CN107225830B - Slim heavy packaging low temperature heat shrink films of one kind and preparation method thereof - Google Patents

Slim heavy packaging low temperature heat shrink films of one kind and preparation method thereof Download PDF

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Publication number
CN107225830B
CN107225830B CN201710484698.2A CN201710484698A CN107225830B CN 107225830 B CN107225830 B CN 107225830B CN 201710484698 A CN201710484698 A CN 201710484698A CN 107225830 B CN107225830 B CN 107225830B
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layer
heat shrink
shrink films
metallocene
thickness
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CN107225830A (en
Inventor
顾文秀
方波
何志毅
邹路易
孙余凭
顾瑾
周小兰
滕跃
游鑫标
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WUXI FANGCHENG COLOR PRINTING PACKING CO Ltd
Jiangnan University
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WUXI FANGCHENG COLOR PRINTING PACKING CO Ltd
Jiangnan University
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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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • 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
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • 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
    • 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
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (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
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • 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
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/406—Bright, glossy, shiny surface
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582—Tearability
    • B32B2307/5825—Tear resistant

Abstract

Slim heavy packaging low temperature heat shrink films of one kind and preparation method thereof, belong to packing film technical field.Heat shrink films of the present invention with a thickness of 25~45 μm, be made of the film of three-layer co-extruded bonding, i.e. outer layer, middle layer and internal layer；The thickness ratio of Wai Ceng ︰ Zhong Jian Ceng ︰ internal layer are as follows: 1 ︰, 3~5 ︰ 1；The outer layer is made of high density polyethylene (HDPE), metallocene PE (1), linear low density polyethylene and amorphism copolyesters；The middle layer is made of block copolymer, high density polyethylene (HDPE), metallocene PE (2), the amorphism copolyesters of polystyrene polybutadiene；The internal layer is made of high density polyethylene (HDPE), linear low density polyethylene, metallocene PE (1) and amorphism copolyesters；Heat shrink films thickness ultrathin of the invention saves material 50.0%~72.2%, has excellent low-temperature shrink performance, intensity big and simple process, is suitable for large-scale industrial production.

Description

Slim heavy packaging low temperature heat shrink films of one kind and preparation method thereof
Technical field
Slim heavy packaging low temperature heat shrink films of one kind and preparation method thereof, belong to technical field of polymer materials, further Belong to novel high polymer functional film material field, particularly belongs to packing film technical field.
Background technique
With the scarcity of natural resources, existing wooden package, papery packaging and metal packing material are badly in need of novel low Cost environmental-friend packing material substitutes.Heat shrink films are a kind of orientations that is stretched in process, and in use The thermoplastic film of heat shrinkable.By heat shrink films, the vertical or horizontal energy stretched passes through quenching under elastomeric state when processing Storage in the film, when film heat again, can be returned to loose molecular state, to have to the form before stretching Memory effect can restore the form before stretching when film heat again, be reached by this morphological feature of heat shrink films The purpose of convenient packaging.Heat shrink films are a kind of novel packaging materials, compared with traditional made of paper, wooden, metal packing box, Have many advantages, such as that light weight, good appearance, packed and transported expense be low, environmental protection and energy saving, is widely used in packing extensive stock, such as eat The outer packing of the extensive stocks such as product, drug, sterilizing dinnerware, stationery sports goods, electronic apparatus, especially in anomalistic object article or In terms of commodity bundling package, it is able to satisfy the moisture-proof, dust-proof, touch-proof of commodity, transparent display etc., it is complete to be able to achieve " fitting closely formula " Perspective packaging, sees so that commodity beauty is resistance to.
Current common heat shrink films, thickness is thicker, and intensity and mechanical performance are generally only applicable to volume it is still necessary to improve The outer packing of small, lighter weight article, generally for the thermal stability and photostability for maintaining heat shrink films, frequently with addition The method of a variety of complex function auxiliary agents is also easy to produce dissolution and pollution degradation risk to limit the use scope of heat shrink films, Defect is used with biggish.In addition, common heat shrink films often need to obtain preferable printing performance by sided corona treatment Process or addition surface modified additive, this method make process complications and increase production cost.With the rapid hair of society Exhibition, modern enterprise and logistics industry are badly in need of bigger thinner and lighter, intensity, environmental protection and energy saving and have both excellent adhesive property and excellent The novel heavy duty of good printing performance is packed for heat shrink films.
