CN113500769A - Biodegradable biaxially oriented composite film and preparation method and application thereof - Google Patents
Biodegradable biaxially oriented composite film and preparation method and application thereof Download PDFInfo
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- CN113500769A CN113500769A CN202110838498.9A CN202110838498A CN113500769A CN 113500769 A CN113500769 A CN 113500769A CN 202110838498 A CN202110838498 A CN 202110838498A CN 113500769 A CN113500769 A CN 113500769A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 title abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 102
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- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 41
- 239000004626 polylactic acid Substances 0.000 claims abstract description 40
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 39
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 23
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 23
- 229920001971 elastomer Polymers 0.000 claims abstract description 17
- 239000000806 elastomer Substances 0.000 claims abstract description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims abstract description 15
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 claims abstract description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Natural products O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims abstract description 6
- -1 polybutylene adipate Polymers 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 21
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000004631 polybutylene succinate Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 12
- 239000002216 antistatic agent Substances 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 7
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 7
- AQFWNELGMODZGC-UHFFFAOYSA-N o-ethylhydroxylamine Chemical compound CCON AQFWNELGMODZGC-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 5
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 5
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
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- 229920001707 polybutylene terephthalate Polymers 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 3
- 229920000704 biodegradable plastic Polymers 0.000 description 3
- 238000006065 biodegradation reaction Methods 0.000 description 3
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- 230000001360 synchronised effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010096 film blowing Methods 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000012748 slip agent Substances 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
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- 239000004408 titanium dioxide Substances 0.000 description 2
- AOJJSUZBOXZQNB-VTZDEGQISA-N 4'-epidoxorubicin Chemical group O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@@H](O)[C@H](C)O1 AOJJSUZBOXZQNB-VTZDEGQISA-N 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- 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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
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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
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/244—All polymers belonging to those covered by group B32B27/36
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/716—Degradable
- B32B2307/7163—Biodegradable
-
- 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
- B32B2553/00—Packaging equipment or accessories not otherwise provided for
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The invention relates to the technical field of biodegradable films, in particular to a biodegradable biaxially oriented composite film and a preparation method and application thereof, wherein the composite film comprises at least one first resin layer, and the first resin layer comprises the following components: polylactic acid, biodegradable elastomer and functional master batch; the biodegradable elastomer is selected from at least one of poly (butylene adipate/terephthalate), poly (butylene succinate), poly (adipate/butylene succinate), carbon dioxide copolymer and polycaprolactone; and the biodegradable biaxially oriented laminated film is formed by coextrusion and biaxially orientation. The biodegradable biaxially oriented composite film provided by the invention has good effects of high light transmittance, high haze and low glossiness.
Description
Technical Field
The invention relates to the technical field of biodegradable films, in particular to a biodegradable biaxially oriented composite film and a preparation method and application thereof.
Background
The use of plastics brings convenience to human beings and also causes a plurality of environmental problems, and with the improvement of living standard, the problem of plastic pollution is sought to be solved worldwide. The fully biodegradable plastic attracts attention due to unique biodegradation characteristics, is completely converted into water, carbon dioxide and biomass after being degraded, and is harmless to the environment, so that the fully biodegradable plastic can be used as a substitute scheme of the existing non-degradable plastic.
Packaging is one of the fields with the largest application amount of plastics, and with the application of various biodegradable plastics in the packaging industry, the surface characteristics of packaging materials are required to be diversified. The development of matting films as a product with special visual effects on biodegradable materials is still relatively rare. Meanwhile, the application of the biaxial tension film technology in the full-biodegradable material is still less.
The patent application with the application number of CN202010355757.8, the publication date of which is 31.7.2020, discloses a fully degradable polylactic acid single-sided matte film and a preparation method thereof, and a composite film consists of an A layer matte film and a B layer bright film and is prepared by a film blowing process. The matte film effect is realized by adding titanium dioxide serving as a flatting agent, but the light transmittance of the film is obviously reduced due to the obvious light shading effect of the titanium dioxide.
Patent application No. US13363230, published as 2014 08 and 19, discloses a matte biaxially oriented polylactic acid film prepared by combining polylactic acid, polyolefin and a compatibilizer formulation. The matte film is prepared by utilizing the incompatible characteristics of polyolefin and polylactic acid, but the introduction of the polyolefin can influence the biodegradation performance of the material.
