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WO2020256090A1 - Composition de résine pour film thermorétractable et film thermorétractable l'utilisant - Google Patents

Composition de résine pour film thermorétractable et film thermorétractable l'utilisant Download PDF

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Publication number
WO2020256090A1
WO2020256090A1 PCT/JP2020/024067 JP2020024067W WO2020256090A1 WO 2020256090 A1 WO2020256090 A1 WO 2020256090A1 JP 2020024067 W JP2020024067 W JP 2020024067W WO 2020256090 A1 WO2020256090 A1 WO 2020256090A1
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WIPO (PCT)
Prior art keywords
heat
shrinkable film
film
resin composition
weight
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.)
Ceased
Application number
PCT/JP2020/024067
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English (en)
Japanese (ja)
Inventor
朋弥 中村
誠 大西
祐輔 笠木
松田　博行
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Okura Industrial Co Ltd
Original Assignee
Okura Industrial Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Okura Industrial Co Ltd filed Critical Okura Industrial Co Ltd
Priority to CN202080044281.4A priority Critical patent/CN113993949A/zh
Priority to JP2021526895A priority patent/JPWO2020256090A1/ja
Publication of WO2020256090A1 publication Critical patent/WO2020256090A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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

Definitions

  • the present invention relates to a heat-shrinkable film used for shrink wrapping and the like, which has biodegradability.
  • shrink wrapping in which the object to be packaged is roughly wrapped with a heat-shrinkable film and then passed through a shrink tunnel to shrink the film along the object to be packaged.
  • Most of the heat-shrinkable films used for shrink packaging are made by forming a film of highly chemically stable resin such as polypropylene resin, polyethylene resin, polyvinyl chloride resin, and polystyrene resin, and then the film. Is manufactured by stretching. A heat-shrinkable film made of such a stable resin is hardly decomposed naturally, and if it is improperly dumped, it causes soil pollution and marine pollution.
  • Patent Document 1 has both outer layers composed of polylactic acid (A) having a composition ratio of L-lactic acid and D-lactic acid of 94: 6 to 79:21, and mainly contains an aliphatic polyhydric alcohol and an aliphatic dicarboxylic acid. Alternatively, it has at least one layer composed of an aliphatic polyester (B) synthesized from the derivative thereof or a mixture (C) of the polylactic acid (A) and the aliphatic polyester (B), and the polylactic acid (A) in all layers.
  • polylactic acid (A) having a composition ratio of L-lactic acid and D-lactic acid of 94: 6 to 79:21
  • an aliphatic polyhydric alcohol and an aliphatic dicarboxylic acid Alternatively, it has at least one layer composed of an aliphatic polyester (B) synthesized from the derivative thereof or a mixture (C) of the polylactic acid (A) and the aliphatic polyester (B), and the polylactic acid (A) in all layers.
  • the heat-shrinkable film has a problem that the stretchable temperature range is narrow.
  • Both outer layers shown in Table 3 below are composed of polylactic acid
  • the intermediate layer is composed of a mixture of polylactic acid and polybutylene succinate adipate (resin composition o), and a film having a thickness ratio of 1: 6: 1 (Structure 8).
  • Patent Document 2 includes at least one layer containing a resin composition containing a polylactic acid-based polymer and an aliphatic polyester resin A having a melting point of 100 ° C. to 170 ° C. and a glass transition temperature of 0 ° C. or lower as a main component.
  • the present invention relates to a heat-shrinkable film, which is characterized by having and being a film stretched in at least one axis.
  • a heat-shrinkable film in which both outer layers are made of polylactic acid and the intermediate layer is mainly composed of polylactic acid and polybutylene succinate is disclosed, but the temperature range in which the film can also be stretched. There was a problem that it was narrow.
