CN115179629A - Polyolefin shrink film with high mechanical properties and chemical stability and method of manufacture - Google Patents

Polyolefin shrink film with high mechanical properties and chemical stability and method of manufacture Download PDF

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CN115179629A
CN115179629A CN202210781830.7A CN202210781830A CN115179629A CN 115179629 A CN115179629 A CN 115179629A CN 202210781830 A CN202210781830 A CN 202210781830A CN 115179629 A CN115179629 A CN 115179629A
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film
layer
shrink film
polyolefin shrink
cooling
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CN115179629B (en
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徐子超
周忠强
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Shandong Huihe Plastic Industry Co ltd
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Shandong Huihe Plastic Industry Co ltd
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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
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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    • C08J5/18—Manufacture of films or sheets
    • 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
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    • 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
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08J2323/06—Polyethene
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
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    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
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    • C08J2401/28—Alkyl ethers
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    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2493/00—Characterised by the use of natural resins; Derivatives thereof
    • C08J2493/04—Rosin

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Laminated Bodies (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

The invention belongs to the technical field of film materials, and relates to a polyolefin shrink film with high mechanical property and chemical stability and a manufacturing method thereof. The polyolefin shrink film comprises five layers, respectively: 5-20% of upper and lower polypropylene-containing layers; 5 to 20 percent of upper and lower middle layers containing isobutene-n-butene copolymer; the inner layer contains polyethylene and polypentene, and accounts for 60-90%. The mechanical property and the chemical stability of the polyolefin heat shrinkable film are integrally improved through the flexible proportioning of different materials and auxiliary materials in each layer. In addition, by utilizing a five-layer coextrusion technology, the melt mixing temperature of the upper and lower middle layers, the inner layer and the upper and lower outer layers and the heating temperature of transverse stretching and longitudinal stretching are respectively adjusted, so that the comprehensive performance of the polyolefin shrink film is improved.

Description

Polyolefin shrink film with high mechanical properties and chemical stability and method of manufacture
Technical Field
The invention belongs to the technical field of film materials, and particularly relates to a polyolefin shrink film with high mechanical property and chemical stability and a manufacturing method thereof.
Background
The multilayer co-extruded polyolefin heat shrinkable film (POF) is prepared by taking various polyolefin polymers as a middle layer, an inner layer and an outer layer, adding necessary auxiliaries and processing by a co-extrusion blow molding process. The PVC heat shrinkable film is mainly used for packaging products with regular and irregular shapes, is a substitute product of the traditional PVC heat shrinkable film due to the characteristics of no toxicity, environmental protection, high transparency, high shrinkage, good heat sealing performance, high glossiness, toughness, tear resistance, uniform heat shrinkage, suitability for full-automatic high-speed packaging and the like, and is widely applied to products such as automobile products, plastic products, stationery, books, electronics, circuit boards, artware, wooden products, toys, insecticides, daily necessities, food, cosmetics, canned beverages, dairy products, medicines, cassette tapes, video tapes and the like.
The POF heat shrinkable packaging film has wide application and wide market, has the advantages of environmental protection and no toxicity, is widely regarded by developed countries in the world, and is a mainstream product in heat shrinkable packaging materials by basically replacing PVC heat shrinkable packaging films. Due to the certain gap between the packaging technology of China and the developed countries, the five-layer co-extrusion series heat-shrinkable packaging film is still in the preliminary stage of domestic application, the technology is not mature enough, and the comprehensive performance of the polyolefin shrink film is not excellent enough.
Disclosure of Invention
The five-layer co-extruded polyolefin heat shrinkable film provided by the invention overcomes the defects of the prior art, and is divided into an upper middle layer, a lower middle layer, an inner layer and an upper outer layer, wherein each layer is flexibly prepared from different materials and auxiliary materials, so that the mechanical property and the chemical stability of the polyolefin heat shrinkable film are integrally improved.
Specifically, the technical scheme of the invention is as follows:
the invention provides a polyolefin shrink film, which comprises five layers:
5-20% of upper and lower surface layers containing polypropylene, acrylic resin, rosin pentaerythritol ester and xanthan gum;
5 to 20 percent of upper and lower middle layers containing isobutene-n-butene copolymer, poly-1-butene, hydroxypropyl methylcellulose and white oil;
60% -90% of an inner layer containing polyethylene, poly-4-methyl-1-pentene and silica gel micropowder;
the upper surface layer and the lower surface layer respectively account for 1/2 of the total proportion of the upper surface layer and the lower surface layer, and the upper middle layer and the lower middle layer respectively account for 1/2 of the total proportion of the upper surface layer and the lower surface layer.