Disclosure of Invention
In order to solve the above-mentioned deficiencies in the prior art, the present invention provides a biodegradable biaxially oriented laminated film, comprising at least one first resin layer, wherein the first resin layer comprises the following components:
polylactic acid, biodegradable elastomer and functional master batch;
the biodegradable elastomer is selected from at least one of poly (adipic acid)/butylene terephthalate (PBAT), poly (butylene succinate) (PBS), poly (adipic acid)/butylene succinate (PBSA), carbon dioxide copolymer (PPC) and Polycaprolactone (PCL);
and the biodegradable biaxially oriented laminated film is formed by coextrusion and biaxially orientation.
In some embodiments, the temperature of the biaxial stretching is within 120 ℃.
In some embodiments, the first resin layer comprises the following components in parts by weight:
50-95 parts of polylactic acid, 5-45 parts of biodegradable elastomer and 0.5-6 parts of functional master batch.
In some embodiments, further comprising at least one second resin layer, of said second resin layer;
the second resin layer comprises one or more of polylactic acid (PLA), polybutylene adipate/terephthalate (PBAT), polybutylene succinate (PBS) and Polycaprolactone (PCL);
in some embodiments, the polylactic acid has an optical purity of 95% or more and a melting point of 155-180 ℃.
In some embodiments, the functional masterbatch comprises the following components: slipping agent, anti-caking agent, antistatic agent and master batch matrix resin.
In some embodiments, the functional masterbatch comprises the following components in parts by weight: 1-10 parts of a slipping agent, 1-10 parts of an anti-caking agent, 1-5 parts of an antistatic agent and 75-97 parts of a master batch matrix resin.
In some embodiments, the slip agent is selected from one or more of erucamide, silicone, ethylene bis stearamide.
In some embodiments, the anti-caking agent is selected from one or more of silica, talc and calcium carbonate.
In some embodiments, the antistatic agent is selected from one or more of ethoxyamine and oleamide.
In some embodiments, the masterbatch matrix resin is selected from one or more of polylactic acid, polybutylene adipate/terephthalate, polybutylene succinate, and polycaprolactone.
The invention provides a preparation method of a biodegradable biaxially oriented composite film, which comprises the following steps:
co-extruding to obtain an unstretched raw material film, wherein the film comprises at least one first resin layer, and the first resin layer comprises the following components:
polylactic acid, biodegradable elastomer and functional master batch;
the biodegradable elastomer is selected from at least one of poly (butylene adipate/terephthalate), poly (butylene succinate), poly (adipate/butylene succinate), carbon dioxide copolymer and polycaprolactone;
and (3) carrying out biaxial stretching on the film.
In some embodiments, the temperature of the biaxial stretching is within 120 ℃.
In some embodiments, the first resin layer comprises the following components in parts by weight:
50-95 parts of polylactic acid, 5-45 parts of biodegradable elastomer and 0.5-6 parts of functional master batch.
In some embodiments, further comprising at least one second resin layer, of said second resin layer;
the second resin layer comprises one or a combination of more of polylactic acid, polybutylene adipate/terephthalate, polybutylene succinate and polycaprolactone;
in some embodiments, the polylactic acid has an optical purity of 95% or more and a melting point of 155-180 ℃.
In some embodiments, the functional masterbatch comprises the following components: slipping agent, anti-caking agent, antistatic agent and master batch matrix resin.
In some embodiments, the functional masterbatch comprises the following components in parts by weight: 1-10 parts of a slipping agent, 1-10 parts of an anti-caking agent, 1-5 parts of an antistatic agent and 75-97 parts of a master batch matrix resin.
In some embodiments, the slip agent is selected from one or more of erucamide, silicone, ethylene bis stearamide.
In some embodiments, the anti-caking agent is selected from one or more of silica, talc and calcium carbonate.
In some embodiments, the antistatic agent is selected from one or more of ethoxyamine and oleamide.
In some embodiments, the masterbatch matrix resin is selected from one or more of polylactic acid, polybutylene adipate/terephthalate, polybutylene succinate, and polycaprolactone.
The present invention provides a packaging material comprising the biodegradable biaxially oriented laminated film as described above.
Based on the above, compared with the prior art, the biodegradable biaxially oriented laminated film provided by the invention realizes good effects of high light transmittance (not less than 80%), high haze (not less than 80%), and low glossiness (not more than 15%); the self-extinction property of the film is realized through the process and the formula, and the environment-friendly characteristic of biodegradable materials is ensured.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts; in the following description, the drawings are illustrated in a schematic view, and the drawings are not intended to limit the present invention.
