CN118085776A - Adhesive resin for multilayer co-extrusion high barrier film, preparation method thereof and high barrier film structure - Google Patents
Adhesive resin for multilayer co-extrusion high barrier film, preparation method thereof and high barrier film structure Download PDFInfo
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- CN118085776A CN118085776A CN202410266109.3A CN202410266109A CN118085776A CN 118085776 A CN118085776 A CN 118085776A CN 202410266109 A CN202410266109 A CN 202410266109A CN 118085776 A CN118085776 A CN 118085776A
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- 239000004840 adhesive resin Substances 0.000 title claims abstract description 67
- 229920006223 adhesive resin Polymers 0.000 title claims abstract description 67
- 230000004888 barrier function Effects 0.000 title claims abstract description 62
- 238000001125 extrusion Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000004698 Polyethylene Substances 0.000 claims abstract description 74
- -1 polyethylene Polymers 0.000 claims abstract description 56
- 229920000573 polyethylene Polymers 0.000 claims abstract description 55
- 229920001971 elastomer Polymers 0.000 claims abstract description 47
- 239000000806 elastomer Substances 0.000 claims abstract description 47
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920006132 styrene block copolymer Polymers 0.000 claims abstract description 20
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 12
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 12
- 239000010410 layer Substances 0.000 claims description 77
- 239000000155 melt Substances 0.000 claims description 35
- 239000012790 adhesive layer Substances 0.000 claims description 34
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 17
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 10
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 10
- 239000012793 heat-sealing layer Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 239000004677 Nylon Substances 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical group C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 11
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 35
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- ALSOCDGAZNNNME-UHFFFAOYSA-N ethene;hex-1-ene Chemical compound C=C.CCCCC=C ALSOCDGAZNNNME-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 239000008187 granular material Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011185 multilayer composite material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007652 sheet-forming process Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
The invention relates to the technical field of bonding resins, in particular to a bonding resin for a multilayer co-extrusion high barrier film, a preparation method thereof and a high barrier film structure. The adhesive resin for the multilayer co-extrusion high-barrier film comprises the following components in parts by weight: 20-40 parts of grafted modified polyethylene, 20-30 parts of styrene block copolymer, 20-40 parts of polyethylene and 20-30 parts of ethylene-butene elastomer; in the ethylene-butene elastomer, the content of comonomer butene is 10% -30%. The adhesive resin disclosed by the invention has excellent adhesive property through the matching of the components, and has high and durable and stable adhesive strength with a specific barrier layer, a printing layer and a heat seal layer; meanwhile, the toughness of the material can be enhanced and the overall mechanical property of the material can be improved by matching with each component.
Description
Technical Field
The invention relates to the technical field of bonding resins, in particular to a bonding resin for a multilayer co-extrusion high barrier film, a preparation method thereof and a high barrier film structure.
Background
In recent years, the high-barrier composite film industry is rapidly developed, the types of composite film products are more and more, and the performance requirements of the composite film products in various fields are more and more strict. Among them, the multi-layer co-extrusion composite film based on the polymer material has been widely used for food packaging, logistics transportation, new energy sources, etc. Multilayer composite films are typically prepared by multilayer coextrusion techniques, such as coextrusion using suitable inner and outer layers and an intermediate barrier layer. The existing barrier layers are mostly made of polar materials, are incompatible with common inner and outer layer structures such as nonpolar materials of ethylene and the like, and have no adhesion with each other. In order to improve the bonding performance between the inner layer and the outer layer and the middle barrier layer, bonding resin is adopted between the inner layer and the middle barrier layer and between the outer layer and the middle barrier layer for bonding.
However, the existing adhesive resin has poor adhesive performance to polyethylene, polypropylene, PET and the like, is easy to cause delamination and other problems, and cannot meet the use requirements of the multilayer composite material. The existing printing layer is mainly PE or PA, however, poor adhesion of PE as the printing layer and ink easily causes ink drop, and PA as the printing layer has high cost. Therefore, the adhesive resin which is low in cost and can realize good adhesion to various base materials is provided, and has important significance for the development of composite films.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide the adhesive resin for the multilayer co-extrusion high-barrier film, which has good adhesive property on PA, PE and PET, so that the printing layer of the high-barrier film structure can adopt PET to replace PE or PA, and the adhesive force of strong ink and low cost are both ensured.
