CN115368715B - Completely biodegradable self-adhesive film material and preparation method thereof - Google Patents
Completely biodegradable self-adhesive film material and preparation method thereof Download PDFInfo
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- CN115368715B CN115368715B CN202211159019.1A CN202211159019A CN115368715B CN 115368715 B CN115368715 B CN 115368715B CN 202211159019 A CN202211159019 A CN 202211159019A CN 115368715 B CN115368715 B CN 115368715B
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- 239000000463 material Substances 0.000 title claims abstract description 63
- 239000002313 adhesive film Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 239000012530 fluid Substances 0.000 claims abstract description 16
- 230000000149 penetrating effect Effects 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 229920001896 polybutyrate Polymers 0.000 claims abstract 3
- 238000005266 casting Methods 0.000 claims description 21
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 16
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 16
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 11
- 239000011343 solid material Substances 0.000 claims description 11
- -1 acetyl trioctyl citrate Chemical compound 0.000 claims description 10
- 239000008187 granular material Substances 0.000 claims description 10
- 239000012466 permeate Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 150000003505 terpenes Chemical class 0.000 claims description 5
- 235000007586 terpenes Nutrition 0.000 claims description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 241000255789 Bombyx mori Species 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 claims description 3
- IIGMITQLXAGZTL-UHFFFAOYSA-N octyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCCCCC IIGMITQLXAGZTL-UHFFFAOYSA-N 0.000 claims description 3
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 claims description 3
- 125000005456 glyceride group Chemical group 0.000 claims 2
- 230000015556 catabolic process Effects 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 18
- 229920000747 poly(lactic acid) Polymers 0.000 description 14
- 239000004626 polylactic acid Substances 0.000 description 14
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 12
- 229920001610 polycaprolactone Polymers 0.000 description 12
- 239000004632 polycaprolactone Substances 0.000 description 12
- 229920000903 polyhydroxyalkanoate Polymers 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 11
- 229920002367 Polyisobutene Polymers 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000003755 preservative agent Substances 0.000 description 7
- 230000002335 preservative effect Effects 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- 229920000704 biodegradable plastic Polymers 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 238000006065 biodegradation reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009264 composting Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229940049964 oleate Drugs 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- APVVRLGIFCYZHJ-UHFFFAOYSA-N trioctyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CCCCCCCCOC(=O)CC(O)(C(=O)OCCCCCCCC)CC(=O)OCCCCCCCC APVVRLGIFCYZHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- PTIXVVCRANICNC-UHFFFAOYSA-N butane-1,1-diol;hexanedioic acid Chemical compound CCCC(O)O.OC(=O)CCCCC(O)=O PTIXVVCRANICNC-UHFFFAOYSA-N 0.000 description 1
- JYLRDAXYHVFRPW-UHFFFAOYSA-N butane-1,1-diol;terephthalic acid Chemical compound CCCC(O)O.OC(=O)C1=CC=C(C(O)=O)C=C1 JYLRDAXYHVFRPW-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229940040452 linolenate Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2493/00—Characterised by the use of natural resins; Derivatives thereof
- C08J2493/04—Rosin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
Abstract
The invention discloses a completely biodegradable self-adhesive film material and a preparation method thereof, wherein the completely biodegradable self-adhesive film material is prepared from the following components in parts by weight: 70-95 parts of one or more than two of PBAT, PHA, PCL, 0-20 parts of PLA, 1-5 parts of biodegradable penetrating fluid, 1-5 parts of biodegradable tackifying resin and 0.1-2 parts of antioxidant. The self-adhesive film material has good effects on degradation performance, tensile strength and viscosity, can meet the use requirement and is superior to the industry standard.
Description
Technical Field
The invention belongs to the field of high polymer materials, relates to a self-adhesive film material and a preparation method thereof, and in particular relates to a completely biodegradable self-adhesive film material and a preparation method thereof.