Fig. 1 is a schematic structural diagram of biodegradable biaxially oriented laminated films according to examples 1, 3 and 4 provided in the present invention;
fig. 2 is a schematic structural diagram of a biodegradable biaxially oriented laminated film according to example 2 of the present invention.
Reference numerals:
a a first resin layer B a second resin layer
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments; the technical features designed in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be noted that all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs, and are not to be construed as limiting the present invention; it will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The invention provides a preparation method of a biodegradable biaxially oriented composite film, which comprises the following steps:
co-extruding to obtain an unstretched raw material film, wherein the raw material film comprises at least one first resin layer A, and the first resin layer A comprises the following components:
polylactic acid, biodegradable elastomer and functional master batch;
the biodegradable elastomer is selected from at least one of poly (butylene adipate/terephthalate), poly (butylene succinate), poly (adipate/butylene succinate), carbon dioxide copolymer and polycaprolactone;
and (3) carrying out biaxial stretching on the raw material film.
In some embodiments, referring to fig. 1, fig. 1 is a schematic structural view of some embodiments provided in the present invention, the biodegradable biaxially oriented laminated film includes a three-layer structure, which includes, from top to bottom, a first resin layer a, a second resin layer B, and a first resin layer a;
in some embodiments, referring to fig. 2, fig. 2 is a schematic structural view of another embodiment provided by the present invention, the biodegradable biaxially oriented laminated film includes a two-layer structure, which includes a first resin layer a and a second resin layer B from top to bottom;
in some embodiments, referring to fig. 2, fig. 2 is a schematic structural diagram of other embodiments provided by the present invention, the biodegradable biaxially oriented laminated film includes a two-layer structure, which includes a first resin layer a and a second resin layer B from top to bottom, and when the second resin layer B is used as an outer resin layer, the second resin layer B may further include a functional masterbatch in addition to one or more of polylactic acid, polybutylene adipate/terephthalate, polybutylene succinate, and polycaprolactone;
in other embodiments, the biodegradable biaxially oriented laminated film may adopt a three-layer structure of a first resin layer a/a first resin layer a, a three-layer structure of a first resin layer a/a second resin layer B, a three-layer structure of a first resin layer a/a second resin layer B, and the like, but the embodiments of the present disclosure are not limited thereto;
the first resin layer A comprises the following components in parts by weight: the adding part of the polylactic acid can be 50-95 parts, the adding part of the biodegradable elastomer can be 5-45 parts, and the adding part of the functional master batch can be 0.5-6 parts;
wherein the optical purity of the polylactic acid is more than or equal to 95 percent, and the melting point is 155-180 ℃;
the biodegradable elastomer is selected from at least one of poly (butylene adipate/terephthalate), poly (butylene succinate), poly (adipate/butylene succinate), carbon dioxide copolymer and polycaprolactone;
the functional master batch comprises the following components in parts by weight: 1-10 parts of a slipping agent, 1-10 parts of an anti-caking agent, 1-5 parts of an antistatic agent and 75-97 parts of a master batch matrix resin;
the slipping agent is selected from one or more of erucamide, silicone and ethylene bis-stearamide; the master batch matrix resin is selected from one or more of polylactic acid, polybutylene adipate/terephthalate, polybutylene succinate and polycaprolactone; the anti-caking agent is selected from one or more of silicon dioxide, talcum powder and calcium carbonate; the antistatic agent is selected from one or more of ethoxyamine and oleamide.
The second resin layer B comprises one or a combination of a plurality of polylactic acid, polybutylene adipate/terephthalate, polybutylene succinate and polycaprolactone;
in addition, the second resin layer B may be a combination of several substances at any ratio.
In some embodiments, the method for preparing the biodegradable biaxially oriented laminated film comprises the following steps:
s1, fully drying the raw materials to below 200ppm, putting the components of the first resin layer A into an auxiliary extruder, putting the components of the second resin layer B into a main extruder, and heating and melting at the temperature of 150-180 ℃;
s2, converging the melts of the auxiliary extruder and the main extruder in a three-layer T-shaped die head and then extruding to obtain a mixed melt, wherein the temperature of the three-layer T-shaped die head is 150-200 ℃;
s3, pasting the extruded mixed melt on the surface of a chill roll through an air knife to form a cast sheet, wherein the temperature of the chill roll is 5-40 ℃;
s4, performing bidirectional stretching on the casting sheet;
in some embodiments, the temperature of the biaxial stretching is within 120 ℃, and when the temperature is higher than 120 ℃, the film is easy to break, so that the film cannot be formed.
