CN113993949A - Resin composition for heat shrinkable film and heat shrinkable film using same - Google Patents
Resin composition for heat shrinkable film and heat shrinkable film using same Download PDFInfo
- Publication number
- CN113993949A CN113993949A CN202080044281.4A CN202080044281A CN113993949A CN 113993949 A CN113993949 A CN 113993949A CN 202080044281 A CN202080044281 A CN 202080044281A CN 113993949 A CN113993949 A CN 113993949A
- Authority
- CN
- China
- Prior art keywords
- shrinkable film
- resin composition
- film
- heat shrinkable
- heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920006257 Heat-shrinkable film Polymers 0.000 title claims abstract description 94
- 239000011342 resin composition Substances 0.000 title claims abstract description 72
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 49
- 239000004626 polylactic acid Substances 0.000 claims abstract description 48
- -1 polybutylene succinate Polymers 0.000 claims abstract description 39
- 229920009537 polybutylene succinate adipate Polymers 0.000 claims abstract description 33
- 239000004631 polybutylene succinate Substances 0.000 claims abstract description 29
- 229920002961 polybutylene succinate Polymers 0.000 claims abstract description 29
- 239000004630 polybutylene succinate adipate Substances 0.000 claims abstract description 29
- 239000002028 Biomass Substances 0.000 claims description 39
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 21
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 20
- 239000001384 succinic acid Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 64
- 230000000052 comparative effect Effects 0.000 description 31
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 10
- 229920003232 aliphatic polyester Polymers 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 5
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 4
- 229930182843 D-Lactic acid Natural products 0.000 description 3
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 3
- 229920006167 biodegradable resin Polymers 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 229940022769 d- lactic acid Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NGEWQZIDQIYUNV-UHFFFAOYSA-N 2-hydroxy-3-methylbutyric acid Chemical compound CC(C)C(O)C(O)=O NGEWQZIDQIYUNV-UHFFFAOYSA-N 0.000 description 2
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 2
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- FWVNWTNCNWRCOU-UHFFFAOYSA-N 2-hydroxy-3,3-dimethylbutanoic acid Chemical compound CC(C)(C)C(O)C(O)=O FWVNWTNCNWRCOU-UHFFFAOYSA-N 0.000 description 1
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 1
- ZCSHACFHMFHFKK-UHFFFAOYSA-N 2-methyl-1,3,5-trinitrobenzene;2,4,6-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)C1NC([N+]([O-])=O)NC([N+]([O-])=O)N1.CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O ZCSHACFHMFHFKK-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- 229940006015 4-hydroxybutyric acid Drugs 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000331 Polyhydroxybutyrate Polymers 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008636 plant growth process Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000005015 poly(hydroxybutyrate) Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- 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
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
-
- 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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- 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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
-
- 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
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Laminated Bodies (AREA)
Abstract
The technical problem of the present invention is to provide a resin composition for a heat shrinkable film having biodegradability, which has a wide temperature range in which stretching treatment can be performed. The invention provides a resin composition for a heat shrinkable film, which is characterized by comprising polylactic acid, polybutylene succinate and polybutylene succinate-adipate as main components, wherein the polylactic acid is 5-45 wt% of the polybutylene succinate-adipate and 50-90 wt% of the polylactic acid.
Description
Technical Field
The present invention relates to a heat-shrinkable film for shrink packaging and the like, which has biodegradability.
Background
There is known a shrink package in which after a packaged article is roughly wrapped with a heat shrinkable film, the film is shrunk in a manner to follow the packaged article through a shrink tunnel. Most of heat shrinkable films for shrink packaging are produced by forming a film of a resin having high chemical stability, such as a polypropylene resin, a polyethylene resin, a polyvinyl chloride resin, or a polystyrene resin, into a film and then stretching the film. The heat-shrinkable film made of such a stable resin is hardly naturally degraded, and when it is improperly discarded, it causes soil pollution and marine pollution.
In view of such problems, a heat shrinkable film using a biodegradable resin has been proposed.
Patent document 1 discloses a heat shrinkable film obtained by stretching a multilayer film in at least one direction, the multilayer film having a double outer layer composed of a polylactic acid (a) having a composition ratio of L-lactic acid to D-lactic acid of 94:6 to 79:21, and having at least one layer composed mainly of an aliphatic polyester (B) synthesized from an aliphatic polyol and an aliphatic dicarboxylic acid or a derivative thereof, or a mixture (C) of the polylactic acid (a) and the aliphatic polyester (B), wherein the ratio of the polylactic acid (a) to the aliphatic polyester (B) in all the layers is (a): 30:70 wt% to 75:25 wt%. In the examples of patent document 1, it is disclosed that when polybutylene succinate-polybutylene adipate is used as the aliphatic polyester (B), simultaneous biaxial stretching can be performed at a stretching temperature of 90 ℃ by about 4 times in both the machine direction and the transverse direction.