Background
The self-adhesive film comprises a winding film, a preservative film, a protective film and the like, is prepared from PE, PP, PVC and other traditional plastics serving as base materials at home and abroad, cannot be biodegraded, can be degraded and eliminated after being abandoned in natural environment within one hundred to hundreds of years after being used, and is one of serious environmental pollution sources. The good adhesion of the self-adhesive film enables the outer surface of the article to be adhered with the packaging film layer so as to fix and wrap the article. The acquisition of the tackiness of the self-adhesive film is mainly carried out in two ways: the first way is to add PIB (polyisobutylene) or its masterbatch to the polymer; another way is to blend EVA (ethylene vinyl acetate copolymer), metallocene polyolefin, etc. The current viscosity acquisition mode is based on PIB addition. However, PIB, EVA and metallocene polyolefin are all non-biodegradable substances, and PIB is affected by temperature and has strong viscosity at high temperature; the adhesive is not too sticky when the air temperature is low, and the viscosity is greatly reduced after the stretching. With the emphasis placed on plastic pollution in various countries around the world, there is a need in the market for an adhesive film material that is completely biodegradable.
Chinese patent No. 202111084268.4 discloses a novel biodegradable wrapping film special material and a preparation method thereof, wherein tackifying resin is one or two of glycerol and polyisobutylene. Glycerol is a plasticizer which is easy to separate out and has no tackifying effect; polyisobutenes are the most commonly used self-adhesive film tackifying resins, but polyisobutenes are olefin polymers and are not biodegradable. In addition, the invention patent can not meet the standards of biodegradable materials in China, the United states, european Union and the like, for example, the requirements of degrading properties and identification of biodegradable plastics and products of Chinese Standard GB/T41010-2021 are not met after more than 1% of polyisobutene is added.
There is currently no fully biodegradable self-adhesive film and material therefor in the market, the most important reason being that no tackifying system capable of fully biodegradation has been found.
Disclosure of Invention
In order to overcome the defects of the prior art, one of the purposes of the invention is to provide a completely biodegradable self-adhesive film material. The film material has good effects on degradation performance, tensile strength and viscosity, can meet the use requirement and is superior to the industry standard.
The second purpose of the invention is to provide a preparation method of the completely biodegradable self-adhesive film material. The film material prepared by the process has good effects on degradation performance, tensile strength and viscosity, can meet the use requirement, is superior to the industry standard, has simple process operation and controllable conditions, and is suitable for industrial large-scale production.
One of the purposes of the invention is realized by adopting the following technical scheme: the completely biodegradable self-adhesive film material is prepared from the following components in parts by weight: 70-95 parts of one or more than two of PBAT, PHA, PCL, 0-20 parts of PLA, 1-5 parts of biodegradable penetrating fluid, 1-5 parts of biodegradable tackifying resin and 0.1-2 parts of antioxidant.
Further, the fully biodegradable self-adhesive film material is prepared from the following components in parts by weight: 80-95 parts of one or more than two of PBAT, PHA, PCL, 3-15 parts of PLA, 2-4 parts of biodegradable penetrating fluid, 2-4 parts of biodegradable tackifying resin and 0.2-1 part of antioxidant.
Further, the biodegradable penetrating fluid is selected from one or more than two of epoxy acetyl linolenate methyl ester, epoxy soybean oil, epoxy silkworm chrysalis butyl oleate, epoxy furfuryl butyl oleate, 9, 10-epoxy octyl stearate, epoxy octyl soyate, acetyl triethyl citrate, trioctyl citrate, tributyl citrate, acetyl tributyl citrate and acetyl trioctyl citrate.
Further, the biodegradable tackifying resin is selected from one or a mixture of more than two of rosin, polymerized rosin, disproportionated rosin, rosin glycol ester, rosin glycerol ester, rosin pentaerythritol ester, terpene resin, polymerized terpene, terpene-styrene resin.
Further, the antioxidant is selected from one or a mixture of more than two of antioxidant 1010, antioxidant 168 and antioxidant 264.
The second purpose of the invention is realized by adopting the following technical scheme: a preparation method of a completely biodegradable self-adhesive film material comprises the following steps:
1) PBAT, PHA, PCL, PLA, biodegradable tackifying resin and antioxidant with the formula amount are added into a high-speed mixer, and the ingredients are mixed to obtain a solid material;
2) Then adding the solid materials mixed in the step 1) into a feeding hopper of a double-screw device for modification; feeding a formula amount of biodegradable permeate from a liquid filling device on the side of the twin-screw device;
3) Controlling the temperature of the double screws, extruding the material in the step 2) through a die head, bracing, cooling, granulating and packaging to obtain granules;
4) And 3) feeding the granules obtained in the step 3) into a casting machine for casting and forming a film to obtain the completely biodegradable self-adhesive film material.