In some embodiments, the biaxial stretching may be a step biaxial stretching method or a simultaneous biaxial stretching method.
In some embodiments, the biaxial synchronous stretching method may include the following specific method steps:
preheating for 5-40 s at 95-120 ℃, and simultaneously performing longitudinal stretching and transverse stretching at the temperature, wherein the longitudinal stretching magnification is 2.5-6 times, and the transverse stretching magnification is 2.5-6 times; performing heat setting at 110-140 ℃ for 5-30 s; finally, the product is prepared by corona treatment, rolling, curing and slitting.
In some embodiments, preferably, the bi-directional step-and-stretch method may include the following specific method steps:
preheating for 5-30 s at 55-75 ℃, and longitudinally stretching at the temperature, wherein the stretching ratio is 2.5-6 times; preheating for 5-30 s at 95-120 ℃, and performing transverse stretching at the temperature, wherein the stretching ratio is 2.5-6 times; performing heat setting at 110-140 ℃ for 5-30 s;
and S6, carrying out corona treatment, rolling, curing and slitting on the heat-set film to obtain the biodegradable biaxially oriented composite film.
In some embodiments, preferably, the thickness of the first resin layer a may be 5 to 30 μm, and the thickness of the second resin layer B may be 15 to 50 μm, but the embodiment of the disclosure is not limited thereto.
For a better understanding of the present invention, reference will now be made in detail to the following examples taken in conjunction with the accompanying drawings.
Example 1
(1) Preparation of functional masterbatch Y:
uniformly mixing 3 parts of erucamide, 5 parts of silicon dioxide, 1 part of ethoxyamine, 80 parts of polylactic acid and 11 parts of polybutylene succinate in parts by weight, and extruding and granulating at 160-165 ℃ by using a double-screw extruder to obtain a mixture for later use;
(2) preparing a biodegradable biaxially oriented composite film:
referring to fig. 1, a schematic structural view of a biodegradable biaxially oriented laminated film disclosed in embodiment 1 of the present invention includes three layers arranged in sequence, wherein the first resin layer a, the second resin layer B and the first resin layer a are arranged in sequence from top to bottom;
the components of the first resin layer A comprise 77 parts by weight of polylactic acid, 20 parts by weight of poly adipic acid/butylene terephthalate (PBAT) and 3 parts by weight of functional master batch Y;
the second resin layer B comprises 100 parts by weight of polylactic acid.
The thickness of the first resin layer A is 6um, and the thickness of the second resin layer B is 15 um;
the preparation method of the biodegradable biaxially oriented laminated film comprises the following steps:
s1, fully drying the raw materials to below 200ppm, putting the components of the first resin layer A into an auxiliary extruder, putting the components of the second resin layer B into a main extruder, and heating and melting at the temperature of 160-180 ℃;
s2, converging the melts of the auxiliary extruder and the main extruder in a three-layer T-shaped die head, and then extruding to obtain a mixed melt, wherein the temperature of the three-layer T-shaped die head is 190 ℃;
s3, pasting the extruded mixed melt on the surface of a chill roll through an air knife to form a cast sheet, wherein the temperature of the chill roll is 33 ℃;
s4, longitudinally preheating the cast sheet at 60 ℃, longitudinally stretching the cast sheet, wherein the longitudinal stretching magnification is 3.0 times, the longitudinal stretching temperature is 65 ℃, and then entering a 50 ℃ longitudinal stretching and shaping area;
s5, transversely preheating the longitudinally stretched sheet at 90 ℃, transversely stretching the sheet at a transverse stretching ratio of 4 times and a transverse stretching temperature of 105 ℃, and then entering a transverse stretching and shaping zone at 120 ℃;
and S6, carrying out corona treatment, rolling, curing and slitting on the heat-set film to obtain the biodegradable biaxially oriented composite film.