However, this heat shrinkable film has a problem that the stretchable temperature range is narrow. In the film (composition 8) in which the double outer layers described in table 3 below were composed of polylactic acid and the intermediate layer was composed of a mixture of polylactic acid and polybutylene succinate-adipate (resin composition o) at a thickness ratio of 1:6:1, the weight ratio of polylactic acid to polybutylene succinate-adipate in all layers was 40:60, and the film was substantially the same as that in example 3 of patent document 1. When the film was stretched 4.5 times in both the longitudinal and transverse directions at a stretching temperature of 75 ℃, 80 ℃, 85 ℃, 90 ℃ and 95 ℃ (stretching was performed so that the film area became 20.25 times), the stretching treatment was possible at 80 ℃ and 85 ℃, but the stretching treatment was not possible at other temperatures.
Patent document 2 relates to an invention relating to a heat-shrinkable film having at least one layer mainly composed of a resin composition comprising a polylactic acid-based polymer and an aliphatic polyester resin a having a melting point of 100 to 170 ℃ and a glass transition temperature of 0 ℃ or lower, and being subjected to at least one-axis stretching. In the example of patent document 2, a heat shrinkable film in which both outer layers are made of polylactic acid and the intermediate layer is made of polylactic acid and polybutylene succinate as main components is disclosed, but this film also has a problem that the temperature range in which stretching can be performed is narrow. Further, since the heat-shrinkable film has a high tensile modulus and is very rigid, a phenomenon called "corner erection" or "dog ear" occurs in which corner portions (both edge portions of the fusion seal) of the package rise like dog ears when shrink-wrapping is performed. If the shrink-wrapped package has an erected corner, the corner tip portion may damage other shrink-wrapped packages. Further, when the finger touches the corner portion, the finger may feel "pain".
Patent document 3 discloses a heat shrinkable film having a double outer layer mainly composed of a polylactic acid polymer (a) and at least one inner layer mainly composed of a mixture of a polybutylene succinate (B) and a polybutylene succinate-adipate copolymer (C), wherein the weight ratio of the polylactic acid polymer (a) to the polybutylene succinate (B) and the polybutylene succinate-adipate copolymer (C) [ (a): ((B) + (C)) ] in all the layers is 30:70 to 10: 90. This film also has a problem that the temperature range in which the stretching treatment can be performed is narrow. In addition, in this film, since the proportion of the polylactic acid based polymer as a whole is 30% by weight or less, there is a problem that the degree of biomass is low.
In recent years, a plastic film for packaging is required to have not only biodegradability but also a high biomass level. The biomass degree is a dry weight ratio of a biomass raw material (plant-derived raw material) in the film. When plastic films are disposed of by incineration or degraded by microorganisms, carbon dioxide, which is a greenhouse gas, is discharged, and therefore there is a concern that global warming may be accelerated. However, when a biomass raw material is used, since carbon dioxide is absorbed in a process of manufacturing the raw material (a process of plant growth), an influence on global warming is reduced.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2001 + 047583
Patent document 2: japanese patent laid-open No. 2004-002776
Patent document 3: japanese patent laid-open No. 2007 & 320290
Disclosure of Invention
Technical problem to be solved by the invention
The technical problem of the present invention is to provide a heat-shrinkable film which is biodegradable, can be stretched over a wide temperature range, and does not have a problem of standing. Further, it is an object of the present invention to provide a heat shrinkable film having a high biomass content and excellent transparency.
Means for solving the problems
The present invention provides a resin composition for a heat-shrinkable film, which comprises polylactic acid, polybutylene succinate and polybutylene succinate-adipate as main components, wherein the polylactic acid is 5 to 45 wt% and 50 to 90 wt% of the polybutylene succinate-adipate as the polylactic acid, and the polylactic acid is 10 to 25 wt% and 5 to 40 wt% and 50 to 70 wt% of the polybutylene succinate-adipate as the polylactic acid.
Further, the resin composition for a heat shrinkable film is characterized in that the polylactic acid is made of a biomass material, the polybutylene succinate is a copolymer of biomass-derived succinic acid and 1, 4-butanediol, and the polybutylene succinate-adipic acid butanediol ester is a copolymer of biomass-derived succinic acid, 1, 4-butanediol, and adipic acid.
Further, a heat shrinkable film characterized by having a layer containing the resin composition as a main component is provided.
Also disclosed is a heat-shrinkable film which is characterized by comprising an outer layer, an intermediate layer and an outer layer in this order, wherein the intermediate layer comprises the resin composition as a main component, and the outer layer comprises a resin composition containing 90 wt% or more of polylactic acid.
The heat-shrinkable film is characterized in that the thickness ratio of the outer layer to the intermediate layer is 1:2:1 to 1:10:1, and the thickness ratio of the outer layer to the intermediate layer is 1:4:1 to 1:7: 1.
Effects of the invention
The resin composition for a heat shrinkable film of the present invention is biodegradable and therefore less likely to pollute the global environment. The heat-shrinkable film using the resin composition has flexibility and heat shrinkability equal to or more excellent than those of conventional polypropylene heat-shrinkable films. Further, since the stretchable temperature range is wide, a good heat shrinkable film can be obtained even if the film temperature slightly changes during the stretching treatment. Further, biaxial stretching can be performed in both the machine direction and the transverse direction by more than 4 times, and a heat shrinkable film having a high shrinkage can be obtained.
