CN115179629B - 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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CN115179629B
CN115179629B CN202210781830.7A CN202210781830A CN115179629B CN 115179629 B CN115179629 B CN 115179629B CN 202210781830 A CN202210781830 A CN 202210781830A CN 115179629 B CN115179629 B CN 115179629B
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shrink film
film
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CN115179629A (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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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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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    • 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
    • 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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    • C08J2401/26—Cellulose ethers
    • C08J2401/28—Alkyl ethers
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    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08J2423/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • 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
    • 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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  • 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, namely: upper and lower surface layers containing polypropylene accounting for 5 to 20 percent; an upper middle layer and a lower middle layer which contain isobutene-n-butene copolymer and account for 5% -20%; an inner layer containing polyethylene and polypentene accounting for 60-90 percent. The mechanical property and chemical stability of the polyolefin heat-shrinkable film are integrally improved through flexible proportion of different materials and auxiliary materials in each layer. In addition, the five-layer coextrusion technology is utilized to respectively adjust the melting mixing temperature of the upper middle layer, the lower middle layer, the inner layer and the upper outer layer and the heating temperature of transverse stretching and longitudinal stretching, 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-extrusion polyolefin heat shrinkage film (POF) is prepared by using a plurality of polyolefin polymers as an intermediate layer, an inner layer and an outer layer, adding necessary auxiliary agents 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, high 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, wood products, toys, pesticides, daily necessities, foods, cosmetics, canned beverages, dairy products, medicines, cassette tapes, video tapes and the like.
The POF heat-shrinkable packaging film has very wide application, wide market and environmental protection and no toxicity, and is widely valued by developed countries in the world, and the POF heat-shrinkable packaging film is basically replaced by PVC heat-shrinkable packaging film to become a main stream product in heat-shrinkable packaging materials. Because of a certain gap between the packaging technology in China and the internationally developed countries, five-layer co-extrusion series heat shrink packaging films are in a preliminary stage in domestic application, the technology is not mature enough, and the comprehensive performance of the polyolefin shrink films is not excellent enough.
Disclosure of Invention
The invention provides a five-layer co-extrusion polyolefin heat-shrinkable film, which is divided into an upper middle layer, a lower middle layer, an inner layer and an upper outer layer, wherein each layer is flexibly proportioned with auxiliary materials through different materials, and 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, namely:
5-20% of upper and lower surface layers containing polypropylene, acrylic resin, rosin pentaerythritol ester and xanthan gum;
5-20% of upper and lower middle layers containing isobutene-n-butene copolymer, poly-1-butene, hydroxypropyl methyl cellulose and white oil;
60% -90% of an inner layer containing polyethylene, poly 4-methyl-1-pentene and micro powder silica gel;
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.
Further, the weight ratio of the components in the upper surface layer and the lower surface layer is as follows:
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 weight ratio of the components in the upper middle layer and the lower middle layer is as follows:
comprises 4-8 parts of isobutene-n-butene copolymer, 1-5 parts of poly-1-butene, 1-5 parts of hydroxypropyl methylcellulose and 0.5-4 parts of white oil.
The components in the inner layer are calculated according to 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.
The proportion design of each material in the upper surface layer and the lower surface layer is as follows:
polypropylene as a base material, a white wax-like material, transparent in appearance and light in melting point 189 deg.C, softens at about 155 deg.C, and is used at a temperature in the range of-30 to 140 deg.C.
The rosin pentaerythritol ester has the advantages of light color, high viscosity, good heat resistance and the like, can be compatible with various high-molecular polymers, and can greatly improve the adhesive force, and has higher hardness and higher melting point.