Summary of the invention
The purpose of the present invention: being to obtain to solve defect of the existing technology for substituting carton, wooden case, metal The high-strength hot shrink film of the assembly package of the large size heavy mail such as case, realizes that thickness is thin, light weight, in the base for realizing larger stent On plinth, stable shrinking percentage can be maintained well, be easy to that printing, good appearance, packed and transported expense be low, energy conservation and environmental protection.Meanwhile In view of foodsafety, product avoids being heat-shrinked using the additive of the complicated formula such as age resister, antioxidant to improve The characteristics such as film strength, service life, light transmittance, but excellent performance is realized by characteristic aggregation composition formula, it can effectively avoid The risks such as dissolution, the degradation of micromolecule additive and processing aid, being directly realized by gained heat shrink films has excellent printing Can, exempt sided corona treatment process, avoids addition surface modified additive, technique can be greatly simplified, cost is reduced and ensured product In the safety that food, medicine and other fields use, while realizing excellent performance.
Technical solution of the present invention: slim heavy packaging low temperature heat shrink films of one kind and preparation method thereof can pass through following skill Art scheme is realized:
Slim heavy packaging low temperature heat shrink films of one kind and preparation method thereof, include the following steps:
The heat shrink films with a thickness of 25~45 μm, be made of the film of three-layer co-extruded bonding, i.e., outer layer, middle layer and Internal layer；
The thickness ratio of the thickness of the Hou Du ︰ internal layer of the Hou Du ︰ middle layer of the outer layer are as follows: 1 ︰, 3~5 ︰ 1；
The mixed raw material of the outer layer are as follows: the low close poly- second alkene ︰ of degree of poly- second alkene ︰ metallocene PE (1) the ︰ line of Gao Midu is non- The mass ratio of crystallinity copolyesters is 1~2 ︰, 5~10 ︰, 10~20 ︰ 1；
The mixed raw material of the middle layer are as follows: the Gong Ju Wu ︰ Gao Mi degree Ju Yi Xi ︰ cyclopentadienyl gold of the Qian section of polystyrene polybutadiene Belonging to polyethylene, (mass ratio of 2) ︰ amorphism copolyesters is 6~8 ︰, 2~3 ︰, 1~2 ︰ 1；
The mixed raw material of the internal layer are as follows: low close poly- second alkene ︰ metallocene PE (1) ︰ of degree of the poly- second alkene ︰ line of Gao Midu is non- The mass ratio of crystallinity copolyesters is 3~4 ︰, 2~3 ︰, 1 ︰ 1；
Metallocene PE (1) the preferred molten index is 0.3~0.5g/10min, and density is 0.927~0.944g/ cm3Metallocene PE；Metallocene PE (2) the preferred molten index is 0.8~1.0 g/10min, and density is 0.917~0.925g/cm3Metallocene PE；High density polyethylene (HDPE) preferred molten index is 0.5~0.7g/10min, close Degree is 0.950~0.970g/cm3High density polyethylene (HDPE)；Linear low density polyethylene preferred molten index is 1.7~2.3 g/ 10min, density are 0.916~0.920 g/cm3Linear low density polyethylene.
Further, Ben Yi Xi ︰ butadiene list in the block copolymer preferred copolymer of the polystyrene polybutadiene The molar ratio of member is the block copolymer of 8~9 ︰ 1.
Further, the amorphism copolyesters is to be copolymerized resulting block copolymerization by mixing diacid and mixing glycol Ester, the mixing diacid are the mixing diacid that the molar ratio of Dui Ben bis- Jia Suan ︰ succinic acid is 8~9 ︰ 1；The mixing glycol is second The molar ratio of Er Chun ︰ sorbierite is the mixing glycol of 5~15 ︰ 1.
Further, the preparation method of the slim heavy packaging low temperature heat shrink films, is to mix each layer raw material respectively to stir After mixing uniformly, 10~15min of refining modeling at a temperature of 120~200 DEG C, then the mass ratio by the thickness of each layer than, i.e. each layer, outer layer Hou Du ︰ middle layer Hou Du ︰ internal layer thickness thickness ratio are as follows: 1 ︰, 3~5 ︰ 1 is squeezed out, automatic wind by three-layer co-extruded equipment Ring is cooling, and the heat shrink films are made；The draw ratio of the extrusion screw rod of the three-layer co-extruded equipment is 33~35 ︰ 1, extrusion temperature It is 130~170 DEG C, the vane cooling temperature of the three-layer co-extruded equipment is 18~25 DEG C.
