WO2013097570A1 - 一种聚烯烃热收缩薄膜及其制备方法 - Google Patents

一种聚烯烃热收缩薄膜及其制备方法 Download PDF

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Publication number
WO2013097570A1
WO2013097570A1 PCT/CN2012/085352 CN2012085352W WO2013097570A1 WO 2013097570 A1 WO2013097570 A1 WO 2013097570A1 CN 2012085352 W CN2012085352 W CN 2012085352W WO 2013097570 A1 WO2013097570 A1 WO 2013097570A1
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WIPO (PCT)
Prior art keywords
ethylene
random copolymer
film
shrinkable film
norbornene
Prior art date
Application number
PCT/CN2012/085352
Other languages
English (en)
French (fr)
Inventor
胡卓荣
邹晓明
徐文树
朱健民
区雄锐
荣立平
Original Assignee
广东德冠薄膜新材料股份有限公司
广东德冠包装材料有限公司
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Application filed by 广东德冠薄膜新材料股份有限公司, 广东德冠包装材料有限公司 filed Critical 广东德冠薄膜新材料股份有限公司
Priority to EP12861649.7A priority Critical patent/EP2799230B1/en
Priority to US14/369,337 priority patent/US10005262B2/en
Priority to JP2014549326A priority patent/JP5933750B2/ja
Publication of WO2013097570A1 publication Critical patent/WO2013097570A1/zh

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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
    • 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
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • 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
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • 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
    • B29C61/00—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor
    • B29C61/003—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor characterised by the choice of material
    • 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
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02—Forms or constructions
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/04—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps to be fastened or secured by the material of the label itself, e.g. by thermo-adhesion
    • 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
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • 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
    • B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
    • B29C63/38—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor by liberation of internal stresses
    • B29C63/42—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor by liberation of internal stresses using tubular layers or sheathings
    • B29C63/423—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor by liberation of internal stresses using tubular layers or sheathings specially applied to the mass-production of externally coated articles, e.g. bottles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/38—Polymers of cycloalkenes, e.g. norbornene or cyclopentene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/02—Condition, form or state of moulded material or of the material to be shaped heat shrinkable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0049—Heat shrinkable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • 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
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • 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
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • 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
    • B32B2307/54—Yield strength; Tensile strength
    • 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
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B32B2307/736—Shrinkable
    • 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
    • B32B2519/00—Labels, badges
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02—Forms or constructions
    • G09F2003/0251—Sleeve shaped label, i.e. wrapped around a device
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02—Forms or constructions
    • G09F2003/0272—Labels for containers
    • G09F2003/0273—Labels for bottles, flasks
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree

