CN115991022A - Low-haze high-impact coloring heat-sealing polypropylene composite film and preparation method and application thereof - Google Patents
Low-haze high-impact coloring heat-sealing polypropylene composite film and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of films, and relates to a low-haze high-impact-resistance coloring heat-sealing polypropylene composite film, and a preparation method and application thereof. The polypropylene composite film comprises at least one film layer A formed from a polypropylene composition A and at least one film layer B formed from a polypropylene composition B, wherein the polypropylene composition A comprises a resin component and a colorant, the resin component comprises a homo-polypropylene a, a propylene impact copolymer B and a polyolefin elastomer c, and the polypropylene composition B comprises a random polypropylene x and optionally a polyolefin elastomer y. The polypropylene composite film has good impact resistance, tensile property and optical property, and has good heat sealing strength at a lower heat sealing temperature.
Description
Technical Field
The invention belongs to the field of films, and particularly relates to a low-haze high-impact-resistance coloring heat-sealing polypropylene composite film, and a preparation method and application thereof.
Background
Polypropylene films are typically produced by casting, biaxially oriented drawing, and the like, but polypropylene films produced from homopolymerized polypropylene materials typically have lower impact strength. Polypropylene films are commonly used in packaging applications where high impact properties are required, while good optical properties are also desired for the film for visual and aesthetic purposes of the contents. The method for improving the impact property of the polypropylene film can be used for preparing the film by using the block impact polypropylene or adding the polyolefin elastomer into the polypropylene, but the film prepared by the method generally has higher haze and poorer optical properties such as transparency and the like. It is also possible to add a nucleating agent to the film at the same time to reduce the haze of the film by thinning the crystals in the film, but this method results in a decrease in impact properties.
In order to improve the impact resistance and toughness of the film, the film can be prepared by a multilayer coextrusion method, for example, CN101913279A adopts a three-layer coextrusion method to prepare a composite film, the middle layer of the film is elastomer and PP which are blended according to the proportion of 1:10-1:3, and the elastomer provides better impact resistance, but the method has the problem that the elastomer is difficult to disperse uniformly under the condition of higher content, the film with better optical performance is still difficult to obtain, and the addition amount of the elastomer has a certain limit because the phase separation problem occurs when the addition amount is up to a certain level, so that the further improvement of the impact resistance is limited. Moreover, when the film is used for packaging purposes, it is generally desirable to have better heat seal properties and a color-pleasing appearance at lower heat seal temperatures.
Disclosure of Invention
The invention aims to solve the problem that the existing polypropylene film is difficult to have better optical performance and impact resistance at the same time, and provides a low-haze high-impact coloring heat-sealing film and a preparation method thereof. The polypropylene film of the invention has good impact resistance, optical property and tensile property, expected color and good heat seal strength at lower heat seal temperature.
In a first aspect the present invention provides a low haze, high impact colored heat sealable polypropylene composite film comprising at least one film layer a formed from a polypropylene composition a and at least one film layer B formed from a polypropylene composition B, wherein the polypropylene composition a comprises a resin component comprising a homo-polypropylene a, a propylene impact copolymer B and a polyolefin elastomer c, and a colorant, and the polypropylene composition B comprises a random polypropylene x and optionally a polyolefin elastomer y.
The second aspect of the present invention provides a method for preparing the low haze high impact colored heat sealable polypropylene composite film described above, comprising: the raw material composition for forming each layer is extrusion-cast after an optional granulating process to form the composite film.
A third aspect of the present invention provides the use of the low haze high impact color heat sealable polypropylene composite film described above in the packaging material field.
The polypropylene composite film has good impact resistance, tensile property and optical property, and has good heat sealing strength at a lower heat sealing temperature. The tensile strength of the film in the Machine Direction (MD) is more than or equal to 39MPa, and preferably the tensile strength of the film in the Machine Direction (MD) is more than or equal to 48MPa; the impact strength of the pendulum bob is more than or equal to 0.3J, and preferably the impact strength of the pendulum bob is more than or equal to 0.8J; the heat sealing strength at 150 ℃ is more than or equal to 14N/15mm, and the heat sealing strength at 150 ℃ is more than or equal to 17N/15mm; the film haze is less than or equal to 6 percent, preferably less than or equal to 3 percent.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The invention provides a low-haze high-impact colored heat-seal polypropylene composite film, which comprises at least one film layer A formed by a polypropylene composition A and at least one film layer B formed by a polypropylene composition B, wherein the polypropylene composition A comprises a resin component and a colorant, the resin component comprises homo-polypropylene a, a propylene impact copolymer B and a polyolefin elastomer c, and the polypropylene composition B comprises random polypropylene x and optional polyolefin elastomer y.