The invention has the benefit that the slim heavy packaging low temperature heat shrink films of present invention gained can be substituted for carton, wood The assembly package of the large size heavy mail such as case, metal box, thin, light weight the advantage with thickness, on the basis of realizing larger stent, Stable shrinking percentage can be maintained well, without adding the processing of the complicated formula such as age resister, antioxidant, surface modifier Auxiliary agent；Without sided corona treatment, there can be excellent printing performance, effectively prevent the wind such as dissolution, the degradation of small molecule auxiliary agent Danger is environmentally friendly heat shrink films, has ensured the safety that product is used in food, medicine and other fields；Heat of the invention is received Contracting film thickness is 25~45 μm, and the thickness than common heat shrink films greatly reduces, and heat shrink temperature is heat-shrinked significantly lower than common Film, tearing strength, fracture tensile strength, elongation at break, impact strength, glossiness and mist degree are substantially better than common thermal contraction Film is calculated by 90 μm of common heat shrink films average thickness, saves material 50.0%~72.2%；Present invention process is simple, is easy control System is suitble to industrialization large-scale production.
Specific embodiment
Below with reference to embodiment, the invention will be further described, but of the invention using without being limited thereto.
Embodiment 1
The present embodiment is the preparation of slim heavy packaging low temperature heat shrink films.Detailed process are as follows: the outer layer is former using mixing Material are as follows: the mass ratio of the low close poly- second alkene ︰ amorphism copolyesters of degree of poly- second alkene ︰ metallocene PE (1) the ︰ line of Gao Midu is 1 ︰ 5 ︰, 10 ︰ 1；The middle layer uses mixed raw material are as follows: the Gong Ju Wu ︰ Gao Mi degree Ju Yi Xi ︰ cyclopentadienyl of the Qian section of polystyrene polybutadiene (mass ratio of 2) ︰ amorphism copolyesters is 6 ︰, 2 ︰, 1 ︰ 1 to metal polyethylene；The internal layer uses mixed raw material are as follows: high density is poly- (mass ratio of 1) ︰ amorphism copolyesters is 3 ︰, 2 ︰, 1 ︰ 1 to Yi Xi ︰ Xian Di Mi degree Ju Yi Xi ︰ metallocene PE；The cyclopentadienyl Metal polyethylene (1) is that melt index is 0.3g/10min, density 0.927g/cm3Metallocene PE；The metallocene Polyethylene (2) is that melt index is 0.8 g/10min, density 0.917g/cm3Metallocene PE；The high density is poly- Ethylene is that melt index is 0.5g/10min, density 0.950g/cm3High density polyethylene (HDPE)；The linear low density polyethylene Alkene is that melt index is 1.7g/10min, density 0.916g/cm3Linear low density polyethylene.
The block copolymer of the polystyrene polybutadiene is that the molar ratio of Ben Yi Xi ︰ butadiene unit in copolymer is The block copolymer of 8 ︰ 1.
The amorphism copolyesters is to be copolymerized resulting blocked copolyester, the mixing by mixing diacid and mixing glycol Diacid is the mixing diacid that the molar ratio of Dui Ben bis- Jia Suan ︰ succinic acid is 8 ︰ 1；The mixing glycol is Yi bis- Chun ︰ sorbierite Molar ratio is the mixing glycol of 5 ︰ 1.
After each layer raw material is mixed evenly respectively, at a temperature of 120 DEG C refining modeling 10min, then by each layer thickness ratio, The mass ratio of i.e. each layer, the thickness ratio of the thickness of the Hou Du ︰ internal layer of the Hou Du ︰ middle layer of outer layer are as follows: 1 ︰, 3 ︰ 1, altogether by three layers It squeezes equipment to squeeze out, automatic air ring is cooling, and the high strength slim is made and packs heat shrink films again；The three-layer co-extruded equipment is squeezed The draw ratio of screw rod is 33 ︰ 1 out, and extrusion temperature is 130 DEG C, and the vane cooling temperature of the three-layer co-extruded equipment is 18 DEG C.
Heat shrink films obtained by the present embodiment are with a thickness of 25 μm of (wherein, 5 μm of outer layer, 15 μm of middle layer, 5 μm of internal layer), mist degrees 5%, glossiness (45 °) 60%, fall mark impact strength 350g, be Elmendorf tear strength (MD/TD) 480/1480N/cm, disconnected Split 45/55 MPa of tensile strength (MD/TD), elongation at break (MD/TD) 660/860%, percent thermal shrinkage (100 DEG C × 20 seconds； MD/TD) 65/17%；It is calculated by 90 μm of common heat shrink films average thickness, saves material 72.2%.