Further, the fully biodegradable self-adhesive film material is prepared from the following components in parts by weight: 70-95 parts of one or more than two of PBAT, PHA, PCL, 0-20 parts of PLA, 1-5 parts of biodegradable penetrating fluid, 1-5 parts of biodegradable tackifying resin and 0.1-2 parts of antioxidant.
Further, in step 1), the mixing speed of the high-speed mixer is 100-600 rpm, and the mixing time is 1-5 minutes.
Further, in step 3), the twin screw temperature is controlled to be 130-180 ℃.
Further, in step 4), the screw of the casting machine is set at 140 to 170 ℃ and the die temperature is raised stepwise at 150 to 170 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the innovation of the invention is to invent a novel biodegradation system, namely the combination of the biodegradable penetrating fluid and the biodegradable tackifying resin. Tackifying resins are commonly used in the adhesive and ink arts to improve the bond strength between the adhesive or ink coating and the substrate, typically at a level of 20% or more in the adhesive or ink. However, the wrapping film, the preservative film and the protective film are required to have lower peel strength and shearing strength to the base material or the base material, so that the proportion of the tackifying resin is obviously reduced, and the mass percent is generally controlled below 5 percent through researches. Meanwhile, the protective film, the preservative film and the winding film are usually stuck in a solid form at normal temperature, and the surface of the film needs to keep viscosity at normal temperature.
Detailed Description
The present invention will be further described with reference to the following specific embodiments, and it should be noted that, on the premise of no conflict, new embodiments may be formed by any combination of the embodiments or technical features described below.
In the present invention, unless otherwise specified, all parts and percentages are by weight, and the equipment, materials, etc. used are commercially available or are conventional in the art. The methods in the following examples are conventional in the art unless otherwise specified.
The completely biodegradable self-adhesive film material is used for producing biodegradable wrap films, preservative films or protective films, and is prepared from the following components in parts by weight: 70-95 parts of PBAT (copolymer of butanediol adipate and butanediol terephthalate), PHA (polyhydroxyalkanoate) and PCL (polycaprolactone), 0-20 parts of PLA (polylactic acid), 1-5 parts of biodegradable penetrating fluid, 1-5 parts of biodegradable tackifying resin and 0.1-2 parts of antioxidant.
As a further embodiment, the fully biodegradable self-adhesive film material is prepared from the following components in parts by weight: 80-95 parts of one or more than two of PBAT, PHA, PCL, 3-15 parts of PLA, 2-4 parts of biodegradable penetrating fluid, 2-4 parts of biodegradable tackifying resin and 0.2-1 part of antioxidant.
The selected biodegradable materials of the invention, namely PBAT (polybutylene adipate/terephthalate), PHA (polyhydroxyalkanoate) and PCL (polycaprolactone), are all commercial soft biodegradable plastics, and are suitable for film application. However, due to the different tensile strength, aging speed and heat resistance of the materials, the three plastics are reasonably selected or combined according to the difference of application requirements. And PLA (polylactic acid) is hard biodegradable plastic, the tensile strength of the PLA (polylactic acid) is obviously higher than that of PBAT, PHA and PCL, and the addition of a certain proportion of PLA is beneficial to improving the tensile strength of the self-adhesive biodegradable film.
The innovation of the invention is to invent a novel biodegradation system, namely the combination of the biodegradable penetrating fluid and the biodegradable tackifying resin. Tackifying resins are commonly used in the adhesive and ink arts to improve the bond strength between the adhesive or ink coating and the substrate, typically at a level of 20% or more in the adhesive or ink. However, the wrapping film, the preservative film and the protective film are required to have lower peel strength and shearing strength to the base material or the base material, so that the proportion of the tackifying resin is obviously reduced, and the mass percent is generally controlled below 5 percent through researches. Meanwhile, the protective film, the preservative film and the winding film are usually stuck in a solid form at normal temperature, and the surface of the film needs to keep viscosity at normal temperature.