According to some embodiments of the invention, the polypropylene composite film has at least one of the following features: the tensile strength in the Machine Direction (MD) is more than or equal to 39MPa, and preferably the tensile strength in the Machine Direction (MD) is more than or equal to 48MPa; the impact strength of the pendulum bob is more than or equal to 0.3J, and preferably the impact strength of the pendulum bob is more than or equal to 0.8J; the heat sealing strength at 150 ℃ is more than or equal to 14N/15mm, and the heat sealing strength at 150 ℃ is more than or equal to 17N/15mm; the film haze is less than or equal to 6 percent, preferably less than or equal to 3 percent.
According to some embodiments of the invention, the melt mass flow rate of the homo-polypropylene a at 230℃under a load of 2.16kg is from 2 to 15g/10min, the isotacticity is greater than 97% and the molecular weight distribution Mw/Mn is from 4.5 to 7.0. Homo-polypropylene meeting the above characteristics is commercially available. Such as the homopolypropylene with the brand of PPH-FA03 refined in Qingdao and the homopolypropylene with the brand of PPH-FA03 refined in China. Or may be prepared by methods conventional in the art.
According to the present invention, the propylene impact copolymer is preferably a propylene impact copolymer containing ethylene units, the propylene impact copolymer comprising an elastic portion which is a copolymerized portion containing ethylene units, preferably selected from the group consisting of an ethylene-propylene copolymerized portion and an ethylene-butene copolymerized portion.
Preferably, the propylene impact copolymer comprises a propylene homo-polymer portion and the ethylene unit containing co-polymer portion. The propylene homo-portion may comprise an isotactic polymeric structure.
The content of the copolymerized portion containing ethylene units in the propylene impact copolymer b is preferably 3 to 15% by weight based on the total weight of the propylene impact copolymer b by 13 C NMR measurement.
The ethylene content of the propylene impact copolymer b is preferably from 1 to 12wt%, based on the total weight of the propylene impact copolymer b.
The melt mass flow rate of the propylene impact copolymer b at 230℃under a load of 2.16kg is preferably from 1 to 10g/10min.
The propylene impact copolymer may have a block structure or comprise a propylene block copolymer.
Propylene impact copolymers meeting the above characteristics are commercially available. Such as propylene impact copolymer with the trade name EP200K and propylene impact copolymer with the trade name PPB-M02D. Or may be prepared by methods conventional in the art.
According to some embodiments of the invention, the polyolefin elastomer C is an elastomeric copolymer of ethylene and an alpha olefin, wherein the alpha olefin is preferably C 3 -C 12 More preferably at least one selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene.
According to some embodiments of the invention, the polyolefin elastomer y is an elastomeric copolymer of ethylene and an alpha olefin, wherein the alpha olefin is preferably C 3 -C 12 More preferably at least one selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene.
Polyolefin elastomers meeting the above characteristics are commercially available. For example, the polyolefin elastomer of Exxon brand 6102, the polyolefin elastomer of ExACT 3139. Or may be prepared by methods conventional in the art.
According to some embodiments of the present invention, the random polypropylene x is a copolymer of propylene and ethylene and/or butene, that is, at least one of a copolymer of propylene and ethylene, a copolymer of propylene and butene, and a copolymer of propylene and ethylene and butene, preferably at least one selected from an ethylene-propylene-butene ternary random copolymer, a propylene-ethylene binary random copolymer, and a propylene-butene binary random copolymer.
The melt mass flow rate of the atactic polypropylene x at 230℃under a load of 2.16kg is preferably 2-10g/10min.
Random polypropylene meeting the above characteristics is commercially available. Such as atactic polypropylene with the petrifaction brand F5006 and atactic polypropylene with the petrifaction brand F800 EPS. Or may be prepared by methods conventional in the art.
According to some embodiments of the present invention, the colorant may be a conventional choice in the art, including but not limited to at least one of azo pigments, phthalocyanine pigments, heterocyclic pigments, lake pigments, dyes, fluorescent brighteners, and fluorescent pigments. The above colorants are all commercially available.
According to some embodiments of the present invention, the colorant is contained in the polypropylene composition a in an amount of 0.1 to 1 part by weight based on 100 parts by weight of the resin component including 50 to 90wt% of the homo-polypropylene a, 5 to 40wt% of the propylene impact copolymer b, and 2 to 30wt% of the polyolefin elastomer c.
According to a preferred embodiment of the present invention, the colorant is contained in the polypropylene composition A in an amount of 0.3 to 0.8 parts by weight based on 100 parts by weight of the resin component comprising 55 to 75% by weight of the homo-polypropylene a, 10 to 30% by weight of the propylene impact copolymer b and 5 to 20% by weight of the polyolefin elastomer c.
