CN113561588A - High-gloss and high-toughness multilayer polyester film for heat-shrinkable label, and preparation method and application thereof - Google Patents
High-gloss and high-toughness multilayer polyester film for heat-shrinkable label, and preparation method and application thereof Download PDFInfo
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- CN113561588A CN113561588A CN202110829502.5A CN202110829502A CN113561588A CN 113561588 A CN113561588 A CN 113561588A CN 202110829502 A CN202110829502 A CN 202110829502A CN 113561588 A CN113561588 A CN 113561588A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/022—Mechanical properties
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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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/027—Thermal properties
- B32B7/028—Heat-shrinkability
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/41—Opaque
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
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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
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- C08J2423/10—Homopolymers or copolymers of propene
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- 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
- C08J2433/04—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 esters
- C08J2433/06—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 esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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Abstract
The invention provides a high-gloss high-toughness multilayer polyester film for a heat-shrinkable label, and a preparation method and application thereof. The multilayer polyester film consists of A, B, C three-layer structure, wherein the layer B is positioned between the layer A and the layer C; the raw material components for preparing the layer A or the layer C comprise: the functional material taking dihydric alcohol modified polyethylene terephthalate, thermoplastic polyester resin and copolyester as a carrier, the white functional additive, and the polyethylene terephthalate or the dibasic acid modified polyethylene terephthalate; the raw material components for preparing the layer B comprise: glycol modified polyethylene glycol terephthalate and black functional additive; the functional material with the copolyester as the carrier contains microbeads and incompatible resin. The multilayer polyester film has good high-gloss and high-toughness characteristics, and simultaneously has excellent tensile strength, elongation at break, wear resistance coefficient and heat shrinkage; the heat shrinkable label film can be widely applied to containers or bottles in the fields of dairy products, foods and beverages.
Description
Technical Field
The invention belongs to the technical field of high polymer packaging materials, and particularly relates to a high-gloss high-toughness multilayer polyester film for a heat-shrinkable label, and a preparation method and application thereof.
Background
In order to solve the problem of light resistance of photosensitive dairy products such as ultrahigh-temperature sterilized milk, high-protein yoghourt and the like, a mode of adding a light-resistant agent into a bottle body heat shrinkage label is generally adopted in the process of bottling products, and the inventor develops the light-resistant label in the early stage and applies the light-resistant label to a bottle body with a low or no light-resistant agent, so that the light-resistant problem is solved, the high-value recovery of the bottle body is facilitated, and the packaging material cost is effectively reduced.
However, the polyester light-blocking shrink films with white and black structures developed earlier have the problems of easy film breakage, poor printing quality, poor label-palm fastness, high packaging material cost and the like due to the high content of white fillers in the two surface layers.
Disclosure of Invention
Based on the defects of the prior art, the first object of the invention is to provide a high-gloss high-toughness multilayer polyester film for a heat-shrinkable label; the second object of the present invention is to provide a method for preparing a high gloss and high toughness multilayer polyester film for a heat shrinkable label; the third purpose of the invention is to provide the application of the high-gloss high-toughness multilayer polyester film for the heat-shrinkable label as the heat-shrinkable label in the film shrink packaging of containers or bottles in the fields of dairy products, foods and beverages.
The purpose of the invention is realized by the following technical means:
in one aspect, the invention provides a high-gloss high-toughness multilayer polyester film for a heat-shrinkable label, which consists of A, B, C three-layer structures, wherein a layer A and a layer C are white functional layers, a layer B is a black functional layer, and the layer B is positioned between the layer A and the layer C;
the raw material components for preparing the layer A and the layer C respectively comprise: the functional material taking dihydric alcohol modified polyethylene terephthalate, thermoplastic polyester resin and copolyester as a carrier, the white functional additive, and the polyethylene terephthalate or the dibasic acid modified polyethylene terephthalate;
the raw material components for preparing the layer B comprise: glycol modified polyethylene glycol terephthalate and black functional additive;
the functional material with the copolyester as the carrier contains microbeads and incompatible resin.
According to the invention, through the design of the polyester film formula, the problem of low film strength caused by high inorganic filler content is solved on the premise of ensuring high light-blocking performance, and through the design of the microbeads and the incompatible resin, the refraction angle of light rays is changed when the light rays pass through the microbeads and the incompatible resin, so that the light-blocking performance and apparent whiteness of the material are ensured; the density of the micro-beads and the incompatible resin is lower than that of the polyester shrinkage material, and the unit weight of the polyester film and the unit cost of the material are effectively reduced due to the introduction of the two materials; and meanwhile, a three-layer structure and the matching of high-toughness resin are designed, so that the flexibility and the tensile strength of the high-light-resistance polyester film are further improved.
