WO2022145364A1 - Film étiré, sac d'étanchéité découpé par fusion et stratifié - Google Patents

Film étiré, sac d'étanchéité découpé par fusion et stratifié Download PDF

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Publication number
WO2022145364A1
WO2022145364A1 PCT/JP2021/048195 JP2021048195W WO2022145364A1 WO 2022145364 A1 WO2022145364 A1 WO 2022145364A1 JP 2021048195 W JP2021048195 W JP 2021048195W WO 2022145364 A1 WO2022145364 A1 WO 2022145364A1
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Prior art keywords
layer
resin
thermoplastic resin
stretched film
crystalline thermoplastic
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PCT/JP2021/048195
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English (en)
Japanese (ja)
Inventor
由郎 水原
亮太 中干場
拓明 上田
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王子ホールディングス株式会社
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Priority to JP2022570239A priority Critical patent/JP7268804B2/ja
Publication of WO2022145364A1 publication Critical patent/WO2022145364A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

  • the present invention relates to a stretched film, a fusing seal bag, and a laminated body.
  • Resin films are excellent in various performances such as moisture resistance, water resistance and oil resistance, and also have good mechanical strength, so they are widely applied to various applications such as packaging materials for foods and chemicals, protective films for displays, etc. It is a functional material with high utility value.
  • thermoplastic resin particularly the crystalline thermoplastic resin, and the biomass plastic are materials that are difficult to mix with each other, even if a film in which both are combined is formed, they do not mix uniformly with each other (incompatibility). Often. Due to this, it is difficult to obtain a sufficiently stretched film, and there are various problems that the transparency is easily impaired. Therefore, a film obtained by blending a crystalline thermoplastic resin and a biomass plastic. The material has severely limited its use.
  • the present invention has been made in view of the above, and an object of the present invention is to provide a stretched film having excellent stretchability and high transparency, and a fusing seal bag and a laminate formed from the stretched film.
  • the present inventors have found that the above object can be achieved by using a crystalline polyolefin resin having a specific melting point and a biomass plastic having a specific melting point. , The present invention has been completed.
  • the present invention includes, for example, the subjects described in the following sections.
  • Item 1 A layer a containing a resin component containing a crystalline thermoplastic resin A and a crystalline thermoplastic resin B is provided.
  • the crystalline thermoplastic resin A is a crystalline polyolefin resin having a melting point of 135 ° C. to 175 ° C.
  • the crystalline thermoplastic resin B is a biomass plastic having a melting point of 110 ° C. to 200 ° C.
  • the layer a contains 30 to 96% by mass of the crystalline thermoplastic resin A with respect to the total mass of the crystalline thermoplastic resin A and the crystalline thermoplastic resin B. Stretched film with a haze of 0.5-30%.
  • Item 2 Item 2.
  • the stretched film according to Item 1 wherein the absolute value of the difference between the melting point of the crystalline thermoplastic resin A and the melting point of the crystalline thermoplastic resin B is 0 to 50 ° C.
  • the resin component further contains the thermoplastic resin C.
  • Item 2 The stretched film according to Item 1 or 2, wherein the thermoplastic resin C is a thermoplastic resin having a glass transition temperature of ⁇ 60 ° C. to 10 ° C.
  • the layer a contains 96 to 30% by mass of the crystalline thermoplastic resin A, 3 to 60% by mass of the crystalline thermoplastic resin B, and the thermoplastic resin C based on the total mass of the resin components.
  • Item 3 The stretched film according to Item 3, which contains 1 to 20% by mass.
  • Item 5 Item 3.
  • thermoplastic resin C is a thermoplastic elastomer.
  • Item 6 Item 2.
  • the layer b is provided on one side or both sides of the layer a.
  • Item 2 The stretched film according to any one of Items 1 to 6, wherein the layer b contains a crystalline polyolefin resin D having a melting point of 100 to 175 ° C.
  • Item 8 Item 2.
  • Item 9 Item 2.
  • Item 10 Item 2.
  • Item 11 Item 6.
  • the stretched film according to any one of Items 1 to 10 which is used for a fusing seal.
  • Item 12 A fusing seal bag comprising the stretched film according to Items 1 to 10.
  • Item 13 Item 7.
  • a step of providing the layer b on one side or both sides of the layer a is provided.
  • the layer a and the layer b are laminated, and a single layer portion made of crystalline thermoplastic resin A is provided at both ends in the lateral direction to form a resin sheet, and at least the single layer portions to be both ends are gripped.
  • a method for producing a stretched film to be stretched Item 14 Item 7. The method for producing a stretched film according to Item 7 or 8.