In the resin component of the present invention, since the homo-polypropylene contains larger spherulites, the propylene impact copolymer and the polyolefin elastomer contain rubber phases of different sizes, and the components are affected together. According to the composition provided by the invention, the rubber phase in the composition can absorb impact energy well, so that the requirement of impact performance is met, and the film has good impact performance. Meanwhile, as the macromolecular chain segments of the homo-polymer phase are more regular, crystallization occurs in the film preparation process, so that the film also has better tensile property.
According to some embodiments of the invention, the polypropylene composition B comprises from 60 to 100wt% of the random polypropylene x and from 0 to 40wt% of the polyolefin elastomer y, based on the total weight of the polypropylene composition B.
According to a preferred embodiment of the present invention, the polypropylene composition B comprises from 75 to 90wt% of atactic polypropylene x and from 10 to 25wt% of polyolefin elastomer y, based on the total weight of the polypropylene composition B.
The polyolefin elastomer can play a role in improving the impact property of the film, but can be separated from the matrix under the condition of larger addition amount, so that the mechanical property and the optical property are reduced. According to the composition B provided by the invention, the optical performance of the film can be ensured, and the heat sealing strength of the film can be improved.
According to some embodiments of the invention, the weight parts of the polyolefin elastomer c are Wc based on 100 weight parts of the total weight of the polypropylene composition a, the weight parts of the polyolefin elastomer y are Wy based on 100 weight parts of the total weight of the polypropylene composition B, the ratio of Wc to Wy is 4:1-1:4, for example, may be 3.5:1, 3:1, 2.5:1, 2:1, 1.5:1, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5 and any value in between.
According to a preferred embodiment of the invention, the ratio of Wc to Wy is 1:1-1:2.
As a result of the study of the present inventors, when the ratio of Wc to Wy is within the range of the present invention, the impact properties and optical properties of the film can be further improved and at the same time the extrusion process can be more stable.
According to some embodiments of the invention, the melt mass flow rate of the resin component of the polypropylene composition A is in the range of 2-10g/10min, preferably 2-7g/10min, at 230℃under a load of 2.16kg.
According to some embodiments of the invention, the melt mass flow rate of the polypropylene composition B is 2-10g/10min, preferably 3-8g/10min, at 230℃under a load of 2.16kg.
When the melt mass flow rates of the resin component of the polypropylene composition A and the polypropylene composition B are within the above ranges, the film preparation process can be made smoother, thereby ensuring that the film has better uniformity, mechanical properties and optical properties.
The composite film can be of a double-layer structure, can also be of a three-layer or more than three-layer film structure, and other layers can be the same as the resin component of the film layer A or the component of the film layer B, can also be different from the resin component of the film layer A or the component of the film layer B, and can also be formed by mixing the resin component of the polypropylene composition A and the polypropylene composition B. When the polypropylene composite film has a structure with more than three layers, the film layer A is preferably used as an intermediate layer, such as a three-layer film comprising a film layer A, a film layer B and a film layer C, wherein the layer B and the layer C can be respectively positioned at two sides of the layer A.
According to some embodiments of the invention, the ratio of the sum of the thicknesses of the other film layers to the thickness of the film layer a is 1:4-2:1, for example, 1:3.5, 1:3, 1:2.5, 1:2, 1:1.5, 1:1, 1.5:1 and any value therebetween.
According to a preferred embodiment of the present invention, in the polypropylene composite film, the ratio of the sum of the thicknesses of the other film layers to the thickness of the film layer A is 1:2 to 1:1. At this ratio, the composite film has good mechanical properties.
In the present invention, in order to improve the performance of the composite film during processing, it is preferable that the composite film further contains an antioxidant and/or a lubricant.
In the present invention, the antioxidant may be various antioxidants commonly used in the art, and is not particularly limited. For example, antioxidant 1076, antioxidant 1010, antioxidant 168, and thioester antioxidants (such as DLTP and DSTP) can be used. The antioxidant may be contained in an amount of 0.1 to 0.8 parts by weight, preferably 0.2 to 0.4 parts by weight, based on 100 parts by weight of the total amount of the polypropylene composition A or the polypropylene composition B.
In the present invention, the lubricant is preferably a PEG-based lubricant and/or a mono Gan Zhilei lubricant. The lubricant is contained in an amount of 0.01 to 0.5 parts by weight, preferably 0.05 to 0.2 parts by weight, based on 100 parts by weight of the total amount of the polypropylene composition A or the polypropylene composition B.
In order to enhance other properties (e.g., stability, etc.) of the composite film according to the present invention, the composite film preferably further comprises a film forming aid. The film forming aid may be at least one selected from the group consisting of an anti-halogen agent, a light stabilizer, a heat stabilizer, a filler, a slip agent, and an anti-blocking agent (anti-blocking agent). The specific type of the film forming aid may be selected as is conventional in the art and will not be described in detail herein.