In the above multilayer polyester film, preferably, the raw material components for preparing the B layer further include: thermoplastic polyester resin, white functional additive, and polyethylene terephthalate or diacid-modified polyethylene terephthalate.
In the above multilayer polyester film, the thickness of the multilayer polyester film is preferably 10 to 80 μm; the film thickness of the A layer accounts for 5-90%, the film thickness of the B layer accounts for 5-90%, and the film thickness of the C layer accounts for 5-90% based on 100% of the thickness of the multilayer polyester film.
In the above multilayer polyester film, preferably, the raw material components for producing the a layer and the C layer respectively include, based on 100% by mass of the raw material components for producing the a layer and the C layer respectively:
in the above multilayer polyester film, preferably, the raw material components for preparing the B layer include, based on 100% by mass of the raw material components for preparing the B layer:
50 to 99.9975 percent of polyethylene glycol terephthalate modified by dihydric alcohol;
0.0025 to 15 percent of black functional additive.
In the above multilayer polyester film, preferably, the raw material components for preparing the B layer include, based on 100% by mass of the raw material components for preparing the B layer:
in the above multilayer polyester film, the light transmittance of the multilayer polyester film is preferably less than 1%.
In the above multilayer polyester film, the multilayer polyester film preferably has a heat shrinkage temperature of 60 to 150 ℃, a shrinkage in the stretched direction of 10 to 90%, and a shrinkage in the non-stretched direction of-1 to 10%.
In the above multilayer polyester film, the multilayer polyester film preferably has a longitudinal tensile strength of 40 to 80MPa and a transverse tensile strength of 200 to 260 MPa; the longitudinal elongation at break is 300-400%; the transverse elongation at break is 30-80%.
In the above multilayer polyester film, the static friction coefficient of the multilayer polyester film is preferably 0.2 to 0.65 μ s; the rolling friction coefficient is 0.25 to 0.6 mu k.
In the above multilayer polyester film, the diol used in the modification of the diol-modified polyethylene terephthalate preferably includes one or more of 1, 4-cyclohexanedimethanol, octanediol, diethylene glycol, and propylene glycol, but is not limited thereto.
In the above multilayer polyester film, the diol is preferably used in an amount of 5 to 100% by mole, based on 100% by mole of ethylene glycol or terephthalic acid used in the production of the diol-modified polyethylene terephthalate.
In the above multilayer polyester film, the glycol-modified polyethylene terephthalate preferably has an intrinsic viscosity of 0.6 to 1.5dL/g and a melting temperature of 160 to 260 ℃.
In the above-mentioned multilayered polyester film, preferably, the thermoplastic polyester resin includes polybutylene terephthalate and/or TPEE polyester elastomer, but is not limited thereto.
In the above-mentioned multilayer polyester film, preferably, the dibasic acid used in the modification of the dibasic acid-modified polyethylene terephthalate includes one or more of isophthalic acid, phthalic acid, 2, 6-naphthalenedicarboxylic acid, adipic acid, and sebacic acid, but is not limited thereto.
In the above multilayer polyester film, preferably, the dibasic acid comprises isophthalic acid and/or phthalic acid.
In the above multilayer polyester film, the molar amount of the dibasic acid is preferably 0.1 to 40% based on 100% by mole of ethylene glycol or terephthalic acid used for producing the dibasic acid-modified polyethylene terephthalate.
In the multilayer polyester film, the diacid-modified polyethylene terephthalate preferably has an intrinsic viscosity of 0.6 to 1.5dL/g and a melting temperature of 160 to 260 ℃.
In the above multilayer polyester film, preferably, the copolyester of the functional material as a carrier includes one or more of polyethylene terephthalate, glycol-modified polyethylene terephthalate, and diacid-modified polyethylene terephthalate, but is not limited thereto.
In the above multilayer polyester film, preferably, the beads include hollow glass beads and/or PMMA beads, but are not limited thereto.
In the multilayer polyester film, the diameter of the beads is preferably 1 to 15 μm, more preferably 2 to 8 μm.