  • a step of providing the layer b on one side or both sides of the layer a is provided.
  • the layer a is provided on both sides of the layer c made of the crystalline thermoplastic resin A
  • the layer b is provided on at least one surface opposite to the layer c side of the layer a
  • the layers c are provided at both ends in the lateral direction.
  • a method for producing a stretched film wherein a single-layer portion is provided to form a resin sheet, and at least the single-layer portions at both ends are gripped and stretched.
  • Item 15 A laminated body having the stretched film according to any one of Items 1 to 11 and a base material.
  • the stretched film of the present invention has excellent stretchability and high transparency.
  • the stretched film of the present invention includes a layer a containing a resin component containing a crystalline thermoplastic resin A and a crystalline thermoplastic resin B.
  • the crystalline thermoplastic resin A is a crystalline polyolefin resin having a melting point of 135 ° C. to 175 ° C.
  • the crystalline thermoplastic resin B is a biomass plastic having a melting point of 110 ° C. to 200 ° C.
  • the layer a contains 30 to 96% by mass of the crystalline thermoplastic resin A with respect to the total mass of the crystalline thermoplastic resin A and the crystalline thermoplastic resin B.
  • the stretched film of the present invention has a haze of 0.5 to 30%.
  • the stretched film of the present invention contains biomass plastic, it has excellent stretchability and high transparency.
  • the fact that the stretched film is excellent in stretchability means that the material for forming the stretched film (raw sheet) is easily stretched, and as a result, the obtained stretched film is sufficiently stretched. It means that it can be in a state of being.
  • the stretched film of the present invention includes at least a layer a.
  • Such layer a is a layer that serves as a core layer in the stretched film.
  • the layer a contains a resin component containing a crystalline thermoplastic resin A and a crystalline thermoplastic resin B.
  • the resin component may also contain the thermoplastic resin C described later, if necessary. First, each component contained in the resin component will be described.
  • the type of the crystalline thermoplastic resin A is not particularly limited as long as it is crystalline and has a melting point of 135 ° C. to 175 ° C.
  • the crystalline thermoplastic resin is 20 ° C./min from ⁇ 40 ° C. to 300 ° C. using a differential scanning calorimeter (for example, input compensation type DSC, Diamond DSC manufactured by PerkinElmer) under nitrogen flow.
  • a differential scanning calorimeter for example, input compensation type DSC, Diamond DSC manufactured by PerkinElmer
  • the temperature is raised at 300 ° C. for 5 minutes, cooled to -40 ° C at 20 ° C / min, held at -40 ° C for 5 minutes, and then heated again to 300 ° C at 20 ° C / min.
  • the amorphous thermoplastic resin refers to a thermoplastic resin in which a clear melting peak does not appear in the above measurement using DSC.
  • the crystalline thermoplastic resin A for example, known crystalline polyolefin-based resins can be widely mentioned.
  • the crystalline polyolefin resin is, for example, a polymer obtained by polymerizing an olefin, and preferably polymerizes an olefin having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably 3 to 6 carbon atoms. Polymers can be mentioned.
  • crystalline polyolefin resin crystalline polyethylene resin, polypropylene resin, poly (1-butene) resin, polyisobutene resin, poly (1-pentene) resin, poly (4-methylpentene-1) Resin is mentioned.
  • the crystalline polyolefin-based resin is preferably a crystalline polypropylene-based resin in that it is easily mixed (easily compatible with) the biomass plastic.
  • the crystalline polyolefin resin can be one kind alone or a mixture of two or more kinds.
  • the crystalline thermoplastic resin A is a crystalline polypropylene-based resin
  • the crystalline polypropylene-based resin is at least one selected from the group consisting of a homopolymer of propylene and a copolymer of propylene and ethylene. More preferred.
  • the crystalline polyolefin resin is a crystalline propylene homopolymer
  • the mechanical strength and heat resistance of the film are likely to be improved
  • the crystalline polyolefin resin is a crystalline propylene-ethylene copolymer
  • the temperature is low. Foldability is improved and surface gloss is easily lowered.
  • the crystalline polyolefin resin contains two components, a crystalline propylene homopolymer and a crystalline propylene-ethylene copolymer, it is easy to obtain a film having excellent heat resistance and breakability at low temperature.
  • a crystalline isotactic polypropylene resin is preferable.
  • Such crystalline isotactic polypropylene resin preferably has a mesopentad fraction ([mm mm]) of 92% to 98%, which is a stereoregularity obtained by high temperature nuclear magnetic resonance (NMR) measurement. It is more preferably% to 97%.