Further, the components in the upper surface layer and the lower surface layer are calculated according to the weight ratio:
6-10 parts of polypropylene, 1-5 parts of acrylic resin, 2-7 parts of rosin pentaerythritol ester and 1-5 parts of xanthan gum;
the upper and lower middle layers are prepared from the following components in percentage by weight:
contains 4-8 parts of isobutene-n-butene copolymer, 1-5 parts of poly-1-butene, 1-5 parts of hydroxypropyl methyl cellulose and 0.5-4 parts of white oil.
The inner layer comprises the following components in percentage by weight:
5-10 parts of polyethylene, 1-5 parts of poly-4-methyl-1-pentene and 0.5-4 parts of micro silica gel powder.
The proportion design of materials in the upper surface layer and the lower surface layer is as follows:
the polypropylene is used as a base material, is a white waxy material, has a transparent appearance and a light melting point of 189 ℃, is softened at about 155 ℃, and has a use temperature range of-30-140 ℃.
The rosin pentaerythritol ester has the advantages of light color, high viscosity, good heat resistance and the like, can be dissolved with various high molecular polymers, can greatly improve the bonding force, and has higher hardness and higher melting point.
The addition of the rosin pentaerythritol ester improves the melting points of the upper and lower surface layers, the outer film is more resistant to high temperature, and the application temperature range is enlarged. However, in the subsequent use and storage processes, the rosin pentaerythritol ester product is easy to oxidize and deepen, the grade of the product is influenced, and the use range of the product is limited, so that the acrylic resin is added by the inventor, the light and color protection effects are achieved to a certain degree, and the rosin pentaerythritol ester is water-resistant, chemical-resistant and quick to dry and is suitable for being flexibly added into the upper and lower surface layers. However, the acrylic resin has limited effect, and oxidation reaction can occur due to the influence of environmental factors such as exposure and the like in the long-term storage or use process, so the inventor researches a method for slowing down the discoloration of the rosin pentaerythritol ester.
The proportioning design of materials in the upper middle layer and the lower middle layer is as follows:
the isobutene-n-butene copolymer is a high molecular inert polymer, has stable chemical properties, is used as a base material of the middle layer, is added with the poly-1-butene in parts by weight for improving the rigidity and the hardness of the middle layer film, is thermoplastic resin, is semitransparent, colorless and has a regular molecular structure, and can be changed into a relatively stable crystal form at room temperature after being cooled and crystallized from a melt state, so that the strength and the rigidity of the middle layer can be improved. It was found through studies that the intermediate layer increased rigidity and hardness and became brittle, and in order to increase toughness, the inventors added thereto an inactive, viscoelastic polymer, hydroxypropyl methylcellulose, which indirectly increased the elasticity and toughness of the intermediate layer by increasing adhesion and water retention properties. The small amount of white oil is added, so that the smoothness of the extrusion process can be improved, the lubricating effect on high-speed running mechanical equipment can be realized, and the equipment can be protected.
The proportioning design of materials in the inner layer is as follows:
the polyethylene is odorless, nontoxic, has wax-like hand feeling, excellent low-temperature resistance and good chemical stability, can resist corrosion of most of acid and alkali, and is used as one of the base materials of the inner layer of the invention.
The poly-4-methyl-1-pentene is thermoplastic resin with low density, has excellent heat resistance, visible light transmittance of 90 percent, high ultraviolet light transmittance and excellent electrical insulation and chemical resistance, and is used as one of base materials of the inner layer.
Because the inner layer accounts for 60-90% of the total thickness of the film material, on the premise of ensuring that the physical properties such as tensile strength, shrinkage tension and the like and the chemical properties such as corrosion resistance and the like which are required by the inner layer material are excellent, the light transmittance and the water vapor permeability are difficult to solve and consider, so that the inventor utilizes the combination of polyethylene and poly-4-methyl-1-pentene as the main material of the inner layer, the thermal stability of the polyolefin shrink film is obviously improved, the water vapor permeability of the film material is reduced, and the breeze silica gel is used as a slip agent, so that the smoothness of the extrusion process can be improved, all the materials can be fully and uniformly mixed, and the comprehensive performance of the film material is generally improved.