In the present invention, the content of the film forming aid may be 0.01 to 0.5 parts by weight, preferably 0.05 to 0.3 parts by weight, based on 100 parts by weight of the total amount of the polypropylene composition a or the polypropylene composition B.
According to some embodiments of the invention, the polypropylene composition a further comprises a dispersant. The dispersant is capable of improving the processability and uniformity between the resin component of the polypropylene composition A and the colorant, and the kind, use and amount thereof may be selected conventionally in the art, for example, the dispersant may be a low molecular weight polyethylene wax and the weight content of the dispersant may be 20 to 30% by weight of the colorant.
The invention also provides a preparation method of the polypropylene composite film, which comprises the following steps: the raw material composition for forming each layer is extrusion-cast after an optional granulating process to form the composite film.
In the preparation method of the present invention, the process of granulating the pellets may generally include: and uniformly mixing the components of the polypropylene composition, optional antioxidants and film forming additives in a high-speed stirrer, adding the uniformly mixed materials into a double-screw extruder for melt mixing, uniformly extruding and granulating, and drying to obtain granules. Wherein, the processing temperature of the double-screw extruder can be controlled to be 170-230 ℃.
According to some embodiments of the invention, the pellets may be processed using extrusion casting. The process of the extrusion casting method can comprise the steps of respectively conveying the granules of different compositions into a plurality of extruders, enabling the granules to flow out through coextrusion compounding of die openings of the extruders, sequentially passing through a casting roller, a traction roller, cutting edges and rolling, and thus obtaining the composite film. Wherein the temperature of the extrusion casting may be controlled to 170-230 ℃ and the temperature of the casting roll may be 10-50 ℃. The specific process of preparing the film by the extrusion casting method is a common choice in the field, and will not be described herein.
The resulting composite film may be stretched in a subsequent process, such as biaxially stretching, to advantageously further improve the mechanical properties of the composite film.
According to one embodiment of the present invention, the polypropylene composite film is produced by extrusion casting and optionally stretching the polypropylene composition a and the polypropylene composition B after pelletization.
The composite film of the invention has good impact resistance and optical performance, and the film has good uniformity.
The polypropylene composite film of the present invention can be used in the field of packaging materials, such as high-end packaging fields with high impact resistance and optical performance on films at the same time, including but not limited to battery packaging, electronic product packaging or high-end food packaging.
Specific embodiments of the present invention will be described in detail below by way of examples. It should be understood that the examples described below are illustrative and explanatory only and are not restrictive of the invention.
In the following examples and comparative examples:
the film casting apparatus was purchased from Labtech, sweden under the model LCR400.
The polypropylene composition and polypropylene composite film properties were tested according to the following methods, the film test results are shown in table 1:
(1) Melt Mass Flow Rate (MFR): the measurement was carried out according to the method specified in GB/T3682-2000, wherein the test temperature was 230℃and the load was 2.16kg.
(2) Film tensile strength: the measurement was carried out according to the method specified in GB/T1040.3-2006.
(3) Film pendulum impact strength: the measurement was performed according to the method specified in GB/T8809-2015.
(4) Film haze: the measurement was carried out according to the method specified in GB/T2410-2008.
(5) Film heat seal strength: the measurement was performed according to the method specified in QB/T2358. When the sample is prepared, the heat sealing temperature is 150 ℃, the heat sealing pressure is 0.2MPa, and the heat sealing time is 3s.
(6) Degree of isotacticity: by passing through 13 C NMR measurement, nuclear magnetic carbon Spectrometry of propylene Polymer at 400MHz was measured by Nuclear magnetic resonance spectrometer (NMR) of model AVANCE III of Bruker, switzerland 13 C-NMR), wherein the solvent was deuterated o-dichlorobenzene and the sample concentration was 250mg sample/2.5 mL solvent. To prevent oxidative degradation of the sample during dissolution and data collection, 2mg of 2, 6-di-tert-butyl-4-methylphenol antioxidant (BHT for short) was added to the sample. Dissolving the sample at 140 ℃ and collecting 13 C-NMR, test temperature 125 ℃, probe gauge 10 mm, 90 pulse, sampling time AQ 5 seconds, delay time D1 seconds, number of scans 6000. Isotatic with two sets of units [ mm]The content of (2) is taken as isotacticity.
(7) Molecular weight distribution (Mw/Mn): the gel permeation chromatograph was used in combination with an IR5 type infrared detector, and the gel permeation chromatograph was used as a model PL-GPC 220 by UK Polymer Laboratories, wherein the gel permeation chromatograph comprises 3 columns of Plgel 10 μm MIXED-B connected in series, the solvent and mobile phase were 1,2, 4-trichlorobenzene (containing 0.3g/1000mL of antioxidant 2, 6-di-tert-butyl-p-cresol), the column temperature was 150℃and the flow rate was 1.0mL/min, and the well-suited calibration was performed using EasiCal PS-1 narrow distribution polystyrene standard produced by PL.