Further, by using a resin obtained by copolymerizing succinic acid derived from biomass as polybutylene succinate or polybutylene succinate-adipate, the biomass content of the heat-shrinkable film can be increased.
Further, by providing the double outer layers made of the resin composition containing 90 wt% or more of polylactic acid, the transparency of the obtained film can be improved.
Further, by setting the thickness ratio of the outer layer to the intermediate layer within a specific range, a heat shrinkable film excellent in stretchability, transparency, biomass degree, and the like can be obtained.
Detailed Description
The present invention will be described in detail below, but the present invention is not limited to the following, and various embodiments can be made within the scope of achieving the same effects.
[ resin composition for Heat-shrinkable film ]
The resin composition for a heat shrinkable film of the present invention contains, as main components, polylactic acid (hereinafter, abbreviated as "PLA" if necessary), polybutylene succinate (hereinafter, abbreviated as "PBS" if necessary), and polybutylene succinate-adipate (hereinafter, abbreviated as "PBSA" if necessary).
< polylactic acid (PLA) >
PLA is obtained, for example, by fermenting starch contained in corn, potato, or the like to produce lactic acid, and polymerizing the lactic acid. A resin composed of 100% biomass material of PLA is commercially available, and a heat shrinkable film having a high biomass level can be obtained by using the resin.
In addition, in the PLA, other hydroxycarboxylic acids may be copolymerized, or a small amount of a chain extender residue may be contained, within a range that does not affect the properties of the resin. Examples of the other hydroxycarboxylic acid units include bifunctional aliphatic hydroxycarboxylic acids such as lactic acid optical isomers (D-lactic acid for L-lactic acid and L-lactic acid for D-lactic acid), glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxy-3, 3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, 2-methyllactic acid and 2-hydroxycaproic acid, and lactones such as caprolactone, butyrolactone and valerolactone. Such other hydroxycarboxylic acid units may be used in less than 15 mole% in the PLA.
< polybutylene succinate (PBS) >
PBS is an aliphatic polyester obtained by a condensation reaction of 1, 4-butanediol and succinic acid, and contains a substance obtained by converting the aliphatic polyester into a high molecular weight such as polyisocyanate.
In recent years, succinic acid derived from a living organism is produced by fermentation of corn or the like, and a product obtained by polymerizing 1, 4-butanediol (hereinafter, abbreviated as "biopestic PBS" as needed) is commercially available. By using such a resin, the biomass content of the heat shrinkable film can be improved. Typical bioppbs has a biomass size of slightly less than 50% by weight.
In addition, the development of bio-derived 1, 4-butanediol has been advanced, and the market of PBS having a biomass degree of approximately 100% composed of bio-derived 1, 4-butanediol and bio-derived succinic acid is expected. When this PBS is used, the biomass content of the resulting heat shrinkable film is further improved.
< polybutylene succinate-adipate (PBSA) >
PBSA is an aliphatic polyester obtained from 1, 4-butanediol, succinic acid, and adipic acid, and contains a high molecular weight material such as polyisocyanate.
As with PBS, a substance using succinic acid derived from a living organism (hereinafter, simply referred to as "biological PBSA" as needed) is commercially available. By using the bio-PBSA, the biomass of the heat shrinkable film can be improved. The biomass degree of the general biological PBSA is about 33% by weight. Further, PBSA using bio-derived 1, 4-butanediol and bio-derived succinic acid is expected to be commercially available, and the biomass density of the resulting heat shrinkable film is further improved when such PBSA is used.
< mixing ratio >
The resin composition of the present invention comprises 5 to 45 wt% of PLA, 5 to 45 wt% of PBS and 50 to 90 wt% of PBSA. The resin composition of the present invention contains the resin at the highest blending ratio, PBSA. By blending PBSA in an amount of 50% by weight or more, the stretchable temperature range can be expanded toward the low temperature side. Further, as the blend ratio of PBSA increases, the tensile elastic modulus of the resulting heat shrinkable film decreases, and the occurrence of the "standing angle" can be suppressed. In view of the above, the blending ratio of PBSA is preferably 60 to 90% by weight, and particularly preferably 70 to 90% by weight.
In addition, biological PBSA has a low biomass level compared to PLA and biological PBS. Therefore, when the biomass degree of the heat shrinkable film needs to be increased, the amount of the bio-PBSA to be used is preferably suppressed. In order to improve the breaking strength of the heat-shrinkable film, to improve the biomass content without narrowing the stretchable temperature range, the blend ratio of the bio-PBSA is preferably 50 to 80 wt%, particularly 50 to 70 wt%.