The invention also aims to provide a preparation method of the adhesive resin for the multilayer co-extrusion high-barrier film.
It is a further object of the present invention to provide a high barrier film structure.
In order to achieve the above object, the present invention provides, in one aspect, an adhesive resin for a multilayer co-extrusion high barrier film, comprising the following components in parts by weight:
20-40 parts of grafted modified polyethylene, 20-30 parts of styrene block copolymer, 20-40 parts of polyethylene and 20-30 parts of ethylene-butene elastomer;
in the ethylene-butene elastomer, the content of comonomer butene is 10% -30%.
In the specific embodiment of the invention, the adhesive resin for the multilayer co-extrusion high-barrier film comprises the following components in parts by weight:
25-30 parts of grafted modified polyethylene, 20-25 parts of styrene block copolymer, 20-25 parts of polyethylene and 25-30 parts of ethylene-butene elastomer.
In a specific embodiment of the present invention, the melt index of the adhesive resin is 1 to 6g/10min at 190℃and 2.16 kg.
In a specific embodiment of the present invention, the ethylene-butene elastomer has a melt index of 0.5 to 7g/10min at 190℃under 2.16 kg. Further, the ethylene-butene elastomer has a density of 0.85 to 0.91g/cm 3.
In the specific embodiment of the invention, in the grafted modified polyethylene, the grafting agent is maleic anhydride, and the grafting rate is 0.6-1.2%. Further, the graft modified polyethylene is a graft modified linear low density polyethylene.
In a specific embodiment of the present invention, the melt index of the graft-modified polyethylene is 1 to 4g/10min at 190℃under 2.16 kg. Further, the density of the grafted modified polyethylene is 0.9-0.95 g/cm 3.
In a specific embodiment of the present invention, the styrenic block copolymer is a hydrogenated styrene-butadiene block copolymer.
In a specific embodiment of the present invention, the styrene-based block copolymer has a melt index of 1 to 40g/10min at 190℃under 2.16 kg. Further, the density of the styrene-based block copolymer is 0.8-1.2 g/cm 3.
In a specific embodiment of the invention, the polyethylene is a linear low density polyethylene. Further, the melt index of the polyethylene is 1-4 g/10min under the conditions of 190 ℃ and 2.16 kg; the density of the polyethylene is 0.9-0.95 g/cm 3.
In another aspect, the present invention provides a method for preparing any one of the above adhesive resins, comprising the steps of:
Mixing the components according to the proportion, and carrying out melt extrusion granulation.
The invention further provides a high barrier film structure, which comprises a heat sealing layer, a first bonding layer, a barrier layer, a second bonding layer and a printing layer which are sequentially arranged; the first adhesive layer and/or the second adhesive layer is made of any one of the adhesive resins described above;
The barrier layer is a nylon layer, the heat sealing layer is a PE layer, and the printing layer is a PET layer.
In a specific embodiment of the present invention, the sum of the weights of the first adhesive layer and the second adhesive layer is 8% to 20% of the weight of the high barrier film structure.
Compared with the prior art, the invention has the beneficial effects that:
(1) The adhesive resin disclosed by the invention has excellent adhesive property through the matching of the components, and has high and durable and stable adhesive strength with a specific barrier layer, a printing layer and a heat seal layer; meanwhile, the toughness of the material can be enhanced by matching with each component, and the overall mechanical property of the material is improved;
(2) The bonding resin has excellent bonding performance on the nylon layer, the PET layer and the PE layer, can obtain a high-barrier film structure with PET as a printing layer and PE as a heat sealing layer, and solves the problems that PE as the printing layer is easy to take off ink and PA as the printing layer has high cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a DSC graph of the adhesive resin provided in example 1 of the present invention;
Fig. 2 is an infrared spectrum of the adhesive resin provided in example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The existing bonding resin has poor bonding effect on PE and PET, meanwhile, the existing printing layer mainly comprises PE and PA, the printing ink is easy to remove when the PE layer is printed, and the cost of the PA as the printing layer is high. Therefore, the conventional barrier film structure has a problem that ink release is easily caused by using a PE layer as a printing layer, and has poor adhesion performance, or a problem that cost is high by using a PA layer as a printing layer.