Example 1
This example is used to illustrate the preparation of the polypropylene composite film provided by the present invention.
(1) Preparation of polypropylene composition A:
the component a is homopolymerized polypropylene with the brand name of PPH-FA03, and is purchased from Qingdao refining, the mass flow rate of a melt is 3.1g/10min, the isotacticity is 98%, and the molecular weight distribution Mw/Mn is 4.7; component b is EP200K propylene impact copolymer, purchased from Zhongsha petrochemical industry, with ethylene content of 8wt%, ethylene-propylene copolymer portion content of 13wt%, melt mass flow rate of 3.2g/10min; component c was a polyolefin elastomer having a trade designation 6102, available from Exxon, and was an ethylene-propylene copolymer having an ethylene structural unit content of 16% by weight. The components prepared above are weighed and mixed according to the proportion, wherein the weight part Wa of the component a is 75 weight parts, the weight part Wb of the component b is 10 weight parts, and the weight part Wc of the component c is 15 weight parts. Then adding a lubricant (the lubricant is PEG lubricant produced by Switzerland, and has a molecular weight of 10000, and the addition amount of the lubricant is 0.1 part by weight based on 100 parts by weight of the sum of the mass of the component a, the mass of the component b and the mass of the component c); adding a colorant of fast brilliant red BBS (dye index C.I.P.R.48:3, commercially available) in an amount of 0.5 parts by weight based on 100 parts by weight of the sum of the mass of the above-mentioned component a, component b and component c; dispersing agent (low molecular weight polyethylene wax, commercially available) was added in an amount of 25 parts by weight based on 100 parts by weight of the colorant. Then the mixture is added into a high-speed stirrer to be mixed uniformly, and the mixed material is added into W&In a feeder of a twin-screw extruder manufactured by P company, materials enter twin screws through the feeder, the temperature of the screws is kept between 160 ℃ and 230 ℃ in the processing process, the materials are melted and mixed uniformly through the screws, extruded, granulated and dried to obtain polypropylene composition granules, and the melt mass flow rate MFR of the resin component is detected A ＝3.6g/10min。
(2) Preparation of polypropylene composition B:
the component x is random polypropylene with the brand number of F5006, is purchased from the petrifaction of Yanshan and is an ethylene-propylene-butene terpolymer, and the melt mass flow rate is 5.2g/10min; component y was a polyolefin elastomer having a trade designation 6102, available from Exxon and was an ethylene-propylene copolymer having an ethylene structural unit content of 16% by weight. The components prepared above are weighed and mixed according to the proportion, wherein the weight part Wx of the component x is 75 weight parts, and the weight part Wy of the component y is 25 weight parts. Wc: wy is 3:5. Other steps are the same as the step (1), and the polypropylene composition B granules are finally obtained and inspectedMeasuring the melt mass flow rate MFR thereof B ＝3.2g/10min。
(3) Preparation of a composite film:
drying the polypropylene composition A and the polypropylene composition B pellets obtained in the step (1) and the step (2), and then adding the polypropylene composition A into a core layer extruder of a multilayer extrusion casting machine, and adding the polypropylene composition B into an upper surface layer extruder of the multilayer extrusion casting machine, wherein an inorganic anti-sticking agent (silicon dioxide, the same applies below) is added into the upper surface layer extruder, and the weight ratio of the anti-sticking agent to the polypropylene composition pellets is 0.2:100. In the casting process, the casting chill roll temperature was set to 30 ℃, and wound up to produce a composite film consisting of an upper skin layer (film layer B) and a core layer (film layer a). The film thickness was 50 μm, with a thickness ratio of film layer B to film layer A of 1:2.
Example 2
This example is used to illustrate the preparation of the polypropylene composite film provided by the present invention.