Definitions

  • the present invention generally relates to a heat-shrinkable film comprising an ethylene-propylene random copolymer, an ethylene-norbornene copolymer having different norbornene contents, and a hydrogenated petroleum resin, and a process for producing the same. More particularly, the present invention relates to a temperature-resistant and heat-resistant biaxially oriented polyolefin heat-shrinkable film suitable for use as a heat shrinkable label and a method of producing the same.
  • the heat-shrinkable film improves the heat-resistant filling of soft drinks or the packaging required for packaging with PE shrink film, on the basis of maintaining high temperature shrinkage, complete shrinkage pattern, low density, low natural shrinkage, and easy recycling. Temperature performance, can be used as an environmentally friendly heat shrink label widely used in high-speed packaging, steam drying shrink packaging and PE packaging.
  • thermothermal shrink labels are mainly made of polyvinyl chloride.
  • Polyvinyl chloride has the advantages of high gloss, low haze, high stiffness, moderate heat shrinkage, pattern distortion after shrinkage and low natural shrinkage. It is often preferred as a heat shrinkable label, but PVC is difficult to recover and burn. It is easy to produce environmental pollution problems such as dioxins.
  • BOPET biaxially stretched polyester
  • BOPS biaxially oriented polystyrene
  • BOPO biaxially oriented polyolefin
  • the traditional biaxially oriented polyolefin (BOPO) material has the advantages of low density (less than lg/cm 3 ), easy recovery, and no pollution of combustion products, and thus has become a research hotspot of environmentally friendly heat shrinkable film.
  • BOPO biaxially oriented polyolefin
  • it also has a high shrinkage temperature, especially when the labels between the bottles are easily adhered during hot filling of the beverage or when the bottles of the group are packed with the shrinkable PE shrink film, the label and the PE shrink film are easily adhered. Its application is greatly limited.
  • the traditional polyolefin shrink film can achieve 40% shrinkage above 110 °C, and this temperature will also make the PET bottle deformable and can not be used. In order to improve the contraction The problem of high temperature is high.
  • Chinese Patent ZL03104526.X discloses a combination of a copolymer obtained by random copolymerization of propylene and a ct-olefin having 2 to 20 carbon atoms, a random polypropylene resin and an alicyclic saturated hydrocarbon.
  • the shrink film produced by the material can achieve a shrinkage of more than 40% at 90 °, but the patent does not take into account the process characteristics of the shrink film in the production and sales of the actual bottle to pack the bottles in PE shrink film (see Figure 1), therefore, it is difficult to carry out industrial production in the sleeve labeling process.
  • ZL200480015992.X uses a coating such as an acrylic resin on the inner and outer surface layers or a method of further adding an anti-blocking component such as silicone oil, polyethylene wax or flux wax as a solution for blocking.
  • an anti-blocking component such as silicone oil, polyethylene wax or flux wax
  • the invention provides a polyolefin heat shrinkable film and a preparation method thereof, and the film prepared thereby has good temperature resistance and high transverse heat shrinkage rate, and the labels between the bottles are not easy to stick to each other or group in the hot filling of the beverage.
  • the label and PE shrink film adhesion problems are less likely to occur.
  • a multi-layer heat shrinkable film which is a multilayer heat-shrinkable film laminated with at least three layers, which has a glass transition temperature (Tg) of 138 ° C and a norborne film of 70 to 80 wt%.
  • An inner and outer surface layer of a resin composition having an olefin content of 76% by weight of an ethylene-norbornene copolymer and 20 to 30% by weight of an ethylene-propylene random copolymer having a melting point (Tm) of 140 ° C; and comprising 54 wt% of Tm Ethylene-propylene random copolymer (A) at 140 ° C, 8 wt% ethylene-butene random copolymer (B) having a Tm of 66 ° C, 20% Tg of 78 ° C and norbornene content of 65 wt % of the ethylene-norbornene copolymer (C), 18 wt% softening point (Ts) of a hydrogenated petroleum resin (D) core layer of 140 °C.
  • Tm melting point
  • the core layer is the same as the ethylene-norbornene copolymer selected for the inner and outer sub-surface layers, and has a Tg of 78 ° C and a norbornene content of 65 wt %; the ethylene-norbornene copolymer selected for the inner and outer skin layers is the same, The Tg was 138 ° C and the norbornene content was 65 wt%.
  • the melt volume fraction (MVR) of the above ethylene-norbornene is: 11 cm 3 /10 min.;
  • the ethylene-propylene random copolymer has an ethylene content of 6.5 wt% and a melt index of 2 g/10 min (2.16 kg, 230 ° C);
  • the ethylene-butene random copolymer has a butene content of 25 wt% and a melt index of 3.6 g/10 min (2.16 kg, 190 ° C);
  • the hydrogenated petroleum resin is a C9 type resin having a softening point of 140 °C.
  • an inner and outer surface layer is further disposed between the core layer and the inner and outer surface layers of the multilayer heat shrinkable film, and the layer contains 60 to 90% by weight of Tg of 78 ° C and norbornene content. It is a 65 wt% ethylene-norbornene copolymer and a hydrogenated petroleum resin having a softening point of 140 ° C of 10 to 40%. Further, it is characterized in that the lateral heat shrinkage rate is not less than 40% under the conditions of immersion in water at 90 ° C for 10 seconds.
  • transverse longitudinal and transverse tensile elastic modulus is 1419 to 1530 MPa.
  • the purpose of the inner and outer skin layers of the present invention is to improve the temperature resistance of the heat shrinkable film, so that a strong temperature resistant ethylene-norbornene copolymer and an ethylene-propylene random copolymer are selected, but this will reduce the heat of the film. Shrinkage.
  • the thickness of the inner and outer skin layers or the sum of the inner and outer skin layers and the thickness of the adjacent sub-surface layers should be controlled to about 7 ⁇ . Too thin will occur when the label is subjected to post-processing of the inner and outer layers. If it is too thick, there will be a problem that the heat shrinkage rate of the film is lowered due to the improvement of the temperature resistance of the surface material.
  • the purpose of the inner and outer skin layers of the present invention is to increase the bonding strength of the inner and outer layers when the solvent is used in the solvent of the cyclohexane, and to improve the heat shrinkage and gloss of the film.
  • the inner and outer subsurface layers are composed of 60 to 90% by weight of an ethylene-norbornene copolymer having a Tg of 78 ° C and a norbornene content of 65 wt % and a hydrogenated petroleum resin having a softening point of 140 ° C of 10 to 40% by weight. .
  • the purpose of the core layer of the present invention is to obtain a high heat shrinkage rate, and therefore an ethylene-butyl group containing 54 wt% of an ethylene-propylene random copolymer (A) having a Tm of 140 ° C, 8 wt% and a Tm of 66 ° C is used.
  • the role of component A is to strengthen the tensile strength and elastic modulus of the film; the role of component B is to improve the impact strength of the film; the role of component C is to increase the thermal shrinkage of the film; the role of component D is to improve Film heat shrinkage and stretchability.
  • the present invention also provides a method for preparing the above multilayer heat-shrinkable film, comprising the steps of: pre-mixing the screened raw materials according to a design formula, forming a homogenized melt, and co-extruding the melt through the die.
  • the film can be chilled into a thick sheet by a cast film according to a flat film method, and the thick sheet is biaxially stretched into a film; or according to the tubular film method, the melt is made into an initial film and quenched.
  • the initial film is then blown and stretched longitudinally into a film; after cooling and corona treatment or flame treatment or plasma treatment, the film is finished.
  • the flat film process of vertical and horizontal transverse direction can be adopted.
  • the specific process flow is as follows: blanking ⁇ co-extrusion of multiple extruders ⁇ ⁇ die bonding ⁇ quenching ⁇ longitudinal stretching
  • the polyolefin heat-shrinkable film is prepared according to the following method:
  • the three-layer or more co-extruded film structure is used to inhale the raw materials of each component into the batching unit and electronically weigh it into an extruder of about 250 ° C to be melt-plasticized and After metering into the flow channel distributor, it is extruded through a T-die, and then cast into a slab through a chill roll at about 25 ° C, and then enters the longitudinal drawing, and the longitudinal pre-heating temperature and the stretching temperature are both about 100 ° C.
  • the setting temperature is about 110 ° C
  • the stretching ratio is about 1.2 times; then it enters the transverse stretching, the transverse preheating temperature is about 115 ° C, the stretching temperature is about 85 ° C, the setting temperature is about 70 ° C, and the air cooling temperature is about