In the above multilayer polyester film, the mass percentage of the microbeads to the functional material using the copolymer ester as a carrier is preferably 0.1% to 50%, and more preferably 5% to 30%.
In the above-described multilayered polyester film, preferably, the incompatible resin includes one or more of polypropylene (PP) resin, Polyethylene (PE) resin, PMP resin, PMMA resin, and TPE resin, but is not limited thereto.
In the multilayer polyester film, the incompatible resin is preferably present in an amount of 0.1 to 50% by mass, more preferably 5 to 30% by mass, based on the functional material with the copolymer as a carrier.
In the above multilayered polyester film, preferably, the white functional additive includes titanium dioxide and/or calcium carbonate, but is not limited thereto.
In the above multilayered polyester film, preferably, the black functional additive includes carbon black and/or graphite, but is not limited thereto.
In another aspect, the present invention also provides a method for preparing the above multilayer polyester film, comprising the steps of:
respectively mixing and drying raw material components for preparing the layer A, the layer B and the layer C to obtain a layer A functional mixture, a layer B functional mixture and a layer C functional mixture, filling the layer A functional mixture, the layer B functional mixture and the layer C functional mixture into a three-layer co-extrusion film machine according to the sequence of the layer A, the layer B and the layer C, extruding through a three-layer co-extrusion die head, and cooling to form a cast sheet after being adhered into a whole;
and stretching the cast sheet longitudinally and transversely to form a film, thereby obtaining the multilayer polyester film.
In the preparation method, the extrusion temperature of the three-layer co-extrusion film machine is preferably 200-300 ℃.
In the above preparation method, preferably, the specific processes of longitudinally and transversely stretching the cast sheet into a film are as follows:
longitudinally stretching the cast sheet and carrying out heat setting, wherein the stretching ratio is 0-2.5 times, the heat setting temperature is 90-150 ℃, and the heat setting time is 1-10 s; then, transversely stretching to form a film, wherein the stretching ratio is 2-6.5 times, and the stretching film-forming temperature is 60-150 ℃;
or, longitudinally stretching the cast sheet in a single direction, wherein the stretching ratio is 2-6.5 times, and the stretching temperature is 60-150 ℃; not stretching in the transverse direction;
cooling to obtain a multilayer polyester film;
in the above preparation method, preferably, after cooling, the non-or single-sided or double-sided corona treatment, winding and slitting operations are selectively performed.
In a further aspect, the present invention also provides the use of the above-described multilayer polyester film as a heat-shrinkable label in film shrink packaging of containers or bottles in the field of dairy products, food, beverages.
The invention has the beneficial effects that:
the multilayer polyester film has good high-gloss and high-toughness characteristics, and simultaneously has excellent tensile strength, elongation at break, wear resistance coefficient and heat shrinkage; the polyester film serving as the polyester film for the heat-shrinkable label with high light resistance and high toughness has wide application prospect in film shrink packaging of containers or bottles in the fields of dairy products, foods and beverages.
Drawings
Fig. 1 is a schematic view showing the structure of a high gloss and high toughness multilayer polyester film for a heat shrinkable label of the present invention.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1:
this example provides a high-gloss high-toughness multilayer polyester film for heat-shrinkable labels and a method for preparing the same, the multilayer polyester film is composed of A, B, C three-layer structure, as shown in fig. 1, wherein, a layer and a layer C are white functional layers, a layer B is a black functional layer, and the layer B is located between the layer a and the layer C;
the coating comprises the following raw material components in percentage by mass of 100% for preparing the layer A or the layer C:
the B layer comprises the following raw material components in percentage by mass of 100 percent:
wherein, the polyethylene terephthalate modified by the 1, 4-cyclohexanedimethanol and the octanediol is prepared by the conventional method in the field, and the molar amount of the ethylene glycol or the terephthalic acid used for preparing the polyethylene terephthalate modified by the 1, 4-cyclohexanedimethanol and the octanediol is 100 percent, the molar amount of the 1, 4-cyclohexanedimethanol is 20 percent, and the molar amount of the octanediol is 20 percent. The intrinsic viscosity of the polyethylene terephthalate jointly modified by the 1, 4-cyclohexanedimethanol and the octanediol is 0.67dL/g, and the melting temperature is 170-180 ℃.
The intrinsic viscosity of the polyethylene terephthalate was 0.7dL/g, and the melting temperature was 256 ℃.