  • the heat-shrinkable film has a high tensile elastic modulus and is extremely hard, when shrink-wrapped, the corners of the package (both edges of the fusing seal) stand like dog ears, or A phenomenon called "dog year” occurs. If the shrink wrapping has cornering, the tip of the corner may damage other shrink wrapping. Also, if your fingers hit the corners, you may feel "painful".
  • Patent Document 3 describes both outer layers mainly composed of a polylactic acid polymer (A) and at least one inner layer mainly composed of a mixture of polybutylene succinate (B) and polybutylene succinate-adipate copolymer (C).
  • the weight ratio of the polylactic acid-based polymer (A) to the polybutylene succinate (B) and the polybutylene succinate-adipate copolymer (C) in all layers [(A): ((B) + (C) ))] Is disclosed as a heat-shrinkable film having a value of 30:70 to 10:90.
  • the film also has a problem that the temperature range that can be stretched is narrow. Further, the film has a problem that the degree of biomass is low because the compounding ratio of the polylactic acid-based polymer in the whole is 30% by weight or less.
  • plastic films for packaging are required to have a high degree of biomass as well as biodegradability.
  • the degree of biomass is the dry weight ratio of the biomass raw material (plant-derived raw material) in the film.
  • plant-derived raw material plant-derived raw material
  • plastic film When plastic film is incinerated or decomposed by microorganisms, it emits carbon dioxide, which is a greenhouse gas, and it is feared that it may accelerate the progress of global warming.
  • a resin composition for a heat-shrinkable film containing polylactic acid, polybutylene succinate, and polybutylene succinate adipate as main components, and each resin.
  • Polylactic acid: the polybutylene succinate: the polybutylene succinate adipate 5-45% by weight: 5-45% by weight: 50 to 90% by weight, preferably the polylactic acid: the polybutylene succi.
  • Nate: A resin composition for a heat-shrinkable film is provided, wherein the polybutylene succinate adipate 10 to 25% by weight: 5 to 40% by weight: 50 to 70% by weight.
  • the polylactic acid is composed of a biomass raw material
  • the polybutylene succinate is a copolymer of succinic acid derived from biomass and 1,4-butanediol
  • the polybutylene succinate adipate is a succinic acid derived from biomass.
  • the resin composition for a heat-shrinkable film which is a copolymer of an acid, 1,4-butanediol, and succinic acid.
  • a heat-shrinkable film comprising a layer containing the resin composition as a main component.
  • a heat-shrinkable film including an outer layer, an intermediate layer, and an outer layer in this order, wherein the intermediate layer contains the resin composition as a main component, and the outer layers all contain 90% by weight or more of polylactic acid.
  • the heat shrinkable film is provided, characterized in that it is: 7: 1.
  • the resin composition for a heat-shrinkable film of the present invention has biodegradability, it does not easily pollute the global environment. Further, the heat-shrinkable film using the resin composition has flexibility and heat-shrinkability equal to or higher than that of the conventional polypropylene-based heat-shrinkable film. Further, since the stretchable temperature range is wide, a good heat-shrinkable film can be obtained even if the film temperature changes slightly during the stretching treatment. Further, simultaneous biaxial stretching exceeding 4 times in both the vertical direction and the horizontal direction is possible, and a heat-shrinkable film having a high shrinkage rate can be obtained.
  • the degree of biomass in the heat-shrinkable film can be increased. Furthermore, the transparency of the obtained film can be enhanced by providing both outer layers made of a resin composition containing 90% by weight or more of polylactic acid. Furthermore, by setting the thickness ratio of the outer layer and the intermediate layer within a specific range, a heat-shrinkable film having good stretchability, transparency, biomass degree and the like can be obtained.
  • the resin composition for a heat-shrinkable film of the present invention comprises polylactic acid (hereinafter, abbreviated as "PLA” if necessary), polybutylene succinate (hereinafter, abbreviated as “PBS” if necessary), and poly.