Example 2
(1) Preparation of functional masterbatch Y:
uniformly mixing 3 parts of erucamide, 5 parts of silicon dioxide, 1 part of ethoxyamine, 80 parts of polylactic acid and 11 parts of polybutylene succinate in parts by weight, and extruding and granulating at 160-165 ℃ by using a double-screw extruder to obtain a mixture for later use;
(2) preparing a biodegradable biaxially oriented composite film:
referring to fig. 2, a schematic structural view of a biodegradable biaxially oriented laminated film disclosed in embodiment 2 of the present invention includes two layers sequentially arranged, wherein a first resin layer a and a second resin layer B are sequentially disposed from top to bottom;
the first resin layer A comprises, by weight, 90 parts of polylactic acid, 8 parts of polybutylene succinate (PBS) and 2 parts of functional master batch Y;
the second resin layer B comprises 98 parts of polylactic acid and 2 parts of functional master batch Y in parts by weight.
The thickness of the first resin layer A is 10um, and the thickness of the second resin layer B is 15 um;
the preparation method of the biodegradable biaxially oriented laminated film comprises the following steps:
s1, fully drying the raw materials to below 200ppm, putting the components of the first resin layer A into an auxiliary extruder, putting the components of the second resin layer B into a main extruder, and heating and melting at the temperature of 160-180 ℃;
s2, converging the melts of the auxiliary extruder and the main extruder in a three-layer T-shaped die head, and then extruding to obtain a mixed melt, wherein the temperature of the three-layer T-shaped die head is 190 ℃;
s3, pasting the extruded mixed melt on the surface of a chill roll through an air knife to form a cast sheet, wherein the temperature of the chill roll is 33 ℃;
s4, longitudinally preheating the cast sheet at 60 ℃, longitudinally stretching the cast sheet, wherein the longitudinal stretching magnification is 3.0 times, the longitudinal stretching temperature is 65 ℃, and then entering a 50 ℃ longitudinal stretching and shaping area;
s5, transversely preheating the longitudinally stretched sheet at 90 ℃, transversely stretching the sheet at a transverse stretching ratio of 4 times and a transverse stretching temperature of 110 ℃, and then entering a transverse stretching and shaping zone at 120 ℃;
and S6, carrying out corona treatment, rolling, curing and slitting on the heat-set film to obtain the biodegradable biaxially oriented composite film.
Example 3
(1) Preparation of functional masterbatch Y:
uniformly mixing 3 parts of erucamide, 5 parts of silicon dioxide, 1 part of ethoxyamine, 80 parts of polylactic acid and 11 parts of polybutylene succinate in parts by weight, and extruding and granulating at 160-165 ℃ by using a double-screw extruder to obtain a mixture for later use;
(2) preparing a biodegradable biaxially oriented composite film:
referring to fig. 1, a schematic structural view of a biodegradable biaxially oriented laminated film disclosed in embodiment 3 of the present invention includes three layers arranged in sequence, wherein the first resin layer a, the second resin layer B and the first resin layer a are arranged in sequence from top to bottom;
the components of the first resin layer A comprise 87 parts of polylactic acid, 10 parts of carbon dioxide copolymer (PPC) and 3 parts of functional master batch Y in parts by weight;
the components of the second resin layer B comprise 90 parts of poly (adipic acid)/polybutylene terephthalate (PBAT) and 10 parts of polylactic acid in parts by weight;
the thickness of the first resin layer A is 5um, and the thickness of the second resin layer B is 20 um;
the preparation method of the biodegradable biaxially oriented laminated film comprises the following steps:
s1, fully drying the raw materials to below 200ppm, putting the components of the first resin layer A into an auxiliary extruder, putting the components of the second resin layer B into a main extruder, and heating and melting at the temperature of 150-180 ℃;
s2, converging the melts of the auxiliary extruder and the main extruder in a three-layer T-shaped die head, and then extruding to obtain a mixed melt, wherein the temperature of the three-layer T-shaped die head is 180 ℃;
s3, pasting the extruded mixed melt on the surface of a chill roll through an air knife to form a cast sheet, wherein the temperature of the chill roll is 20 ℃;
s4, performing synchronous biaxial stretching after the cast sheet is stretched and preheated at 90 ℃, wherein the stretching temperature is 100 ℃, the longitudinal and transverse stretching multiplying power is 4.5 x 4.5, and then entering a 115 ℃ shaping area;
and S5, carrying out corona treatment, rolling, curing and slitting on the heat-set film to obtain the biodegradable biaxially oriented composite film.