The functional material taking the copolyester as a carrier contains hollow glass beads and polypropylene resin (PP); the hollow glass beads account for 20 mass percent of the functional material taking the copolyester as the carrier, and the polypropylene resin accounts for 10 mass percent of the functional material taking the copolyester as the carrier; the diameter of the hollow glass bead is 8-15 mu m; the remaining 70% of the copolyester was polyethylene terephthalate.
The thickness of the multilayer polyester film was 50.3 μm; wherein, the thickness of the A layer is 30% (15.09 μm), the thickness of the B layer is 65% (32.695 μm), and the thickness of the C layer is 30% (2.515 μm).
The light transmittance of the multilayer polyester film was 0.5%; the thermal shrinkage temperature is 70-90 ℃, the shrinkage in the stretching direction is 64.5%, and the shrinkage in the non-stretching direction is 4%.
The preparation method of the multilayer polyester film comprises the following steps:
respectively mixing and drying raw material components for preparing the layer A, the layer B and the layer C to obtain a layer A functional mixture, a layer B functional mixture and a layer C functional mixture, filling the layer A functional mixture, the layer B functional mixture and the layer C functional mixture into a three-layer co-extrusion film machine according to the sequence of the layer A, the layer B and the layer C, extruding through a three-layer co-extrusion die head, wherein the extrusion temperature is 280-300 ℃, and cooling into a casting sheet after being adhered into a whole;
longitudinally stretching the cast sheet, and then carrying out heat setting, wherein the stretching ratio is 1.05 times, the heat setting temperature is 120 ℃, and the heat setting time is 8 s; and then stretched in the transverse direction (TD direction) to form a film, wherein the film-forming temperature is 120 ℃, and the stretching ratio is 5.5 times.
After cooling, the multilayer polyester film was obtained without corona treatment, winding and slitting.
The technical index test of the multilayer polyester film is shown in table 1 below.
Table 1:
example 2:
this example provides a high-gloss high-toughness multilayer polyester film for heat-shrinkable labels and a method for preparing the same, the multilayer polyester film is composed of A, B, C three-layer structure, as shown in fig. 1, wherein, a layer and a layer C are white functional layers, a layer B is a black functional layer, and the layer B is located between the layer a and the layer C;
the coating comprises the following raw material components in percentage by mass of 100% for preparing the layer A or the layer C:
the B layer comprises the following raw material components in percentage by mass of 100 percent:
98.5 percent of polyethylene glycol terephthalate modified by octanediol;
1.5 percent of carbon black.
Wherein, the polyethylene terephthalate modified by the octanethioglycol is prepared by the conventional method in the field, and the molar quantity of the octanethioglycol is 35 percent based on 100 percent of the mole number of the ethylene glycol or the terephthalic acid used for preparing the polyethylene terephthalate modified by the octanethioglycol. The polyethylene glycol terephthalate modified by the octanediol has the intrinsic viscosity of 0.68dL/g and the melting temperature of 175-185 ℃.
The functional material taking the copolyester as a carrier contains PMMA micro-beads and polypropylene resin (PP); the mass percent of the PMMA microspheres in the functional material taking the copolyester as the carrier is 15 percent, and the mass percent of the polypropylene resin in the functional material taking the copolyester as the carrier is 15 percent; the diameter of the PMMA micro-beads is 8-15 mu m; the remaining 70% of the copolyester was polyethylene terephthalate.
The thickness of the multilayer polyester film was 40.1 μm; wherein, the thickness of the A layer is 25% (10.025 μm), the thickness of the B layer is 65% (26.065 μm), and the thickness of the C layer is 10% (4.01 μm).
The light transmittance of the multilayer polyester film was 0; the thermal shrinkage temperature is 70-90 ℃, the shrinkage in the stretching direction is 75%, and the shrinkage in the non-stretching direction is 1%.
The preparation method of the multilayer polyester film comprises the following steps:
respectively mixing and drying raw material components for preparing the layer A, the layer B and the layer C to obtain a layer A functional mixture, a layer B functional mixture and a layer C functional mixture, filling the layer A functional mixture, the layer B functional mixture and the layer C functional mixture into a three-layer co-extrusion film machine according to the sequence of the layer A, the layer B and the layer C, extruding through a three-layer co-extrusion die head, wherein the extrusion temperature is 280-300 ℃, and cooling into a casting sheet after being adhered into a whole;
longitudinally stretching the cast sheet, and then carrying out heat setting, wherein the stretching ratio is 1.01 times, the heat setting temperature is 120 ℃, and the heat setting time is 8 s; and then stretched in the transverse direction (TD direction) to form a film, wherein the film-forming temperature is 120 ℃, and the stretching ratio is 6.0 times.
