CN115368715A - 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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- CN115368715A CN115368715A CN202211159019.1A CN202211159019A CN115368715A CN 115368715 A CN115368715 A CN 115368715A CN 202211159019 A CN202211159019 A CN 202211159019A CN 115368715 A CN115368715 A CN 115368715A
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- biodegradable
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- adhesive film
- film material
- self
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- 239000000463 material Substances 0.000 title claims abstract description 65
- 239000002313 adhesive film Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 42
- 239000011347 resin Substances 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000012530 fluid Substances 0.000 claims abstract description 21
- 230000000149 penetrating effect Effects 0.000 claims abstract description 21
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 229920001896 polybutyrate Polymers 0.000 claims abstract 5
- 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 19
- 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 19
- 238000005266 casting Methods 0.000 claims description 19
- 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 19
- 239000004593 Epoxy Substances 0.000 claims description 18
- -1 octyl ester Chemical class 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000008187 granular material Substances 0.000 claims description 9
- 239000011343 solid material Substances 0.000 claims description 9
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 6
- 150000003505 terpenes Chemical class 0.000 claims description 6
- 235000007586 terpenes Nutrition 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 239000003549 soybean oil Substances 0.000 claims description 5
- 235000012424 soybean oil Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 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
- 241000382353 Pupa Species 0.000 claims description 3
- 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 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- IIGMITQLXAGZTL-UHFFFAOYSA-N octyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCCCCC IIGMITQLXAGZTL-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 4
- 239000003921 oil Substances 0.000 claims 2
- 235000019198 oils Nutrition 0.000 claims 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 2
- PESZCXUNMKAYME-UHFFFAOYSA-N Citroflex A-4 Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)C(C(C)=O)C(=O)OCCCC PESZCXUNMKAYME-UHFFFAOYSA-N 0.000 claims 1
- 239000000944 linseed oil Substances 0.000 claims 1
- 235000021388 linseed oil Nutrition 0.000 claims 1
- WBBUYACCVIYKCV-UHFFFAOYSA-N triethyl 2-hydroxy-4-oxopentane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)C(C(C)=O)C(=O)OCC WBBUYACCVIYKCV-UHFFFAOYSA-N 0.000 claims 1
- LNYCJZRLMAMTQW-UHFFFAOYSA-N trioctyl 2-hydroxy-4-oxopentane-1,2,3-tricarboxylate Chemical compound CCCCCCCCOC(=O)CC(O)(C(=O)OCCCCCCCC)C(C(C)=O)C(=O)OCCCCCCCC LNYCJZRLMAMTQW-UHFFFAOYSA-N 0.000 claims 1
- 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 6
- 239000010408 film Substances 0.000 description 54
- 230000000052 comparative effect Effects 0.000 description 18
- 229920000747 poly(lactic acid) Polymers 0.000 description 13
- 239000004626 polylactic acid Substances 0.000 description 13
- 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
- 239000000853 adhesive Substances 0.000 description 9
- 229920002367 Polyisobutene Polymers 0.000 description 8
- 238000004804 winding Methods 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 7
- 238000006065 biodegradation reaction Methods 0.000 description 7
- 238000009472 formulation Methods 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
- 239000000976 ink Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 4
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 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
- 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
- 244000068988 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- 240000006240 Linum usitatissimum Species 0.000 description 2
- 235000004431 Linum usitatissimum Nutrition 0.000 description 2
- 239000005662 Paraffin oil Substances 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
- 235000004426 flaxseed Nutrition 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QTDSLDJPJJBBLE-PFONDFGASA-N octyl (z)-octadec-9-enoate Chemical compound CCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC QTDSLDJPJJBBLE-PFONDFGASA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000011160 research 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
- 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 description 2
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000209 biodegradability test Toxicity 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 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
- 125000005456 glyceride group Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 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
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 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
- 230000000717 retained effect Effects 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
- 239000010409 thin film Substances 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 a mixture of more than two of PBAT, PHA and 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 disclosed by the invention has good effects on degradation performance, tensile strength and viscosity, can meet the use requirements, and is superior to the industrial 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 particularly 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 made of traditional plastics such as PE, PP, PVC and the like at home and abroad, cannot be biodegraded, can be degraded and lost after being discarded into a natural environment after being used, and is one of serious sources of environmental pollution. The good viscosity 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. Self-adhesive films acquire their tackiness in two main ways: the first way is to add PIB (polyisobutylene) or its mother material to the high polymer; another way is to blend EVA (ethylene vinyl acetate), metallocene polyolefins, etc. Currently, the viscosity acquisition mode is mainly based on the addition of PIB. However, PIB, EVA and metallocene polyolefin are all non-biodegradable substances, and the PIB is influenced by temperature and has strong viscosity when the temperature is high; the adhesive is not too sticky at low temperature, and the viscosity is greatly reduced after stretching. With the attention of various countries around the world on the plastic pollution problem, a completely biodegradable adhesive film material is urgently needed in the market.