The addition of the rosin pentaerythritol ester improves the melting points of the upper surface layer and the lower surface layer, the outer film is more resistant to high temperature, and the use temperature range is enlarged. However, in the subsequent use and storage process, the rosin pentaerythritol ester product is easy to oxidize and deepen in color, the grade of the product is influenced, and the application range of the product is limited, so that the inventor adds acrylic resin to play a role in protecting light and color to a certain extent, has water resistance, chemical resistance and quick drying, and is suitable for being flexibly added in the upper surface layer and the lower surface layer. However, the effect of the acrylic resin is limited, and oxidation reaction still occurs due to the influence of environmental factors such as insolation and the like in the long-term storage or use process, so the inventor researches a method for slowing down the discoloration of the pentaerythritol rosin ester, and surprisingly discovers that after the xanthan gum with the weight part range is added, the oxidation reaction is avoided in the long-term storage, so the stability and weather resistance of the pentaerythritol rosin ester are improved, the color of a colorless or light-colored pentaerythritol rosin ester product can be kept for a long time without discoloration, in addition, the air can be blocked more efficiently, the oxygen permeability of a film material is reduced, and the sealing performance is higher.
The proportion design of each material in the upper and lower middle layers is as follows:
the isobutylene-n-butene copolymer is a high molecular inert polymer with stable chemical property, and is used as the basic material of the intermediate layer, and the poly-1-butene with the weight portions is added to improve the rigidity and hardness of the intermediate layer film, is thermoplastic resin, is semitransparent, colorless and regular in molecular structure, can be changed into a stable crystal form at room temperature after being cooled and crystallized from a melt state, and can improve the strength and rigidity of the intermediate layer. It has been found by research that the increased stiffness and hardness of the intermediate layer can become brittle, and in order to increase toughness, the inventors have added to it an inactive, viscoelastic polymer, hydroxypropyl methylcellulose, indirectly increases the elasticity and toughness of the intermediate layer by increasing the adhesion and water retention properties. The addition of a small amount of white oil can not only improve the smoothness of the extrusion process, but also lubricate the highly-operating mechanical equipment, so that the equipment can be protected.
The proportion design of each material in the inner layer:
polyethylene is odorless, nontoxic, wax-like in hand feeling, has excellent low temperature resistance and good chemical stability, can resist most of acid and alkali corrosion, and is used as one of the base materials of the inner layer of the invention.
Poly 4-methyl-1-pentene is a thermoplastic resin with a low density, excellent heat resistance, visible light transmittance up to 90%, high ultraviolet light transmittance, excellent electrical insulation and chemical resistance, and is one of the base materials for the inner layer of the present invention.
The inner layer accounts for 60% -90% of the total thickness of the film material, and the light transmittance and the water vapor permeability are required to be solved and considered on the premise of ensuring that the inner layer material has excellent physical properties such as tensile strength, shrinkage tension and the like and excellent chemical properties such as corrosion resistance and the like, so that the inventor uses the combination of polyethylene and poly 4-methyl-1-pentene as the main material of the inner layer, the heat stability of the polyolefin shrink film is obviously improved, the water vapor permeability of the film material is reduced, the breeze silica gel is used as a slip agent, the smoothness of the extrusion process is improved, the materials are 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 improve a method for producing the above polyolefin shrink film, comprising the steps of:
(1) Extrusion: heating and mixing the materials of the upper surface layer, the lower surface layer, the upper middle layer and the lower middle layer respectively, and sending the materials to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: cooling and molding the extrusion material in the step (1) to form a casting film;
(3) Stretching: feeding the casting film into an asynchronous transverse stretcher for transverse stretching and then longitudinal stretching to obtain a film;
(4) Traction: the film is sent into a tractor cooling roller for cooling, and then cut edge rolling is carried out to obtain a film roll;
(5) And (5) drying and rolling.
Further, in the step (1),
the temperature of the materials on the upper surface layer and the lower surface layer is 140-165 ℃ when the materials are heated and mixed;
the temperature of the materials of the upper and lower middle layers is 150-180 ℃;
the temperature of the inner layer material is 160-190 ℃.
The heating and mixing temperature of the materials of each layer is also critical, if the upper surface layer, the lower surface layer, the upper middle layer and the inner layer share the uniform temperature for heating and mixing, the processed polyolefin shrink film has poor tensile property, and the breaking stretch-breaking rate is only about 70 percent.