Example 4
(1) Preparation of functional masterbatch X:
uniformly mixing 8 parts of ethylene bis stearamide, 4 parts of talcum powder, 2 parts of oleamide, 75 parts of polylactic acid and 11 parts of polycaprolactone in parts by weight, and extruding and granulating at 160-165 ℃ through a double-screw extruder to obtain a mixture for later use;
(2) preparing a biodegradable biaxially oriented composite film:
referring to fig. 1, a schematic structural view of a biodegradable biaxially oriented laminated film disclosed in embodiment 4 of the present invention includes three layers arranged in sequence, wherein the first resin layer a, the second resin layer B and the first resin layer a are arranged in sequence from top to bottom;
the first resin layer A comprises 87 parts by weight of polylactic acid, 10 parts by weight of Polycaprolactone (PCL) and 3 parts by weight of functional master batch X;
the second resin layer B comprises, by weight, 95 parts of polybutylene succinate (PBS) and 5 parts of Polycaprolactone (PCL);
the thickness of the first resin layer A is 5um, and the thickness of the second resin layer B is 20 um;
the preparation method of the biodegradable biaxially oriented laminated film comprises the following steps:
s1, fully drying the raw materials to below 200ppm, putting the components of the first resin layer A into an auxiliary extruder, putting the components of the second resin layer B into a main extruder, and heating and melting at the temperature of 150-180 ℃;
s2, converging the melts of the auxiliary extruder and the main extruder in a three-layer T-shaped die head, and then extruding to obtain a mixed melt, wherein the temperature of the three-layer T-shaped die head is 180 ℃;
s3, pasting the extruded mixed melt on the surface of a chill roll through an air knife to form a cast sheet, wherein the temperature of the chill roll is 20 ℃;
s4, carrying out synchronous biaxial stretching on the cast sheet after the cast sheet is stretched and preheated at 105 ℃, wherein the stretching temperature is 120 ℃, the longitudinal and transverse stretching multiplying power is 4.5 x 4.5, and then entering a 120 ℃ shaping area;
and S5, carrying out corona treatment, rolling, curing and slitting on the heat-set film to obtain the biodegradable biaxially oriented composite film.
Comparative example 1
Comparative example 1 is different from example 1 only in the components used for the first resin layer a, and the remaining components, preparation method and film thickness are the same; the components of the first resin layer A comprise 20 parts of poly (adipic acid)/butylene terephthalate (PBAT) and 3 parts of functional master batch Y in parts by weight.
Comparative example 2
Comparative example 2 is different from example 1 only in the components used for the first resin layer a, and the remaining components, preparation method and film thickness are the same; the components of the first resin layer A are 77 parts of polylactic acid and 3 parts of functional master batch Y in parts by weight.
Comparative example 3
Comparative example 3 is different from example 1 only in the components used for the first resin layer a, and the remaining components, preparation method and film thickness are the same; the components of the first resin layer A comprise, by weight, 45 parts of polylactic acid, 52 parts of poly (adipic acid)/polybutylene terephthalate (PBAT) and 3 parts of a functional master batch Y.
Comparative example 4
The difference between the comparative example 4 and the example 3 is that the preparation method of the biodegradable biaxially oriented laminated film is replaced by a film blowing process from biaxial orientation.
Comparative example 5
Comparative example 5 differs from example 2 only in the transverse direction preheating temperature and the transverse direction stretching temperature in step S5, the transverse direction preheating temperature being 80 ℃ and the transverse direction stretching temperature being 85 ℃.
Comparative example 6
Comparative example 6 is different from example 3 only in the stretching preheating temperature and the stretching temperature in step S4, the stretching preheating temperature being 80 c and the stretching temperature being 85 c.
Comparative example 7
Comparative example 7 differs from example 3 only in that the simultaneous biaxial stretching process temperature in step S4 is higher than 120 ℃.
The above examples and comparative examples were subjected to the related item tests as shown in the following table:
TABLE 1 film main performance index detection items and method/Standard Table
| Numbering | Item | Detection method/Standard |
| 1 | Transmittance (2mm) | ASTM D1003 |
| 2 | Haze (2mm) | ASTM D1003 |
| 3 | Glossiness (45 degree) | ASTM D2457 |
| 4 | MD/TD tensile Strength, MPa | ASTM D882 |
The biodegradable biaxially oriented laminated films prepared in the above examples and comparative examples were tested according to the main performance indexes shown in the table, and the results are shown in the following table:
table 2 examples performance test table
It should be noted that the specific parameters or some common reagents in the above embodiments are specific examples or preferred embodiments of the present invention, and are not limited thereto; those skilled in the art can adapt the same within the spirit and scope of the present invention.