Embodiment 2
The present embodiment is the preparation of slim heavy packaging low temperature heat shrink films.Detailed process are as follows: the outer layer is former using mixing Material are as follows: the mass ratio of the low close poly- second alkene ︰ amorphism copolyesters of degree of poly- second alkene ︰ metallocene PE (1) the ︰ line of Gao Midu is 2 ︰ 10 ︰, 20 ︰ 1；The middle layer uses mixed raw material are as follows: the Gong Ju Wu ︰ Gao Mi degree Ju Yi Xi ︰ cyclopentadienyl of the Qian section of polystyrene polybutadiene (mass ratio of 2) ︰ amorphism copolyesters is 8 ︰, 3 ︰, 2 ︰ 1 to metal polyethylene；The internal layer uses mixed raw material are as follows: high density is poly- (mass ratio of 1) ︰ amorphism copolyesters is 4 ︰, 3 ︰, 1 ︰ 1 to Yi Xi ︰ Xian Di Mi degree Ju Yi Xi ︰ metallocene PE；The cyclopentadienyl Metal polyethylene (1) is that melt index is 0.5g/10min, density 0.944g/cm3Metallocene PE；The metallocene Polyethylene (2) is that melt index is 1.0 g/10min, density 0.925g/cm3Metallocene PE；The high density is poly- Ethylene is that melt index is 0.7g/10min, density 0.970g/cm3High density polyethylene (HDPE)；The linear low density polyethylene Alkene is that melt index is 2.3 g/10min, and density is 0.920 g/cm3Linear low density polyethylene.
The molar ratio of Ben Yi Xi ︰ butadiene unit in the block copolymer preferred copolymer of the polystyrene polybutadiene For the block copolymer of 9 ︰ 1.
The amorphism copolyesters is to be copolymerized resulting blocked copolyester, the mixing by mixing diacid and mixing glycol Diacid is the mixing diacid that the molar ratio of Dui Ben bis- Jia Suan ︰ succinic acid is 9 ︰ 1；The mixing glycol is Yi bis- Chun ︰ sorbierite Molar ratio is the mixing glycol of 15 ︰ 1.
After each layer raw material is mixed evenly respectively, at a temperature of 200 DEG C refining modeling 15min, then by each layer thickness ratio, The mass ratio of i.e. each layer, the thickness ratio of the thickness of the Hou Du ︰ internal layer of the Hou Du ︰ middle layer of outer layer are as follows: 1 ︰, 5 ︰ 1, altogether by three layers It squeezes equipment to squeeze out, automatic air ring is cooling, and the high strength slim is made and packs heat shrink films again；The three-layer co-extruded equipment is squeezed The draw ratio of screw rod is 35 ︰ 1 out, and extrusion temperature is 170 DEG C, and the vane cooling temperature of the three-layer co-extruded equipment is 25 DEG C.
Heat shrink films obtained by the present embodiment are with a thickness of 45 μm of (wherein, 6.4 μm of outer layer, 32 μm of middle layer, 6.4 μ of internal layer M), mist degree 10%, glossiness (45 °) 90%, fall mark impact strength 450g, Elmendorf tear strength (MD/TD) 570/1600 N/cm, 52/65 MPa of fracture tensile strength (MD/TD), 850/998 % of elongation at break (MD/TD), percent thermal shrinkage (110 DEG C × 20 seconds；MD/TD) 82/23%；It is calculated by 90 μm of common heat shrink films average thickness, saves material 50.0%.
