EVA/Tie/PA/EVOH/PA/Tie/POP+mLLDPE。
在本发明的一个优选实施方式中，所述的热收缩膜具体膜结构为：
PA/Tie/EVA/Tie/PA/EVOH/PA/Tie/POP+mLLDPE。
本发明的第三方面，提供一种如上所述的适用于生产线自动快速包装的热收缩膜的生产工艺，包括以下步骤：
生产工艺，包括挤出塑化、多层共挤模头成型、冷却水骤冷、第一膜管预热、二次吹胀、牵引、热定型、牵引、收卷，多层共挤模头成型步骤中对形成阻隔层保护层的PA树脂的加热温度为255～265℃，冷却水骤冷定型步骤中冷却水的温度为5～15℃。热封层的POP和PE的加热温度为220～230℃。
优选的，具体包括以下步骤：
S1：将原料置于挤出机中共挤制得膜管，对膜管冷却处理；
S2：加热冷却后的膜管至预热温度，对膜管进行拉伸，然后利用压缩空气进行二次吹胀；
S3：将二次吹胀所得薄膜牵引至定型机构，再次加热至定型温度对薄膜定型处理，得多层共挤收缩膜成品。
其中，S1共挤薄膜由上而下挤出采用水冷，实现薄膜猝冷，控制结晶的生成，以利于分子链段的取向，可降低薄膜的雾度。优选的，S1中的水冷处理水温为5～15℃，流速为20～35L/min。
优选的，S2中预热温度为30～80℃；二次吹胀的吹胀比为1.5～4，牵引比为2.5～3.0。二次吹胀的吹胀比和牵引比与S1中共挤薄膜的结晶度相匹配。吹胀比和牵引比太大容易造成膜泡不稳定，且薄膜容易出现皱折；太小则成品的收缩率低于30％，达不到成品包装的要求。
优选的，S3中定型温度为30～70℃。三泡的定型作用可以有效的抑制普通收缩膜在存储过程中的自由收缩(存储环境温度下，分子链的自然解取向)。
更优选的，S1中的水冷处理水温为10℃，流速为20～30L/min。
S2中预热温度为75℃；二次吹胀的吹胀比为3.0，牵引比为3.0。
S3中定型温度为60℃。
与现有技术相比，本发明优点和有益效果在于：
1、热封材料的选择：为提高材料的抗污染热封能力及热封热粘强度，在热封层使用POP、ULDPE、SURLYN等材料；热封层采用了密度在0.9g/cm3左右的PE热封层，或沙林热封层。具有优异的低温热封性与高效的抗污染热封性能。起封温度比常规材料降低10-20℃。
除了低起封温度，还需要提高热封强度上升速度，即在同样的温度区间内，热封强度增加更多。通常低熔点的材料会有较低的起封温度，但是其热封强度相应较弱，在快速自动包装的过程中，由于材料受热时间较短，瞬间热封强度不够会导致热封问题，因此在降低热封起封温度的同时，提高热封强度是这种自动包装线应用需解决的一大要点。本发明通过热封层和次内层做辅助热封，来达到低起封温度和高热封强度的协调。
2、薄膜平整度：通过结构层材料的选择来控制薄膜的柔软度，使用较低密度≤0.91g/cm3的PE，或EVA等较柔软的材料用在结构层，使其具有较好的 薄膜平整度，柔软性。
3.薄膜的收缩性能：一方面通过工艺条件来控制，另一方面通过材料来控制，特别是PA层材料会限制薄膜的收缩率，选择结晶较慢的PA材料，增加共聚尼龙的比例，添加无定型尼龙等来提高薄膜的收缩率。
本发明的新型热收缩膜具有收缩袋所拥有的优异性能高阻隔，高强度，热封性能好，同时具有优良的走机性能，适用于全自动在线包装，本发明将改变收缩袋的包装方式及包装效率。
附图说明
图1是实施例1中热收缩膜的截面结构示意图。
附图中涉及的附图标记和组成部分如下所示：
1-表层             2-结构层
3-阻隔层           4-热封层
5-粘接树脂         31-EVOH阻隔中间层
32-阻隔层保护层
具体实施方式
下面结合实施例对本发明提供的具体实施方式作详细说明。
实施例1
所述的热收缩膜由外至内依次包括表层1(PA)、结构层2(PE)、阻隔层3(PA/EVOH/PA，包括EVOH阻隔中间层31和两侧的阻隔层保护层32为PA层)、热封层4(POP+mLLDPE)。所述的表层1、结构层2、阻隔层3和热封层4之间分别通过粘接树脂5(Tie)连接。
具体膜结构为：PA/Tie/PE/Tie/PA/EVOH/PA/Tie/POP+mLLDPE；
表层1和中间两层的PA均采用PA6、共聚PA和无定型PA共混而成，PA层的树脂中共聚PA的质量百分比为10％，热封层4POP的含量为90％，薄膜总厚度为75um。PE为较低密度(≤0.91g/cm3)的PE。
生产工艺包括以下步骤：
S1：将原料置于挤出机中共挤制得膜管，对膜管冷却处理；S1中的水冷处理水温为10℃，流速为20～30L/min。
S2：加热冷却后的膜管至预热温度，对膜管进行拉伸，然后利用压缩空气 进行二次吹胀；S2中预热温度为75℃；二次吹胀的吹胀比为3.0，牵引比为3.0。
S3：将二次吹胀所得薄膜牵引至定型机构，再次加热至定型温度对薄膜定型处理，得多层共挤收缩膜成品。S3中定型温度为60℃。
实施例2-4
在热封层加入茂金属材料mLLDPE，与实施例1的区别是热封层POP的含量分别为85％、70％、50％。
实施例5-8
表层和中间两层PA，PA层的树脂中共聚PA的质量百分比分别为20％、30％、40％、50％。其中S2中二次吹胀的吹胀比为2.0-4.5，牵引比为3.0-3.5。
对比例1