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 molding is indirectly cooled through a closed circulating cooling demineralized water system, so that the consumption power is low, the electricity consumption rate is low, the cooling water completely circulates in a closed way in the circulating process, the loss of water is basically avoided, and the energy conservation and the environmental protection are realized.
Specifically, the method for manufacturing the polyolefin shrink film comprises the following steps:
(1) Extrusion: 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 of the inner layer at 160-190 ℃, respectively and uniformly mixing the materials, and then conveying the materials to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material in the step (1) into a calender, indirectly cooling through a closed circulating cooling desalted water system, and forming to form a casting film;
(3) Stretching: feeding the casting film into an asynchronous transverse stretcher for transverse stretching at the temperature of 90-120 ℃ and then for longitudinal stretching at the temperature of 110-120 ℃ to obtain a film;
(4) Traction: the film is sent into a tractor cooling roller for cooling, and then cut edge rolling is carried out to obtain a film roll;
(5) And (5) drying and rolling.
Further, the thickness of the manufactured polyolefin shrink film is 5-50um, films with different thicknesses can be produced according to the temperature and the strength of adjusting the transverse stretching and the longitudinal stretching, and specific thickness types 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 shrink film is divided into an upper middle layer, a lower middle layer, an inner layer and an upper outer layer, and each layer is flexibly proportioned with auxiliary materials by different materials, so that the mechanical property and the chemical stability of the polyolefin shrink film are integrally improved.
(2) The five-layer coextrusion technology is utilized to respectively adjust the melting mixing temperatures of the upper middle layer, the lower middle layer, the inner layer and the upper outer layer, flexibly adjust the heating temperatures of transverse stretching and longitudinal stretching according to the thickness of the processed polyolefin shrink film, improve the comprehensive performance of the polyolefin shrink film, optimize the cooling mode, save energy and protect environment.
Drawings
FIG. 1 is a schematic view of a polyolefin shrink film
FIG. 2 influence of upper and lower skin layer Material Components of polyolefin shrink film on oxygen permeability
FIG. 3 Effect of polyolefin shrink film upper and lower skin Material Components on light transmittance
FIG. 4 influence of the material composition of the upper and lower middle layers of polyolefin shrink film on shrinkage
FIG. 5 influence of the material composition of the upper and lower middle layers of polyolefin shrink film on tensile Strength
FIG. 6 Effect of the material composition of the inner layer of polyolefin shrink film on moisture vapor transmission rate
FIG. 7 Effect of the interlayer Material Components of polyolefin shrink films on thermal stability
FIG. 8 evaluation of comprehensive quality of polyolefin shrink films of examples 1-5 and comparative examples 1-2
FIG. 9 effect of various operating temperatures in the preparation process on polyolefin shrink film tensile properties
FIG. 10 effect of various operating temperatures on shrinkage of polyolefin shrink film in the manufacturing process
Detailed Description
The present invention will be further described with reference to examples for the purpose of making the objects and technical aspects of the present invention more apparent, but the scope of the present invention is not limited to these examples, which are only for explaining the present invention. It will be understood by those skilled in the art that variations or equivalent substitutions that do not depart from the spirit of the invention are intended to be included within the 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) Extrusion: 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 of the inner layer at 175 ℃, respectively and uniformly mixing the materials, and then conveying the materials to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material in the step (1) into a calender, indirectly cooling through a closed circulating cooling desalted water system, and forming to form a casting film;
(3) Stretching: feeding the casting film into an asynchronous transverse stretcher 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: the film is sent into a tractor cooling roller for cooling, and then cut and rolled to obtain a film roll 22um;
(5) And (5) 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) Extrusion: 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 and uniformly mixing the materials, and then conveying the materials to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material in the step (1) into a calender, indirectly cooling through a closed circulating cooling desalted water system, and forming to form a casting film;