Embodiment 3
The present embodiment is the preparation of slim heavy packaging low temperature heat shrink films.Detailed process are as follows: the outer layer is former using mixing Material are as follows: high density polyethylene (HDPE), metallocene PE (1), linear low density polyethylene and amorphism copolyesters mass ratio be 2:8:15:1；The middle layer uses mixed raw material are as follows: the block copolymer of polystyrene polybutadiene, high density polyethylene (HDPE), The mass ratio of metallocene PE (2) and amorphism copolyesters is 7:2.5:1.5:1；The internal layer uses mixed raw material are as follows: The mass ratio of low close poly- second alkene ︰ metallocene PE (1) the ︰ amorphism copolyesters of degree of the poly- second alkene ︰ line of Gao Midu is 3.5 ︰ 2.5 ︰, 1 ︰ 1；The metallocene PE (1) is that melt index is 0.4g/10min, density 0.933g/cm3Metallocene it is poly- Ethylene；The metallocene PE (2) is that melt index is 0.9 g/10min, density 0.921g/cm3The poly- second of metallocene Alkene；The high density polyethylene (HDPE) is that melt index is 0.6 g/10min, and density is 0.965 g/cm3High density polyethylene (HDPE)；Institute It is 1.8 g/10min that state linear low density polyethylene, which be melt index, and density is 0.918 g/cm3Linear low density polyethylene Alkene.
The molar ratio of Ben Yi Xi ︰ butadiene unit in the block copolymer preferred copolymer of the polystyrene polybutadiene For the block copolymer of 8.5 ︰ 1.
The amorphism copolyesters is to be copolymerized resulting blocked copolyester, the mixing by mixing diacid and mixing glycol Diacid is the mixing diacid that the molar ratio of Dui Ben bis- Jia Suan ︰ succinic acid is 8.5 ︰ 1；The mixing glycol is Yi bis- Chun ︰ sorbierite Molar ratio be 10 ︰ 1 mixing glycol.
After each layer raw material is mixed evenly respectively, at a temperature of 140 DEG C refining modeling 13min, then by each layer thickness ratio, The mass ratio of i.e. each layer, the thickness ratio of the thickness of the Hou Du ︰ internal layer of the Hou Du ︰ middle layer of outer layer are as follows: 1 ︰, 4 ︰ 1, altogether by three layers It squeezes equipment to squeeze out, automatic air ring is cooling, and the high strength slim is made and packs heat shrink films again；The three-layer co-extruded equipment is squeezed The draw ratio of screw rod is 34 ︰ 1 out, and extrusion temperature is 150 DEG C, and the vane cooling temperature of the three-layer co-extruded equipment is 20 DEG C.
Heat shrink films obtained by the present embodiment are with a thickness of 40 μm of (wherein, 6.7 μm of outer layer, 26.6 μm of middle layer, 6.7 μ of internal layer M), mist degree 8%, glossiness (45 °) 89%, fall mark impact strength 430g, Elmendorf tear strength (MD/TD) 560/1530 N/cm, fracture tensile strength (MD/TD) 46/62MPa, elongation at break (MD/TD) 780/910%, percent thermal shrinkage (105 DEG C × 20 seconds；MD/TD) 71/23%；It is calculated by 90 μm of common heat shrink films average thickness, saves material 55.6%.
Embodiment 4
The present embodiment is the preparation of slim heavy packaging low temperature heat shrink films.Detailed process are as follows: the outer layer is former using mixing Material are as follows: the mass ratio of the poly- second alkene ︰ amorphism copolyesters of the low close degree of poly- second alkene ︰ metallocene PE (1) the ︰ line of Gao Midu is 1.5 ︰, 7 ︰, 13 ︰ 1；The middle layer uses mixed raw material are as follows: the Gong Ju Wu ︰ high-density polyethylene of the Qian section of polystyrene polybutadiene (mass ratio of 2) ︰ amorphism copolyesters is 8 ︰, 2.5 ︰, 1.5 ︰ 1 to Xi ︰ metallocene PE；The internal layer uses mixed raw material Are as follows: the mass ratio of low close poly- second alkene ︰ metallocene PE (1) the ︰ amorphism copolyesters of degree of the poly- second alkene ︰ line of Gao Midu is 3.5 ︰ 2 ︰, 1 ︰ 1；The metallocene PE (1) is that melt index is 0.5g/10min, density 0.927g/cm3The poly- second of metallocene Alkene；The metallocene PE (2) is that melt index is 1.0 g/10min, density 0.925g/cm3Metallocene PE； High density polyethylene (HDPE) is that melt index is 0.7g/10min, density 0.970g/cm3High density polyethylene (HDPE)；It is described linear low Density polyethylene is that melt index is 2.1g/10min, and density is 0.919 g/cm3Linear low density polyethylene.
The molar ratio of Ben Yi Xi ︰ butadiene unit in the block copolymer preferred copolymer of the polystyrene polybutadiene For the block copolymer of 8 ︰ 1.