具体膜结构为：PA/Tie/PE/Tie/PA/EVOH/PA/Tie/PE。
对比例2
具体膜结构为：PA/Tie/PE/Tie/PA/EVOH/PA/Tie/POP。
对比例1-2的生产工艺步骤与实施例1相同，表层和中间两层的PA均采用PA6。
实施例9
性能检测对比：
对实施例1-8和对比例1-2薄膜的低温热封性和收缩率进行对比。
实施例1-5和对比例1-2低温热封性数据(取热封温度点值90℃、100℃、110℃、120℃、130℃、140℃)见下表1，实施例1-8和对比例1-2的90℃收缩率％见下表2：
表1
Figure PCTCN2017108349-appb-000001
表2
90℃收缩率％ 实施例1 实施例2 实施例3 实施例4 实施例5 对比例1 对比例2
MD 36.75 37.50 41.00 44.13 45.38 30.65 31.50
TD 36.65 37.50 37.88 42.75 43.88 30.55 30.85
表2(续)
90℃收缩率％ 实施例6 实施例7 实施例8
MD 45.4 45.8 46.45
TD 44.12 44.57 45.53
(1)通过对比例1和2可以看到，热封层单使用POP或mLLDPE，薄膜均不具备低温热封的性能，且热封强度在所需要的温度区间都不高。
(2)通过对比例1和2和实施例1可以看到，在PA层加入共聚PA和无定型PA后，薄膜的热收缩率有了明显的提高。
(3)通过实施例5/6/7/8可以看到，通过增加共聚PA的比例，可以提高薄膜的热收缩率。这主要是由于共聚PA中可取向的无规链段更多。
(4)通过实施例3～4可以看到，通过POP和mLLDPE的辅配，具有很好的协同效应，既降低了起封温度，又提高了热封强度，解决了低起封温度，在同样的温度区间内，热封强度增加更多的问题。
(5)通过实施例1和对比例1对比例2，POP的加入使得薄膜的起封温度降低20-40℃，随着混合POP的量减少mLLDPE增加，低温热封强度有所提升。
以上已对本发明创造的较佳实施例进行了具体说明，但本发明创造并不限于所述实施例，熟悉本领域的技术人员在不违背本发明创造精神的前提下还可做出种种的等同的变型或替换，这些等同的变型或替换均包含在本申请权利要求所限定的范围内。

Claims (10)

  1. 一种适用于生产线自动快速包装的热收缩膜，其特征在于，包括位于外表面的表层，位于内表面的热封层，和设置在表层和热封层之间的阻隔层；所述的阻隔层包括一层EVOH阻隔中间层，所述的EVOH阻隔中间层至少一侧设有一层阻隔层保护层，所述的阻隔层保护层为PA层；所述的表层为PA层；所述的热封层为POP层或mLLDPE层、ULDPE层、Surlyn树脂层中的一种，或POP和mLLDPE的共混层；所述的表层和阻隔层、阻隔层和热封层之间分别通过粘接树脂连接。
  2. 根据权利要求1所述的适用于生产线自动快速包装的热收缩膜，其特征在于，所述的表层和阻隔层之间设有结构层，所述的结构层为选自PE层、EVA层、POP层、PP层中的一种或两种的共混层，所述的结构层与表层、阻隔层之间分别通过粘接树脂连接；所述的PE为密度≤0.91g/cm3的PE。
  3. 根据权利要求1所述的适用于生产线自动快速包装的热收缩膜，其特征在于，所述的热封层和阻隔层之间还设有次内层，所述的次内层为选自PE层、EVA层、POP层中的一种或两种的共混层，所述的次内层与阻隔层之间通过粘接树脂连接。
  4. 根据权利要求1所述的适用于生产线自动快速包装的热收缩膜，其特征在于，所述的表层PA层由PA6、共聚PA和无定型PA共混而成，树脂中无定型PA的质量百分比为10～30％，共聚PA的质量百分比为10～60％。
  5. 根据权利要求1所述的适用于生产线自动快速包装的热收缩膜，其特征在于，所述的阻隔层保护层的PA层的树脂由PA6、共聚PA和无定型PA共混而成，PA层的树脂中无定型PA的质量百分比不大于40％。
  6. 根据权利要求1所述的适用于生产线自动快速包装的热收缩膜，其特征在于，所述的热封层为POP和mLLDPE的共混层，其中热封层中POP的含量为30-70％。
  7. 根据权利要求1所述的适用于生产线自动快速包装的热收缩膜，其特征在于，所述的适用于生产线自动快速包装的热收缩膜的膜层数为4～11层；所述的适用于生产线自动快速包装的热收缩膜的总厚度为40～100um。
  8. 一种如权利要求1-7任一所述的适用于生产线自动快速包装的热收缩膜的生产工艺，其特征在于，包括以下步骤：
    S1：将原料置于挤出机中共挤制得膜管，对膜管冷却处理；
    S2：加热冷却后的膜管至预热温度，对膜管进行拉伸，然后利用压缩空气进行二次吹胀；
    S3：将二次吹胀所得薄膜牵引至定型机构，再次加热至定型温度对薄膜定型处理，得多层共挤收缩膜成品。
  9. 根据权利要求8所述的适用于生产线自动快速包装的热收缩膜的生产工艺，其特征在于，S2中预热温度为30～80℃；二次吹胀的吹胀比为1.5～4，牵引比为2.5～3.0。
  10. 根据权利要求8所述的适用于生产线自动快速包装的热收缩膜的生产工艺，其特征在于，S3中定型温度为30～70℃。
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