  • NMR nuclear magnetic resonance
  • the mesopentad fraction [mm mm] is 92% or more, the crystallinity of the resin is improved due to the high stereoregularity component, and high thermal stability and mechanical strength can be easily obtained.
  • the mesopentad fraction [mm mm] by setting the mesopentad fraction [mm mm] to 98% or less, the stretchability tends to be good.
  • the high-temperature NMR apparatus that can be used for measuring the mesopentad fraction ([mm mm]) is not particularly limited, and for example, a generally commercially available high-temperature nuclear magnetic resonance (NMR) capable of measuring the stereoregularity of polyolefins is available.
  • the apparatus can be used, and examples thereof include a high temperature type Fourier transform nuclear magnetic resonance apparatus (high temperature FT-NMR) JNM-ECP500 manufactured by JEOL Ltd.
  • the observation nucleus is 13 C (125 MHz), the measurement temperature is 135 ° C.
  • the method by high temperature NMR can be carried out by a known method, for example, the method described in "Japan Analytical Chemistry / Polymer Analysis Research Council, New Edition Polymer Analysis Handbook, Kinokuniya Bookstore, 1995, p. 610". ..
  • the pentad fraction which represents the degree of stereoregularity, is a combination (mmmm or mrrm) of a 5-series (pentad) of a series “meso (m)” arranged in the same direction and a mixture “racemo (r)” arranged in a different direction. Etc.), calculated as a percentage from the integrated intensity of each signal.
  • mmmm 5-series
  • mrrm a mixture
  • Etc. calculated as a percentage from the integrated intensity of each signal.
  • the mesopentad fraction ([mm mm]) can be controlled by appropriately adjusting the polymerization conditions such as the polymerization conditions of the polypropylene resin, the type of catalyst, and the amount of catalyst.
  • the crystalline thermoplastic resin A has a melting point of 135 ° C to 175 ° C.
  • the melting point of the crystalline thermoplastic resin A is less than 135 ° C., the heat resistance of the obtained stretched film may decrease, the productivity of the stretched film may decrease, and the desired stretchability cannot be obtained.
  • the melting point of the crystalline thermoplastic resin A exceeds 175 ° C, it becomes difficult for the crystalline thermoplastic resin A and the crystalline thermoplastic resin B to be compatible with each other, and the desired stretchability cannot be obtained. Even if it can be stretched, it is unlikely to have a transparent or translucent appearance.
  • the melting point of the crystalline thermoplastic resin A is preferably 138 ° C to 170 ° C, more preferably 140 ° C to 166 ° C, still more preferably 145 ° C to 164 ° C, and particularly preferably 150 ° C to 163 ° C.
  • the glass transition temperature of the crystalline thermoplastic resin A is not particularly limited, and can be, for example, 50 ° C. or lower, more preferably ⁇ 30 ° C. to 30 ° C.
  • the melting point and the glass transition temperature of the crystalline resin A are values measured using a differential scanning calorimeter (for example, an input compensation type DSC manufactured by Perkin Elmer, Diamond DSC).
  • the melt mass flow rate of the crystalline thermoplastic resin A is not particularly limited.
  • the melt mass flow rate of the crystalline thermoplastic resin A is preferable in that the fluidity of the resin is in an appropriate range, the size of the fine dispersion can be easily controlled, and a desired stretched film can be easily produced. Is 0.5 g / 10 minutes to 8 g / 10 minutes, more preferably 1 g / 10 minutes to 6 g / 10 minutes.
  • the melt mass flow rate referred to in the present specification is a value measured at 230 ° C. and 21.18N in accordance with JIS K-7210 (1999).
  • the crystalline thermoplastic resin A can be produced by a known method.
  • the crystalline thermoplastic resin A is a crystalline propylene homopolymer
  • the crystalline propylene homopolymer can be obtained from a commercially available product or the like, and as a typical commercial product, for example, a homopolymer of the Prime Polypro (registered trademark) series manufactured by Prime Polymer Corporation, manufactured by Sun Aroma Co., Ltd.
  • PC412A etc.
  • a homopolymer of the Novatec (registered trademark) series manufactured by Japan Polypropylene Corporation the Dataly series manufactured by Borearis, the 5014L series manufactured by Korea Yuka Kogyo Co., Ltd., and the Sumitomo Noblen (registered trademark) series manufactured by Sumitomo Chemical Corporation. Examples thereof include homopolymers of the above.
  • the crystalline thermoplastic resin A is a crystalline propylene-ethylene copolymer
  • it may be either a random copolymer of propylene and ethylene or a block copolymer of propylene and ethylene.