After cooling, the multilayer polyester film was obtained without corona treatment, winding and slitting.
The technical index test of the multilayer polyester film is shown in table 2 below.
Table 2:
example 3:
this example provides a high-gloss high-toughness multilayer polyester film for heat-shrinkable labels and a method for preparing the same, the multilayer polyester film is composed of A, B, C three-layer structure, as shown in fig. 1, wherein, a layer and a layer C are white functional layers, a layer B is a black functional layer, and the layer B is located between the layer a and the layer C;
the coating comprises the following raw material components in percentage by mass of 100% for preparing the layer A or the layer C:
the B layer comprises the following raw material components in percentage by mass of 100 percent:
wherein the polyethylene terephthalate modified by the octanediol is prepared by the conventional method in the field, and the molar quantity of the octanediol is 30 percent based on the mole number of the ethylene glycol or the terephthalic acid used for preparing the polyethylene terephthalate modified by the octanediol as 100 percent. The intrinsic viscosity of the polyethylene glycol terephthalate modified by the octanediol is 0.68dL/g, and the melting temperature is 170-180 ℃.
The isophthalic acid modified polyethylene terephthalate is prepared by a method conventional in the art, and the isophthalic acid is 8% by mole based on 100% by mole of ethylene glycol or terephthalic acid used to prepare the isophthalic acid modified polyethylene terephthalate. The isophthalic acid modified polyethylene terephthalate had an intrinsic viscosity of 0.7dL/g and a melting point of 235 ℃.
The functional material taking the copolyester as a carrier contains hollow glass beads and polypropylene resin (PP); the hollow glass beads account for 20 mass percent of the functional material taking the copolyester as the carrier, and the polypropylene resin accounts for 20 mass percent of the functional material taking the copolyester as the carrier; the diameter of the hollow glass bead is 8-15 mu m; the remaining 60% of the copolyester was polyethylene terephthalate.
The thickness of the multilayer polyester film was 34.9 μm; wherein, the thickness of the A layer is 40% (13.96 μm), the thickness of the B layer is 50% (17.45 μm), and the thickness of the C layer is 10% (3.49 μm).
The light transmittance of the multilayer polyester film was 0.05%; the thermal shrinkage temperature is 70-90 ℃, the shrinkage in the stretching direction is 68%, and the shrinkage in the non-stretching direction is 5%.
The preparation method of the multilayer polyester film comprises the following steps:
respectively mixing and drying raw material components for preparing the layer A, the layer B and the layer C to obtain a layer A functional mixture, a layer B functional mixture and a layer C functional mixture, filling the layer A functional mixture, the layer B functional mixture and the layer C functional mixture into a three-layer co-extrusion film machine according to the sequence of the layer A, the layer B and the layer C, extruding through a three-layer co-extrusion die head, wherein the extrusion temperature is 280-300 ℃, and cooling into a casting sheet after being adhered into a whole;
longitudinally stretching the cast sheet, and then carrying out heat setting, wherein the stretching ratio is 1.1 times, the heat setting temperature is 120 ℃, and the heat setting time is 8 s; and then stretched in the transverse direction (TD direction) to form a film, wherein the film-forming temperature is 120 ℃, and the stretching ratio is 5.7 times.
And after cooling, performing corona treatment on the surface of the layer A, rolling and slitting to obtain the multilayer polyester film.
The technical index test of the multilayer polyester film is shown in table 3 below.
Table 3:
in conclusion, the multilayer polyester film disclosed by the invention has better high-light-resistance and high-toughness characteristics, and meanwhile, has excellent tensile strength, elongation at break, wear-resistant coefficient and heat shrinkage; the polyester film serving as the polyester film for the heat-shrinkable label with high light resistance and high toughness has wide application prospect in film shrink packaging of containers or bottles in the fields of dairy products, foods and beverages.