In view of this, the present invention provides, in one aspect, an adhesive resin for a multilayer co-extruded high barrier film, comprising the following components in parts by weight:
20-40 parts of grafted modified polyethylene, 20-30 parts of styrene block copolymer, 20-40 parts of polyethylene and 20-30 parts of ethylene-butene elastomer;
in the ethylene-butene elastomer, the content of comonomer butene is 10% -30%.
The adhesive resin for the multilayer co-extrusion high-barrier film has good adhesive property by compounding the grafted modified polyethylene, the styrene block copolymer, the polyethylene and the ethylene-butene elastomer. Meanwhile, the research shows that when the ethylene-butene elastomer is adopted, the bonding performance of the bonding resin to PET can be improved; if common POE is adopted instead of ethylene-butene elastomer, the obtained adhesive resin has insufficient adhesion performance to PET, and can not meet the application requirement of the barrier film.
As in the various embodiments, the amounts of the components in the adhesive resin for the multilayer coextruded high barrier film may be as follows, in parts by weight:
the amount of the graft-modified polyethylene may be 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, or a range consisting of any two thereof;
the amount of the styrenic block copolymer may be in the range of 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, or any two thereof;
The polyethylene may be used in an amount ranging from 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, or any two thereof;
The ethylene-butene elastomer may be used in an amount ranging from 20 parts, 22 parts, 25 parts, 28 parts, 30 parts or any two thereof.
As in the various embodiments, the comonomer butene content in the ethylene-butene based elastomer may be in the range of 10%, 15%, 20%, 25%, 30% or any two of these. The content of comonomer butene in the ethylene-butene elastomer is regulated and controlled within the range, so that the adhesion performance of PET and the adhesion performance of PA and PE are both ensured.
In the specific embodiment of the invention, the adhesive resin for the multilayer co-extrusion high-barrier film comprises the following components in parts by weight:
25-30 parts of grafted modified polyethylene, 20-25 parts of styrene block copolymer, 20-25 parts of polyethylene and 25-30 parts of ethylene-butene elastomer.
In a specific embodiment of the present invention, the mass ratio of the styrene-based block copolymer to the ethylene-butene-based elastomer is 1: (0.8 to 1.25).
As in the various embodiments, the mass ratio of the styrenic block copolymer to the ethylene-butene elastomer may be in the range of 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.25, or any two thereof.
In a specific embodiment of the present invention, the melt index of the adhesive resin is 1 to 6g/10min at 190℃and 2.16 kg.
As in the various embodiments, the melt index of the bonding resin at 190 ℃, 2.16kg, may be 1g/10min, 2g/10min, 3g/10min, 4g/10min, 5g/10min, 6g/10min, or a range of any two of these. The melt index of the bonding resin can be ensured to be within the range and the processing performance can be ensured while the bonding performance of the bonding resin on different base materials is considered by regulating and controlling the dosage of each component.
In a specific embodiment of the present invention, the ethylene-butene based elastomer has a melt index of 0.5 to 7g/10min at 190℃under 2.16 kg. Further, the ethylene-butene elastomer has a density of 0.85 to 0.91g/cm 3.
As in the various embodiments, the melt index of the ethylene-butene based elastomer at 190℃under 2.16kg may be in the range of 0.5g/10min, 1g/10min, 1.5g/10min, 2g/10min, 3g/10min, 4g/10min, 5g/10min, 6g/10min, 7g/10min or any two thereof, preferably 1.5 to 2.5g/10min.
As in the various embodiments, the ethylene-butene based elastomer may have a density in the range of 0.85g/cm3、0.86g/cm3、0.87g/cm3、0.88g/cm3、0.89g/cm3、0.9g/cm3、0.91g/cm3 or any two of these compositions, preferably 0.88 to 0.9g/cm 3.
In the specific embodiment of the invention, in the grafted modified polyethylene, the grafting agent is maleic anhydride, and the grafting rate is 0.6-1.2%. Further, the graft modified polyethylene is a graft modified linear low density polyethylene.