(1) Preparation of polypropylene composition A:
component a is homo-polypropylene with the brand of FC801, which is purchased from Shanghai petrochemical industry, the melt mass flow rate is 7.8g/10min, the isotacticity is 98%, and the molecular weight distribution Mw/Mn is 4.8; the component b is propylene impact copolymer with the brand name of PPB-M02D, which is purchased from the luxuriant petrochemical industry, has the ethylene content of 8wt%, the ethylene-propylene copolymer part content of 10wt% and the melt mass flow rate of 1.5g/10min; component c was a polyolefin elastomer having the trade designation EXACT3139, available from Exxon and was an ethylene-1-octene copolymer having an octene structural unit content of 14wt%. The components prepared above are weighed and mixed according to the proportion, wherein the weight part Wa of the component a is 55 weight parts, the weight part Wb of the component b is 25 weight parts, and the weight part Wc of the component c is 20 weight parts. Then adding a lubricant (the lubricant is PEG lubricant produced by Switzerland, and has a molecular weight of 10000, and the addition amount of the lubricant is 0.1 part by weight based on 100 parts by weight of the sum of the mass of the component a, the mass of the component b and the mass of the component c); adding a colorant of phthalocyanine green (dye index C.I.P.G.7, commercially available) to give a total of 100% by mass of the above-mentioned components a, b and cThe addition amount of the colorant is 0.8 weight part; dispersing agent (low molecular weight polyethylene wax, commercially available) was added in an amount of 20 parts by weight based on 100 parts by weight of the colorant. Then the mixture is added into a high-speed stirrer to be mixed uniformly, and the mixed material is added into W&In a feeder of a twin-screw extruder manufactured by P company, materials enter twin screws through the feeder, the temperature of the screws is kept between 160 ℃ and 230 ℃ in the processing process, the materials are melted and mixed uniformly through the screws, extruded, granulated and dried to obtain polypropylene composition A granules, and the melt mass flow rate MFR of a resin component of the polypropylene composition A granules is detected A ＝6.6g/10min。
(2) Preparation of polypropylene composition B:
the component x is random polypropylene with the brand of F800EPS, is purchased from Shanghai petrochemical industry, is an ethylene-propylene-butene terpolymer, and has a melt mass flow rate of 8.2g/10min; component y was a polyolefin elastomer having the trade designation EXACT3139, available from Exxon and was an ethylene-1-octene copolymer having an octene structural unit content of 14wt%. The components prepared above are weighed and mixed according to the proportion, wherein the weight part Wx of the component x is 80 weight parts, and the weight part Wy of the component y is 20 weight parts. Wc: wy is 1:1. Other steps are the same as in step (1), and pellets of the polypropylene composition B are finally obtained, which are examined for melt mass flow rate MFR B ＝7.9g/10min。
(3) Preparation of a composite film:
the preparation procedure is the same as in step (3) of example 1.
Example 3
A polypropylene composite film was prepared as in example 1. The difference is that the polypropylene composition B contains only component x and the colorant is permanent violet (dye index C.I.P.V.23).
Example 4
This example is used to illustrate the preparation of the polypropylene composite film provided by the present invention.
(1) Preparation of polypropylene composition A:
the procedure is as in example 1. The difference is that the part by weight Wa of the component a is 65 parts by weight and the part by weight Wb of the component b is 30 parts by weightThe weight portion Wc of the component c is 5 weight portions. To obtain pellets of the polypropylene composition A, the melt mass flow rate MFR of the resin component thereof was measured A ＝3.1g/10min。
(2) Preparation of polypropylene composition B:
the procedure is as in example 1. The difference is that the weight part Wx of the component x is 90 parts by weight and the weight part Wy of the component y is 10 parts by weight. Wc: wy is 1:2. Other steps are the same as in step (2), and pellets of the polypropylene composition B are finally obtained, which are examined for melt mass flow rate MFR B ＝6.0g/10min。
(3) Preparation of a composite film:
the procedure is as in example 1. The film thickness was 50 μm, with a thickness ratio of film layer B to film layer A of 1:3.
Example 5
A polypropylene composite film was prepared as in example 1. In the preparation of the polypropylene composition A, the component a was 50 parts by weight of Wa, the component b was 40 parts by weight of Wb, and the component c was 10 parts by weight of Wc. Wc: wy is 2:5.
To obtain pellets of the polypropylene composition A, the melt mass flow rate MFR of the resin component thereof was measured A ＝3.0g/10min。
Example 6
A polypropylene composite film was prepared as in example 1. In the preparation of the polypropylene composition A, the component a was 80 parts by weight of Wa, the component b was 10 parts by weight of Wb, and the component c was 10 parts by weight of Wc. Wc: wy is 2:5. To obtain pellets of the polypropylene composition A, the melt mass flow rate MFR of the resin component thereof was measured A ＝3.4g/10min。
Example 7
A polypropylene composite film was prepared as in example 1. In the preparation of the polypropylene composition B, the component x was 70 parts by weight of Wx and the component y was 30 parts by weight of Wy. Wc: wy is 1:2. To obtain pellets of the polypropylene composition B, the melt mass flow rate MFR of which was measured B ＝4.4g/10min。
Example 8
A polypropylene composite film was prepared as in example 1. In the preparation of the polypropylene composition B, the component x was 95 parts by weight of Wx and the component y was 5 parts by weight of Wy. Wc: wy is 3:1. Finally, pellets of the polypropylene composition B were obtained, the melt mass flow rate MFR of which was examined B ＝5.7g/10min。
Comparative example 1
A polypropylene composite film was prepared as in example 1. Except that the polypropylene composition A alone was extrusion-cast as a monolayer film having a film thickness of 50. Mu.m.