In the resin composition of the present invention, 5 to 45% by weight of each of PLA and PBS is added. Both PLA and PBS can expand the stretchable temperature range to the high temperature side. When the proportion of PLA or PBS is less than 5 wt%, the stretchable temperature range is only the low temperature side. When the proportion of PLA exceeds 45 wt%, the resulting film may become hard, which may cause a problem of corner stand. When the blending ratio of PBS exceeds 45 wt%, it is difficult to stretch the film. When the sum of the proportion of PLA and the proportion of PBS exceeds 50 wt%, the stretchable temperature range is only the high temperature side. In view of flexibility, biomass degree, and the like to be imparted to the heat-shrinkable film, it is preferable that the PLA, PBS, and PBSA are 10 to 25 wt%, 5 to 40 wt%, and 50 to 70 wt%.
< Heat shrinkable film >
The heat-shrinkable film of the present invention can be obtained by forming the resin composition into a film and subjecting the film to uniaxial stretching or biaxial stretching. For example, when the film is formed by a blown film forming method, the film can be produced by performing a stretching treatment by increasing the blow ratio. Further, a tubular film formed by a blown film method may be stretched by a tubular stretching method. Further, the film produced by the T-mold film method may be produced by stretching the film by a roll stretching method or a tenter stretching method. In addition, other conventionally known methods can be used for the production method of the heat shrinkable film of the present invention.
The thickness of the heat shrinkable film of the present invention is preferably 5 to 100. mu.m, more preferably 10 to 50 μm, particularly 12 to 30 μm.
< multilayer film >
The heat shrinkable film of the present invention may be a single layer film composed of only a layer containing the above resin composition as a main component, and the transparency of the film is not so high. Therefore, it is preferable to provide the resin composition as an intermediate layer and an outer layer made of a resin composition containing 90% by weight or more of PLA. Specifically, a multilayer film having an outer layer, an intermediate layer, and an outer layer in this order is preferable.
The ratio of the thickness of the outer layer to the thickness of the intermediate layer to the thickness of the outer layer is preferably 1:2:1 to 1:10:1, and particularly preferably 1:2:1 to 1:9:1 in view of stretchability. In consideration of the flexibility of the film, the thickness ratio of the intermediate layer is preferably high, and the thickness ratio of each layer is preferably 1:4:1 to 1:10: 1. In order to increase the biomass of the film, it is preferable that the blend ratio of PLA is high and the outer layer is thick, and the thickness ratio is preferably 1:2:1 to 1:7: 1. In consideration of flexibility and biomass of the heat-shrinkable film, the thickness ratio of each layer is 1:4:1 to 1:7:1, and particularly preferably 1:4:1 to 1:6.9: 1.
In addition, the heat shrinkable film of the present invention may have another resin layer between the outer layer and the intermediate layer. For example, an adhesive layer is provided between the outer layer and the intermediate layer, whereby the adhesive strength between the outer layer and the intermediate layer can be improved. The adhesive layer is preferably a mixture of the resin composition constituting the outer layer and the resin composition constituting the intermediate layer, and contributes to effective utilization of resources also when, for example, a cut edge (edge loss) generated in the process of producing the heat shrinkable film of the present invention is recycled and used.
In the resin composition for a heat shrinkable film or the resin composition for an outer layer, a biodegradable resin such as a polycaprolactone-based resin or polyhydroxybutyrate, a non-biodegradable resin in an amount of 5 wt% or less, and various additives such as a lubricant, a plasticizer, an anti-blocking agent, an antifogging agent, an antioxidant, a filler, and a colorant may be blended within a range not to impair the object of the present invention.
Examples
The effects of the present invention are confirmed by examples and comparative examples. The resins used in examples and comparative examples of the present invention are as follows.
PLA 1: polylactic acid, LuminyLX175 (biomass 100%)
PLA 2: polylactic acid manufactured by Haishen corporation, REVODE101 (biomass degree 100%)
Biological PBS: polybutylene succinate manufactured by PTT MCC Biochem, BioPBS FZ91PM (using biomass-derived succinic acid, biomass degree: 48.5%)
Biological PBSA: polybutylene succinate-adipate manufactured by PTT MCC Biochem, BioPBS FD92PM (using succinic acid derived from biomass, biomass degree: 33.5%)
< confirmation of stretchable temperature Range >
The resin compositions shown in Table 1 were formed into films having a thickness of 240 μm by a T-die film method, and the films were simultaneously biaxially stretched 4 times in the machine direction and 4 times in the transverse direction by a bench biaxial stretcher. The film thickness was 15 μm as a result of the stretching treatment to 16 times the original area. The film temperature was changed to 75 ℃, 80 ℃, 85 ℃ and 90 ℃ during biaxial stretching, and the appearance of the obtained heat-shrinkable film was visually confirmed. Further, when the heat-shrinkable film is subjected to a stretching treatment at a low temperature (about 75 to 90 ℃), it is easily heat-shrunk at a low temperature. Therefore, in the case where the packaged article is easily deteriorated by heat, it is preferable to shrink-wrap the packaged article using a heat-shrinkable film subjected to a stretching treatment at a low temperature.
In table 1, the case where the film was broken and could not be stretched to a predetermined magnification, local deformation was observed in the film after the stretching treatment, and the resin was melted and could not be stretched was marked with x, and the case where the film after the stretching treatment had good appearance was marked with o.