  • the draw ratio was 5.5 times, and then the film was subjected to corona treatment to bring the film surface tension to 43 dynes/cm or more, and then subjected to winding and slitting treatment, and finally packaged into the warehouse.
  • the stretching ratio in the longitudinal stretching is about 1.2 times, and the preheating and stretching temperatures are about 100 ° C. Excessive stretching or low temperature stretching may cause the sleeve shrinkage effect to be affected due to the excessive longitudinal tensile shrinkage.
  • the draw ratio taken by the transverse stretching is about 5.5 times, and the stretching temperature is 85 ° C or less. Generally, the larger the stretching ratio, the lower the stretching temperature, and the higher the heat shrinkage rate of the film, but the production with an excessively high stretching ratio or an excessively low stretching temperature tends to cause the film to be broken and cannot be stably produced.
  • the present invention also provides a container comprising: a container body and the above-described multilayer heat shrinkable film which is heat-shrink-attached to the container body.
  • the invention provides a polyolefin heat shrinkable film and a preparation method thereof, the film has good temperature resistance and high transverse heat shrinkage, and solves the problem that the labels between the bottles are easy to stick to each other during the hot filling of the beverage or shrink the PE of the bottles in the group.
  • the label and the PE shrink film are prone to sticking, which is most suitable for use as a shaped bottle label substrate.
  • the physical property indicators used in the present invention are determined according to the following standards:
  • L2 The longitudinal or transverse dimension of the sample after heat shrinkage, in millimeters (mm).
  • PE shrink film packaging adhesion test PET bottles that have been filled and heat-shrinkable sleeves are packaged in 24 groups with PE shrink film, and each group of bottles stays in the 180 °C drying tunnel for 2se C. After the removal, the visual evaluation was carried out, and it was confirmed that there was no mark " ⁇ ” which was adhered to the PE shrink film, and the mark "x" which adhered to the ⁇ shrink film was confirmed.
  • Figure 1 Schematic diagram of the heat-shrinkable label.
  • Figure 2 Schematic diagram of PE shrink film packaging for canned PET container bottles.
  • Figure 3 is a schematic view showing the structure of a multilayer heat-shrinkable film according to a preferred embodiment of the present invention.
  • Figure 4 is a schematic view showing the structure of a multilayer heat shrinkable film according to Embodiment 4 of the present invention.
  • a polyolefin heat shrinkable film which is a five-layer coextruded structure (see Fig. 3), including inner and outer skin layers, inner and outer skin layers And the inner layer; the inner and outer surface layer is composed of 70 wt% Tg of 138 ° C and norbornene content of 76 wt % of ethylene-norbornene copolymer (TOPAS 6013F-04 manufactured by Polyplastics Co., Ltd.) and 30 wt% Tm of 140 ° C An ethylene-propylene random copolymer (CLYRELL RC1890 manufactured by Leander Basel).
  • the inner and outer sub-layers are composed of an ethylene-norbornene copolymer having 90 wt% Tg of 78 ° C and a norbornene content of 65 wt% (TOPAS 8007F-400 manufactured by Polyplastics Co., Ltd.) and a B 10 wt% Ts of 140 ° C hydrogenation. It is composed of petroleum resin (P140 manufactured by Idemitsu Kosan Co., Ltd.).
  • the core layer composition was composed of an ethylene-propylene random copolymer (CLYRELL RC1890 manufactured by Leander Basel Co., Ltd.) of 54 wt% Tm of 140 ° C, ethylene of 80 wt% Tg of 78 ° C and a norbornene content of 65 wt%.
  • CLYRELL RC1890 manufactured by Leander Basel Co., Ltd.
  • the polyolefin heat shrinkable film was prepared as follows: The mixed raw materials were respectively poured into an extruder at 250 ° C, coextruded in a five-layer T-die, cooled by a 25 ° C chill roll, and then introduced into a longitudinal pull.
  • the longitudinal preheating temperature and the stretching temperature are both 100 ° C, the setting temperature is 110 ° C, the stretching ratio is 1.2 times; the transverse stretching is further carried out, the transverse preheating temperature is 115 ° C, and the stretching temperature is 85 ° C, the setting temperature is 70 ° C, the air cooling temperature is 25 ° C, the stretching ratio is 5.5 times, then the film is corona treated to make the film surface tension reach 43 dynes / cm, after winding And slitting processing, and finally packaging into the warehouse.
  • the thickness of the film is: 2 ⁇ in the inner and outer skin layers, 5 ⁇ in the inner and outer skin layers, 31 ⁇ in the core layer, and 45 ⁇ in total thickness.
  • the longitudinal and transverse tensile strength and fracture nominal strain, longitudinal and transverse shrinkage, friction coefficient, longitudinal and transverse tensile modulus, surface tension, haze and gloss of the film are shown in Table 1.
  • the inner and outer skin layer composition is an ethylene-norbornene copolymer (TOPAS 6013F-04 manufactured by Polyplastics Co., Ltd.) having an 80 wt% Tg of 138 ° C and a norbornene content of 76 wt%.
  • the B 20 wt% Tm is 140 ° C.
  • the ethylene-propylene random copolymer (CLYRELL RC1890 manufactured by Leander Basel Co., Ltd.); the inner and outer sub-layers, the core layer and the preparation method thereof are the same as those in the first embodiment.
  • the thickness of the film is: 2 ⁇ in the inner and outer skin layers, 5 ⁇ in the inner and outer skin layers, 31 ⁇ in the core layer, and the total thickness is
  • the inner and outer sub-surface composition consists of an ethylene-norbornene copolymer (TOPAS 8007F-400 manufactured by Polyplastics Co., Ltd.) having 60 wt% Tg of 78 ° C and a norbornene content of 65 wt% and a softening point of 40% by weight. Hydrogenated petroleum tree at 140 ° C
  • the composition of the company (P140 manufactured by Idemitsu Kosan Co., Ltd.); the inner and outer skin layers, the core layer and the preparation method thereof are the same as those in the first embodiment.
  • the thickness of the film is: 2 ⁇ m of the inner and outer skin layers, 5 ⁇ m of the inner and outer skin layers, 31 ⁇ m of the core layer, and a total thickness of 45 ⁇ m.
  • the longitudinal and transverse tensile strength and fracture nominal strain, longitudinal and transverse shrinkage, friction coefficient, longitudinal and transverse tensile modulus, surface tension, haze and gloss of the film are shown in Table 1.
  • a three-layer co-extrusion structure is adopted, and the specific structure is as follows: an ethylene-norbornene copolymer having an inner and outer surface layer of 70 wt% Tg of 138 ° C and a norbornene content of 76 wt% (TOPAS 6013F-04 manufactured by Polyplastics Co., Ltd.) And 30 wt% ethylene-propylene random copolymer having a Tm of 140 ° C (CLYRELL RC1890 manufactured by Leander Basel Co., Ltd.); core layer composition comprising 54 wt% Tm of 140 ° C ethylene-propylene random copolymer ( Ethylene-norbornene copolymer (manufactured by Polyplastics Co., Ltd.
  • TOPAS 8007F-400 8 wt% CLYRELL RC1890
  • 20 wt% Tg 78 ° C 20 wt% Tg 78 ° C
  • norbornene content 65 wt%
  • the ethylene-butene copolymer (manufactured by Mitsui Chemicals, Inc., A4085S) having a %Tm of 66 ° C and 18 wt% of Ts was a hydrogenated petroleum resin (P140 manufactured by Idemitsu Kosan Co., Ltd.) of 140 ° C.
  • the polyolefin heat shrinkable film is prepared by pouring the mixed raw materials into an extruder of 185 to 250 ° C, coextruding in a five-layer T-die, cooling by a 25 ° C chill roll, and then entering.
  • Longitudinal drawing, longitudinal pre-heating temperature and stretching temperature are both 100 ° C, setting temperature is 110 ° C, stretching ratio is 1.2 times; then entering transverse stretching, cross-rolling preheating temperature is 115 ° C, stretching The temperature is 85 ° C, the setting temperature is 70 ° C, the air cooling temperature is 25 ° C, the stretching ratio is 5.5 times, and then the film is subjected to corona treatment to make the surface tension of the film reach 43 dynes/cm. Winding and slitting, and finally packaging.
  • the thickness of the film was: inner and outer skin layer 7 ⁇ , core layer 31 ⁇ , total thickness 45 ⁇ .
  • the longitudinal and transverse tensile strength and fracture nominal strain, longitudinal and transverse shrinkage, friction coefficient, longitudinal and transverse tensile modulus, surface tension, haze and gloss of the film are shown in Table 1.
  • a three-layer co-extruded structure, an inner-outer surface layer composition comprising 70 wt% Tg of 78 ° C and a norbornene content of 65 wt % of an ethylene-norbornene copolymer (TOPAS 8007F-400 manufactured by Polyplastics Co., Ltd.) It is composed of 30 wt% LLDPE (produced by Mitsui Chemicals Co., Ltd. SP3020), and its core layer and its preparation method are the same as those in Example 4.
  • the thickness of the film is: 7 ⁇ m of the inner and outer skin layers, 31 ⁇ m of the core layer, and a total thickness of 45 ⁇ m.
  • the longitudinal/transverse tensile strength and fracture nominal strain, longitudinal/lateral shrinkage, friction coefficient, longitudinal and transverse tensile modulus, surface tension, haze, and gloss of the film are shown in Table 1. It can be seen that the polyolefin heat shrinkable film disclosed in Comparative Example 1 has obvious adhesion during the process of packaging the shrink film, and does not meet the appearance quality requirements of the heat shrinkable label of the canned beverage. Table 1