The amorphism copolyesters is to be copolymerized resulting blocked copolyester, the mixing by mixing diacid and mixing glycol Diacid is the mixing diacid that the molar ratio of Dui Ben bis- Jia Suan ︰ succinic acid is 9 ︰ 1；The mixing glycol is Yi bis- Chun ︰ sorbierite Molar ratio is the mixing glycol of 8 ︰ 1.
After each layer raw material is mixed evenly respectively, at a temperature of 160 DEG C refining modeling 15min, then by each layer thickness ratio, The mass ratio of i.e. each layer, the thickness ratio of the thickness of the Hou Du ︰ internal layer of the Hou Du ︰ middle layer of outer layer are as follows: 1 ︰, 3 ︰ 1, altogether by three layers It squeezes equipment to squeeze out, automatic air ring is cooling, and the high strength slim is made and packs heat shrink films again；The three-layer co-extruded equipment is squeezed The draw ratio of screw rod is 33 ︰ 1 out, and extrusion temperature is 140 DEG C, and the vane cooling temperature of the three-layer co-extruded equipment is 19 DEG C.
Heat shrink films obtained by the present embodiment are with a thickness of 30 μm of (wherein, 6 μm of outer layer, 18 μm of middle layer, 6 μm of internal layer), mists Degree 9%, glossiness (45 °) 88%, fall mark impact strength 450g, 480/1499 N/cm of Elmendorf tear strength (MD/TD), 45/60 MPa of fracture tensile strength (MD/TD), elongation at break (MD/TD) 760/930%, percent thermal shrinkage (107 DEG C × 20 seconds； MD/TD) 78/19%；It is calculated by 90 μm of common heat shrink films average thickness, saves material 66.7%.
Embodiment 5
The present embodiment is the preparation of slim heavy packaging low temperature heat shrink films.Detailed process are as follows: the outer layer is former using mixing Material are as follows: the mass ratio of the low close poly- second alkene ︰ amorphism copolyesters of degree of poly- second alkene ︰ metallocene PE (1) the ︰ line of Gao Midu is 2 ︰ 8 ︰, 17 ︰ 1；The middle layer uses mixed raw material are as follows: the Gong Ju Wu ︰ Gao Mi degree Ju Yi Xi ︰ cyclopentadienyl of the Qian section of polystyrene polybutadiene (mass ratio of 2) ︰ amorphism copolyesters is 6 ︰, 2 ︰, 2 ︰ 1 to metal polyethylene；The internal layer uses mixed raw material are as follows: high density is poly- (mass ratio of 1) ︰ amorphism copolyesters is 4 ︰, 2 ︰, 1 ︰ 1 to Yi Xi ︰ Xian Di Mi degree Ju Yi Xi ︰ metallocene PE；The cyclopentadienyl Metal polyethylene (1) is that melt index is 0.5g/10min, density 0.944g/cm3Metallocene PE；The metallocene Polyethylene (2) is that melt index is 0.8g/10min, density 0.917g/cm3Metallocene PE；The high-density polyethylene Alkene is that melt index is 0.7g/10min, density 0.970g/cm3High density polyethylene (HDPE)；The linear low density polyethylene It is 2.3 g/10min for melt index, density is 0.919 g/cm3Linear low density polyethylene.
The molar ratio of Ben Yi Xi ︰ butadiene unit in the block copolymer preferred copolymer of the polystyrene polybutadiene For the block copolymer of 9 ︰ 1.
The amorphism copolyesters is to be copolymerized resulting blocked copolyester, the mixing by mixing diacid and mixing glycol Diacid is the mixing diacid that the molar ratio of Dui Ben bis- Jia Suan ︰ succinic acid is 9 ︰ 1；The mixing glycol is Yi bis- Chun ︰ sorbierite Molar ratio is the mixing glycol of 15 ︰ 1.
After each layer raw material is mixed evenly respectively, at a temperature of 140 DEG C refining modeling 12min, then by each layer thickness ratio, The mass ratio of i.e. each layer, the thickness ratio of the thickness of the Hou Du ︰ internal layer of the Hou Du ︰ middle layer of outer layer are as follows: 1 ︰, 4 ︰ 1, altogether by three layers It squeezes equipment to squeeze out, automatic air ring is cooling, and the high strength slim is made and packs heat shrink films again；The three-layer co-extruded equipment is squeezed The draw ratio of screw rod is 35 ︰ 1 out, and extrusion temperature is 140 DEG C, and the vane cooling temperature of the three-layer co-extruded equipment is 19 DEG C.