(3) Stretching: feeding the casting film into an asynchronous transverse stretcher for transverse stretching at 120 ℃, and then performing longitudinal stretching at 120 ℃ to obtain a film;
(4) Traction: the film is sent into a tractor cooling roller for cooling, and then cut and rolled 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) Extrusion: 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 of the inner layer at 190 ℃, respectively and uniformly mixing the materials, and then conveying the materials to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material in the step (1) into a calender, indirectly cooling through a closed circulating cooling desalted water system, and forming to form a casting film;
(3) Stretching: feeding the casting film into an asynchronous transverse stretcher for transverse stretching at 90 ℃ and then for longitudinal stretching at 110 ℃ to obtain a film;
(4) Traction: the film is sent into a tractor cooling roller for cooling, and then cut and rolled to obtain a film roll 10um;
(5) And (5) 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) Extrusion: 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 of the inner layer at 175 ℃, respectively and uniformly mixing the materials, and then conveying the materials to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material in the step (1) into a calender, indirectly cooling through a closed circulating cooling desalted water system, and forming to form a casting film;
(3) Stretching: feeding the casting film into an asynchronous transverse stretcher 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: the film is sent into a tractor cooling roller for cooling, and then cut and rolled to obtain a film roll 22um;
(5) And (5) drying and rolling.
Example 5 polyolefin shrink film
The mixture ratio is as follows:
Figure BDA0003728179780000092
the manufacturing method comprises the following steps:
(1) Extrusion: 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 of the inner layer at 175 ℃, respectively and uniformly mixing the materials, and then conveying the materials to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material in the step (1) into a calender, indirectly cooling through a closed circulating cooling desalted water system, and forming to form a casting film;
(3) Stretching: feeding the casting film into an asynchronous transverse stretcher 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: the film is sent into a tractor cooling roller for cooling, and then cut and rolled 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) Extrusion: 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 of the inner layer at 175 ℃, respectively and uniformly mixing the materials, and then conveying the materials to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material in the step (1) into a calender, indirectly cooling through a closed circulating cooling desalted water system, and forming to form a casting film;
(3) Stretching: feeding the casting film into an asynchronous transverse stretcher 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: the film is sent into a tractor cooling roller for cooling, and then cut and rolled to obtain a film roll 22um;
(5) And (5) 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) Extrusion: 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 of the inner layer at 140 ℃, respectively and uniformly mixing the materials, and then conveying the materials to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material in the step (1) into a calender, indirectly cooling through a closed circulating cooling desalted water system, and forming to form a casting film;
(3) Stretching: feeding the casting film into an asynchronous transverse stretcher for transverse stretching at 80 ℃ and then for longitudinal stretching at 130 ℃ to obtain a film;
(4) Traction: the film is sent into a tractor cooling roller for cooling, and then cut and rolled to obtain a film roll 22um;
(5) And (5) drying and rolling.
1. Single factor testing of mechanical and chemical stability of polyolefin shrink films
1. Test characterization method
1.1 thermal stability test
Thermogravimetric analysis (TG): shearing the film by Thermogravimetric Analysis TA Q thermal gravimetric analyzer, placing into Pt crucible under nitrogen protection, and heating to 300K-850K at 10K.min -1 TG testing was performed on the polyolefin shrink film at the rate of temperature rise.
1.2 measurement of tensile Properties
Reference 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 times per sample, averaged, and standard deviation was calculated.
1.3 shrinkage measurement
Taking a certain-size sample according to the specification of the standard GB/T10003-2008, placing the sample in the middle of an oven, blasting air, heating for 120 seconds, placing the sample at room temperature for cooling, and measuring the length in the length direction (TD). The heat Shrinkage (SR) was calculated as follows.
SR＝(L-L 1 )/L×100％
Wherein: l is the length (mm) of the sample before heating; l (L) 1 Is the length (mm) of the sample after heating.
Each group of samples was measured 5 times for averaging and standard deviation was calculated.