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Abstract

本发明涉及一种双向拉伸聚烯烃多层热收缩薄膜，它是叠层了至少三层的热收缩性薄膜，其具有包含70~80wt%玻璃化转变温度（Tg）为138℃、降冰片烯含量为76wt%的乙烯-降冰片烯共聚物和20~30wt%且熔点（Tm）为140℃的乙烯-丙烯无规共聚物的树脂组合物的内、外表层；以及包含54wt% Tm为140℃的乙烯-丙烯无规共聚物、8wt%且Tm为66℃的乙烯-丁烯无规共聚物、20%Tg为78℃且降冰片烯含量为65wt%的乙烯-降冰片烯共聚物、18wt%软化点（Ts）为140℃的氢化石油树脂的芯层。本发明提供了一种聚烯烃热收缩膜及其制备方法，该薄膜耐温性好、横向热收缩高，解决了饮料热灌装时瓶子间标签易互粘或对成组的瓶子以PE收缩膜打包时容易出现标签与PE收缩膜粘连的问题，最适合用作异形瓶标签基材。

Description

一种聚烯烃热收缩薄膜及其制备方法
技术领域
本发明主要涉及包含乙烯 -丙烯无规共聚物、 不同降冰片烯含量的乙烯-降冰片烯共聚 物和氢化石油树脂的热收縮薄膜及其制造方法。 更具体的说， 本发明涉及一种适合用作热 收縮标签的耐温性耐热的双向拉伸聚烯烃热收縮薄膜及其制备方法。 该热收縮薄膜在保持 高耐温性热收縮率、 收縮图案完整、 密度低、 自然收縮率少、 易回收等特点的基础上， 改 进了软饮料热灌装或使用 PE收縮膜打包所需要的耐温性能， 可用作高速包装、 蒸汽烘道 收縮包装以及 PE打包等领域所广泛使用的环保热收縮标签。
技术背景
果汁、绿茶等饮品通常都是罐装到 PET瓶之类的容器中进行生产销售的。生产厂家为 了与其他商品相区别或者提高商品的识别性和推广性， 通常都会在容器瓶外侧贴附有印刷 了文字和 /或图案的热收縮性标签。 当前普遍使用的热热收縮标签主要采用聚氯乙烯材料。 聚氯乙烯的光泽度高、 雾度低、 挺度高、 热收縮率适中， 收縮后图案变形和自然收縮率少 等优点， 往往作为热收縮标签的首选， 但聚氯乙烯存在回收难、 燃烧容易产生二噁英等环 境污染问题， ，德国、 瑞士、 奥地利、 韩国、 台湾等国家或地区， 已明令禁止使用聚氯乙烯 作为标签材料。 现在已经开发出双向拉伸聚酯 （BOPET)、 双向拉伸聚苯乙烯 (BOPS)、 双 向拉伸聚烯烃 （BOPO) 等材料作为 PVC热收縮标签的替代产品。
但是， 由于 BOPET (密度 1.28〜1.32g/cm3)和 BOPS (密度 1.02〜1.04g/cm3)两者的密 度都大于 lg/cm3，因此当使用这些材料作为热收縮标签时就很难通过快捷简便的方法（如水 选法或风力分离）使标签与软饮料瓶 （一般为 PET材料， 密度 1.37〜1.40 g/cm3)有效分离 从而使之得以循环利用。
而传统的双向拉伸聚烯烃（BOPO)材料具有密度小 （小于 lg/cm3)、 易回收、 燃烧产 物无污染等优点， 因此成为环保热收縮膜研究热点。但它也存在收縮温度偏高，尤其是在饮 料热灌装时瓶间的标签易互粘或对成组的瓶子以收縮 PE收縮膜打包时容易出现标签与 PE 收縮膜粘连的问题， 从而使其应用大大受限。 同时传统的聚烯烃收縮膜在 110°C以上才能 获得 40%的收縮， 这样的温度也会让 PET瓶产生变形从而无法使用。对此， 为了改善收縮 温度偏高问题，中国专利 ZL03104526.X公开了利用由丙烯和碳原子数为 2〜20的 ct-烯烃经 无规共聚得到的共聚物、无规聚丙烯树脂和脂环族饱和烃构成的组合物制备的收縮膜在 90 °〇便能达到 40%以上的收縮， 但该专利没有考虑到收縮膜在实际包装瓶的生产和销售环节 需要将成组的瓶子以 PE收縮膜打包的工艺特点 （参见附图 1 )， 因此难以在套标工艺中进 行工业化生产。 而中国专利 ZL200480015992.X所公开的多层热收縮性薄膜虽然采用在内 外表层涂布丙烯酸树脂等涂层或进一步添加硅油、 聚乙烯蜡、 氟希蜡等抗粘连组分的方法 作为解决粘连的方法， 但该工艺实施过程繁琐， 成本高， 不适宜工业化生产。
发明内容
本发明提供了一种聚烯烃热收縮膜及其制备方法， 由此制得的薄膜耐温性好、 横向热 收縮率高， 在饮料热灌装时瓶子间标签不易互粘或对成组的瓶子以 PE收縮膜打包时不容 易出现标签与 PE收縮膜粘连问题。
具体技术方案为： 一种多层热收縮薄膜， 它是叠层了至少三层的多层热收縮性薄膜， 其具有包含 70〜80wt% 玻璃化转变温度 （Tg) 为 138°C且降冰片烯含量为 76wt%的乙烯- 降冰片烯共聚物和 20〜30^%且 熔点 （Tm) 为 140°C的乙烯-丙烯无规共聚物的树脂组合 物的内外表层； 以及包含 54wt% Tm为 140 °C的乙烯-丙烯无规共聚物 （A)、 8wt% 且 Tm 为 66°C的乙烯-丁烯无规共聚物 （B)、 20%Tg为 78°C且降冰片烯含量为 65wt%的乙烯-降 冰片烯共聚物 （C) ，18wt%软化点 （Ts) 为 140°C的氢化石油树脂 （D) 的芯层。
所述芯层与内外次表层所选用的乙烯-降冰片烯共聚物相同， 其 Tg为 78°C， 降冰片烯 含量均为 65wt%；内外表层所选用的乙烯-降冰片烯共聚物相同， 其 Tg为 138°C、 降冰片烯 含量均为 65wt%。 上述乙烯-降冰片烯的熔体体积率 （MVR) 均为： 11 cm3/10min.;
所述的乙烯-丙烯无规共聚物中乙烯含量为 6.5wt%，，熔融指数为 2g/10min (2.16kg, 230 °C );
所述的乙烯-丁烯无规共聚物中丁烯含量为 25wt%，， 熔融指数为 3.6 g/10min (2.16kg, 190°C );
所述的氢化石油树脂是软化点为 140°C的 C9类树脂。
此外， 其特征还在于： 在上述多层热收縮膜的芯层和内外表层之间还设置有内、 外次 表层， 该层包含 60〜90wt% 的 Tg为 78°C、 降冰片烯含量均为 65wt%的乙烯 -降冰片烯共 聚物和 10〜40^%软化点为 140°C的氢化石油树脂。 此外， 其特征还在于： 在 90°C的水中浸渍 10秒钟的条件下， 其横向热收縮率不少于 40%。
此外， 其特征还在于： 其纵向断裂标称应变在 282〜291 %。
此外， 其特征还在于： 其横向拉伸强度在 115〜134MPa。