As in the various embodiments, the grafting ratio in the graft modified polyethylene may be in the range of 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.2% or any two of these.
In a specific embodiment of the present invention, the melt index of the graft-modified polyethylene is 1 to 4g/10min at 190℃and 2.16 kg. Further, the density of the grafted modified polyethylene is 0.9-0.95 g/cm 3.
As in the various embodiments, the melt index of the graft-modified polyethylene at 190 ℃, 2.16kg, may be in the range of 1g/10min, 2g/10min, 3g/10min, 4g/10min, or any two of these, and the density may be 0.9g/cm3、0.91g/cm3、0.92g/cm3、0.93g/cm3、0.94g/cm3、0.95g/cm3, or any two of these.
In a specific embodiment of the present invention, the styrenic block copolymer is a hydrogenated styrene-butadiene block copolymer (SEBS).
In a specific embodiment of the present invention, the styrene-based block copolymer has a melt index of 1 to 40g/10min at 190℃and 2.16 kg. Further, the density of the styrene-based block copolymer is 0.8 to 1.2g/cm 3.
As in the various embodiments, the melt index of the styrenic block copolymer at 190 ℃, 2.16kg may be in the range of 1g/10min, 5g/10min, 10g/10min, 15g/10min, 25g/10min, 30g/10min, 35g/10min, 40g/10min, or any two thereof, and the density may be in the range of 0.8g/cm 3、0.9g/cm3、1g/cm3、1.1g/cm3、1.2g/cm3, or any two thereof.
In a specific embodiment of the invention, the polyethylene is a linear low density polyethylene. Further, the melt index of the polyethylene is 1-4 g/10min under the conditions of 190 ℃ and 2.16 kg; the density of the polyethylene is 0.9-0.95 g/cm 3.
As in the various embodiments, the polyethylene may have a melt index at 190 ℃, 2.16kg, in the range of 1g/10min, 2g/10min, 3g/10min, 4g/10min, or any two of these, and a density in the range of 0.9g/cm3、0.91g/cm3、0.92g/cm3、0.93g/cm3、0.94g/cm3、0.95g/cm3, or any two of these.
The invention also provides a preparation method of any adhesive resin, which comprises the following steps:
Mixing the components according to the proportion, and carrying out melt extrusion granulation.
Among them, melt extrusion can be performed using a conventional twin screw extruder. Further, each temperature zone and the temperature setting of the machine head can be as follows: 150 ℃, 170 ℃, 210 ℃, 220 ℃, 190 ℃.
The invention further provides a high barrier film structure, which comprises a heat sealing layer, a first bonding layer, a barrier layer, a second bonding layer and a printing layer which are sequentially arranged; the first adhesive layer and/or the second adhesive layer is made of any one of the adhesive resins described above;
the barrier layer is a nylon layer, the heat sealing layer is a PE layer, and the printing layer is a PET layer.
The adhesive resin can ensure excellent adhesive property to PET, PA and PE base materials through the composition and the dosage, and the PET/PA/PE-based multilayer co-extrusion high-barrier film structure can be prepared through the adhesive resin, so that the adhesive property is considered, the requirement of a high-barrier film is met, and meanwhile, PET is adopted as a printing layer, the adhesive force of printing ink is strong, and the cost is low.
In a specific embodiment of the present invention, the sum of the weight of the first adhesive layer and the second adhesive layer is 8% to 20% of the weight of the high barrier film structure.
As in the various embodiments, the sum of the weights of the first and second adhesive layers may be 8%, 10%, 12%, 15%, 18%, 20% or any two of the ranges of compositions of the high barrier film structure.
The elongation at break of the adhesive resin can be more than or equal to 680%, such as more than or equal to 700%, more than or equal to 720%, more than or equal to 750%, more than or equal to 760%, more than or equal to 780%, more than or equal to 800%, and the like, and the peel strength of the prepared high-barrier film structure can be more than or equal to 4.5N/15mm, such as more than or equal to 4.8N/15mm, more than or equal to 5N/15mm, more than or equal to 5.2N/15mm, more than or equal to 5.5N/15mm, more than or equal to 6N/15mm, more than or equal to 6.2N/15mm, more than or equal to 6.3N/15mm, and the like.