Comparative example 2
A polypropylene composite film was prepared as in example 1. Except that the polypropylene composition A contained no colorant, and was extrusion-cast as a single-layer film with a film thickness of 50. Mu.m, using only the polypropylene composition A.
Comparative example 3
A polypropylene composite film was prepared as in example 1. The polypropylene composition A, however, contained only the component a and the component c, wherein the component a was 75 parts by weight of Wa and the component c was 25 parts by weight of Wc.
TABLE 1
As can be seen from the results of the examples in Table 1, the polypropylene composite film provided by the present invention has both a bright color and good impact resistance, optical properties and tensile properties, and also has good heat seal strength. The film has the tensile strength in the Machine Direction (MD) of more than or equal to 39MPa, the haze of the film of less than or equal to 6 percent, the pendulum impact strength of more than or equal to 0.3J and the heat sealing strength at 150 ℃ of more than or equal to 14N/15mm. As can be seen from the preferred examples, the films of the present invention have a Machine Direction (MD) tensile strength of not less than 48MPa, a film haze of not more than 3%, a pendulum impact strength of not less than 0.8J, and a heat seal strength at 150℃of not less than 17N/15mm. It can be seen from the comparative examples that it is difficult to achieve a balance of various properties only with a single film or a change in the composition ratio of the film components, and that the film surface is unstable during extrusion casting, and it is difficult to obtain a film having a uniform thickness.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (18)
1. A low haze high impact colored heat sealable polypropylene composite film comprising at least one film layer a formed from a polypropylene composition a and at least one film layer B formed from a polypropylene composition B, wherein the polypropylene composition a comprises a resin component comprising a homo-polypropylene a, a propylene impact copolymer B and a polyolefin elastomer c, and a colorant, and the polypropylene composition B comprises a random polypropylene x and optionally a polyolefin elastomer y.
2. The low haze, high impact color heat sealable polypropylene composite film of claim 1, wherein the polypropylene composite film has at least one of the following characteristics: the longitudinal tensile strength is more than or equal to 39MPa, preferably more than or equal to 48MPa; the impact strength of the pendulum bob is more than or equal to 0.3J, and preferably the impact strength of the pendulum bob is more than or equal to 0.8J; the heat sealing strength at 150 ℃ is more than or equal to 14N/15mm, and the heat sealing strength at 150 ℃ is more than or equal to 17N/15mm; the film haze is less than or equal to 6 percent, preferably less than or equal to 3 percent.
3. The low haze high impact colored heat sealable polypropylene composite film according to any of claims 1 to 2, wherein the melt mass flow rate of the resin component of the polypropylene composition a is from 2 to 10g/10min, preferably from 2 to 7g/10min, at 230 ℃ under a load of 2.16 kg; and/or
The melt mass flow rate of the polypropylene composition B is 2-10g/10min, preferably 3-8g/10min, at 230℃under a load of 2.16kg.
4. A low haze high impact colored heat sealable polypropylene composite film according to any of claims 1 to 3 wherein the melt mass flow rate of the homo-polypropylene a is from 2 to 15g/10min at 230 ℃, under a 2.16kg load, the isotacticity is greater than 97% and the molecular weight distribution Mw/Mn is from 4.5 to 7.0.
5. The low haze, high impact colored heat sealable polypropylene composite film of any of claims 1 to 4 wherein the propylene impact copolymer b is a propylene impact copolymer comprising ethylene units, the ethylene content of the propylene impact copolymer b being from 1 to 12wt% based on the total weight of the propylene impact copolymer b; and/or the number of the groups of groups,
the content of the copolymerization part containing ethylene units in the propylene impact copolymer b is 3-15wt%; and/or the number of the groups of groups,
the melt mass flow rate of the propylene impact copolymer b at 230 ℃ and under a load of 2.16kg is 1-10g/10min.
6. The low haze, high impact colored heat sealable polypropylene composite film according to any of claims 1 to 5 wherein the polyolefin elastomer C and the polyolefin elastomer y are each independently an elastomeric copolymer of ethylene and an alpha olefin, wherein the alpha olefin is preferably C 3 -C 12 More preferably selected from propylene, 1-At least one of butene, 1-hexene and 1-octene.
7. The low haze high impact colored heat sealable polypropylene composite film of any of claims 1 to 6 wherein the random polypropylene x is a copolymer of propylene with ethylene and/or butene, preferably at least one selected from the group consisting of ethylene-propylene-butene terpolymers, propylene-ethylene co-random copolymers, propylene-butene co-random copolymers; and/or the melt mass flow rate of the atactic polypropylene x at 230 ℃ under a load of 2.16kg is 2-10g/10min.