此外， 其特征还在于： 其横向纵横向拉伸弹性模量在 1419〜1530 MPa。
此外， 其特征还在于： 在饮料热灌装时瓶子间标签不易互粘或对成组的瓶子以 PE收 縮膜打包时不容易出现标签与 PE收縮膜粘连问题。
本发明内外表层设置的目的是为了提高热收縮膜的耐温性， 因而选用了耐温性较强的 乙烯 -降冰片烯共聚物以及乙烯 -丙烯无规共聚物， 但这样会降低薄膜的热收縮率。 内外表 层的厚度或内外表层与相邻次表层的厚度之和应控制在 7μηι左右，太薄会出现标签在进行 内外层搭接合掌的后加工时因粘结强度不够而导致热收縮成型时爆标， 太厚则会出现因表 层材料耐温性提高而使薄膜热收縮率下降的问题。内外表层采用 70〜80^%的丁§为 138°C、 密度为 1.02 g/cm3的乙烯 -降冰片烯共聚物和 20〜30^%且 Tm为 140°C的乙烯 -丙烯无规共 聚物。
本发明内外次表层设置的目的是为了提高在使用环己烷溶剂合掌时的内外层搭接强 度， 提高薄膜的热收縮率和光泽度。 内外次表层采用该层包含 60〜90wt% 的 Tg为 78°C、 降冰片烯含量均为 65wt%的乙烯 -降冰片烯共聚物和 10〜40^%软化点为 140°C的氢化石油 树脂。
本发明芯层设置的目的是为了获得高的热收縮率， 因此采用包含 54wt% Tm为 140°C 的乙烯-丙烯无规共聚物 （A)、 8wt% 且 Tm为 66°C的乙烯-丁烯无规共聚物 （B)、 20%Tg 为 78°C且降冰片烯含量为 65wt%的乙烯-降冰片烯共聚物（C ) ，18^%软化点为 140°C的氢 化石油树脂 （D) 的组分作为芯层。 其中， 组分 A的作用为加强薄膜的拉伸强度和弹性模 量； 组分 B的作用为提高薄膜抗冲击强度； 组分 C的作用为提高薄膜热收縮率； 组分 D 的作用为提高薄膜热收縮率和可拉伸性。
同时本发明还提供了一种制备上述多层热收縮薄膜的方法， 包括如下步骤： 将经过筛 选的原料按设计配方预混， 制成均化的熔体， 将熔体通过模头共挤出后， 可以按照平膜法， 即熔体通过流延铸片激冷成厚片， 厚片经双向拉伸成薄膜； 或者按照管膜法， 即将熔体制 成初管膜并经骤冷， 再将初管膜经横向吹胀和纵向拉伸成薄膜； 再经过冷却和电晕处理或 火焰处理或等离子处理， 即成薄膜成品。 如要求横向热收縮， 可采取先纵向后横向的平膜法工艺， 具体工艺流程如下： 落料 → 多台挤出机共挤出 → τ 型模头汇合 → 急冷成型 → 纵向拉伸
(预热、 微拉伸、 定型） → 横向拉伸 （预热、 大拉伸、 定型、 冷却） → 牵引及表 面处理 → 收卷 → 时效处理 → 分切收卷 → 包装
该聚烯烃热收縮薄膜按照如下方法制备： 按三层或以上共挤出薄膜结构将各组分原料 吸入配料单元经电子称计量后进入约 250°C的挤出机， 待熔融塑化并经计量进入流道分配 器后再经 T型模头挤出， 经过约 25°C激冷辊流延成厚片， 然后进入纵拉， 纵拉预热温度和 拉伸温度均约 100°C， 定型温度约 110°C， 拉伸倍率约 1.2倍； 再进入横向拉伸， 横拉预热 温度约 115°C， 拉伸温度约 85°C， 定型温度约 70°C， 风淋冷却温度约 25 °C， 拉伸倍率为 5.5倍， 接着对薄膜进行电晕处理以使薄膜表面张力达到 43达因 /厘米或以上， 后经收卷及 分切处理， 最后包装入库。
其中纵向拉伸采取的拉伸倍率在 1.2倍左右， 预热及拉伸温度为 100°C左右， 过度拉 伸或低温拉伸会导致因纵拉收縮率偏大而影响套标收縮效果。 横向拉伸采取的拉伸倍率在 5.5倍左右， 拉伸温度在 85°C以下。 通常拉伸倍率越大， 拉伸温度越低， 薄膜热收縮率越 高， 但是采用过高的拉伸倍率或过低的拉伸温度生产容易导致薄膜破裂而无法稳定生产。
本发明同时还提供了一种容器， 其具有： 容器主体以及热收縮地贴附于上述容器主体 上的上述多层热收縮薄膜。
本发明提供了一种聚烯烃热收縮膜及其制备方法， 该薄膜耐温性好、 横向热收縮高， 解决了饮料热灌装时瓶子间标签易互粘或对成组的瓶子以 PE收縮膜打包时容易出现标签 与 PE收縮膜粘连的问题， 最适合用作异形瓶标签基材。
本发明所使用的物理性能指标按以下标准测定：
( 1 ) 厚度测定： 按 GB/T 6672-2001规定进行。
(2) 拉伸强度及断裂标称应变测定： 按 GB/T 10003-2008中 5.6规定进行。
(3 ) 热收縮率的测定：
在恒温 （23°C )、 恒湿 （湿度 55% ) 的环境中， 分别沿纵向及横向方向裁取 10 张 lOOmmx 100mm 的样品， 分别测定其横向和纵向的长度 Ll。 分别浸入 （90±1 ) °C的水中 lOsec, 立即取出放入 （25±1 ) °C的恒温水浴中冷却 lmin.， 取出晾干 5min.，测定横向和纵 向上的长度 L2。
热收縮率按式 （1 ) 计算， 结果取 10个样品的算术平均值： X = ^— ^χ 100%
( 1 )
式中：
X—热收縮率， 单位为百分比 （％)；
L1一热收縮前样品纵向或横向尺寸， 单位为毫米 （mm);
L2—热收縮后样品纵向或横向尺寸， 单位为毫米 （mm)。
(4) 摩擦系数的测定： 按 GB/T 10006规定进行。
(5)纵横向拉伸弹性模量的测定： 试样形状、 尺寸及试样制备按 GB/T 1040.3规定进 行。 试样测定按 GB/T 1040.1—2006的第 9章规定进行。
(6) 表面张力的测定： 按 GB/T 14216规定进行。
(7) 雾度的测定： 按 GB/T 2410规定进行。
( 8) 光泽度的测定： 按 GB/T 8807规定进行， 入射角为 45°。
(9) PE收縮膜打包粘连测试： 把已经灌装并经热收縮套标的 PET饮料瓶按 24个一 组用 PE收縮膜打包后， 将每组瓶子在 180°C烘道中停留 2seC.， 取出后进行目视评价， 确 认没有与 PE收縮膜粘连的标识符号 "Θ"， 确认有与 ΡΕ收縮膜粘连的标识符号" x"。 附图说明
图 1 : 热收縮标签合掌示意图。
1-涂布头 2-压辊 3-搭接处 4-机器运行方向。
图 2: 已罐装的 PET容器瓶进行 PE收縮膜打包示意图。
1-热收縮标签 2-PE收縮膜。
图 3: 本发明优选实施例所述的多层热收縮薄膜的结构示意图。
1-外表层 2-外次表层 3-芯层 4-内次表层 5-内表层。