  • the main component is butylene succinate adipate (hereinafter, abbreviated as "PBSA” if necessary).
  • PLA Polylactic acid
  • PLA is obtained by producing lactic acid by fermenting starch contained in, for example, corn or potato, and polymerizing this.
  • PLA a resin made of 100% biomass raw material has already been put on the market, and by using the resin, a heat-shrinkable film having a high degree of biomass can be obtained.
  • the PLA may be copolymerized with another hydroxycarboxylic acid as long as the properties of the resin are not impaired, or may contain a small amount of chain extender residue.
  • Other hydroxycarboxylic acid units include optical isomers of lactic acid (D-lactic acid for L-lactic acid, L-lactic acid for D-lactic acid), glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid.
  • 2-Hydroxy-n-butyric acid 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, 2-methyllactic acid, 2-hydroxycaproic acid and other bifunctional aliphatic hydroxycarboxylic acids, and Examples thereof include lactones such as caprolactone, butyrolactone and valerolactone.
  • lactones such as caprolactone, butyrolactone and valerolactone.
  • Such other hydroxycarboxylic acid units are preferably used in less than 15 mol% in PLA.
  • PBS Polybutylene succinate
  • a general bio-PBS has a biomass content of less than 50% by weight.
  • PBS which consists of bio-derived 1,4-butanediol and bio-derived succinic acid, has a biomass content close to 100%. ..
  • the biomass degree of the heat-shrinkable film obtained by using the PBS is further increased.
  • PBSA Polybutylene succinate adipate
  • Bio-PBSA bio-derived succinic acid
  • PBSA has the highest blending ratio in the resin composition of the present invention.
  • the stretchable temperature range can be expanded to the low temperature side.
  • the compounding ratio of PBSA is preferably 60 to 90% by weight, particularly preferably 70 to 90% by weight.
  • bio-PBSA has a lower biomass content than PLA and bio-PBS. Therefore, when it is necessary to increase the biomass degree of the heat-shrinkable film, it is desirable to reduce the amount of bioPBSA used.
  • the blending ratio of bioPBSA should be 50 to 80% by weight, particularly 50 to 70% by weight. Is desirable.
  • the resin composition of the present invention contains 5 to 45% by weight of PLA and PBS, respectively.
  • Both PLA and PBS can extend the stretchable temperature range to the high temperature side.
  • the stretchable temperature range is only on the low temperature side.
  • the compounding ratio of PLA exceeds 45% by weight, the obtained film becomes hard, and there is a possibility that the problem of cornering may occur.
  • the compounding ratio of PBS exceeds 45% by weight, it becomes difficult to stretch the film.
  • the stretchable temperature range is limited to the high temperature side.
  • PLA: PBS: PBSA 10 to 25% by weight: 5 to 40% by weight: 50 to 70% by weight.
  • the heat-shrinkable film of the present invention can be obtained by forming the above-mentioned resin composition into a film and stretching it uniaxially or biaxially.
  • the film when the film is formed by the inflation film forming method, it can be produced by increasing the blow-up ratio and stretching the film.
  • the tubular film formed by the inflation film forming method can be produced by stretching it by the tubular stretching method. It is also possible to produce a film formed by the T-die film forming method by stretching it by a roll stretching method or a tenter stretching method.
  • a conventionally known method can be adopted as the method for producing the heat-shrinkable film of the present invention.
  • the thickness of the heat-shrinkable film of the present invention is preferably 5 to 100 ⁇ m, preferably 10 to 50 ⁇ m, and particularly preferably 12 to 30 ⁇ m.