As a further embodiment, the biodegradable permeate is selected from one or a mixture of two or more of methyl epoxy acetyllinoleate, epoxidized soybean oil, epoxidized butyl silkworm oleate, epoxidized butyl furfuryl oleate, 9, 10-epoxy octyl stearate, epoxidized octyl soyate, acetyl triethyl citrate, trioctyl citrate, tributyl citrate, acetyl tributyl citrate, and acetyl trioctyl citrate.
As a further embodiment, the biodegradable tackifying resin is selected from one or a mixture of two or more of rosin, polymerized rosin, disproportionated rosin, ethylene glycol rosin ester, glycerol rosin ester, pentaerythritol rosin ester, terpene resin, polymerized terpene, terpene-styrene resin.
As a further embodiment, the antioxidant is selected from one or a mixture of two or more of antioxidant 1010, antioxidant 168 and antioxidant 264.
The preparation method of the completely biodegradable self-adhesive film material comprises the following steps:
1) PBAT, PHA, PCL, PLA, biodegradable tackifying resin and antioxidant with the formula amount are added into a high-speed mixer, and the ingredients are mixed to obtain a solid material;
2) Then adding the solid materials mixed in the step 1) into a feeding hopper of a double-screw device for modification; the formula amount of biodegradable penetrating fluid is fed from the liquid filling equipment at the side of the double-screw equipment, so that all materials are mixed more uniformly;
3) Controlling the temperature of the double screws, extruding the material in the step 2) through a die head, bracing, cooling, granulating and packaging to obtain granules;
4) And 3) feeding the granules obtained in the step 3) into a casting machine for casting and forming a film to obtain the completely biodegradable self-adhesive film material.
As a further embodiment, in step 1), the mixing speed of the high-speed mixer is 100-600 revolutions per minute and the mixing time is 1-5 minutes.
As a further embodiment, in step 3), the twin screw temperature is controlled to be 130-180 ℃. The biodegradable material thermally degrades rapidly at high temperatures, so the twin screw temperature must be controlled not to be too high to reduce thermal degradation of the material.
As a further embodiment, in step 4), the screw of the casting machine is set at 140-170 ℃ and the die temperature is raised stepwise from 150-170 ℃. The pellets specific for self-adhesive films can be melted well in this temperature range and maintain a suitable melt strength to stably produce films of uniform thickness. The temperature is too low, the material can not be melted completely, the film preparation is uneven, and crystal points are separated out; the problems of thermal degradation of materials, excessive retraction of the two ends of the film towards the middle, insufficient film thickness and the like in the casting process can occur when the temperature is too high.
The following are specific examples of the present invention, in which raw materials, equipment, etc. used are available in a purchase manner except for specific limitations.
Examples 1 to 5 and comparative examples 1 to 4 (formulation comparison)
The raw materials are weighed according to the proportion in the following table 1 respectively, and the fully biodegradable self-adhesive film material is prepared according to the preparation method after the table 1, so that the self-adhesive films of different embodiments are correspondingly obtained, and the specific details are shown in the table 1:
TABLE 1 raw material ratios of examples 1-5 and comparative examples 1-4
The preparation method of the self-adhesive film materials of examples 1-5 and comparative examples 1-4 comprises the following steps:
1) PBAT, PHA, PCL, PLA, biodegradable tackifying resin and antioxidant with the formula amounts shown in Table 1 are added into a high-speed mixer, and all solid materials are mixed for 1-5 minutes at the speed of 100-600 rpm, so that solid materials are obtained;
2) Then adding the solid materials mixed in the step 1) into a feeding hopper of a double-screw device for modification; feeding a formula amount of biodegradable permeate from a liquid filling device on the side of the twin-screw device;
3) Controlling the temperature of the twin screw to be 130-180 ℃, extruding the material in the step 2) through a die head, bracing, cooling, granulating and packaging to obtain granules;
4) And 3) feeding the granules obtained in the step 3) into a casting machine for casting to form a film, wherein the screw of the casting machine is set at 140-170 ℃, the temperature of a die head is gradually increased to 150-170 ℃, and the completely biodegradable self-adhesive film material is obtained.