Further, the polyolefin shrink film is composed of the following components:
Figure BDA0003728179780000031
preferably, the polyolefin shrink film consists of the following components:
Figure BDA0003728179780000032
Figure BDA0003728179780000041
a second object of the present invention is to provide a method for manufacturing the above polyolefin shrink film, comprising the steps of:
(1) Extruding: heating and mixing the materials of the upper surface layer, the lower surface layer, the upper middle layer, the lower middle layer and the inner layer respectively, and conveying the materials to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: cooling and molding the extruded material obtained in the step (1) to form a casting film;
(3) Stretching: feeding the cast film into an asynchronous transverse stretching machine for transverse stretching, and then performing longitudinal stretching to obtain a film;
(4) Traction: sending the film into a cooling roller of a tractor for cooling, and then trimming and winding to obtain a film roll;
(5) And (6) drying and rolling.
Further, in the step (1),
the temperature for heating and mixing the materials on the upper and lower surface layers is 140-165 ℃;
the temperature for heating and mixing the materials of the upper and lower middle layers is 150-180 ℃;
the temperature for heating and mixing the materials in the inner layer is 160-190 ℃.
The heating and mixing temperature of materials of each layer is also important, and if the upper surface layer, the lower surface layer, the upper middle layer, the lower middle layer and the inner layer are heated and mixed at the same temperature, the processed polyolefin shrink film has poor tensile property and the breaking rate is only about 70%.
In the step (3), the transverse stretching temperature is 90-120 ℃, and the longitudinal stretching temperature is 110-120 ℃.
In the step (2), the cooling forming is carried out by indirect cooling through the closed type circulating cooling desalination water system, the consumed power is low, the power consumption is low, the cooling water is completely in closed circulating operation in the circulating process, the water loss is basically avoided, and the energy-saving and environment-friendly effects are achieved.
Specifically, the method for manufacturing the polyolefin shrink film comprises the following steps:
(1) Extruding: heating and mixing the upper surface layer and the lower surface layer at 140-165 ℃, heating and mixing the upper middle layer and the lower middle layer at 150-180 ℃, heating and mixing the materials in the inner layer at 160-190 ℃, respectively uniformly mixing, and then conveying to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material obtained in the step (1) into a calender, and then carrying out indirect cooling and forming through a closed circulating cooling desalination water system to form a cast film;
(3) Stretching: feeding the cast film into an asynchronous transverse stretching machine for transverse stretching at the temperature of 90-120 ℃, and then carrying out longitudinal stretching at the temperature of 110-120 ℃ to obtain a film;
(4) Traction: sending the film into a cooling roller of a tractor for cooling, and then trimming and winding to obtain a film roll;
(5) And (5) drying and rolling.
Further, the thickness of the manufactured polyolefin shrink film is 5-50um, and films with different thicknesses can be produced according to the temperature and the strength for adjusting transverse stretching and longitudinal stretching, wherein specific thickness models include but are not limited to 5um, 10um, 12um, 13um, 15um, 19um, 22um, 25um, 30um, 40um and 50um.
Compared with the prior art, the invention has the beneficial effects that:
(1) The polyolefin heat shrinkable film is divided into an upper middle layer, a lower middle layer, an inner layer and an upper outer layer, wherein the upper middle layer, the lower middle layer, the inner layer and the upper outer layer are five layers, and each layer integrally improves the mechanical property and the chemical stability of the polyolefin heat shrinkable film through flexible proportioning of different materials and auxiliary materials.
(2) By utilizing a five-layer co-extrusion technology, the melt mixing temperatures of the upper and lower intermediate layers, the inner layer and the upper and lower outer layers are respectively adjusted, the heating temperatures of transverse stretching and longitudinal stretching are flexibly adjusted according to the thickness of the processed polyolefin shrink film, the comprehensive performance of the polyolefin shrink film is improved, the cooling mode is optimized, and the energy-saving and environment-friendly effects are achieved.
Drawings
FIG. 1 schematic representation of polyolefin shrink film
FIG. 2 Effect of Material Components of Upper and lower surface layers of polyolefin shrink film on oxygen permeability
FIG. 3 is a graph showing the effect of the material composition of the upper and lower surface layers of the polyolefin shrink film on the light transmittance
FIG. 4 Effect of the Material composition of the Upper and lower intermediate layers of polyolefin shrink film on the shrinkage
FIG. 5 Effect of Material composition of Upper and lower intermediate layers of polyolefin shrink film on tensile Strength
FIG. 6 Effect of the Material composition of the inner layer of polyolefin shrink film on Water vapor Permeability
FIG. 7 Effect of interlayer Material composition on thermal stability in polyolefin shrink films
FIG. 8 comprehensive quality evaluation of polyolefin shrink films of examples 1 to 5 and comparative examples 1 to 2
FIG. 9 Effect of various operation temperatures in the preparation Process on the tensile Properties of polyolefin shrink films
FIG. 10 Effect of various operating temperatures on polyolefin shrink film shrinkage in the preparation Process
Detailed Description
In order to make the purpose and technical solution of the present invention more clear, the present invention is further described with reference to the following examples, but the scope of the present invention is not limited to these examples, and the examples are only used for explaining the present invention. It will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the true scope of the invention.