  • the heat-shrinkable film of the present invention may be a single-layer film composed of only layers containing the above-mentioned resin composition as a main component, but the film is not very transparent. Therefore, it is desirable to use the above-mentioned resin composition as an intermediate layer and provide an outer layer composed of a resin composition containing 90% by weight or more of PLA. Specifically, it is desirable that the film is a multilayer film having an outer layer, an intermediate layer, and an outer layer in this order.
  • the thickness ratio of the outer layer: the intermediate layer: the outer layer is preferably 1: 2: 1 to 1: 10: 1, and particularly preferably 1: 2: 1 to 1: 9: 1 from the viewpoint of stretchability.
  • the thickness ratio of the intermediate layer is high, and the thickness ratio of each layer is preferably 1: 4: 1 to 1: 10: 1. Further, in order to increase the biomass degree of the film, it is desirable to thicken the outer layer having a high proportion of PLA, and the thickness ratio is preferably 1: 2: 1 to 1: 7: 1. Further, considering the flexibility and the degree of biomass of the heat-shrinkable film, the thickness ratio of each layer is 1: 4: 1 to 1: 7: 1, especially 1: 4: 1 to 1: 6.9: 1. desirable.
  • the heat-shrinkable film of the present invention may have another resin layer between the outer layer and the intermediate layer.
  • the adhesive strength between the outer layer and the intermediate layer can be increased.
  • the above-mentioned resin composition for heat-shrinkable film and resin composition for outer layer include biodegradable resins such as polycaprolactone-based resin and polyhydroxybutyrate, as long as the object of the present invention is not impaired.
  • a non-biodegradable resin of 5, 5% by weight or less, and various additives such as a lubricant, a plasticizer, an antiblocking agent, an antifogging agent, an antioxidant, a filler, and a colorant can be blended.
  • PLA2 Polylactic acid REVODE101 manufactured by Kaiseisha (100% biomass)
  • the resin composition shown in Table 1 is formed into a film having a thickness of 240 ⁇ m by the T-die film forming method, and this is simultaneously biaxially stretched four times in the vertical direction and four times in the horizontal direction by a table biaxial stretching machine. .. By the stretching treatment, the film becomes 16 times the original area and the thickness of the film becomes 15 ⁇ m.
  • the film temperature at the time of biaxial stretching is changed to 75 ° C., 80 ° C., 85 ° C., and 90 ° C., and the appearance of the obtained heat-shrinkable film is visually confirmed.
  • the heat-shrinkable film When the heat-shrinkable film is stretched at a low temperature (about 75 to 90 ° C.), the heat-shrinkable film tends to shrink at a low temperature. Therefore, when the object to be packaged is easily deteriorated by heat, it is desirable to shrink-wrap it using a heat-shrinkable film stretched at a low temperature. Those in which the film was broken and could not be stretched to a predetermined magnification, those in which local distortion was observed in the film after the stretching treatment, and those in which the resin was melted and could not be stretched were ⁇ , after the stretching treatment. Table 1 shows ⁇ when the film appearance was good.
  • the resin composition (resin composition a) of the present invention could be stretched at three temperatures of 75 ° C, 80 ° C and 85 ° C. Therefore, even if the film temperature changes slightly during the stretching process, the film is less likely to be distorted. Further, since the stretching treatment can be performed at a low temperature of 75 to 85 ° C., the obtained heat-shrinkable film becomes a film having high shrinkage at a low temperature. Further, the resin composition e and the resin composition f containing 80% by weight or more of bioPBSA had only one temperature at which the stretching treatment could be performed. Further, the resin composition h containing 50% by weight or more of bio-PBS also had only one temperature at which the stretching treatment could be performed. Further, the resin composition i and the resin composition j containing 80% by weight or more of bio-PBS could not be stretched at any temperature.