[ Table 1]
The resin composition (resin composition a) of the present invention can be subjected to a stretching treatment at three temperatures of 75 ℃, 80 ℃ and 85 ℃. Thus, even if the film temperature changes slightly during the stretching treatment, the film is less likely to deform. Further, since the stretching treatment can be performed at a low temperature of 75 to 85 ℃, the heat-shrinkable film obtained can have high shrinkability at a low temperature.
The resin composition e and the resin composition f containing 80 wt% or more of bioppbsa have only one temperature at which the stretching treatment can be performed. In addition, the resin composition h containing 50 wt% or more of biopestin also has only one temperature at which the stretching treatment can be performed. In addition, the resin compositions i and j containing 80 wt% or more of biopestin were not subjected to the stretching treatment at all temperatures.
[ example 1]
A single-layer film having a thickness of 240 μm was produced from the resin composition a by a T-die film method, and then the film was subjected to simultaneous biaxial stretching treatment at a film temperature of 85 ℃ by 4 times in the machine direction and 4 times in the transverse direction by a biaxial stretching apparatus (manufactured by Nippon Seisakusho Co., Ltd.), thereby obtaining a heat shrinkable film having a thickness of about 15 μm.
[ comparative examples 1 to 8]
Using the resin compositions b to h and the resin composition k, heat shrinkable films of comparative examples 1 to 8 were obtained in the same manner as in example 1. Of these, comparative example 4 (resin composition e) and comparative example 5 (resin composition f) were subjected to a stretching treatment at a film temperature of 75 ℃. Comparative example 7 (resin composition h) and comparative example 8 (resin composition k) were subjected to a stretching treatment at a film temperature of 90 ℃.
The obtained heat shrinkable film was evaluated in the following manner.
< tensile modulus of elasticity >
According to ASTM D882. In order to suppress the problem of the standing angle after shrink wrapping, the tensile elastic modulus is preferably 1500MPa or less.
< haze >
According to JIS K7136. From the viewpoint of transparency, the haze is preferably 15% or less, preferably 10% or less, and more preferably 5% or less.
[ Table 2]
| Resin composition | Stretchable temperature number (data table 1) | Degree of Biomass (%) | Modulus of elasticity in tension (MPa) | Haze (%) | |
| Example 1 | Resin composition a | 3 | 50 | 750 | 12 |
| Comparative example 1 | Resin composition b | 3 | 100 | 3000 | 0.2 |
| Comparative example 2 | Resin composition c | 4 | 87 | 2000 | 2 |
| Comparative example 3 | Resin composition d | 4 | 67 | 1300 | 19 |
| Comparative example 4 | Resin compositione | 1 | 47 | 650 | 12 |
| Comparative example 5 | Resin composition f | 1 | 33.5 | 300 | 35 |
| Comparative example 6 | Resin composition g | 3 | 90 | 2500 | 13 |
| Comparative example 7 | Resin composition h | 1 | 74 | 1900 | 10 |
| Comparative example 8 | Resin composition k | 1 | 53 | 850 | 12 |
< Angle hardness >
Three packaged objects in which small containers are placed are collectively shrink-wrapped (stack-wrapped) using the heat shrinkable films of example 1 and comparative examples 1, 3, 4, and 7. The corner portion of the obtained package was touched with a hand to confirm the hardness of the corner. When the heat shrinkable films of comparative examples 1 and 7 having a very high tensile modulus are used, the corner portions are very hard and the finger has a piercing feeling. The heat-shrinkable films of example 1 and comparative examples 3 and 4 having a tensile modulus of elasticity of 1500MPa or less had soft corner portions of the package and the same hand as those of the heat-shrinkable films made of ordinary polypropylene. From these test results, it was confirmed that the tensile elastic modulus and the angular hardness are related to each other. Further, the tensile elastic modulus of the film is preferably 1500MPa or less.
The heat shrinkable film of example 1 had three stretchable temperature degrees and was good in stretchability. Further, since the tensile elastic modulus is 1500MPa or less, a package having a good texture can be obtained, and since the haze is 15% or less, a film having excellent transparency can be obtained.
The heat-shrinkable films of comparative examples 1 to 2 and comparative examples 6 to 7 had high modulus of elasticity in stretching, and it was difficult to obtain a heat-shrinkable package having good hand feeling. The heat-shrinkable films of comparative examples 3, 4, 5 and 8 have a low tensile elastic modulus (1500 MPa or less), but the heat-shrinkable film of comparative example 3 has a high haze and poor transparency, while the heat-shrinkable films of comparative examples 4, 5 and 8 have a single degree of stretchability and temperature, and the film temperature during stretching changes only slightly, and the film may break. Further, the heat-shrinkable films of comparative examples 7 and 8 cannot be subjected to stretching treatment at low temperature, and therefore, it is necessary to set the temperature of the shrink tube high at the time of shrink packaging.
< confirmation of stretchable temperature Range >
Next, the stretchable temperature ranges of the multilayer heat shrinkable films of compositions 1 to 11 shown in Table 3 were confirmed.