Claims (16)
1. A high-light-resistance high-toughness multilayer polyester film for a heat-shrinkable label is composed of A, B, C three-layer structures, wherein a layer A and a layer C are white functional layers, a layer B is a black functional layer, and the layer B is positioned between the layer A and the layer C;
the raw material components for preparing the layer A and the layer C respectively comprise: the functional material taking dihydric alcohol modified polyethylene terephthalate, thermoplastic polyester resin and copolyester as a carrier, the white functional additive, and the polyethylene terephthalate or the dibasic acid modified polyethylene terephthalate;
the raw material components for preparing the layer B comprise: glycol modified polyethylene glycol terephthalate and black functional additive;
the functional material with the copolyester as the carrier contains microbeads and incompatible resin.
2. A multilayer polyester film according to claim 1, wherein the raw material components for preparing the B layer further comprise: thermoplastic polyester resin, white functional additive, and polyethylene terephthalate or diacid-modified polyethylene terephthalate.
3. A multilayer polyester film according to claim 1, wherein the multilayer polyester film has a thickness of 10 to 80 μm; the film thickness of the A layer accounts for 5-90%, the film thickness of the B layer accounts for 5-90%, and the film thickness of the C layer accounts for 5-90% based on 100% of the thickness of the multilayer polyester film.
4. A multilayer polyester film according to any one of claims 1 to 3 wherein the raw material components for preparing the A and C layers each comprise, based on 100% by mass of the raw material components for preparing the A and C layers, respectively:
5 to 94.7 percent of dihydric alcohol modified polyethylene glycol terephthalate;
0.1 to 40 percent of thermoplastic polyester resin;
0.1 to 30 percent of polyethylene terephthalate or dibasic acid modified polyethylene terephthalate;
0.1 to 30 percent of functional material taking the copolyester as a carrier;
5 to 50 percent of white functional additive.
5. A multilayer polyester film according to any one of claims 1 to 3, wherein the raw material components for preparing the B layer comprise, based on 100% by mass of the raw material components for preparing the B layer:
50 to 99.9975 percent of polyethylene glycol terephthalate modified by dihydric alcohol;
0.0025 to 15 percent of black functional additive;
preferably, the raw material components for preparing the layer B include, based on 100% by mass of the raw material components for preparing the layer B:
50 to 99.6975 percent of polyethylene glycol terephthalate modified by dihydric alcohol;
0.1 to 40 percent of thermoplastic polyester resin;
0.1 to 40 percent of polyethylene terephthalate or dibasic acid modified polyethylene terephthalate;
0.1 to 40 percent of white functional additive;
0.0025 to 15 percent of black functional additive.
6. A multilayer polyester film according to any one of claims 1 to 5 wherein the light transmittance of the multilayer polyester film is less than 1%;
preferably, the multilayer polyester film has a thermal shrinkage temperature of 60 to 150 ℃, a shrinkage rate of 10 to 90% in a stretching direction, and a shrinkage rate of-1 to 10% in a non-stretching direction;
preferably, the longitudinal tensile strength of the multilayer polyester film is 40-80 MPa, and the transverse tensile strength of the multilayer polyester film is 200-260 MPa; the longitudinal elongation at break is 300-400%; the transverse elongation at break is 30-80%;
preferably, the static friction coefficient of the multilayer polyester film is 0.2-0.65 mu s; the rolling friction coefficient is 0.25 to 0.6 mu k.
7. A multilayer polyester film according to any one of claims 1 to 6 wherein the diol used in the modification of the diol-modified polyethylene terephthalate comprises one or more of 1, 4-cyclohexanedimethanol, octanediol, diethylene glycol and propylene glycol;
preferably, the molar amount of the glycol is 5 to 100% based on 100% of the moles of ethylene glycol or terephthalic acid used to prepare the glycol-modified polyethylene terephthalate;
preferably, the intrinsic viscosity of the glycol modified polyethylene terephthalate is 0.6-1.5 dL/g, and the melting temperature is 160-260 ℃.
8. A multilayer polyester film according to any of claims 1 to 6 wherein the thermoplastic polyester resin comprises polybutylene terephthalate and/or TPEE polyester elastomer.
9. A multilayer polyester film according to any of claims 1 to 6 wherein the diacid employed in the modification of the diacid-modified polyethylene terephthalate comprises one or more of isophthalic acid, phthalic acid, 2, 6-naphthalenedicarboxylic acid, adipic acid and sebacic acid;
preferably, the dibasic acid comprises isophthalic acid and/or phthalic acid;
preferably, the mole amount of the dibasic acid is 0.1 to 40% based on 100% of the mole of ethylene glycol or terephthalic acid used for preparing the dibasic acid modified polyethylene terephthalate;
preferably, the inherent viscosity number of the dibasic acid modified polyethylene terephthalate is 0.6-1.5 dL/g, and the melting temperature is 160-260 ℃.