Chinese patent CN202111084268.4 discloses a novel biodegradable material special for a winding film and a preparation method thereof, wherein tackifying resin is selected from one or two of glycerol and polyisobutylene. The glycerol is a plasticizer which is easy to separate out, and has no tackifying effect; polyisobutylene is the most commonly used self-adhesive thin film tackifying resin, but is an olefin polymer and is not biodegradable. In addition, the invention has the advantage that the overall formula of the invention can not meet the standards of biodegradable materials in China, america, european Union and the like after more than 1% of polyisobutylene is added, for example, the invention can not meet the requirements of China standard GB/T41010-2021 on the degradation performance and identification of biodegradable plastics and products.
At present, no completely biodegradable self-adhesive film and material thereof exist in the market, and the most important reason is that no tackifying system capable of being completely biodegraded is found.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, one of the objects of the present invention is to provide a completely biodegradable self-adhesive film material. The film material of the invention has good effects on degradation performance, tensile strength and viscosity, can meet the use requirements, and is superior to the industrial standard.
The invention also aims 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 requirements, is superior to the industrial standard, is simple in process operation and controllable in conditions, and is suitable for industrial large-scale production.
One of the purposes of the invention is realized by adopting the following technical scheme: a completely biodegradable self-adhesive film material is prepared from the following components in parts by weight: 70-95 parts of one or a mixture of more than two of PBAT, PHA and 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 completely biodegradable self-adhesive film material is prepared from the following components in parts by weight: 80-95 parts of one or a mixture of more than two of PBAT, PHA and 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 one or a mixture of more than two of epoxy acetyl linseed methyl oleate, epoxy soybean oil, epoxy silkworm pupa butyl oleate, epoxy bran butyl oleate, 9, 10-epoxy octyl stearate, epoxy soybean octyl oleate, 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 glyceride, rosin pentaerythritol ester, terpene resin, polymerized terpene and 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) Adding PBAT, PHA, PCL, PLA, biodegradable tackifying resin and antioxidant in a formula ratio into a high-speed mixer, and mixing the ingredients to obtain a solid material;
2) Then adding the solid material mixed in the step 1) into a feeding hopper of a double-screw device for modification; feeding the biodegradable penetrating fluid with the formula amount from a liquid filling device on the side surface of the double-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) Feeding the granules obtained in the step 3) into a casting machine for casting to form a film, and obtaining the completely biodegradable self-adhesive film material.
Further, the completely biodegradable self-adhesive film material is prepared from the following components in parts by weight: 70-95 parts of one or a mixture of more than two of PBAT, PHA and 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 the 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 temperature of the twin screw is controlled to 130 to 180 ℃.
Further, in step 4), the screw of the casting machine is set at 140 to 170 ℃ and is gradually increased, and the die temperature is 150 to 170 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the invention is characterized in that a brand-new biodegradation system is invented, namely the combination of biodegradable penetrating fluid and biodegradable tackifying resin. Tackifying resins are commonly used in the field of adhesives and inks for improving the bonding strength between an adhesive or ink coating and a substrate, and are generally added in an amount of 20% or more in the adhesive or ink. However, the peeling strength and shear strength of the wrapping film, the preservative film and the protective film to the base material or the base material are required to be relatively low, so that the proportion of the tackifying resin is remarkably reduced, and the weight percentage is generally controlled to be less than 5% through research. Meanwhile, the protective film, the preservative film and the winding film are usually adhered 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 is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.