Comparative examples 5 to 6 (Process alignment)
Comparative example 5
In the process for preparing the self-adhesive film of example 5, the conditions of step 3) are that the temperature of the twin screw is controlled to be 120-170 ℃, the conditions of step 4) are that the screw of the casting machine is set to be 130-165 ℃ and the temperature of the die head is increased gradually to be 145 ℃, and the other steps and conditions are basically the same as those of the used reagent formulation of example 5.
Comparative example 6
In the process for preparing the self-adhesive film of example 5, the conditions of step 3) are that the temperature of the twin screw is controlled to 140-190 ℃, the conditions of step 4) are that the screw of the casting machine is set to 150-185 ℃ and the temperature of the die head is gradually increased to 180 ℃, and the other steps and conditions are basically the same as those of the formula of the used reagent of example 5.
Comparative example 7 (PE wound film currently commercially available)
Comparative example 7 self-adhesive film was purchased from PE wrapping film sold by new country city, zheng packaging materials limited.
Effect evaluation and Performance detection
1. Core properties of the self-adhesive film materials of examples 1 to 5 and comparative examples 1 to 7 were examined, and the examination items and results are shown in Table 1. In table 1, test methods of properties such as crystal point, film thickness, longitudinal breaking force, transverse breaking force, longitudinal breaking elongation, transverse breaking elongation, longitudinal tackiness, and transverse tackiness are specified in "stretch wrap film for transport packaging BB/T0024-2018". The method for testing the biodegradability is described in GB/T19277.1-2011: determination of the final aerobic biological decomposition and disintegration capability of materials under controlled composting conditions the method of determining carbon dioxide released was carried out using the general method described in section 1. The standard for biodegradation is according to GB/T41010-2021: biodegradable plastics and products degradation performance and identification requirements.
Table 2 shows the performance test data for the respective adhesive film materials
As can be seen from the above table, the present invention is capable of producing a fully biodegradable self-adhesive film material, and according to the processing technology required by the present invention, a self-adhesive film meeting the standards can be produced, which can be used as a wrapping film, a preservative film or a protective film, and wherein the biodegradable permeate and the biodegradable tackifying resin are added simultaneously, essentially. The test indicators of examples 1-5 all met the requirements of the product standard and were comparable or better than the data of comparative example 7 (commercially available PE wound film). Example 5 is the preferred embodiment, resulting in a reinforced self-adhesive film with significantly improved film adhesion, significantly improved stretch-break, and a somewhat reduced elongation at break, but still above standard. The formulation of the self-adhesive film of comparative example 1 was different from that of example 5 in that the biodegradable tackifying resin was retained but the biodegradable permeate was removed, and the film viscosity was far from the standard. The formulation of the self-adhesive film of comparative example 2 was different from that of example 5 in that the biodegradable permeate was retained but the biodegradable tackifying resin was removed, and the tackiness of the film was also remarkably inferior to the standard. The comparison effect of comparative examples 1-2 shows that the biodegradable tackifying resin and the biodegradable penetrating fluid have complementary effects on the viscosity performance of the film, but the viscosity of the film can be influenced, and the combination of the biodegradable tackifying resin and the biodegradable penetrating fluid can generate an effect of obviously improving the viscosity of the film.
Compared with example 5, the formulation of the self-adhesive film in comparative example 3 is different in the types of biodegradable penetrating fluid and biodegradable tackifying resin, and the DBP penetrating fluid and the terpene-styrene tackifying resin are both partially biodegradable materials, and although the indexes such as breaking strength, elongation, self-adhesive property and the like of the final film meet the requirements, the film can not meet the requirement that the relative biological decomposition rate exceeds 90% within 180 days under the controllable composting condition, and can not be considered to meet the biological degradation standard.