10. A multilayer polyester film according to any of claims 1 to 6 wherein the copolyester of the functional material in which it is a carrier comprises one or more of polyethylene terephthalate, glycol-modified polyethylene terephthalate and glycol-modified polyethylene terephthalate;
preferably, the functional material taking the copolyester as a carrier comprises hollow glass beads and/or PMMA beads; the incompatible resin comprises one or more of polypropylene resin, polyethylene resin, PMP resin, PMMA resin and TPE resin;
preferably, the diameter of the bead is 1-15 μm, preferably 2-8 μm;
preferably, the mass percentage of the microbeads to the functional material taking the copolymer ester as the carrier is 0.1-50%, preferably 5-30%;
preferably, the mass percentage of the incompatible resin in the functional material taking the copolyester as a carrier is 0.1-50%, preferably 5-30%.
11. A multilayer polyester film according to any of claims 1 to 6 wherein the white functional additive comprises titanium dioxide and/or calcium carbonate.
12. A multilayer polyester film according to any of claims 1 to 6 wherein the black functional additive comprises carbon black and/or graphite.
13. A method of producing a multilayer polyester film as claimed in any one of claims 1 to 12, which comprises the steps of:
respectively mixing and drying raw material components for preparing the layer A, the layer B and the layer C to obtain a layer A functional mixture, a layer B functional mixture and a layer C functional mixture, filling the layer A functional mixture, the layer B functional mixture and the layer C functional mixture into a three-layer co-extrusion film machine according to the sequence of the layer A, the layer B and the layer C, extruding through a three-layer co-extrusion die head, and cooling to form a cast sheet after being adhered into a whole;
and stretching the cast sheet longitudinally and transversely to form a film, thereby obtaining the multilayer polyester film.
14. The preparation method according to claim 13, wherein the extrusion temperature of the three-layer co-extrusion film machine is 200-300 ℃.
15. The method for preparing the alloy sheet according to claim 13, wherein the longitudinal and transverse stretching of the cast sheet into a film is carried out by:
longitudinally stretching the cast sheet and carrying out heat setting, wherein the stretching ratio is 0-2.5 times, the heat setting temperature is 90-150 ℃, and the heat setting time is 1-10 s; then, transversely stretching to form a film, wherein the stretching ratio is 2-6.5 times, and the stretching film-forming temperature is 60-150 ℃;
or, longitudinally stretching the cast sheet in a single direction, wherein the stretching ratio is 2-6.5 times, and the stretching temperature is 60-150 ℃; not stretching in the transverse direction;
cooling to obtain a multilayer polyester film;
preferably, after cooling, the non-or single-sided or double-sided corona treatment, winding and slitting operations are optionally carried out.
16. Use of the multilayer polyester film of any of claims 1 to 12 as a heat shrink label in film shrink packaging of containers or bottles in the field of dairy products, food, beverages.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116001403A (en) * | 2022-12-06 | 2023-04-25 | 河南达新源新材料有限公司 | Durable anti-collision PETG heat-shrinkable film and preparation method thereof |
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| CN1438109A (en) * | 2002-02-14 | 2003-08-27 | 东洋纺织株式会社 | Heat-contractable ployester series film |
| US20200270395A1 (en) * | 2017-10-30 | 2020-08-27 | Eastman Chemical Company | Low density void containing films |
| CN111823679A (en) * | 2020-06-09 | 2020-10-27 | 山东圣和塑胶发展有限公司 | Light-blocking shrink film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438109A (en) * | 2002-02-14 | 2003-08-27 | 东洋纺织株式会社 | Heat-contractable ployester series film |
| US20200270395A1 (en) * | 2017-10-30 | 2020-08-27 | Eastman Chemical Company | Low density void containing films |
| CN111823679A (en) * | 2020-06-09 | 2020-10-27 | 山东圣和塑胶发展有限公司 | Light-blocking shrink film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116001403A (en) * | 2022-12-06 | 2023-04-25 | 河南达新源新材料有限公司 | Durable anti-collision PETG heat-shrinkable film and preparation method thereof |
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