In the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
A completely biodegradable self-adhesive film material is used for producing a biodegradable winding film, a preservative film or a protective film 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), one or a mixture of more than two of 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 completely biodegradable self-adhesive film material is prepared from the following components in parts by weight: 80-95 parts of one or a mixture of more than two of PBAT, PHA and 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 biodegradable materials PBAT (poly (butylene adipate/terephthalate)), PHA (polyhydroxyalkanoate) and PCL (polycaprolactone) selected by the invention are all commercialized soft biodegradable plastics and are suitable for film application. However, due to the differences in tensile strength, aging rate and heat resistance of the above materials, the three plastics are selected or combined reasonably according to the difference in application requirements. PLA (polylactic acid) is hard biodegradable plastic, the tensile strength of the PLA is obviously higher than that of PBAT, PHA and PCL, and the addition of a certain proportion of PLA is helpful for improving the tensile strength of the self-adhesive biodegradable film.
The invention is characterized in that a brand new biodegradation system is invented, namely the combination of biodegradable penetrating fluid and biodegradable tackifying resin. Tackifying resins are commonly used in the field of adhesives and inks for improving the bonding strength between an adhesive or an ink coating and a substrate, and the addition ratio of tackifying resins in adhesives or inks is generally more than 20%. However, the peeling strength and shear strength of the wrapping film, the preservative film and the protective film to the base material or the base material are required to be lower, so that the proportion of the tackifying resin is obviously reduced, and the mass percentage is generally controlled to be less than 5% through research. Meanwhile, the protective film, the preservative film and the winding film are usually adhered 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 penetrant is selected from one or a mixture of two or more of epoxy acetyl linseed methyl ester, epoxy soybean oil, epoxy silkworm pupa butyl oleate, epoxy bran butyl oleate, 9, 10-epoxy octyl stearate, epoxy soybean octyl oleate, acetyl triethyl citrate, trioctyl citrate, tributyl citrate, acetyl tributyl citrate, and acetyl trioctyl citrate.
In a further embodiment, the biodegradable tackifying resin is selected from one or a mixture of two or more of rosin, polymerized rosin, disproportionated rosin, rosin ethylene glycol ester, rosin glycerol ester, rosin pentaerythritol ester, terpene resin, polymerized terpene, terpene-styrene resin.
In 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) Adding PBAT, PHA, PCL, PLA, biodegradable tackifying resin and antioxidant in a formula ratio into a high-speed mixer, and mixing the ingredients to obtain a solid material;
2) Then adding the solid material mixed in the step 1) into a feeding hopper of a double-screw device for modification; feeding the biodegradable penetrating fluid with the formula amount from a liquid filling device on the side surface of the double-screw device, so that all materials are mixed more uniformly;
3) Controlling the temperature of the double screws, and stretching, cooling, granulating and packaging the material obtained in the step 2) after the material is extruded by a die head to obtain granules;
4) Feeding the granules obtained in the step 3) into a casting machine for casting to form a film, and obtaining the completely biodegradable self-adhesive film material.
As a further embodiment, in step 1), the mixing speed of the high-speed mixer is from 100 to 600 revolutions per minute and the mixing time is from 1 to 5 minutes.
As a further embodiment, in step 3), the temperature of the twin screws is controlled to be 130-180 ℃. The biodegradable material can be quickly degraded at high temperature, so the temperature of the twin screw must be controlled not to be too high so as to reduce the thermal degradation of the material.
As a further embodiment, in step 4), the screw of the casting machine is set at 140 to 170 ℃ and is gradually raised, with a die temperature of 150 to 170 ℃. In this temperature range, the special granules for self-adhesive film can be well melted and maintain proper melt strength to stably prepare film with uniform thickness. The material can not be completely melted at a too low temperature, the film is not uniformly prepared, and crystal points are separated out; when the temperature is too high, the problems of thermal degradation of the material, too much retraction of the two ends of the film to the middle, insufficient film thickness, etc. can occur during the casting process.
The following are specific examples of the present invention, and raw materials, equipments and the like used in the following examples can be obtained by purchasing them unless otherwise specified.
Examples 1-5 and comparative examples 1-4 (formulation comparison)
The raw materials are weighed according to the mixture ratio in the following table 1, the completely biodegradable self-adhesive film material is prepared according to the preparation method shown in the table 1, and the self-adhesive films of different embodiments are correspondingly obtained, and the details are shown in the table 1:
TABLE 1 raw material proportioning tables for examples 1 to 5 and comparative examples 1 to 4
Examples 1 to 5 and comparative examples 1 to 4, comprising the following steps:
1) Adding PBAT, PHA, PCL, PLA, biodegradable tackifying resin and antioxidant with the formula amount shown in the table 1 into a high-speed mixer, and mixing all solid materials at the speed of 100-600 r/min for 1-5 min to obtain solid materials;
2) Then adding the solid material mixed in the step 1) into a feeding hopper of a double-screw device for modification; feeding the biodegradable penetrating fluid with the formula amount from a liquid filling device on the side surface of the double-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) Feeding the granules obtained in the step 3) into a casting machine for casting to form a film, wherein a screw of the casting machine is set at 140-170 ℃, the screw is gradually raised, and the die head temperature is 150-170 ℃, so that the completely biodegradable self-adhesive film material is obtained.