1.4 light transmittance test
Light transmittance and haze were measured according to GB/T2410-2008. The ratio of the luminous flux transmitted through the sample to the luminous flux impinging on the sample, expressed as a percentage, was measured spectrophotometrically. The polyolefin shrink films were each tested for light transmittance from 0 months to 24 months storage at 32 ℃.
1.5 oxygen permeability test
The sample is tested by adopting a differential pressure method, and the test process is carried out according to the method standard GB/T1038-2000 differential pressure method for testing the gas permeability of plastic films and sheets.
1.6 Water vapor permeability test
The measurement was carried out according to GB/T30112-2013 method for measuring moisture sensor of Water vapor Transmission Rate of Plastic films and sheets.
2. Design of single factor experiment
2.1 Single factor testing of upper and lower surface Material composition and ratio
Figure BDA0003728179780000121
Figure BDA0003728179780000131
Otherwise, the same as in example 1 was conducted.
The A-E group single factor variables are upper and lower surface layer material components, and the influence of the components on the thermal stability, the tensile property, the shrinkage, the light transmittance, the oxygen permeability and the water vapor permeability is respectively explored. The data show that the upper and lower surface layer material components have larger influence on the light transmittance and oxygen permeability of the polyolefin shrink film.
2.2 Single factor testing of the Material composition and the proportions of the upper and lower intermediate layers
Figure BDA0003728179780000132
Otherwise, the same as in example 1 was conducted.
The A-E group single-factor variables are the material components of the upper and lower middle layers, and the influences of the single-factor variables on the thermal stability, the tensile property, the shrinkage, the light transmittance, the oxygen permeability and the water vapor permeability are respectively explored.
2.3 testing of inner layer Material composition and Single factor of the proportions
Group A Group B Group C Group D
Polyethylene Polyethylene Polyethylene Polypropylene
Poly 4-methyl-1-pentene - Poly 4-methyl-1-pentene Poly 4-methyl-1-pentene
Micro powder silica gel Micro powder silica gel Silica dioxide Micro powder silica gel
Otherwise, the same as in example 1 was conducted.
The A-D group single-factor variables are the inner layer material components, and the influence of the single-factor variables on the thermal stability, the tensile property, the shrinkage, the light transmittance, the oxygen permeability and the water vapor permeability is respectively explored.
2.4 Single factor test for temperature screening in preparation Process
Group A:
the formulation of each layer was the same as in example 1.
(1) Extrusion: 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 of the inner layer at 175 ℃, respectively and uniformly mixing the materials, and then conveying the materials to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material in the step (1) into a calender, indirectly cooling through a closed circulating cooling desalted water system, and forming to form a casting film;
(3) Stretching: feeding the casting film into an asynchronous transverse stretcher 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: the film is sent into a tractor cooling roller for cooling, and then cut and rolled to obtain a film roll 22um;
(5) And (5) drying and rolling.
Group B:
the formulation of each layer was the same as in example 1.
(1) Extrusion: 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 of the inner layer at 175 ℃, respectively and uniformly mixing the materials, and then conveying the materials to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material in the step (1) into a calender, indirectly cooling through a closed circulating cooling desalted water system, and forming to form a casting film;
(3) Stretching: feeding the casting film into an asynchronous transverse stretcher 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: the film is sent into a tractor cooling roller for cooling, and then cut and rolled to obtain a film roll 22um;
(5) And (5) drying and rolling.
Group C:
the formulation of each layer was the same as in example 1.
(1) Extrusion: 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 of the inner layer at 175 ℃, respectively and uniformly mixing the materials, and then conveying the materials to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material in the step (1) into a calender, indirectly cooling through a closed circulating cooling desalted water system, and forming to form a casting film;
(3) Stretching: feeding the casting film into an asynchronous transverse stretcher 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: the film is sent into a tractor cooling roller for cooling, and then cut and rolled to obtain a film roll 22um;
(5) And (5) drying and rolling.