First, a 240 μm multilayer film was produced by a T-molding film method. Then, the 240 μm multilayer film was subjected to simultaneous biaxial stretching 4.5 times in the machine direction and 4.5 times in the transverse direction by a biaxial stretching apparatus to produce a heat shrinkable film. By this stretching treatment, the film had a thickness of about 12 μm, which was 20.25 times the original area. The film temperature was changed to 75 ℃, 80 ℃, 85 ℃, 90 ℃ and 95 ℃ during biaxial stretching, and the appearance of the obtained heat-shrinkable film was visually confirmed.
In table 3, the case where the film was broken and could not be stretched to a predetermined magnification, local deformation was observed in the film after the stretching treatment, and the resin was melted and could not be stretched was marked by x, and the case where the film after the stretching treatment had good appearance was marked by o.
[ Table 3]
Comparing table 1 and table 3, it can be confirmed that the stretchable temperature range is slightly shifted to the high temperature side by providing PLA in the double outer layer, but biaxial stretching can be performed at a high magnification (4.5 times in both vertical and horizontal directions), and the stretchable temperature range is widened. Further, from the results of the constitutions 2 to 5, it was confirmed that when the resin composition of the present invention is used as an intermediate layer, the stretchable temperature range is very wide even if the thickness ratio is changed.
[ example 2]
A240 μm multilayer film (constitution 4) having a resin composition m as an intermediate layer and outer layers composed of 100 wt% of PLA on both sides of the intermediate layer was produced by a T-molding film method. In addition, the thickness ratio of the outer layer to the intermediate layer to the outer layer is 1:6: 1. Subsequently, the multilayer film was biaxially stretched 4.5 times in the machine direction and 4.5 times in the transverse direction at a film temperature of 85 ℃. The haze, heat shrinkage, and tensile elastic modulus of the resulting heat shrinkable film are shown in table 4.
[ example 3]
A heat shrinkable film was obtained in the same manner as in example 2, except that the outer layer was made of PLA90 wt% and bio-PBSA 10 wt% (constituting 7). The haze, heat shrinkage, and tensile elastic modulus of the resulting heat shrinkable film are shown in table 4.
[ examples 4 to 8]
A heat shrinkable film was obtained in the same manner as in example 2, except that the resin composition and the thickness ratio of the intermediate layer were set to, for example, those shown in table 3. The haze, heat shrinkage, and tensile elastic modulus of the resulting heat shrinkable film are shown in table 4.
Comparative examples 9 and 10
A heat shrinkable film of comparative example 9 was obtained in the same manner as in example 2, except that the resin composition o was used as the intermediate layer (constituent 8). A heat shrinkable film of comparative example 10 was obtained in the same manner as in example 2, except that the resin composition f was used as the intermediate layer (structure 9). The haze, heat shrinkage, and tensile elastic modulus of the resulting heat shrinkable film are shown in table 4.
< Heat shrinkage >
The heat shrinkable films of examples 2 to 8 and comparative examples 9 and 10 were cut into a square of 100mm × 100mm, immersed in an oil bath at 100 ℃ for 5 seconds, and then taken out to measure the length of the film. Table 4 shows the thermal shrinkage ratio ((length before immersion-length after immersion)/length before immersion) × 100) in the moving direction (MD direction) of the film and the width direction (TD direction) of the film perpendicular to the moving direction. Further, the heat shrinkage rate of a heat-shrinkable film made of a general polypropylene resin immersed in an oil bath at 100 ℃ for 5 seconds is about 15%.
[ Table 4]
| Resin composition for intermediate layer | Stretchable temperature number (data Table 3) | Biomass degree of film (%) | Haze (%) | Heat shrinkage ratio (MD/TD) (%) | Modulus of elasticity in tension (MPa) | |
| Example 2 | Resin composition m (constitution 4) | 4 | 62 | 0.8 | 64/64 | 1451 |
| Example 3 | Resin composition m (constitution 7) | 4 | 61 | 2.9 | 52.5/52 | 1336 |
| Example 4 | Resin composition 1 (constitution 1) | 4 | 61 | 0.8 | 63/65.5 | 1255 |
| Example 5 | Resin composition m (constitution 3) | 4 | 67 | 1.1 | 62/63 | 1487 |
| Example 6 | Resin composition m (constitution 5) | 4 | 60 | 2.6 | 58/57 | 1141 |
| Example 7 | Resin composition p (constitution 10) | 63 | 1.8 | 57/56 | 1386 | |
| Example 8 | Resin composition q (constitution 11) | 3 | 60 | 1.3 | 53/52 | 1294 |
| Comparative example 9 | Resin composition o (constitution 8) | 2 | 60 | 1.4 | 64/65 | 1306 |
| Comparative example 10 | Resin composition f (constitution 9) | 2 | 50 | 0.3 | 72/72 | 1013 |
Comparing table 2 and table 4, it was confirmed that the haze was lower than that of the polypropylene heat shrinkable film (haze was about 5.0%) by providing a layer made of PLA to the double outer layers. Further, when the PLA layer is provided, the biomass content of the heat-shrinkable film increases, and thus the amount of carbon dioxide discharged can be reduced.