8. The low haze high impact colored heat sealable polypropylene composite film according to any of claims 1 to 7, wherein the colorant is selected from at least one of azo pigments, phthalocyanine pigments, heterocyclic pigments, lake pigments, dyes, fluorescent whitening agents and fluorescent pigments.
9. The low haze high impact colored heat sealable polypropylene composite film of any of claims 1 to 8 wherein the colorant is present in the polypropylene composition a in an amount of from 0.1 to 1 parts by weight based on 100 parts by weight of the resin component comprising from 50 to 90% by weight of the homo-polypropylene a, from 5 to 40% by weight of the propylene impact copolymer b and from 2 to 30% by weight of the polyolefin elastomer c; preferably, the colorant is contained in an amount of 0.3 to 0.8 parts by weight based on 100 parts by weight of the resin component including 55 to 75% by weight of the homo-polypropylene a, 10 to 30% by weight of the propylene impact copolymer b, and 5 to 20% by weight of the polyolefin elastomer c.
10. The low haze high impact colored heat sealable polypropylene composite film according to any of claims 1 to 9, wherein the polypropylene composition B comprises from 60 to 100wt% of atactic polypropylene x and from 0 to 40wt% of polyolefin elastomer y, based on the total weight of the polypropylene composition B; preferably, the polypropylene composition B comprises 75 to 90wt% of a random polypropylene x and 10 to 25wt% of a polyolefin elastomer y.
11. The low haze high impact colored heat sealable polypropylene composite film according to any one of claims 1 to 10, wherein the weight fraction of polyolefin elastomer c is Wc based on 100 parts by weight of the total weight of polypropylene composition a and the weight fraction of polyolefin elastomer y is Wc based on 100 parts by weight of the total weight of polypropylene composition B, the ratio of Wc to Wy being 4:1 to 1:4, preferably 1:1 to 1:2.
12. The low haze high impact color heat sealable polypropylene composite film according to any of claims 1 to 11, wherein the ratio of the sum of the other film layer thicknesses to the thickness of the film layer a in the polypropylene composite film is 1:4 to 2:1, preferably 1:2 to 1:1.
13. The low haze high impact color heat sealable polypropylene composite film according to any of claims 1 to 12, wherein when the polypropylene composite film has a three or more layer structure, the film layer a is an intermediate layer.
14. The low haze high impact colored heat sealable polypropylene composite film according to any of claims 1 to 13 wherein the polypropylene composition a and/or polypropylene composition B further comprises an antioxidant and/or a lubricant;
preferably, the antioxidant is selected from at least one of antioxidant 1076, antioxidant 1010, antioxidant 168 and a thioester antioxidant;
preferably, the antioxidant is contained in an amount of 0.1 to 0.8 parts by weight, preferably 0.2 to 0.4 parts by weight, based on 100 parts by weight of the total amount of the polypropylene composition a or the polypropylene composition B;
preferably, the lubricant is a PEG-based lubricant and/or a mono Gan Zhilei lubricant;
preferably, the lubricant is contained in an amount of 0.01 to 0.5 parts by weight, preferably 0.05 to 0.2 parts by weight, based on 100 parts by weight of the total amount of the polypropylene composition a or the polypropylene composition B.
15. The low haze high impact colored heat sealable polypropylene composite film according to any of claims 1 to 14, wherein the polypropylene composition a and/or polypropylene composition B further comprises a film forming aid, preferably selected from at least one of an anti-halogen agent, a light stabilizer, a heat stabilizer, a filler, a slip agent and an anti-adhesion agent; more preferably, the content of the film forming aid is 0.01 to 0.5 parts by weight, preferably 0.05 to 0.3 parts by weight, based on 100 parts by weight of the total amount of the polypropylene composition a or the polypropylene composition B.
16. The low haze high impact colored heat sealable polypropylene composite film according to any of claims 1 to 15, wherein the polypropylene composition a further comprises a dispersant, preferably a low molecular weight polyethylene wax, in an amount of 20 to 30% by weight of the colorant.
17. The process for preparing a low haze high impact colored heat sealable polypropylene composite film as defined in any one of claims 1 to 16 comprising: extruding and casting the raw material composition for forming each layer after an optional granulating process to form the composite film; optionally, the method further comprises stretching, preferably biaxially stretching, the resulting composite film.
18. Use of the low haze high impact color heat sealable polypropylene composite film of any of claims 1 to 16 in the field of packaging materials; the package is preferably a battery package, an electronic product package or a food package.
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| CN202111221971.5A CN115991022A (en) | 2021-10-20 | 2021-10-20 | Low-haze high-impact coloring heat-sealing polypropylene composite film and preparation method and application thereof |
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