Example 1 polyolefin shrink film
The mixture ratio is as follows:
Figure BDA0003728179780000061
the manufacturing method comprises the following steps:
(1) Extruding: heating and mixing the upper and lower surface layers at 150 deg.C, heating and mixing the upper and lower intermediate layers at 170 deg.C, heating and mixing the materials in the inner layer at 175 deg.C, respectively, and extruding to obtain five layers;
(2) And (3) cooling: adding the extruded material obtained in the step (1) into a calender, and indirectly cooling and forming the extruded material through a closed circulating cooling desalination water system to form a casting film;
(3) Stretching: feeding the cast film into an asynchronous transverse stretching machine to stretch transversely at the temperature of 100 ℃, and then stretching longitudinally at the temperature of 115 ℃ to obtain a film;
(4) Traction: sending the film into a cooling roller of a tractor for cooling, and then trimming and winding to obtain a film roll 22um;
(5) And (6) drying and rolling.
Example 2 polyolefin shrink film
The mixture ratio is as follows:
Figure BDA0003728179780000062
Figure BDA0003728179780000071
the manufacturing method comprises the following steps:
(1) Extruding: heating and mixing the upper surface layer and the lower surface layer at 140 ℃, heating and mixing the upper middle layer and the lower middle layer at 150 ℃, heating and mixing the materials of the inner layer at 160 ℃, respectively uniformly mixing, and then sending to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material obtained in the step (1) into a calender, and then carrying out indirect cooling and forming through a closed circulating cooling desalination water system to form a cast film;
(3) Stretching: feeding the cast film into an asynchronous transverse stretching machine to be transversely stretched at the temperature of 120 ℃, and then longitudinally stretching at the temperature of 120 ℃ to obtain a film;
(4) Traction: sending the film into a cooling roller of a tractor for cooling, and then trimming and winding to obtain a film roll of 50um;
(5) And (5) drying and rolling.
Example 3 polyolefin shrink film
The mixture ratio is as follows:
Figure BDA0003728179780000072
Figure BDA0003728179780000081
the manufacturing method comprises the following steps:
(1) Extruding: heating and mixing the upper surface layer and the lower surface layer at 165 ℃, heating and mixing the upper middle layer and the lower middle layer at 180 ℃, heating and mixing the materials in the inner layer at 190 ℃, respectively uniformly mixing, and then sending to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material obtained in the step (1) into a calender, and indirectly cooling and forming the extruded material through a closed circulating cooling desalination water system to form a casting film;
(3) Stretching: feeding the cast film into an asynchronous transverse stretching machine to be transversely stretched at the temperature of 90 ℃, and then longitudinally stretched at the temperature of 110 ℃ to obtain a film;
(4) Traction: sending the film into a cooling roller of a tractor for cooling, and then trimming and winding to obtain a film roll of 10um;
(5) And (6) drying and rolling.
Example 4 polyolefin shrink film
The mixture ratio is as follows:
Figure BDA0003728179780000082
Figure BDA0003728179780000091
the manufacturing method comprises the following steps:
(1) Extruding: heating and mixing the upper and lower surface layers at 150 deg.C, heating and mixing the upper and lower intermediate layers at 170 deg.C, heating and mixing the materials in the inner layer at 175 deg.C, respectively, and extruding to obtain five layers;
(2) And (3) cooling: adding the extruded material obtained in the step (1) into a calender, and indirectly cooling and forming the extruded material through a closed circulating cooling desalination water system to form a casting film;
(3) Stretching: feeding the cast film into an asynchronous transverse stretching machine for transverse stretching at the temperature of 100 ℃, and then carrying out longitudinal stretching at the temperature of 115 ℃ to obtain a film;
(4) Traction: sending the film into a cooling roller of a tractor for cooling, and then cutting edges and winding to obtain a film roll 22um;
(5) And (6) drying and rolling.