Comparative examples 5 to 6 (Process comparison)
Comparative example 5
In the process for preparing the self-adhesive film of example 5, the conditions of step 3) were such that the twin-screw temperature was controlled to 120 to 170 ℃ and the conditions of step 4) were such that the screw of the casting machine was set at 130 to 165 ℃ and was gradually raised, the die temperature was 145 ℃, and the remaining steps, conditions and the formulation of the reagents used were substantially the same as those of example 5.
Comparative example 6
In the process for preparing the self-adhesive film of example 5, the conditions of step 3) were such that the twin-screw temperature was controlled to be 140 to 190 ℃ and the conditions of step 4) were such that the screw of the casting machine was set at 150 to 185 ℃ and the die temperature was increased stepwise to 180 ℃, and the remaining steps and conditions were substantially the same as those of example 5 in the formulation of the reagents used.
Comparative example 7 (existing commercially available PE winding film)
Comparative example 7 self-adhesive film was purchased from PE wrap film sold by zhengxing packaging materials ltd.
Effect evaluation and Performance detection
1. The 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, the crystal point, the film thickness, the longitudinal breaking force, the transverse breaking force, the longitudinal elongation at break, the transverse elongation at break, the longitudinal viscosity, the transverse viscosity and other performance test methods are specified according to the tensile winding film BB/T0024-2018 for transport packaging. The biodegradability test method is referred to GB/T19277.1-2011: determination of the final aerobic biological decomposition and disintegration capacity of a material under controlled composting conditions "was carried out using the method for determining the carbon dioxide released, the general method in section 1. The standard of biodegradation is according to GB/T41010-2021: the degradation performance of the biodegradable plastic and the product and the marking requirement.
Table 2 shows the respective adhesive film material property test data
As can be seen from the above table, the present invention can produce a completely biodegradable self-adhesive film material, and the processing technology required by the present invention can produce a self-adhesive film meeting the standard, which can be used as a winding film, a preservative film or a protective film, and wherein the biodegradable penetrant and the biodegradable tackifying resin are added at the same time, which is indispensable. The test indexes of examples 1-5 all meet the requirements of product standards and are comparable or better than the data of comparative example 7 (a commercial PE wrap film). Example 5 is the best mode of execution, and the reinforced self-adhesive film is obtained, the viscosity of the film is obviously improved, the tensile strength is obviously improved, and the elongation at break is reduced but still above the standard. The formulation difference of the self-adhesive film of comparative example 1 compared to example 5 is that the adhesion of the film is far from standard, retaining the biodegradable tackifying resin but removing the biodegradable permeate. Compared with example 5, the formulation difference of the self-adhesive film of comparative example 2 is that the biodegradable penetrating fluid is retained but the biodegradable tackifying resin is removed, and the viscosity of the film obviously does not meet the standard requirement. The comparison results of the comparative examples 1-2 show that the biodegradable tackifying resin and the biodegradable penetrating fluid play complementary roles in the viscosity performance of the film, and the viscosity of the film is influenced by the lack of the biodegradable tackifying resin and the biodegradable penetrating fluid, so that the effect of remarkably improving the viscosity of the film can be generated by combining the biodegradable tackifying resin and the biodegradable penetrating fluid.
Compared with example 5, the formulation difference of the self-adhesive film of comparative example 3 is that the types of biodegradable penetrant and biodegradable tackifying resin are different, the selected DBP penetrant and terpene-styrene tackifying resin are partially biodegradable materials, and although the indexes of the final film, such as tensile strength, elongation and self-adhesion, meet the requirements, the film can not reach the requirement that the relative biodegradation rate exceeds 90% within 180 days under the controllable composting condition and is determined not to meet the biodegradation standard.