图 4: 本发明实施例 4所述的多层热收縮薄膜的结构示意图。
1-外表层 3-芯层 5-内表层。
具体实施方式
实施例 1 :
一种聚烯烃热收縮薄膜， 其为五层共挤出结构 （见图 3 )， 包括内外表层、 内外次表层 和芯层； 内外表层由 70wt% Tg为 138°C且降冰片烯含量为 76wt%的乙烯-降冰片烯共聚物 (宝理塑料株式会社制造 TOPAS 6013F-04) 和 30wt% Tm为 140 °C的乙烯-丙烯无规共聚 物（由利安德巴塞尔公司制造 CLYRELL RC1890)组成。 内外次表层由 90wt% Tg为 78°C 且降冰片烯含量为 65wt%的乙烯-降冰片烯共聚物 （由宝理塑料株式会社制造 TOPAS 8007F-400) 禾 B 10wt%Ts为 140°C氢化石油树脂 （出光兴产株式会社制造 P140) 组成。 芯 层组合物由 54wt% Tm 为 140°C的乙烯-丙烯无规共聚物 （由利安德巴塞尔公司制造 CLYRELL RC1890)、 20wt% Tg为 78°C且降冰片烯含量为 65wt%的的乙烯-降冰片烯共聚 物（由宝理塑料株式会社制造 TOPAS8007F-400)、 8wt%Tm为 66°C的乙烯 -丁烯共聚物（由 三井化学株式会社制造 A4085S) 和 18wt% Ts为 140°C氢化石油树脂 （出光兴产株式会社 制造 P140) 组成。
该聚烯烃热收縮薄膜按照如下方法制备： 分别把混合的原料倒入 250°C的挤出机， 在 五层 T型模头共挤出， 经过 25°C激冷辊冷却， 然后进入纵拉， 纵拉预热温度和拉伸温度均 为 100°C，定型温度为 110°C，拉伸倍率为 1.2倍；再进入横向拉伸，横拉预热温度为 115°C， 拉伸温度为 85°C， 定型温度为 70°C， 风淋冷却温度为 25°C， 拉伸倍率为 5.5倍， 接着对 薄膜进行电晕处理以使薄膜表面张力达到 43达因 /厘米， 后经收卷及分切处理， 最后包装 入库。
该膜的厚度为： 内外表层各为 2μηι， 内外次表层各为 5μηι， 芯层为 31μηι， 总厚度为 45μηι。 该薄膜的纵横向拉伸强度及断裂标称应变、 纵横向收縮率、 摩擦系数、 纵横向拉伸 弹性模量、 表面张力、 雾度、 光泽度见表 1。
实施例 2:
内外表层组合物由 80wt% Tg为 138°C且降冰片烯含量为 76wt%的乙烯-降冰片烯共聚 物 （由宝理塑料株式会社制造 TOPAS 6013F-04) 禾 B 20wt% Tm为 140 °C的乙烯-丙烯无规 共聚物 （由利安德巴塞尔公司制造 CLYRELL RC1890)组成； 其内外次表层、 芯层以及其 制备方法同实施例 1。
该膜的厚度为： 内外表层各为 2μηι， 内外次表层各为 5μηι， 芯层为 31μηι， 总厚度为
45μηι。 该膜的纵横向拉伸强度及断裂标称应变、 纵横向收縮率、 摩擦系数、 纵横向拉伸弹 性模量、 表面张力、 雾度、 光泽度见表 1。
实施例 3:
内外次表层组合物由 60wt% Tg为 78°C且降冰片烯含量为 65wt%的的乙烯 -降冰片烯共 聚物 （由宝理塑料株式会社制造 TOPAS 8007F-400) 和 40\^%软化点为 140°C氢化石油树 月旨 （出光兴产株式会社制造 P140) 组成； 其内外表层、 芯层及其制备方法同实施例 1。 该膜的厚度为： 内外表层各为 2μηι， 内外次表层各为 5μηι， 芯层为 31μηι， 总厚度为 45μηι。 该膜的纵横向拉伸强度及断裂标称应变、 纵横向收縮率、 摩擦系数、 纵横向拉伸弹 性模量、 表面张力、 雾度、 光泽度见表 1。
实施例 4:
采用三层共挤出结构，具体结构如下： 内外表层由 70wt% Tg为 138 °C且降冰片烯含量 为 76wt%的的乙烯-降冰片烯共聚物 （宝理塑料株式会社制造 TOPAS 6013F-04 ) 和 30wt% Tm为 140 °C的乙烯-丙烯无规共聚物 （利安德巴塞尔公司制造 CLYRELL RC1890) 组成； 芯层组合物由 54wt% Tm为 140°C的乙烯-丙烯无规共聚物 （由利安德巴塞尔公司制造 CLYRELL RC1890)、 20wt% Tg为 78°C且降冰片烯含量为 65wt%的的乙烯-降冰片烯共聚 物（由宝理塑料株式会社制造 TOPAS 8007F-400)、 8wt%Tm为 66°C的乙烯 -丁烯共聚物（由 三井化学株式会社制造 A4085S ) 和 18wt% Ts为 140°C氢化石油树脂 （出光兴产株式会社 制造 P140) 组成。
该聚烯烃热收縮薄膜按照如下方法制备：分别把混合的原料倒入 185〜250°C的挤出机， 在五层 T型模头共挤出， 经过 25°C激冷辊冷却， 然后进入纵拉， 纵拉预热温度和拉伸温度 均为 100°C，定型温度为 110°C，拉伸倍率为 1.2倍;再进入横向拉伸，横拉预热温度为 115 °C， 拉伸温度为 85°C， 定型温度为 70°C， 风淋冷却温度为 25°C， 拉伸倍率为 5.5倍， 接着对 薄膜进行电晕处理以使薄膜表面张力达到 43达因 /厘米， 后经收卷及分切处理， 最后包装 入库。
该膜的厚度为： 内外表层 7μηι， 芯层为 31μηι， 总厚度为 45μηι。 该膜的纵横向拉伸强 度及断裂标称应变、 纵横向收縮率、 摩擦系数、 纵横向拉伸弹性模量、 表面张力、 雾度、 光泽度见表 1。
对比例 1 :
采用三层共挤出结构， 内外表层组合物由 70wt% Tg为 78°C且降冰片烯含量为 65wt% 的的乙烯-降冰片烯共聚物 （由宝理塑料株式会社制造 TOPAS 8007F-400 ) 和 30wt% LLDPE (三井化学株式会社生产 SP3020)组成， 其芯层及其制备方法同实施例 4。
该膜的厚度为： 内外表层各 7μηι， 芯层为 31μηι， 总厚度为 45μηι。 该膜的纵 /横向拉伸强度 及断裂标称应变、 纵 /横向收縮率、 摩擦系数、 纵横向拉伸弹性模量、 表面张力、 雾度、 光泽度见表 1。对比可见，对比例 1所揭示的聚烯烃热收縮膜在进行 ΡΕ收縮膜打包过程中 出现了明显的粘连， 不符合罐装饮品热收縮标签的外观质量要求。 表 1
Figure imgf000010_0001
： 确认没有与 PE收縮膜粘连为 Θ， 确认有与 PE收縮膜粘连为