Example 1
The embodiment provides an adhesive resin for a multilayer co-extrusion high-barrier film, which comprises the following components in parts by weight:
30 parts of grafted modified polyethylene, 20 parts of styrene block copolymer, 25 parts of polyethylene and 25 parts of ethylene-butene elastomer;
Wherein the grafting modified polyethylene is maleic anhydride grafting modified linear low density polyethylene, the grafting rate of maleic anhydride is 0.6%, the melt index is 1.2g/10min, and the density is 0.92g/cm 3;
the styrene block copolymer is SEBS, the melt index is 5g/10min, and the density is 0.9g/cm 3;
The polyethylene is linear low-density polyethylene, the melt index is 2g/10min, and the density is 0.92g/cm 3;
The ethylene-butene elastomer is ethylene-butene copolymer, the melt index is 2g/10min, the density is 0.89g/cm 3, and the content of comonomer butene is 15%.
The preparation method of the adhesive resin for the multilayer co-extrusion high-barrier film comprises the following steps:
Mixing the raw materials according to the proportion, adding the mixture into a double-screw extruder for melt extrusion granulation, and drying to obtain adhesive resin granules; wherein, in the melt extrusion, each temperature zone of the twin-screw extruder is set as follows: zone I150 ℃, zone II 170 ℃, zone III 210 ℃, zone IV 220 ℃, and head 190 ℃.
DSC curves and infrared spectrograms of the prepared adhesive resin are shown in figures 1 and 2 respectively.
Example 2
This example is a multilayer co-extruded high barrier film adhesive resin according to example 1 and a method for producing the same, and differs only in that: ethylene-butene elastomers are different.
The ethylene-butene elastomer of this example was an ethylene-butene copolymer, the melt index was 3g/10min, the density was 0.88g/cm 3, and the comonomer butene content was 10%.
Example 3
This example is a multilayer co-extruded high barrier film adhesive resin according to example 1 and a method for producing the same, and differs only in that: ethylene-butene elastomers are different.
The ethylene-butene elastomer of this example was an ethylene-butene copolymer, the melt index was 5g/10min, the density was 0.86g/cm 3, and the comonomer butene content was 30%.
Example 4
This example is a multilayer co-extruded high barrier film adhesive resin according to example 1 and a method for producing the same, and differs only in that: ethylene-butene elastomers are different.
The ethylene-butene elastomer of this example was an ethylene-butene copolymer, the melt index was 15g/10min, the density was 0.87g/cm 3, and the comonomer butene content was 15%.
Example 5
This example is a multilayer co-extruded high barrier film adhesive resin according to example 1 and a method for producing the same, and differs only in that: the graft modified polyethylenes are different.
The graft modified polyethylene of this example was a maleic anhydride graft modified linear low density polyethylene, the maleic anhydride graft ratio was 1%, the melt index was 1.8g/10min, and the density was 0.92g/cm 3.
Example 6
This example is a multilayer co-extruded high barrier film adhesive resin according to example 1 and a method for producing the same, and differs only in that: the amounts of the components are different.
The adhesive resin for the multilayer co-extrusion high-barrier film comprises the following components in parts by weight: 25 parts of grafted modified polyethylene, 25 parts of styrene block copolymer, 20 parts of polyethylene and 30 parts of ethylene-butene elastomer.
Example 7
This example is a multilayer co-extruded high barrier film adhesive resin according to example 1 and a method for producing the same, and differs only in that: the amounts of the components are different.
The adhesive resin for the multilayer co-extrusion high-barrier film comprises the following components in parts by weight: 30 parts of grafted modified polyethylene, 25 parts of styrene block copolymer, 25 parts of polyethylene and 20 parts of ethylene-butene elastomer.
Examples 8 to 14
Embodiments 8 to 14 provide a multilayer co-extruded high barrier film structure comprising a heat seal layer, a first adhesive layer, a barrier layer, a second adhesive layer and a print layer arranged in sequence, wherein both sides of the barrier layer are respectively adhered to one sides of the heat seal layer and the print layer through the first adhesive layer and the second adhesive layer. The barrier layer is a PA layer, the heat sealing layer is a PE layer, and the printing layer is a PET layer. The sum of the weights of the first adhesive layer and the second adhesive layer is 15% of the total weight of the high barrier film structure.