  • the content ratio of ethylene units in the crystalline propylene-ethylene copolymer can be 50% by mass or less.
  • the crystalline propylene-ethylene copolymer can be produced by a known method, or can be obtained from a commercially available product or the like.
  • Typical commercial products include, for example, a copolymer of the Prime Polypro (registered trademark) series manufactured by Prime Polymer Co., Ltd., a copolymer of the Novatec PP (registered trademark) series manufactured by Nippon Polypro Co., Ltd., and Wintech (registered trademark). ) Series, copolymers of Sumitomo Noblen (registered trademark) series manufactured by Sumitomo Chemical Co., Ltd., and the like.
  • the type of the crystalline thermoplastic resin B is not particularly limited as long as it is a biomass plastic having a melting point of 110 ° C. to 200 ° C., that is, as long as the crystalline thermoplastic resin B is a biodegradable resin.
  • a biomass plastic having a melting point of 110 ° C. to 200 ° C. that is, as long as the crystalline thermoplastic resin B is a biodegradable resin.
  • known biomass plastics can be widely mentioned.
  • Examples of the crystalline thermoplastic resin B include a biodegradable aliphatic polyester resin.
  • biodegradable aliphatic polyester resins include polylactic acid, polyhydroxyalkanoic acid (excluding polylactic acid), polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polybutylene succinate / adipate, and polyethylene succinate.
  • the natural polymer include starch, cellulose, chitin, chitosan, gluten, gelatin, zein, soybean protein, collagen, keratin and the like.
  • the crystalline thermoplastic resin B can be one kind alone or a mixture of two or more kinds.
  • the crystalline thermoplastic resin B is preferably an aliphatic polyester resin in that it can be easily mixed uniformly with the crystalline thermoplastic resin A and a stretched film having a desired haze can be easily obtained, and polylactic acid and polyhydroxy are particularly preferable. More preferably, it is one or more selected from the group consisting of alkanoic acid and a polymer of a mixed monomer containing lactic acid and polyhydroxy alkanoic acid.
  • polylactic acid known polylactic acid such as polylactic acid obtained by polycondensing a lactic acid component as a raw material monomer can be widely used.
  • polylactic acid can contain only one of the optical isomers of L-lactic acid (L-form) and D-lactic acid (D-form), or both.
  • polyhydroxyalkanoic acid examples include polymers of hydroxycarboxylic acid components containing at least one of hydroxybutyric acid, hydroxyvaleric acid, hydroxypentanoic acid, hydroxycaproic acid, hydroxyheptanic acid glycolic acid and the like.
  • Examples of the polymer of the mixed monomer containing lactic acid and polyhydroxyalkanoic acid include a polymer obtained by polycondensing the lactic acid monomer and the hydroxycarboxylic acid component.
  • the crystalline thermoplastic resin B has a melting point of 110 ° C to 200 ° C.
  • the melting point of the crystalline thermoplastic resin B is preferably 120 ° C. to 190 ° C., more preferably 130 ° C. to 185 ° C., and even more preferably 140 ° C. to 180 ° C.
  • the glass transition temperature of the crystalline thermoplastic resin B is not particularly limited, and can be, for example, ⁇ 40 ° C. to 70 ° C., more preferably 0 ° C. to 70 ° C.
  • the melting point and the glass transition temperature of the crystalline thermoplastic resin B are values measured using a differential scanning calorimeter (for example, an input compensation type DSC manufactured by Perkin Elmer, Diamond DSC).
  • the melt mass flow rate of the crystalline thermoplastic resin B is not particularly limited.
  • the melt mass flow rate of the crystalline thermoplastic resin B is preferable in that the fluidity of the resin is in an appropriate range, the size of the fine dispersion can be easily controlled, and a desired stretched film can be easily produced. Is 0.5 g / 10 minutes to 15 g / 10 minutes, more preferably 1 g / 10 minutes to 10 g / 10 minutes, and even more preferably 2 g / 10 minutes to 10 g / 10 minutes.
  • the melt mass flow rate referred to in the present specification is a value measured at 230 ° C. and 21.18N in accordance with JIS K-7210 (1999).
  • the method for producing the crystalline thermoplastic resin B is not particularly limited, and for example, a known method for producing a biomass plastic can be widely adopted. Further, the crystalline thermoplastic resin B can also be obtained from a commercially available product or the like. Typical commercially available products of polylactic acid include, for example, NatureWorks "4032D” (melting point 163 ° C.), Totalcorbion "L175" (melting point 175 ° C.), “LX175" (melting point 155 ° C.), and “LX930” (melting point 155 ° C.). Melting point 130 ° C.) and the like.