  • Example 1 A single-layer film having a thickness of 240 ⁇ m was produced from the resin composition a by the T-die film forming method, and then the film was subjected to a biaxial stretching apparatus (Iwamoto Seisakusho Co., Ltd.) at a film temperature of 85 ° C. A heat-shrinkable film of about 15 ⁇ m was obtained by performing simultaneous biaxial stretching treatment 4 times in the vertical direction and 4 times in the horizontal direction.
  • a biaxial stretching apparatus Iwamoto Seisakusho Co., Ltd.
  • Comparative Example 4 (resin composition e) and Comparative Example 5 (resin composition f) were stretched at a film temperature of 75 ° C. Further, Comparative Example 7 (resin composition h) and Comparative Example 8 (resin composition k) were stretched at a film temperature of 90 ° C.
  • the obtained heat-shrinkable film is evaluated by the following method.
  • ⁇ Tensile modulus> Compliant with ASTM D882.
  • the tensile elastic modulus is less than 1500 MPa.
  • ⁇ Haze> Compliant with JIS K 7136.
  • the haze is preferably 15% or less, preferably 10% or less, and more preferably 5% or less.
  • the heat-shrinkable film of Example 1 has three stretchable temperatures and has good stretchability. Further, since the tensile elastic modulus is 1500 MPa or less, a package having a good feel 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 and 2 and Comparative Examples 6 to 7 have a high tensile elastic modulus, and it is difficult to obtain a shrink wrapping body having a good feel. Further, 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 is inferior in transparency.
  • the heat-shrinkable films of Comparative Examples 4, 5 and 8 have one stretchable temperature, and there is a concern that the film may break even if the film temperature at the time of stretching changes slightly. Further, since the heat-shrinkable films of Comparative Examples 7 and 8 cannot be stretched at a low temperature, it is necessary to set the temperature of the shrink tunnel high when shrink-wrapping.
  • the stretchable temperature range of the multilayer heat-shrinkable films of configurations 1 to 11 shown in Table 3 is confirmed.
  • a 240 ⁇ m multilayer film is produced by the T-die film forming method.
  • the 240 ⁇ m multilayer film is simultaneously biaxially stretched 4.5 times in the vertical direction and 4.5 times in the horizontal direction with a biaxial stretching device to produce a heat-shrinkable film.
  • the film becomes 20.25 times the original area, and the thickness of the film becomes about 12 ⁇ m.
  • the temperature of the film during biaxial stretching is changed to 75 ° C., 80 ° C., 85 ° C., 90 ° C., and 95 ° C., and the appearance of the obtained heat-shrinkable film is visually confirmed.
  • Example 2 A 240 ⁇ m multilayer film (Structure 4) having the resin composition m as an intermediate layer and having outer layers made of 100% by weight of PLA on both sides of the intermediate layer is produced by a T-die film forming method.
  • the thickness ratio of outer layer: intermediate layer: outer layer is 1: 6: 1.
  • the multilayer film is simultaneously biaxially stretched at a film temperature of 85 ° C. by a biaxial stretching apparatus (Iwamoto Seisakusho Co., Ltd.) 4.5 times in the vertical direction and 4.5 times in the horizontal direction.
  • Table 4 shows the haze, heat shrinkage, and tensile elastic modulus of the obtained heat-shrinkable film.
  • Example 3 A heat-shrinkable film is obtained in the same manner as in Example 2 except that the outer layer is 90% by weight of PLA and 10% by weight of bioPBSA (Structure 7).
  • Table 4 shows the haze, heat shrinkage, and tensile elastic modulus of the obtained heat-shrinkable film.
  • Examples 4 to 8 A heat-shrinkable film is obtained in the same manner as in Example 2 except that the resin composition and the thickness ratio of the intermediate layer are shown in Table 3.
  • Table 4 shows the haze, heat shrinkage, and tensile elastic modulus of the obtained heat-shrinkable film.
  • Heat shrinkage rate ((length before immersion-length after immersion) / length before immersion) ⁇ 100 in the flow direction of the film (MD direction) and the width direction (TD direction) of the film perpendicular to the flow direction. It will be described together with 4.
  • the heat shrinkage rate of a heat shrinkable film made of a general polypropylene resin soaked in a 100 ° C. oil bath for 5 seconds is about 15%.