Heat shrink films obtained by the present embodiment are with a thickness of 38 μm of (wherein, 6.3 μm of outer layer, 25.4 μm of middle layer, 6.3 μ of internal layer M), mist degree 6%, glossiness (45 °) 73%, fall mark impact strength 420g, Elmendorf tear strength (MD/TD) 530/1577 N/cm, 49/58 MPa of fracture tensile strength (MD/TD), elongation at break (MD/TD) 730/967%, percent thermal shrinkage (103 DEG C × 20 seconds；MD/TD) 68/22%；It is calculated by 90 μm of common heat shrink films average thickness, saves material 57.8%.
Embodiment 6
The present embodiment is the preparation of slim heavy packaging low temperature heat shrink films.Detailed process are as follows: the outer layer is former using mixing Material are as follows: the mass ratio of the low close poly- second alkene ︰ amorphism copolyesters of degree of poly- second alkene ︰ metallocene PE (1) the ︰ line of Gao Midu is 2 ︰ 10 ︰, 10 ︰ 1；The middle layer uses mixed raw material are as follows: the Gong Ju Wu ︰ Gao Mi degree Ju Yi Xi ︰ cyclopentadienyl of the Qian section of polystyrene polybutadiene (mass ratio of 2) ︰ amorphism copolyesters is 8 ︰, 3 ︰, 1 ︰ 1 to metal polyethylene；The internal layer uses mixed raw material are as follows: high density is poly- (mass ratio of 1) ︰ amorphism copolyesters is 4 ︰, 3 ︰, 1 ︰ 1 to Yi Xi ︰ Xian Di Mi degree Ju Yi Xi ︰ metallocene PE；The cyclopentadienyl Metal polyethylene (1) is that melt index is 0.3g/10min, density 0.927g/cm3Metallocene PE；The metallocene Polyethylene (2) is that melt index is 1.0 g/10min, density 0.925g/cm3Metallocene PE；The high density is poly- Ethylene is that melt index is 0.7g/10min, density 0.970g/cm3High density polyethylene (HDPE)；The linear low density polyethylene Alkene is that melt index is 2.0g/10min, density 0.918g/cm3Linear low density polyethylene.
The molar ratio of Ben Yi Xi ︰ butadiene unit in the block copolymer preferred copolymer of the polystyrene polybutadiene For the block copolymer of 9 ︰ 1.
The amorphism copolyesters is to be copolymerized resulting blocked copolyester, the mixing by mixing diacid and mixing glycol Diacid is the mixing diacid that the molar ratio of Dui Ben bis- Jia Suan ︰ succinic acid is 9 ︰ 1；The mixing glycol is Yi bis- Chun ︰ sorbierite Molar ratio is the mixing glycol of 5 ︰ 1.
After each layer raw material is mixed evenly respectively, at a temperature of 190 DEG C refining modeling 15min, then by each layer thickness ratio, The mass ratio of i.e. each layer, the thickness ratio of the thickness of the Hou Du ︰ internal layer of the Hou Du ︰ middle layer of outer layer are as follows: 1 ︰, 3 ︰ 1, altogether by three layers It squeezes equipment to squeeze out, automatic air ring is cooling, and the high strength slim is made and packs heat shrink films again；The three-layer co-extruded equipment is squeezed The draw ratio of screw rod is 34 ︰ 1 out, and extrusion temperature is 150 DEG C, and the vane cooling temperature of the three-layer co-extruded equipment is 18 DEG C.
Heat shrink films obtained by the present embodiment are with a thickness of 40 μm of (wherein, 8 μm of outer layer, 24 μm of middle layer, 8 μm of internal layer), mists Degree 7%, glossiness (45 °) 89%, fall mark impact strength 450g, 550/1597 N/cm of Elmendorf tear strength (MD/TD), 51/63 MPa of fracture tensile strength (MD/TD), elongation at break (MD/TD) 847/923%, percent thermal shrinkage (109 DEG C × 20 seconds； MD/TD) 82/22%；It is calculated by 90 μm of common heat shrink films average thickness, saves material 55.6%.
The physical property of the slim heavy packaging low temperature heat shrink films of gained of the invention and the physical property comparison of common heat shrink films are shown in Table 1.