Claims

权利要求书
1 . 一种多层热收縮薄膜， 它是层叠了至少三层的经双向拉伸制成的热收縮性聚烯烃 薄膜， 其中间层为芯层， 芯层的两侧各有一个表层， 所述表层包含 70〜80wt% 玻璃化转变 温度 Tg为 138°C的乙烯-降冰片烯无规共聚物和 20〜30wt%熔点 Tm为 140°C的乙烯-丙烯无 规共聚物； 所述芯层包含 54wt%熔点 Tm为 140°C的乙烯-丙烯无规共聚物 （A)、 8wt% 熔 点 Tm为 66°C的乙烯-丁烯无规共聚物 （B)、 20^%玻璃化转变温度 Tg为 78°C的乙烯-降 冰片烯无规共聚物 （C) 以及 18wt%软化点 Ts为 140°C的氢化石油树脂 （D)。
2. 根据权利要求 1 所述的多层热收縮薄膜， 其特征在于上述多层热收縮膜的芯层和 各表层之间还分别设置有次表层，各次表层包含 60〜90^%玻璃化转变温度 Tg为 78°C的 乙烯-降冰片烯无规共聚物和 10〜40wt%软化点 Ts为 140°C的氢化石油树脂。
3. 根据权利要求 2所述的多层热收縮薄膜， 其中乙烯-丙烯无规共聚物中的乙烯含量 为 6.5wt%，乙烯 -丁烯无规共聚物中的丁烯含量为 25wt%。
4. 根据权利要求 2所述的多层热收縮薄膜， 其中芯层与次表层所选用的乙烯-降冰片 烯无规共聚物相同， 共聚物中降冰片烯的含量均为 65wt%， 其玻璃化转变温度 Tg均为 78 °C ; 表层所选用的乙烯-降冰片烯无规共聚物中降冰片烯的含量为 76wt%， 其玻璃化转变 温度 Tg为 138 °C。
5. 根据权利要求 1-4任一所述的多层热收縮薄膜， 特征在于在 90°C的温水中浸渍 10 秒钟的条件下， 其横向热收縮率不少于 40%。
6. 根据权利要求 1-4 任一所述的多层热收縮薄膜， 特征在于其纵向断裂标称应变为 282〜289 %。
7. 根据权利要求 1-4任一所述的多层热收縮薄膜， 特征在于其横向拉伸强度为 115〜 134MPa 。
8. 根据权利要求 1-4任一所述的多层热收縮薄膜， 其特征在于其横向拉伸弹性模量为 1419〜1530 MPa 。
9. 根据权利要求 1-4任一所述的多层热收縮薄膜， 特征在于在进行饮料热灌装时瓶间 的标签不发生互粘或者对成组的 PET瓶使用 PE收縮膜打包时不出现标签与 PE收縮膜的 互粘。
10. 一种制备权利要求 1-9之一所述的多层热收縮薄膜的方法， 包括如下步骤： 按上 述三层或以上的共挤出薄膜结构将各组分原料投入配料单元经计量后进入约 250°C的挤出 机， 待熔融塑化并经计量进入流道分配器后再经 T型模头挤出， 经过约 25 °C激冷辊流延成 厚片， 然后进行纵向拉伸， 纵向拉伸的预热温度和拉伸温度均为约 100°C， 定型温度约 110°C， 拉伸倍率约为 1.2倍； 再进入横向拉伸， 横向拉伸的预热温度约 115°C， 横向拉伸 温度约 85°C， 定型温度约 70°C， 风淋冷却温度约 25°C， 拉伸倍率约为 5.5倍， 接着对薄 膜进行电晕和 /或火焰处理以使薄膜表面张力达到 43达因 /厘米， 后经收卷及分切处理即制 得多层热收縮薄膜。
11 . 一种容器， 其具有： 容器主体以及热收縮地贴附于上述容器主体上的权利要求 1-9 任一所述的多层热收縮薄膜。
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US10787564B2 (en) 2018-01-11 2020-09-29 Exxonmobil Chemical Patents Inc. Polyethylene compositions and articles manufactured therefrom
US11441023B2 (en) 2018-04-27 2022-09-13 Exxonmobil Chemical Patents Inc. Polyethylene films and methods of making the same
CN109435401A (zh) * 2018-12-05 2019-03-08 大连巨通塑料制品有限公司 一种改性pe镀铝膜及其生产方法
TWI828911B (zh) * 2019-06-20 2024-01-11 日商東洋紡股份有限公司 聚烯烴系樹脂膜、使用有聚烯烴系樹脂膜之積層體以及包裝體
CN112934573B (zh) * 2020-12-28 2022-04-15 江苏双星彩塑新材料股份有限公司 一种用于petg热收缩膜标签的涂抹头
CN113510989A (zh) * 2021-04-27 2021-10-19 天津市浩迪橡塑科技有限公司 一种汽车内饰用真皮热收缩结构及其制备方法
CN114161799B (zh) * 2021-11-30 2022-05-24 广东德冠包装材料有限公司 一种消光均匀的拉伸聚丙烯薄膜及其制备方法
CN115107339B (zh) * 2022-06-28 2023-03-24 广东德冠薄膜新材料股份有限公司 一种高表面能双轴定向拉伸聚乙烯薄膜及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1802252A (zh) * 2003-06-11 2006-07-12 郡是株式会社 多层热收缩性薄膜以及热收缩安装有由该薄膜所形成的标签的容器
CN1960868A (zh) * 2004-05-18 2007-05-09 郡是株式会社 多层热收缩性膜和包装电池
JP2011104816A (ja) * 2009-11-13 2011-06-02 C I Kasei Co Ltd 熱収縮性ポリオレフィン系フィルム
CN102529274A (zh) * 2011-12-30 2012-07-04 广东德冠薄膜新材料股份有限公司 一种聚烯烃热收缩薄膜及其制备方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0627126A (ja) 1991-07-17 1994-02-04 Tokyo Gas Co Ltd 流体速度検出方法
JP2504195Y2 (ja) * 1992-09-10 1996-07-10 株式会社フジシール 集積包装用熱収縮性フイルム
JP3608986B2 (ja) 1998-09-21 2005-01-12 三井化学株式会社 シュリンクフィルム用ポリオレフィン樹脂組成物およびそのシュリンクフィルム
JP2001138441A (ja) * 1999-11-09 2001-05-22 Kao Corp ラッピングフィルム
JP4282259B2 (ja) 2000-10-25 2009-06-17 株式会社フジシールインターナショナル ポリオレフィン系熱収縮性ラベル
JP4068978B2 (ja) 2002-02-14 2008-03-26 三井化学株式会社 ポリオレフィン樹脂組成物およびこれを用いたシュリンクフィルム
JP2004345244A (ja) 2003-05-22 2004-12-09 Mitsubishi Plastics Ind Ltd 熱収縮性ポリオレフィン系積層フィルム
JPWO2004110750A1 (ja) 2003-06-11 2006-07-20 グンゼ株式会社 多層熱収縮性フィルム及びそれからなるラベルが熱収縮装着された容器
JP2005047182A (ja) * 2003-07-30 2005-02-24 Asahi Kasei Life & Living Corp 多層熱収縮性延伸フィルム
JP4651982B2 (ja) * 2004-07-15 2011-03-16 グンゼ株式会社 熱収縮性積層フイルム及び包装軽量ペットボトル
US7662888B2 (en) 2005-04-29 2010-02-16 Japan Polypropylene Corporation Polypropylene based heat shrinkable film
US7713636B2 (en) * 2006-12-15 2010-05-11 Exxonmobil Chemical Patents Inc. Multi-layer films comprising propylene-based polymers
JP5224763B2 (ja) 2007-09-28 2013-07-03 三井化学株式会社 シュリンクラベル