Table 3 comparative example performance test table
Table 4 comparative example performance test table
As can be seen from the above table, the embodiment provided by the invention can realize the effects of high light transmittance (more than or equal to 80%), high haze (more than or equal to 80%), and low glossiness (less than or equal to 15%); the biodegradable material is applied to the biaxial stretching technology, so that the application of the biodegradable material in flexible packaging is widened; and the self-extinction of the film is realized through a process and a formula, and the environmental protection characteristic of full biodegradation of the material is ensured.
In addition, it will be appreciated by those skilled in the art that, although there may be many problems with the prior art, each embodiment or aspect of the present invention may be improved only in one or several respects, without necessarily simultaneously solving all the technical problems listed in the prior art or in the background. It will be understood by those skilled in the art that nothing in a claim should be taken as a limitation on that claim.
Although terms such as the first resin layer, the second resin layer, etc. are used more herein, the possibility of using other terms is not excluded. These terms are used merely to more conveniently describe and explain the nature of the present invention; they are to be construed as being without limitation to any additional limitations that may be imposed by the spirit of the present invention; the terms "first," "second," and the like in the description and in the claims, and in the drawings, if any, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A biodegradable biaxially oriented laminated film comprising at least one first resin layer, the first resin layer comprising the following components:
polylactic acid, biodegradable elastomer and functional master batch;
the biodegradable elastomer is selected from at least one of poly (butylene adipate/terephthalate), poly (butylene succinate), poly (adipate/butylene succinate), carbon dioxide copolymer and polycaprolactone;
and the biodegradable biaxially oriented laminated film is formed by coextrusion and biaxially orientation.
2. The biodegradable biaxially oriented laminated film of claim 1, wherein: the first resin layer comprises the following components in parts by weight:
50-95 parts of polylactic acid, 5-45 parts of biodegradable elastomer and 0.5-6 parts of functional master batch.
3. The biodegradable biaxially oriented laminated film of claim 1, further comprising at least one second resin layer;
the second resin layer comprises one or a combination of more of polylactic acid, polybutylene adipate/terephthalate, polybutylene succinate and polycaprolactone.
4. The biodegradable biaxially oriented laminated film according to any one of claims 1 to 3, wherein: the optical purity of the polylactic acid is more than or equal to 95%, and the melting point of the polylactic acid is 155-180 ℃.
5. The biodegradable biaxially oriented laminated film of claim 1, wherein: the functional master batch comprises the following components: slipping agent, anti-caking agent, antistatic agent and master batch matrix resin.
6. The biodegradable biaxially oriented laminated film of claim 1, wherein: the functional master batch comprises the following components in parts by weight: 1-10 parts of a slipping agent, 1-10 parts of an anti-caking agent, 1-5 parts of an antistatic agent and 75-97 parts of a master batch matrix resin.
7. The biodegradable biaxially oriented laminated film according to claim 5 or 6, wherein: the slipping agent is selected from one or more of erucamide, silicone and ethylene bis-stearamide; the master batch matrix resin is selected from one or more of polylactic acid, polybutylene adipate/terephthalate, polybutylene succinate and polycaprolactone.
8. The biodegradable biaxially oriented laminated film according to claim 5 or 6, wherein: the anti-caking agent is selected from one or more of silicon dioxide, talcum powder and calcium carbonate; the antistatic agent is selected from one or more of ethoxyamine and oleamide.
9. A preparation method of a biodegradable biaxially oriented laminated film comprises the following steps:
co-extruding to obtain an unstretched raw material film, wherein the raw material film comprises at least one first resin layer, and the first resin layer comprises the following components:
polylactic acid, biodegradable elastomer and functional master batch;
the biodegradable elastomer is selected from at least one of poly (butylene adipate/terephthalate), poly (butylene succinate), poly (adipate/butylene succinate), carbon dioxide copolymer and polycaprolactone;
and (3) carrying out biaxial stretching on the raw material film.
10. A packaging material comprising the biodegradable biaxially oriented laminated film according to any one of claim 1 to claim 8.
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Application publication date: 20211015 |