Example 5 polyolefin shrink film
The mixture ratio is as follows:
Figure BDA0003728179780000092
the manufacturing method comprises the following steps:
(1) Extruding: heating and mixing the upper surface layer and the lower surface layer at 150 ℃, heating and mixing the upper middle layer and the lower middle layer at 170 ℃, heating and mixing the materials in the inner layers at 175 ℃, respectively uniformly mixing, and then conveying to corresponding extruders for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material obtained in the step (1) into a calender, and indirectly cooling and forming the extruded material through a closed circulating cooling desalination water system to form a casting film;
(3) Stretching: feeding the cast film into an asynchronous transverse stretching machine to stretch transversely at the temperature of 100 ℃, and then stretching longitudinally at the temperature of 115 ℃ to obtain a film;
(4) Traction: sending the film into a cooling roller of a tractor for cooling, and then trimming and winding to obtain a film roll 22um;
(5) And (5) drying and rolling.
Comparative example 1 polyolefin shrink film
The mixture ratio is as follows:
Figure BDA0003728179780000101
the manufacturing method comprises the following steps:
(1) Extruding: heating and mixing the upper and lower surface layers at 150 deg.C, heating and mixing the upper and lower intermediate layers at 170 deg.C, heating and mixing the materials in the inner layer at 175 deg.C, respectively, and extruding to obtain five layers;
(2) And (3) cooling: adding the extruded material obtained in the step (1) into a calender, and indirectly cooling and forming the extruded material through a closed circulating cooling desalination water system to form a casting film;
(3) Stretching: feeding the cast film into an asynchronous transverse stretching machine to stretch transversely at the temperature of 100 ℃, and then stretching longitudinally at the temperature of 115 ℃ to obtain a film;
(4) Traction: sending the film into a cooling roller of a tractor for cooling, and then cutting edges and winding to obtain a film roll 22um;
(5) And (6) drying and rolling.
Comparative example 2 polyolefin shrink film
The mixture ratio is as follows:
Figure BDA0003728179780000111
the manufacturing method comprises the following steps:
(1) Extruding: heating and mixing the upper surface layer and the lower surface layer at 120 ℃, heating and mixing the upper middle layer and the lower middle layer at 200 ℃, heating and mixing the materials in the inner layer at 140 ℃, respectively uniformly mixing, and then sending to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material obtained in the step (1) into a calender, and then carrying out indirect cooling and forming through a closed circulating cooling desalination water system to form a cast film;
(3) Stretching: feeding the cast film into an asynchronous transverse stretching machine for transverse stretching at the temperature of 80 ℃, and then carrying out longitudinal stretching at the temperature of 130 ℃ to obtain a film;
(4) Traction: sending the film into a cooling roller of a tractor for cooling, and then trimming and winding to obtain a film roll 22um;
(5) And (5) drying and rolling.
1. Mechanical and chemical stability one-factor testing of polyolefin shrink films
1. Test characterization method
1.1 thermal stability test
Thermogravimetric analysis (TG): cutting the film into pieces and placing the pieces into a Pt crucible by adopting a Thermographical Analysis TA Q50 Thermogravimetric analyzer under the protection of nitrogen in a temperature rangeAt 300-850K, at 10 K.min -1 TG test on polyolefin shrink films.
1.2 determination of tensile Properties
Reference is made to the provisions of the standard GB/T1040.1-2006. The tensile strength and elongation at break were measured at room temperature using a universal tensile machine at a tensile speed of 50mm/min, 5 measurements were made for each sample, the average was taken, and the standard deviation was calculated.
1.3 measurement of shrinkage
According to the specification of the reference standard GB/T10003-2008, a sample with a certain size is taken and placed in the middle of an oven, air blowing is carried out, the sample is placed at room temperature for cooling after being heated for 120s, and the length of the sample in the length direction (TD) is measured. The heat Shrinkage Ratio (SR) was calculated as follows.
SR＝(L-L 1 )/L×100％
In the formula: l is the length (mm) of the sample before heating; l is 1 Is the length (mm) of the sample after heating.
Each set of samples was averaged 5 times and the standard deviation calculated.
1.4 light transmittance test
The light transmittance and haze were measured according to GB/T2410-2008. The ratio of the light flux transmitted through the sample to the light flux incident on the sample, expressed as a percentage, was measured by the spectrophotometer method. The light transmittance of the polyolefin shrink film was measured from 0-24 months storage at 32 ℃.
1.5 oxygen permeability test
The samples were tested by the pressure differential method, the test procedure being carried out according to the method standard GB/T1038-2000 "pressure differential method for testing gas permeability of Plastic films and sheets".
1.6 Water vapor Permeability test
The measurement is carried out according to GB/T30412-2013 humidity sensor method for measuring the water vapor transmission rate of plastic films and thin sheets.
2. Design of single factor experiment
2.1 Single-factor test of the components and the ratio of the materials of the upper and lower surface layers
Figure BDA0003728179780000121
Figure BDA0003728179780000131
The rest is the same as example 1.