Compared with example 5, the formula of the self-adhesive film of comparative example 4 is different in that paraffin oil replaces the biodegradable permeate liquid epoxy soybean oil, dicyclopentadiene petroleum resin replaces the biodegradable tackifying resin rosin pentaerythritol ester, the biodegradability of the film is reduced, paraffin oil and dicyclopentadiene petroleum resin are non-degradable components, and the addition amount of each component exceeds 1%, which violates national standard GB/T41010-2021: the requirement that the absolute biodegradation rate of a single organic component with the component more than or equal to 1% in the material in the degradation performance and product identification requirements of biodegradable plastics is more than or equal to 60% is determined that the biodegradable plastics cannot be biodegraded. Comparative examples 5-6 have the same formulation as example 5, except that the process parameters are adjusted, and comparative example 5 lowers the processing temperature of the materials and films (including the step 2 pelletization screw temperature, the step 4 casting screw temperature, the casting die temperature), resulting in defects such as crystallization points of the films and substandard elongation at break. Comparative example 6 increased the processing temperature of the material and film (including step 2 pelleting screw temperature, step 4 casting screw temperature, casting die temperature), resulting in a decrease in the longitudinal breaking force of the film, which only just exceeded the standard, and the film product quality fluctuated and produced a risk of substandard.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (8)
1. The completely biodegradable self-adhesive film material is characterized by being prepared from the following components in parts by weight: 80.8-95 parts of PBAT, 3-15 parts of PLA, 2-4 parts of biodegradable penetrating fluid, 2-4 parts of biodegradable tackifying resin and 0.2-1 part of antioxidant;
the biodegradable penetrating fluid is selected from one or more than two of epoxidized soybean oil, 9, 10-epoxy octyl stearate, acetyl trioctyl citrate and acetyl triethyl citrate;
the biodegradable tackifying resin is selected from one or more of rosin glyceride, rosin pentaerythritol ester and terpene resin.
2. The fully biodegradable self-adhesive film material according to claim 1, wherein said antioxidant is selected from one or a mixture of two or more of antioxidant 1010, antioxidant 168, antioxidant 264.
3. The completely biodegradable self-adhesive film material is characterized by being prepared from the following components in parts by weight: 85 parts of PHA, 6 parts of PCL, 3 parts of PLA, 3 parts of epoxy silkworm chrysalis butyl oleate, 2.8 parts of rosin glyceride and 0.2 part of antioxidant 1010.
4. A method of preparing a fully biodegradable self-adhesive film material according to claim 1, comprising the steps of:
1) Adding the PBAT, PLA, biodegradable tackifying resin and antioxidant with the formula amount into a high-speed mixer, and mixing the ingredients to obtain a solid material;
2) Then adding the solid materials mixed in the step 1) into a feeding hopper of a double-screw device for modification; feeding a formula amount of biodegradable permeate from a liquid filling device on the side of the twin-screw device;
3) Controlling the temperature of the double screws, extruding the material in the step 2) through a die head, bracing, cooling, granulating and packaging to obtain granules;
4) And 3) feeding the granules obtained in the step 3) into a casting machine for casting and forming a film to obtain the completely biodegradable self-adhesive film material.
5. A method of preparing a fully biodegradable self-adhesive film material according to claim 3, comprising the steps of:
1) PHA, PCL, PLA, biodegradable tackifying resin and antioxidant with the formula amount are added into a high-speed mixer, and the ingredients are mixed to obtain a solid material;
2) Then adding the solid materials mixed in the step 1) into a feeding hopper of a double-screw device for modification; feeding a formula amount of biodegradable permeate from a liquid filling device on the side of the twin-screw device;
3) Controlling the temperature of the double screws, extruding the material in the step 2) through a die head, bracing, cooling, granulating and packaging to obtain granules;
4) And 3) feeding the granules obtained in the step 3) into a casting machine for casting and forming a film to obtain the completely biodegradable self-adhesive film material.
6. The method for producing a completely biodegradable self-adhesive film material according to claim 4 or 5, wherein in the step 1), the mixing speed of the high-speed mixer is 100 to 600 rpm and the mixing time is 1 to 5 minutes.
7. The method for producing a completely biodegradable self-adhesive film material according to claim 4 or 5, wherein in step 3), the twin screw is controlled to a temperature of 130 to 180 ℃.
8. The method for producing a completely biodegradable self-adhesive film material according to claim 4 or 5, wherein in step 4), the screw of the casting machine is set at 140 to 170 ℃ and the die temperature is raised stepwise at 150 to 170 ℃.
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