Group D:
the formulation of each layer was the same as in example 1.
(1) Extrusion: 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 of the inner layer at 145 ℃, respectively and uniformly mixing the materials, and then conveying the materials to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material in the step (1) into a calender, indirectly cooling through a closed circulating cooling desalted water system, and forming to form a casting film;
(3) Stretching: feeding the casting film into an asynchronous transverse stretcher 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: the film is sent into a tractor cooling roller for cooling, and then cut and rolled to obtain a film roll 22um;
(5) And (5) drying and rolling.
Group E:
the formulation of each layer was the same as in example 1.
(1) Extrusion: 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 of the inner layer at 175 ℃, respectively and uniformly mixing the materials, and then conveying the materials to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material in the step (1) into a calender, indirectly cooling through a closed circulating cooling desalted water system, and forming to form a casting film;
(3) Stretching: feeding the casting film into an asynchronous transverse stretcher for transverse stretching at 130 ℃, and then for longitudinal stretching at 115 ℃ to obtain a film;
(4) Traction: the film is sent into a tractor cooling roller for cooling, and then cut and rolled to obtain a film roll 22um;
(5) And (5) drying and rolling.
Group F:
the formulation of each layer was the same as in example 1.
(1) Extrusion: 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 of the inner layer at 175 ℃, respectively and uniformly mixing the materials, and then conveying the materials to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: adding the extruded material in the step (1) into a calender, indirectly cooling through a closed circulating cooling desalted water system, and forming to form a casting film;
(3) Stretching: feeding the casting film into an asynchronous transverse stretcher for transverse stretching at the temperature of 100 ℃, and then carrying out longitudinal stretching at the temperature of 90 ℃ to obtain a film;
(4) Traction: the film is sent into a tractor cooling roller for cooling, and then cut and rolled to obtain a film roll 22um;
(5) And (5) drying and rolling.
The A-F group single-factor variables are temperatures in the preparation process, and the influences of the A-F group single-factor variables on thermal stability, tensile property, shrinkage, light transmittance, oxygen permeability and water vapor permeability are respectively explored.
3. Conclusion(s)
As shown in the data of the graph, the upper and lower surface layer material components have larger influence on the light transmittance and oxygen permeability of the polyolefin shrink film; 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, and only the thermal weight curve graph of the group A is displayed, so that the polyolefin shrink film of the group A has good high temperature resistance, the highest temperature can reach 250 ℃, the polyolefin shrink film of the group B-D also carries out corresponding thermal weight test, 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 ℃; the operation temperatures in the preparation process have great influence on the tensile property and the shrinkage rate. As shown in detail.
2. Polyolefin shrink film Synthesis evaluation 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 polyolefin shrink films were comprehensively scored for six indexes of heat stability, tensile property, shrinkage, light transmittance, oxygen permeability and water vapor permeability according to the following scoring criteria:
TABLE 1 comprehensive evaluation scoring criteria for polyolefin shrink films
Figure BDA0003728179780000161
/>
Figure BDA0003728179780000171
The polyolefin shrink films of examples 1-5 and comparative examples 1-2 were subjected to comprehensive quality evaluation according to the scoring index shown in Table 1, and radar figures were drawn, and the results show that the polyolefin shrink films of examples 1-5 of the present invention have good comprehensive properties and very high mechanical properties and chemical stability.
3. Polyolefin shrink film performance display
TABLE 2 Performance display of polyolefin shrink films of different thickness
Figure BDA0003728179780000172
Figure BDA0003728179780000181
/>

Claims (10)

1. A polyolefin shrink film comprising five layers, each:
the upper and lower surface layers containing polypropylene account for 5-20% of the total thickness of the polyolefin shrink film;
the upper and lower middle layers containing isobutylene-n-butene copolymer account for 5% -20% of the total thickness of the polyolefin shrink film;
the inner layer containing polyethylene and polypentene accounts for 60-90% of the total thickness of the polyolefin shrink film;
the thicknesses of 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 thicknesses of 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, wherein the polyolefin shrink film comprises,
the upper surface layer and the lower surface layer comprise polypropylene, acrylic resin, rosin pentaerythritol ester and xanthan gum;
the upper middle layer and the lower middle layer comprise isobutylene-n-butene copolymer, poly-1-butene, hydroxypropyl methylcellulose and white oil;
the inner layer comprises polyethylene, poly 4-methyl-1-pentene and micro silica gel.