The A-E group single factor variables are the components of the materials of the upper and lower surface layers, and the influences of the A-E group single factor variables on the thermal stability, the tensile property, the shrinkage rate, the light transmittance, the oxygen permeability and the water vapor permeability are respectively researched. The data show that the light transmittance and the oxygen permeability of the polyolefin shrink film are greatly influenced by the material components of the upper and lower surface layers.
2.2 Single-factor test of the composition and the ratio of the materials of the upper and lower middle layers
Figure BDA0003728179780000132
The rest is the same as example 1.
The A-E group single factor variables are the material components of the upper and lower middle layers, and the influences of the A-E group single factor variables on the thermal stability, the tensile property, the shrinkage rate, the light transmittance, the oxygen permeability and the water vapor permeability are respectively researched.
2.3 inner layer Material composition and proportioning Single factor test
Group A Group B Group C Group D
Polyethylene Polyethylene Polyethylene (PE) Polypropylene
Poly (4-methyl-1-pentene) - Poly (4-methyl-1-pentene) Poly (4-methyl-1-pentene)
Silica gel micropowder Silica gel micropowder Silicon dioxide Silica gel micropowder
The rest is the same as example 1.
The A-D group single factor variables are inner layer material components, and the influences of the A-D group single factor variables on thermal stability, tensile property, shrinkage rate, light transmittance, oxygen permeability and water vapor permeability are respectively researched.
2.4 temperature Screen Men factor test in preparation Process
Group A:
the respective layer formulations were the same as in example 1.
(1) Extruding: heating and mixing the upper and lower surface layers at 150 deg.C, heating and mixing the upper and lower intermediate layers at 170 deg.C, heating and mixing the materials in the inner layer at 175 deg.C, respectively, and extruding to obtain five layers;
(2) And (3) cooling: adding the extruded material obtained in the step (1) into a calender, and indirectly cooling and forming the extruded material through a closed circulating cooling desalination water system to form a casting film;
(3) Stretching: feeding the cast film into an asynchronous transverse stretching machine for transverse stretching at the temperature of 100 ℃, and then carrying out longitudinal stretching at the temperature of 115 ℃ to obtain a film;
(4) Traction: sending the film into a cooling roller of a tractor for cooling, and then cutting edges and winding to obtain a film roll 22um;
(5) And (6) drying and rolling.
Group B:
the respective layer formulations were the same as in example 1.
(1) Extruding: heating and mixing the upper surface layer and the lower surface layer at 120 ℃, heating and mixing the upper middle layer and the lower middle layer at 170 ℃, heating and mixing the materials in the inner layers at 175 ℃, respectively uniformly mixing, and then conveying to corresponding extruders for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material obtained in the step (1) into a calender, and then carrying out indirect cooling and forming through a closed circulating cooling desalination water system to form a cast film;
(3) Stretching: feeding the cast film into an asynchronous transverse stretching machine for transverse stretching at the temperature of 100 ℃, and then carrying out longitudinal stretching at the temperature of 115 ℃ to obtain a film;
(4) Traction: sending the film into a cooling roller of a tractor for cooling, and then trimming and winding to obtain a film roll 22um;
(5) And (5) drying and rolling.
Group C:
the respective layer formulations were the same as in example 1.
(1) Extruding: heating and mixing the upper surface layer and the lower surface layer at 150 ℃, heating and mixing the upper middle layer and the lower middle layer at 200 ℃, heating and mixing the materials in the inner layers at 175 ℃, respectively uniformly mixing, and then conveying to corresponding extruders for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material obtained in the step (1) into a calender, and indirectly cooling and forming the extruded material through a closed circulating cooling desalination water system to form a casting film;
(3) Stretching: feeding the cast film into an asynchronous transverse stretching machine for transverse stretching at the temperature of 100 ℃, and then carrying out longitudinal stretching at the temperature of 115 ℃ to obtain a film;
(4) Traction: sending the film into a cooling roller of a tractor for cooling, and then trimming and winding to obtain a film roll 22um;
(5) And (5) drying and rolling.
Group D:
the respective layer formulations were the same as in example 1.
(1) Extruding: heating and mixing the upper surface layer and the lower surface layer at 150 ℃, heating and mixing the upper middle layer and the lower middle layer at 170 ℃, heating and mixing the materials in the inner layer at 145 ℃, respectively uniformly mixing, and then sending to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material obtained in the step (1) into a calender, and then carrying out indirect cooling and forming through a closed circulating cooling desalination water system to form a cast film;
(3) Stretching: feeding the cast film into an asynchronous transverse stretching machine for transverse stretching at the temperature of 100 ℃, and then carrying out longitudinal stretching at the temperature of 115 ℃ to obtain a film;
(4) Traction: sending the film into a cooling roller of a tractor for cooling, and then trimming and winding to obtain a film roll 22um;
(5) And (6) drying and rolling.