In addition, it was confirmed that the heat shrinkable films of examples 2 to 8 had a significantly higher shrinkage at 100 ℃ than the polypropylene heat shrinkable film (shrinkage of 15%). In addition, the heat shrinkable films of examples 2 to 8 were not hard and were good without a finger-pricked feeling, while shrink-wrapping was performed in the above manner and the hardness of the corners was confirmed. Thus, even in the case of a packaged object having a complicated shape, the shrink packaging can be performed perfectly at low temperature. Therefore, it is suitable for shrink-wrapping an article which is easily deteriorated by heat capacity.
Claims (7)
1. A resin composition for a heat shrinkable film, characterized in that polylactic acid, polybutylene succinate and polybutylene succinate-butylene adipate are used as main components,
the mixing proportion of the polylactic acid, the polybutylene succinate and the polybutylene succinate-adipate is 5-45 wt%, 5-45 wt% and 50-90 wt%.
2. The resin composition for a heat shrinkable film according to claim 1,
the mixing proportion of the polylactic acid, the poly (butylene succinate) -butylene adipate, 5-40 wt% and 50-70 wt% is 10-25 wt% of the polylactic acid.
3. The resin composition for a heat shrinkable film according to claim 1 or 2,
the polylactic acid is composed of a biomass raw material,
the polybutylene succinate is a copolymer of succinic acid from biomass and 1, 4-butanediol,
the polybutylene succinate-adipate butanediol ester is a copolymer of succinic acid, 1, 4-butanediol and adipic acid from biomass.
4. A heat shrinkable film characterized in that,
the heat shrinkable film has a layer containing the resin composition according to any one of claims 1 to 3 as a main component.
5. A heat shrinkable film characterized by comprising an outer layer, an intermediate layer and an outer layer in this order,
the intermediate layer comprises the resin composition according to any one of claims 1 to 3 as a main component,
the outer layers are each composed of a resin composition containing 90 wt% or more of polylactic acid.
6. The heat shrinkable film of claim 5,
the thickness ratio of the outer layer to the middle layer is 1:2: 1-1: 10: 1.
7. The heat shrinkable film according to claim 5 or 6,
the thickness ratio of the outer layer to the middle layer is 1:4: 1-1: 7: 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019-115579 | 2019-06-21 | ||
| JP2019115579 | 2019-06-21 | ||
| PCT/JP2020/024067 WO2020256090A1 (en) | 2019-06-21 | 2020-06-19 | Resin composition for heat-shrinkable film and heat-shrinkable film using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113993949A true CN113993949A (en) | 2022-01-28 |
Family
ID=74040862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202080044281.4A Pending CN113993949A (en) | 2019-06-21 | 2020-06-19 | Resin composition for heat shrinkable film and heat shrinkable film using same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPWO2020256090A1 (en) |
| CN (1) | CN113993949A (en) |
| WO (1) | WO2020256090A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113912879A (en) * | 2021-08-20 | 2022-01-11 | 山东亿隆薄膜材料有限责任公司 | Environment-friendly heat shrinkable film |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09272794A (en) * | 1996-04-02 | 1997-10-21 | Mitsubishi Plastics Ind Ltd | Biodegradable film |
| JP2001011214A (en) * | 1999-07-01 | 2001-01-16 | Okura Ind Co Ltd | Biodegradable heat-shrinkable film |
| JP2001151906A (en) * | 1999-11-26 | 2001-06-05 | Mitsubishi Plastics Ind Ltd | Polylactic acid-based shrink film or sheet |
| JP2004002776A (en) * | 2002-04-02 | 2004-01-08 | Mitsubishi Plastics Ind Ltd | Thermally shrinkable polylactic acid film |
| JP2005193620A (en) * | 2004-01-09 | 2005-07-21 | Office Media Co Ltd | Co-extruded, multilayered, biodegradable and shrinkable film |
| JP2007106067A (en) * | 2005-10-17 | 2007-04-26 | Asahi Kasei Life & Living Corp | Film with biodegradable sealant layer |
| WO2007046174A1 (en) * | 2005-10-17 | 2007-04-26 | Asahi Kasei Chemicals Corporation | Biodegradable multilayered film with sealant layer |
| JP2007320290A (en) * | 2006-06-05 | 2007-12-13 | Kohjin Co Ltd | Biodegradable heat-shrinkable laminated film |
| KR20080096961A (en) * | 2007-04-30 | 2008-11-04 | 위더스케미칼 주식회사 | Producing method of film for label easily removable it from container |
| JP2012205506A (en) * | 2011-03-29 | 2012-10-25 | Shin Etsu Polymer Co Ltd | Runner stop |
| CN105916919A (en) * | 2013-10-27 | 2016-08-31 | 蒂帕有限责任公司 | Biodegradable sheet |