1 present invention of table and the physical property of common heat shrink films compare
By the comparison of table 1 it can be seen that the thickness of heat shrink films of the present invention subtracts significantly than the thickness of common heat shrink films It is small, heat shrink temperature be significantly lower than common heat shrink films, tearing strength, fracture tensile strength, elongation at break, impact strength, Glossiness and mist degree are substantially better than common heat shrink films, calculate by 90 μm of common heat shrink films average thickness, save material 50.0% ~72.2%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art Member, without departing from the inventive concept of the premise, can also make several improvements and modifications, these improvements and modifications also should be regarded as In protection scope of the present invention.

Claims (4)

1. a kind of slim heavy packaging low temperature heat shrink films, it is characterised in that: the heat shrink films with a thickness of 25~45 μm, by three The film of layer co-extrusion bonding is constituted, i.e. outer layer, middle layer and internal layer；
The thickness ratio of the thickness of the Hou Du ︰ internal layer of the Hou Du ︰ middle layer of the outer layer are as follows: 1 ︰, 3~5 ︰ 1；
The mixed raw material of the outer layer are as follows: the low close degree non-knot of poly- second alkene ︰ of poly- the first poly- second alkene ︰ line of luxuriant metal of second alkene ︰ of the close degree of height The mass ratio of crystalline substance copolyesters is 1~2 ︰, 5~10 ︰, 10~20 ︰ 1；
The mixed raw material of the middle layer are as follows: Gong the second cyclopentadienyl of the Ju Wu ︰ Gao Mi degree Ju Yi Xi ︰ gold of the Qian section of polystyrene polybutadiene The mass ratio for belonging to Ju Yi Xi ︰ amorphism copolyesters is 6~8 ︰, 2~3 ︰, 1~2 ︰ 1；
The mixed raw material of the internal layer are as follows: low close poly- the first poly- non-knot of second alkene ︰ of luxuriant metal of second alkene ︰ of degree of the close poly- second alkene ︰ line of degree of height The mass ratio of crystalline substance copolyesters is 3~4 ︰, 2~3 ︰, 1 ︰ 1；
It is 0.3~0.5g/10min that first metallocene PE, which selects melt index, and density is 0.927~0.944g/cm3 Metallocene PE；It is 0.8~1.0 g/10min, density 0.917 that second metallocene PE, which selects melt index, ~0.925g/cm3Metallocene PE；It is 0.5~0.7g/10min that high density polyethylene (HDPE), which selects melt index, and density is 0.950~0.970g/cm3High density polyethylene (HDPE)；It is 1.7~2.3 g/ that linear low density polyethylene, which selects melt index, 10min, density are 0.916~0.920 g/cm3Linear low density polyethylene.
2. slim heavy packaging low temperature heat shrink films according to claim 1, it is characterised in that: the polystyrene polybutadiene The block copolymer of alkene selects the block copolymer that the molar ratio of Ben Yi Xi ︰ butadiene unit in copolymer is 8~9 ︰ 1.
3. slim heavy packaging low temperature heat shrink films according to claim 1, it is characterised in that: the amorphism copolyesters It is that resulting blocked copolyester is copolymerized by mixing diacid and mixing glycol, the mixing diacid is Dui Ben bis- Jia Suan ︰ succinic acid Molar ratio is the mixing diacid of 8~9 ︰ 1；The mixing glycol is the mixing two that the molar ratio of Yi bis- Chun ︰ sorbierite is 5~15 ︰ 1 Alcohol.
4. the preparation method of slim heavy packaging low temperature heat shrink films described in one of claims 1 to 3, it is characterised in that: will be each After layer raw material is mixed evenly respectively, 10~15min of refining modeling at a temperature of 120~200 DEG C, then the thickness ratio, i.e. by each layer The mass ratio of each layer, the thickness ratio of the thickness of the Hou Du ︰ internal layer of the Hou Du ︰ middle layer of outer layer are as follows: 1 ︰, 3~5 ︰ 1, altogether by three layers It squeezes equipment to squeeze out, automatic air ring is cooling, and the heat shrink films are made；The draw ratio of the extrusion screw rod of the three-layer co-extruded equipment is 33~35 ︰ 1, extrusion temperature are 130~170 DEG C, and the vane cooling temperature of the three-layer co-extruded equipment is 18~25 DEG C.
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JP3051614B2 (en) * 1993-09-29 2000-06-12 三菱樹脂株式会社 Co-extruded composite film for deep drawing
CN1411409A (en) * 1999-12-15 2003-04-16 斯波罗斯股份公司 Multilayer heat shrinkable film
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