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1802252A (zh) * 2003-06-11 2006-07-12 郡是株式会社 多层热收缩性薄膜以及热收缩安装有由该薄膜所形成的标签的容器
CN1960868A (zh) * 2004-05-18 2007-05-09 郡是株式会社 多层热收缩性膜和包装电池
JP2011104816A (ja) * 2009-11-13 2011-06-02 C I Kasei Co Ltd 熱収縮性ポリオレフィン系フィルム
CN102529274A (zh) * 2011-12-30 2012-07-04 广东德冠薄膜新材料股份有限公司 一种聚烯烃热收缩薄膜及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2799230A4

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9593218B2 (en) 2014-05-30 2017-03-14 Pall Corporation Self-assembled structure and membrane comprising block copolymer and process for producing the same by spin coating (IIIa)
US9616395B2 (en) 2014-05-30 2017-04-11 Pall Corportaion Membrane comprising self-assembled block copolymer and process for producing the same by spray coating (Ic)
US9441078B2 (en) 2014-05-30 2016-09-13 Pall Corporation Self-assembling polymers—I
US9193835B1 (en) 2014-05-30 2015-11-24 Pall Corporation Self-assembling polymers—IV
US9469733B2 (en) 2014-05-30 2016-10-18 Pall Corporation Self-assembled structure and membrane comprising block copolymer and process for producing the same by spin coating (IVa)
US9765171B2 (en) 2014-05-30 2017-09-19 Pall Corporation Self-assembling polymers—V
US9163122B1 (en) 2014-05-30 2015-10-20 Pall Corporation Self-assembling polymers—II
US9593219B2 (en) 2014-05-30 2017-03-14 Pall Corporation Membrane comprising self-assembled block copolymer and process for producing the same by spin coating (IIa)
US9328206B2 (en) 2014-05-30 2016-05-03 Pall Corporation Self-assembling polymers—III
US9593217B2 (en) 2014-05-30 2017-03-14 Pall Corporation Self-assembled structure and membrane comprising block copolymer and process for producing the same by spin coating (Va)
US9169361B1 (en) 2014-05-30 2015-10-27 Pall Corporation Self-assembling polymers—VI
US9604181B2 (en) 2014-05-30 2017-03-28 Pall Corporation Membrane comprising self-assembled block copolymer and process for producing the same by spray coating (IIc)
US9598543B2 (en) 2014-05-30 2017-03-21 Pall Corporation Self-assembled structure and membrane comprising block copolymer and process for producing the same by spin coating (VIa)
US9592476B2 (en) 2014-05-30 2017-03-14 Pall Corporation Membrane comprising self-assembled block copolymer and process for producing the same by hybrid casting (IIb)
US9592477B2 (en) 2014-05-30 2017-03-14 Pall Corporation Membrane comprising self-assembled block copolymer and process for producing the same by hybrid casting (Ib)
US9162189B1 (en) 2014-05-30 2015-10-20 Pall Corporation Membrane comprising self-assembled block copolymer and process for producing the same by spin coating (Ia)
US9303133B2 (en) 2014-06-30 2016-04-05 Pall Corporation Hydrophilic membranes and method of preparation thereof (IV)
US9394407B2 (en) 2014-06-30 2016-07-19 Pall Corporation Hydrophilic block copolymers and membranes prepared therefrom (I)
US9962662B2 (en) 2014-06-30 2018-05-08 Pall Corporation Fluorinated polymer and use thereof in the preparation of hydrophilic membranes (vi)
US9309367B2 (en) 2014-06-30 2016-04-12 Pall Corporation Membranes comprising cellulosic material and hydrophilic block copolymer (V)
US9718924B2 (en) 2014-06-30 2017-08-01 Pall Corporation Hydrophilic block copolymers and membranes prepared therefrom (II)
US9260569B2 (en) 2014-06-30 2016-02-16 Pall Corporation Hydrophilic block copolymers and method of preparation thereof (III)
US9254466B2 (en) 2014-06-30 2016-02-09 Pall Corporation Crosslinked cellulosic membranes

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JP2015509861A (ja) 2015-04-02
EP2799230A9 (en) 2016-02-10
JP5933750B2 (ja) 2016-06-15
EP2799230B1 (en) 2017-07-19
US10005262B2 (en) 2018-06-26
US20140353197A1 (en) 2014-12-04

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