Group E:
the respective layer formulations were the same as in example 1.
(1) Extruding: heating and mixing the upper surface layer and the lower surface layer at 150 ℃, heating and mixing the upper middle layer and the lower middle layer at 170 ℃, heating and mixing the materials in the inner layers at 175 ℃, respectively uniformly mixing, and then conveying to corresponding extruders for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material obtained in the step (1) into a calender, and indirectly cooling and forming the extruded material through a closed circulating cooling desalination water system to form a casting film;
(3) Stretching: feeding the cast film into an asynchronous transverse stretching machine for transverse stretching at the temperature of 130 ℃, and then carrying out longitudinal stretching at the temperature of 115 ℃ to obtain a film;
(4) Traction: sending the film into a cooling roller of a tractor for cooling, and then trimming and winding to obtain a film roll 22um;
(5) And (6) drying and rolling.
And group F:
the respective layer formulations were the same as in example 1.
(1) Extruding: heating and mixing the upper surface layer and the lower surface layer at 150 ℃, heating and mixing the upper middle layer and the lower middle layer at 170 ℃, heating and mixing the materials in the inner layers at 175 ℃, respectively uniformly mixing, and then conveying to corresponding extruders for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material obtained in the step (1) into a calender, and indirectly cooling and forming the extruded material through a closed circulating cooling desalination water system to form a casting film;
(3) Stretching: feeding the cast film into an asynchronous transverse stretching machine to stretch transversely at the temperature of 100 ℃, and then stretching longitudinally at the temperature of 90 ℃ to obtain a film;
(4) Traction: sending the film into a cooling roller of a tractor for cooling, and then cutting edges and winding to obtain a film roll 22um;
(5) And (6) drying and rolling.
The A-F group single factor variables are all temperatures in the preparation process, and the influences of the A-F group single factor variables on thermal stability, tensile property, shrinkage rate, light transmittance, oxygen permeability and water vapor permeability are respectively researched.
3. Conclusion
As shown in the figure data, the light transmittance and the oxygen permeability of the polyolefin shrink film are greatly influenced by the material components of the upper and lower surface layers; the material components of the upper and lower middle layers have great influence on the shrinkage rate and tensile strength of the polyolefin shrink film; the inner layer material components have great influence on the water vapor permeability and the thermal stability of the polyolefin shrink film, only the thermogravimetric curve chart of the group A is shown, the high temperature resistance of the polyolefin shrink film of the group A is shown, the highest temperature can reach 250 ℃, the polyolefin shrink film of the group B-D is also subjected to corresponding thermogravimetric tests, the polyolefin shrink film of the group B starts to decompose at 207 ℃, the polyolefin shrink film of the group C starts to decompose at 231 ℃, and the polyolefin shrink film of the group D starts to decompose at 233 ℃; various operation temperatures in the preparation process have great influence on the tensile property and the shrinkage rate. As shown in detail.
2. Comprehensive evaluation of polyolefin shrink films of examples and comparative examples
The polyolefin shrink films of examples 1-5 and comparative examples 1-2 were subjected to comprehensive quality evaluation, and the thermal stability, tensile property, shrinkage, light transmittance, oxygen permeability and water vapor permeability were subjected to comprehensive evaluation, wherein the evaluation criteria were as follows:
TABLE 1 polyolefin shrink film comprehensive evaluation scoring criteria
Figure BDA0003728179780000161
Figure BDA0003728179780000171
The polyolefin shrink films of examples 1-5 and comparative examples 1-2 are subjected to comprehensive quality evaluation according to the scoring indexes in Table 1, radar maps are drawn, and the results show that the polyolefin shrink films of examples 1-5 of the invention have good comprehensive performance and very high mechanical properties and chemical stability.
3. Performance display of polyolefin shrink films
Table 2 polyolefin shrink film property displays with different thicknesses
Figure BDA0003728179780000172
Figure BDA0003728179780000181

Claims (10)

1. A polyolefin shrink film, comprising five layers, each of:
5% -20% of upper and lower polypropylene-containing layers;
5 to 20 percent of upper and lower middle layers containing isobutene-n-butene copolymer;
60% -90% of an inner layer containing polyethylene and polypentene;
the upper surface layer and the lower surface layer respectively account for 1/2 of the total proportion of the upper surface layer and the lower surface layer, and the upper middle layer and the lower middle layer respectively account for 1/2 of the total proportion of the upper middle layer and the lower middle layer.