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  • 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

Le problème décrit par la présente invention est de fournir une composition de résine pour un film thermorétractable qui est biodégradable et a une large plage de températures dans laquelle un traitement d'étirement peut être effectué. La solution selon la présente invention est de fournir une composition de résine pour un film thermorétractable, la composition de résine étant caractérisée en ce qu'elle contient, en tant que composants principaux, un acide polylactique, un succinate de polybutylène et un adipate de succinate de polybutylène, le rapport de mélange de chaque résine étant acide polylactique : succinate de polybutylène : adipate de succinate de polybutylène = 5 à 45 % en poids : 5 à 45 % en poids : 50 à 90 % en poids.
PCT/JP2020/024067 2019-06-21 2020-06-19 Composition de résine pour film thermorétractable et film thermorétractable l'utilisant Ceased WO2020256090A1 (fr)

Priority Applications (2)

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CN202080044281.4A CN113993949A (zh) 2019-06-21 2020-06-19 热收缩性膜用树脂组合物及使用其的热收缩性膜
JP2021526895A JPWO2020256090A1 (fr) 2019-06-21 2020-06-19

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JP2019-115579 2019-06-21

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113912879A (zh) * 2021-08-20 2022-01-11 山东亿隆薄膜材料有限责任公司 一种环保热收缩膜

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004002776A (ja) * 2002-04-02 2004-01-08 Mitsubishi Plastics Ind Ltd 熱収縮性ポリ乳酸系フィルム
JP2005193620A (ja) * 2004-01-09 2005-07-21 Office Media Co Ltd 共押出多層生分解性シュリンクフィルム
JP2007106067A (ja) * 2005-10-17 2007-04-26 Asahi Kasei Life & Living Corp 生分解性シーラント層付フィルム
WO2007046174A1 (fr) * 2005-10-17 2007-04-26 Asahi Kasei Chemicals Corporation Film multicouche biodegradable comportant une couche de scellement
JP2012205506A (ja) * 2011-03-29 2012-10-25 Shin Etsu Polymer Co Ltd ランナー止め
JP2018021103A (ja) * 2016-08-02 2018-02-08 三菱ケミカル株式会社 ポリエステル樹脂組成物、該樹脂組成物を成形してなるフィルム、および該フィルムを成形してなる袋

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3182077B2 (ja) * 1996-04-02 2001-07-03 三菱樹脂株式会社 生分解性フィルム
JP2001011214A (ja) * 1999-07-01 2001-01-16 Okura Ind Co Ltd 生分解性熱収縮フィルム
JP3670912B2 (ja) * 1999-11-26 2005-07-13 三菱樹脂株式会社 ポリ乳酸系収縮フィルムまたはシート
JP4731407B2 (ja) * 2006-06-05 2011-07-27 株式会社興人 生分解性熱収縮性積層フィルム
KR100933242B1 (ko) * 2007-04-30 2009-12-22 위더스케미칼 주식회사 라벨용 생분해성 mdo 열수축 필름 및 그 제조방법
ES2857200T3 (es) * 2013-10-27 2021-09-28 Tipa Corp Ltd Lámina biodegradable

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004002776A (ja) * 2002-04-02 2004-01-08 Mitsubishi Plastics Ind Ltd 熱収縮性ポリ乳酸系フィルム
JP2005193620A (ja) * 2004-01-09 2005-07-21 Office Media Co Ltd 共押出多層生分解性シュリンクフィルム
JP2007106067A (ja) * 2005-10-17 2007-04-26 Asahi Kasei Life & Living Corp 生分解性シーラント層付フィルム
WO2007046174A1 (fr) * 2005-10-17 2007-04-26 Asahi Kasei Chemicals Corporation Film multicouche biodegradable comportant une couche de scellement
JP2012205506A (ja) * 2011-03-29 2012-10-25 Shin Etsu Polymer Co Ltd ランナー止め
JP2018021103A (ja) * 2016-08-02 2018-02-08 三菱ケミカル株式会社 ポリエステル樹脂組成物、該樹脂組成物を成形してなるフィルム、および該フィルムを成形してなる袋

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113912879A (zh) * 2021-08-20 2022-01-11 山东亿隆薄膜材料有限责任公司 一种环保热收缩膜

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