Adopting a coextrusion casting sheet forming process to prepare a multilayer coextrusion high-barrier film structure, wherein the forming speed is 10m/min, and the thickness of the 5 layers of structures is respectively as follows: 25 μm of PE heat seal layer, 15 μm of first adhesive layer, 20 μm of PA barrier layer, 15 μm of second adhesive layer and 25 μm of PET printing layer.
The first and second adhesive layers in examples 8 to 14 were prepared using the adhesive resins in examples 1 to 7, respectively.
Comparative example 1
Comparative example 1 the adhesive resin for a multilayer co-extruded high barrier film of reference example 1 and a method for preparing the same are distinguished in that: the graft modified polyethylenes are different.
The graft modified polyethylene of comparative example 1 was an acrylic acid graft modified linear low density polyethylene, the acrylic acid graft ratio was 0.6%, the melt index was 1.8g/10min, and the density was 0.92g/cm 3.
Comparative example 2
Comparative example 2 the adhesive resin for a multilayer co-extruded high barrier film of reference example 1 and a method for preparing the same are distinguished in that: ethylene-butene elastomers are different.
The ethylene-butene elastomer of comparative example 2 was an ethylene-butene copolymer, the melt index was 5g/10min, the density was 0.89g/cm 3, and the content of comonomer butene was 8%.
Comparative example 3
Comparative example 3 the adhesive resin for a multilayer co-extruded high barrier film of reference example 1 and a method for preparing the same are distinguished in that: ethylene-butene elastomers are different.
The ethylene-butene elastomer of comparative example 3 was an ethylene-butene copolymer, the melt index was 6g/10min, the density was 0.84g/cm 3, and the comonomer butene content was 50%.
Comparative example 4
Comparative example 4 the adhesive resin for a multilayer co-extruded high barrier film of reference example 1 and a method for preparing the same are distinguished in that: an equal weight of ethylene-hexene based elastomer was used in place of the ethylene-butene based elastomer.
The ethylene-hexene based elastomer of comparative example 4 was an ethylene-hexene copolymer, the melt index was 5g/10min, the density was 0.86g/cm 3, and the comonomer hexene content was 20%.
Comparative example 5
Comparative example 5 the adhesive resin for a multilayer co-extruded high barrier film of reference example 1 and a method for preparing the same are distinguished in that: an equal weight of ethylene-octene based elastomer was used in place of the ethylene-butene based elastomer.
The ethylene-octene based elastomer of comparative example 5 was an ethylene-octene copolymer, the melt index was 3.5g/10min, the density was 0.86g/cm 3, and the comonomer octene content was 20%.
Comparative examples 6 to 10
Comparative examples 6-10 the multilayer co-extruded high barrier film structure of reference example 8 and a method of making the same, differing in that: the adhesive resins for preparing the first adhesive layer and the second adhesive layer are different.
The adhesive resin used for the first adhesive layer and the second adhesive layer in the structure of comparative example 6 was the adhesive resin in comparative example 1;
the adhesive resin used for the first adhesive layer and the second adhesive layer in the structure of comparative example 7 was the adhesive resin in comparative example 2;
the adhesive resin used for the first adhesive layer and the second adhesive layer in the structure of comparative example 8 was the adhesive resin in comparative example 3;
The adhesive resin used for the first adhesive layer and the second adhesive layer in the structure of comparative example 9 was the adhesive resin in comparative example 4;
the adhesive resin used for the first adhesive layer and the second adhesive layer in the structure of comparative example 10 was the adhesive resin in comparative example 5.
Experimental example 1
The adhesive resins of examples 1 to 7 and comparative examples 1 to 5 were tested for melt index and elongation at break, respectively, and the barrier film structures prepared according to examples 8 to 14 and comparative examples 6 to 10 were tested for peel strength, respectively, and the test results are shown in table 1.