3. The polyolefin shrink film of claim 2, wherein the upper and lower skin layers comprise the following components in 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.
4. The polyolefin shrink film of claim 2, wherein the upper and lower intermediate layers comprise the following components in weight ratio: comprises 4-8 parts of isobutene-n-butene copolymer, 1-5 parts of poly-1-butene, 1-5 parts of hydroxypropyl methylcellulose 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 weight ratios: 5-10 parts of polyethylene, 1-5 parts of poly 4-methyl-1-pentene and 0.5-4 parts of micro silica gel.
6. The polyolefin shrink film according to any of claims 3-5, wherein the polyolefin shrink film consists of: the upper surface layer and the lower surface layer account for 10 percent of the total thickness of the polyolefin shrink film and consist of 7 to 9 parts by weight of polypropylene, 1 to 4 parts by weight of acrylic resin, 2 to 5 parts by weight of rosin pentaerythritol ester and 1 to 3 parts by weight of xanthan gum;
the upper middle layer and the lower middle layer account for 80 percent of the total thickness of the polyolefin shrink film and consist of 5 to 7 parts by weight of isobutene-n-butene copolymer, 2 to 4 parts by weight of poly 1-butene, 1 to 3 parts by weight of hydroxypropyl methyl cellulose and 0.5 to 2 parts by weight of white oil;
the inner layer accounts for 10% of the total thickness of the polyolefin shrink film, and consists of 6-9 parts by weight of polyethylene, 1-3 parts by weight of poly 4-methyl-1-pentene and 0.5-2 parts by weight of micro silica gel.
7. The polyolefin shrink film of claim 6, wherein the polyolefin shrink film is comprised of:
the upper surface layer and the lower surface layer account for 10 percent of the total thickness of the polyolefin shrink film and consist of 8 parts by weight of polypropylene, 3 parts by weight of acrylic resin, 4 parts by weight of rosin pentaerythritol ester and 2 parts by weight of xanthan gum;
the upper middle layer and the lower middle layer account for 80% of the total thickness of the polyolefin shrink film, and are composed of 6 parts by weight of an isobutylene-n-butene copolymer, 3 parts by weight of poly 1-butene, 2 parts by weight of hydroxypropyl methyl cellulose and 1 part by weight of white oil;
the inner layer accounts for 10% of the total thickness of the polyolefin shrink film, and consists of 7 parts by weight of polyethylene, 2 parts by weight of poly 4-methyl-1-pentene and 1 part by weight of micro silica gel.
8. A method of making the polyolefin shrink film of claim 1, comprising the steps of:
(1) Extrusion: heating and mixing the materials of the upper surface layer, the lower surface layer, the upper middle layer and the lower middle layer respectively, and sending the materials to a corresponding extruder for five-layer coextrusion;
(2) And (3) cooling: cooling and molding the extrusion material in the step (1) to form a casting film;
(3) Stretching: feeding the casting film into an asynchronous transverse stretcher for transverse stretching and then longitudinal stretching to obtain a film;
(4) Traction: the film is sent into a tractor cooling roller for cooling, and then cut edge rolling is carried out 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 of the materials on the upper surface layer and the lower surface layer is 140-165 ℃ when the materials are heated and mixed;
the temperature of the materials of the upper and lower middle layers is 150-180 ℃;
the temperature of the inner layer material 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 of claim 8, wherein in step (2), the cooling molding is indirectly cooled by a closed circulation cooling demineralized water system.
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