2. The polyolefin shrink film of claim 1,
the upper surface layer and the lower surface layer comprise polypropylene, acrylic resin, rosin pentaerythritol ester and xanthan gum;
the upper and lower middle layers comprise isobutene-n-butene copolymer, poly-1-butylene, hydroxypropyl methyl cellulose and white oil;
the inner layer comprises polyethylene, poly-4-methyl-1-pentene and superfine silica gel powder.
3. The polyolefin shrink film of claim 2, wherein the upper and lower skin layers comprise, in weight ratios: 6-10 parts of polypropylene, 1-5 parts of acrylic resin, 2-7 parts of rosin pentaerythritol ester and 1-5 parts of xanthan gum.
4. The polyolefin shrink film of claim 2, wherein the upper and lower intermediate layers comprise, in weight ratios: contains 4-8 parts of isobutene-n-butene copolymer, 1-5 parts of poly-1-butene, 1-5 parts of hydroxypropyl methyl cellulose and 0.5-4 parts of white oil.
5. The polyolefin shrink film of claim 2, wherein the components in the inner layer are in the weight ratio: 5-10 parts of polyethylene, 1-5 parts of poly-4-methyl-1-pentene and 0.5-4 parts of micro silica gel powder.
6. The polyolefin shrink film of any of claims 3-5, wherein the polyolefin shrink film is comprised of:
Figure FDA0003728179770000011
Figure FDA0003728179770000021
7. the polyolefin shrink film of claim 6, wherein the polyolefin shrink film is comprised of:
Figure FDA0003728179770000022
8. a method of making the polyolefin shrink film of claim 1, comprising the steps of:
(1) Extruding: heating and mixing the materials of the upper surface layer, the lower surface layer, the upper middle layer, the lower middle layer and the inner layer respectively, and conveying the materials to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: cooling and molding the extruded material obtained in the step (1) to form a casting film;
(3) Stretching: feeding the cast film into an asynchronous transverse stretching machine for transverse stretching, and then performing longitudinal stretching to obtain a film;
(4) Traction: sending the film into a cooling roller of a tractor for cooling, and then trimming and winding to obtain a film roll;
(5) And (5) drying and rolling.
9. The method according to claim 8, wherein, in the step (1),
the temperature for heating and mixing the materials of the upper and lower surface layers is 140-165 ℃;
the temperature for heating and mixing the materials of the upper and lower middle layers is 150-180 ℃;
the temperature for heating and mixing the materials in the inner layer is 160-190 ℃;
in the step (3), the transverse stretching temperature is 90-120 ℃, and the longitudinal stretching temperature is 110-120 ℃.
10. The method as claimed in claim 8, wherein in the step (2), the cooling forming is indirectly cooled by a closed circulation cooling desalination water system.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004091712A (en) * 2002-09-03 2004-03-25 Asahi Kasei Chemicals Corp Heat shrink film
CN102765190A (en) * 2012-07-27 2012-11-07 江苏恒创包装材料有限公司 Method for producing biaxially oriented multilayer co-extruded polyolefin shrink film by flat film process
CN104943131A (en) * 2014-03-31 2015-09-30 山东中塑泰富科技有限公司 Three-five layer coextrusion polyolefin environment-friendly thermal shrink film processing technology
WO2018175253A1 (en) * 2017-03-22 2018-09-27 Dow Global Technologies Llc Optical cable with channel structure
CN108943929A (en) * 2018-06-08 2018-12-07 黄山至德新材料科技有限公司 A kind of Polyolefin Heat Shrinkable Film and its preparation method and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004091712A (en) * 2002-09-03 2004-03-25 Asahi Kasei Chemicals Corp Heat shrink film
CN102765190A (en) * 2012-07-27 2012-11-07 江苏恒创包装材料有限公司 Method for producing biaxially oriented multilayer co-extruded polyolefin shrink film by flat film process
CN104943131A (en) * 2014-03-31 2015-09-30 山东中塑泰富科技有限公司 Three-five layer coextrusion polyolefin environment-friendly thermal shrink film processing technology
WO2018175253A1 (en) * 2017-03-22 2018-09-27 Dow Global Technologies Llc Optical cable with channel structure
CN108943929A (en) * 2018-06-08 2018-12-07 黄山至德新材料科技有限公司 A kind of Polyolefin Heat Shrinkable Film and its preparation method and application

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