Table 1 test results for different examples and comparative examples
| Numbering device | MI(g/10min) | Peel strength (N/15 mm) | Elongation at break (%) |
| Example 1 | 2.3 | 5.3 | 780 |
| Example 2 | 2.5 | 5.2 | 760 |
| Example 3 | 3.4 | 4.8 | 800 |
| Example 4 | 3.2 | 4.5 | 680 |
| Example 5 | 2.5 | 6.2 | 720 |
| Example 6 | 3.5 | 4.8 | 680 |
| Example 7 | 4.0 | 6.3 | 680 |
| Comparative example 1 | 3.2 | 2.4 | 700 |
| Comparative example 2 | 1.6 | 3.2 | 730 |
| Comparative example 3 | 2.5 | 2.7 | 690 |
| Comparative example 4 | 2.7 | 1.9 | 680 |
| Comparative example 5 | 3.0 | 2.5 | 700 |
From the test results, the adhesive resin disclosed by the invention has excellent adhesive property through the combination of the components, and has high and durable and stable adhesive strength with a specific barrier layer, a printing layer and a heat sealing layer; meanwhile, the toughness of the material can be enhanced and the overall mechanical property of the material can be improved by matching with each component.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The adhesive resin for the multilayer co-extrusion high-barrier film is characterized by comprising the following components in parts by weight:
20-40 parts of grafted modified polyethylene, 20-30 parts of styrene block copolymer, 20-40 parts of polyethylene and 20-30 parts of ethylene-butene elastomer;
in the ethylene-butene elastomer, the content of comonomer butene is 10% -30%.
2. The adhesive resin for a multilayer co-extruded high barrier film according to claim 1, comprising the following components in parts by weight: 25-30 parts of grafted modified polyethylene, 20-25 parts of styrene block copolymer, 20-25 parts of polyethylene and 25-30 parts of ethylene-butene elastomer.
3. The adhesive resin for a multilayer coextruded high barrier film according to claim 1, wherein the adhesive resin has a melt index of 1 to 6g/10min at 190 ℃ under 2.16 kg.
4. The adhesive resin for a multilayer coextruded high barrier film according to claim 1, wherein the ethylene-butene elastomer has a melt index of 0.5 to 7g/10min at 190 ℃ under 2.16 kg;
Preferably, the ethylene-butene elastomer has a density of 0.85 to 0.91g/cm 3.
5. The adhesive resin for a multilayer co-extruded high barrier film according to claim 1, wherein the grafting agent in the graft modified polyethylene is maleic anhydride, and the grafting ratio is 0.6 to 1.2%;
Preferably, the graft modified polyethylene is a graft modified linear low density polyethylene;
Preferably, the melt index of the grafted modified polyethylene is 1-4 g/10min under the conditions of 190 ℃ and 2.16 kg;
Preferably, the density of the grafted modified polyethylene is 0.9-0.95 g/cm 3.
6. The adhesive resin for a multilayer coextruded high barrier film according to claim 1, wherein the styrenic block copolymer is a hydrogenated styrene-butadiene block copolymer;
preferably, the melt index of the styrene block copolymer is 1-40 g/10min under the conditions of 190 ℃ and 2.16 kg;
preferably, the density of the styrenic block copolymer is 0.8 to 1.2g/cm 3.
7. The adhesive resin for a multilayer coextruded high barrier film according to claim 1, wherein the polyethylene is a linear low density polyethylene;
Preferably, the melt index of the polyethylene is 1-4 g/10min under the conditions of 190 ℃ and 2.16 kg; the density of the polyethylene is 0.9-0.95 g/cm 3.
8. The method for producing a binder resin for a multilayer co-extruded high barrier film according to any one of claims 1 to 7, wherein the components are mixed in a ratio and melt-extruded to be pelletized.
9. The high barrier film structure is characterized by comprising a heat sealing layer, a first bonding layer, a barrier layer, a second bonding layer and a printing layer which are sequentially arranged; the first adhesive layer and/or the second adhesive layer is made of the adhesive resin according to any one of claims 1 to 7;
The barrier layer is a nylon layer, the heat sealing layer is a PE layer, and the printing layer is a PET layer.
10. The high barrier film structure of claim 9, wherein the sum of the weights of the first adhesive layer and the second adhesive layer is 8% to 20% of the weight of the high barrier film structure.
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