Compared with the example 5, the formula difference of the self-adhesive film of the comparative example 4 is that the paraffin oil replaces the biodegradable penetrating fluid epoxidized soybean oil, and the dicyclopentadiene petroleum resin replaces the biodegradable tackifying resin rosin pentaerythritol ester, so that the biodegradation performance of the film is reduced, and the paraffin oil and the dicyclopentadiene petroleum resin are both non-degradable components, and the addition amount of each is more than 1 percent, which violates the national standard GB/T41010-2021: in the specification of ' the absolute biodegradation rate of a single organic component with the component of more than or equal to 1% in a material is more than or equal to 60% ' in the degradation performance and identification requirements of biodegradable plastics and products ', the biodegradable plastic cannot be biodegraded. Comparative examples 5-6 are the same as example 5 in the formulation of self-adhesive films, with the difference that the process parameters are adjusted, and comparative example 5 reduces the processing temperature of the material and the film (including step 2 granulation screw temperature, step 4 casting screw temperature, casting die temperature), resulting in the film having defects such as crystalline points and not reaching the elongation at break. Comparative example 6 increases the processing temperature of the material and film (including the granulation screw temperature of step 2, the casting screw temperature of step 4, the casting die temperature), resulting in a decrease in the longitudinal breaking force of the film, just exceeding the standard, and a risk of failure to meet standards when the quality of the film product fluctuates.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (10)
1. The completely biodegradable self-adhesive film material is characterized by being prepared from the following components in parts by weight: 70-95 parts of one or a mixture of more than two of PBAT, PHA and 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.
2. The completely biodegradable self-adhesive film material according to claim 1, which is prepared from the following components in parts by weight: 80-95 parts of one or a mixture of more than two of PBAT, PHA and 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.
3. The completely biodegradable self-adhesive film material according to claim 1 or 2, wherein the biodegradable penetrant is selected from one or a mixture of two or more of epoxy acetyl linseed oil acid methyl ester, epoxy soybean oil, epoxy silkworm pupa oil acid butyl ester, epoxy bran oil acid butyl ester, 9, 10-epoxy octyl stearate, epoxy soybean oil acid octyl ester, acetyl citric acid triethyl ester, citric acid trioctyl ester, citric acid tributyl ester, acetyl citric acid tributyl ester, and acetyl citric acid trioctyl ester.
4. A fully biodegradable self-adhesive film material according to claim 1 or 2, wherein said biodegradable tackifying resin is selected from one or a mixture of two or more of rosin, polymerized rosin, disproportionated rosin, rosin glycol ester, rosin glycerol ester, rosin pentaerythritol ester, terpene resin, polymerized terpene, terpene-styrene resin.
5. The fully biodegradable self-adhesive film material according to claim 1 or 2, wherein the antioxidant is selected from one or a mixture of two or more of antioxidant 1010, antioxidant 168 and antioxidant 264.
6. A preparation method of a completely biodegradable self-adhesive film material is characterized by comprising the following steps:
1) Adding PBAT, PHA, PCL, PLA, biodegradable tackifying resin and antioxidant in a formula ratio into a high-speed mixer, and mixing the ingredients to obtain a solid material;
2) Then adding the solid material mixed in the step 1) into a feeding hopper of a double-screw device for modification; feeding the biodegradable penetrating fluid with the formula amount from a liquid filling device on the side surface of the double-screw device;
3) Controlling the temperature of the double screws, and stretching, cooling, granulating and packaging the material obtained in the step 2) after the material is extruded by a die head to obtain granules;
4) Feeding the granules obtained in the step 3) into a casting machine for casting to form a film, and obtaining the completely biodegradable self-adhesive film material.
7. The method for preparing the fully biodegradable self-adhesive film material according to claim 6, wherein the fully biodegradable self-adhesive film material is prepared from the following components in parts by weight: 70-95 parts of one or a mixture of more than two of PBAT, PHA and 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.
8. The process for the preparation of fully biodegradable self-adhesive film material according to claim 6, wherein in step 1), the mixing speed of the high-speed mixer is 100-600 rpm and the mixing time is 1-5 minutes.
9. The process for the preparation of fully biodegradable self-adhesive film material according to claim 6, wherein in step 3) the twin screws are controlled at a temperature of 130-180 ℃.
10. Process for the preparation of fully biodegradable self-adhesive film material according to claim 6, characterized in that in step 4) the screw of the casting machine is set at 140-170 ℃ and is gradually raised with a die temperature of 150-170 ℃.
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