| JP2018021103A (en) * | 2016-08-02 | 2018-02-08 | 三菱ケミカル株式会社 | Polyester resin composition, film obtained by molding the resin composition, and bag obtained by molding the film |
-
2020
- 2020-06-19 CN CN202080044281.4A patent/CN113993949A/en active Pending
- 2020-06-19 WO PCT/JP2020/024067 patent/WO2020256090A1/en active Application Filing
- 2020-06-19 JP JP2021526895A patent/JPWO2020256090A1/ja active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09272794A (en) * | 1996-04-02 | 1997-10-21 | Mitsubishi Plastics Ind Ltd | Biodegradable film |
| JP2001011214A (en) * | 1999-07-01 | 2001-01-16 | Okura Ind Co Ltd | Biodegradable heat-shrinkable film |
| JP2001151906A (en) * | 1999-11-26 | 2001-06-05 | Mitsubishi Plastics Ind Ltd | Polylactic acid-based shrink film or sheet |
| JP2004002776A (en) * | 2002-04-02 | 2004-01-08 | Mitsubishi Plastics Ind Ltd | Thermally shrinkable polylactic acid film |
| JP2005193620A (en) * | 2004-01-09 | 2005-07-21 | Office Media Co Ltd | Co-extruded, multilayered, biodegradable and shrinkable film |
| JP2007106067A (en) * | 2005-10-17 | 2007-04-26 | Asahi Kasei Life & Living Corp | Film with biodegradable sealant layer |
| WO2007046174A1 (en) * | 2005-10-17 | 2007-04-26 | Asahi Kasei Chemicals Corporation | Biodegradable multilayered film with sealant layer |
| JP2007320290A (en) * | 2006-06-05 | 2007-12-13 | Kohjin Co Ltd | Biodegradable heat-shrinkable laminated film |
| KR20080096961A (en) * | 2007-04-30 | 2008-11-04 | 위더스케미칼 주식회사 | Producing method of film for label easily removable it from container |
| JP2012205506A (en) * | 2011-03-29 | 2012-10-25 | Shin Etsu Polymer Co Ltd | Runner stop |
| CN105916919A (en) * | 2013-10-27 | 2016-08-31 | 蒂帕有限责任公司 | Biodegradable sheet |
| JP2018021103A (en) * | 2016-08-02 | 2018-02-08 | 三菱ケミカル株式会社 | Polyester resin composition, film obtained by molding the resin composition, and bag obtained by molding the film |
Non-Patent Citations (2)
| Title |
|---|
| WORASAK PHETWAROTAI，等: "Thermal behaviors and characteristics of polylactide/poly(butylene succinate) blend films via reactive compatibilization and plasticization", 《POLYMERS FOR ADVANCED TECHNOLOGIES》 * |
| 白久林: "PBS膜材料的改性及生物降解性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2020256090A1 (en) | 2020-12-24 |
| WO2020256090A1 (en) | 2020-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100898443B1 (en) | Heat-shrinkable polylactic acid film | |
| TWI387534B (en) | Heat-shrinkable film, and molded article and heat-shrinkable label using the same, and container using the molded articale or having the label attached thereto | |
| US7993745B2 (en) | Polylactic acid stretched film | |
| JP6759828B2 (en) | A polylactic acid-based film, a heat-shrinkable film using the film, a molded product or a heat-shrinkable label using the heat-shrinkable film, and a container using the molded product or having the label attached. | |
| JPH11222528A (en) | Biodegradable film and its production | |
| JP4804203B2 (en) | Multilayer stretched film and method for producing the same | |
| JP3655619B2 (en) | Heat-shrinkable polylactic acid film | |
| JP4243926B2 (en) | Biodegradable heat shrinkable film and shrink package using the same | |
| JP4949604B2 (en) | Heat-shrinkable polylactic acid-based laminated film | |
| CN113993949A (en) | Resin composition for heat shrinkable film and heat shrinkable film using same | |
| US10633522B1 (en) | Renewable resin composition and product prepared from the same | |
| JP5623479B2 (en) | Resin composition, and film and laminate using the same | |
| Phattarateera et al. | The ternary blends of TPS/PBAT/PLA films: A study on the morphological and mechanical properties | |
| KR20120052088A (en) | Environment-friendly heat shrinkable film | |
| JP2010001369A (en) | Resin composition, and film and laminate using the same | |
| JP4947892B2 (en) | Heat shrinkable film | |
| JP4430528B2 (en) | Heat shrinkable biodegradable film | |
| JP2005193620A (en) | Co-extruded, multilayered, biodegradable and shrinkable film | |
| JPH09132701A (en) | Microorganism-decomposable film | |
| JP2001047583A (en) | Biodegradable heat shrinkage laminated film | |
| JP4518933B2 (en) | Biaxially stretched biodegradable film | |
| JP4430503B2 (en) | Biodegradable biaxially stretched film | |
| JP2006027113A (en) | Lactic acid shrinkable packaging film | |
| JP2022095436A (en) | Heat-shrinkable film | |
| KR20100013012A (en) | Heat-shrinkable polyester film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20220128 |
|
| WD01 | Invention patent application deemed withdrawn after publication |