  • thermoplastic resin B examples include, for example, polyhydroxyalkanoate “ENMAT (registered trademark) Y1000P” manufactured by Tianan Biological Material and polybutylene succinate “BioPBS” manufactured by Mitsubishi Chemical Co., Ltd. (Registered trademark) FZ91 “,” BioPBS (registered trademark) FD82 “and the like.
  • thermoplastic resin C is an optional component contained in the resin component, and is, for example, a component that can play a role as a compatibilizer for enhancing the compatibility between the crystalline thermoplastic resin A and the crystalline thermoplastic resin B.
  • a thermoplastic resin having a glass transition temperature of ⁇ 60 ° C. to 90 ° C. preferably ⁇ 60 ° C. to 10 ° C.
  • the glass transition temperature of the thermoplastic resin C is in the above range, the compatibility between the crystalline resin A and the crystalline resin B can be easily increased, and the stretchability of the film is improved by the thermoplastic resin C existing at the interface between them. It is easy to increase. This is because it is required that the molecular motion is not constrained in order to obtain excellent stretchability, and therefore a glass transition temperature considerably lower than the stretching temperature is required.
  • the glass transition temperature of the thermoplastic resin C is more preferably ⁇ 55 ° C. to 0 ° C.
  • the glass transition temperature of the thermoplastic resin C is a value measured using a differential scanning calorimeter (for example, an input compensation type DSC manufactured by Perkin Elmer, Diamond DSC).
  • the thermoplastic resin C may be either crystalline or amorphous, but is amorphous in that the compatibility between the crystalline thermoplastic resin A and the crystalline thermoplastic resin B can be further enhanced. Is preferable. That is, it is preferable that the melting point of the thermoplastic resin C is not detected by the differential scanning calorimeter.
  • thermoplastic resin C examples include thermoplastic elastomers, for example, widely known thermoplastic elastomers having a glass transition temperature of ⁇ 60 ° C. to 90 ° C. (preferably ⁇ 60 ° C. to 10 ° C.). Can be mentioned.
  • the thermoplastic resin C is a random copolymer, a block copolymer, and a graft formed by two or more segments having good affinity for each of the crystalline thermoplastic resin A and the crystalline thermoplastic resin B. Polymers and the like are preferred. In this case, the compatibility between the crystalline thermoplastic resin A and the crystalline thermoplastic resin B tends to increase, and the transparency of the film tends to increase.
  • thermoplastic elastomer examples include styrene graft polyethylene, hydrogenated styrene-butadiene block copolymer (hereinafter referred to as “SEBS”), and a graft of an ethylene-glycidyl methacrylate copolymer and an acrylonitrile-styrene copolymer.
  • SEBS hydrogenated styrene-butadiene block copolymer
  • EGMA-g-AS ethylene-glycidyl methacrylate copolymer
  • acrylonitrile-styrene copolymer examples include compounds (hereinafter abbreviated as "EGMA-g-AS”) and the like.
  • the melt flow rate of the thermoplastic resin C is not particularly limited, and is equivalent to or the melt flow of both, for example, in that it is easy to knead with the crystalline thermoplastic resin A and the crystalline thermoplastic resin B. Higher than the rate is preferred.
  • thermoplastic resin C is not particularly limited, and for example, a known method for producing a thermoplastic elastomer can be widely adopted.
  • the thermoplastic resin C can also be obtained from a commercially available product or the like.
  • Typical commercial products of thermoplastic resin C include, for example, JSR's hydrogenated SBR "Dynaron”, Asahi Kasei's “Tough Tech”, Kuraray's "Septon”, NOF's "Modiper A1100”, and “Modiper”. Examples thereof include “A1401”, “Modiper A3400", and “Modiper A5400".
  • the layer a is a layer containing a resin component having at least the crystalline thermoplastic resin A and the crystalline thermoplastic resin B. That is, the layer a is a layer formed by the resin component. It is a layer that functions as a core layer of the stretched film of the present invention.
  • the layer a contains 30 to 96% by mass of the crystalline thermoplastic resin A with respect to the total mass of the crystalline thermoplastic resin A and the crystalline thermoplastic resin B.
  • the crystalline thermoplastic resin A and the crystalline thermoplastic resin B have good compatibility, and a stretched film having a desired haze and stretching ratio can be obtained. Further, when the content ratio of the crystalline thermoplastic resin A is in the above range, it becomes easy to obtain a film having desired transparency and excellent mechanical strength.
  • the content ratio of the crystalline thermoplastic resin A is more preferably 50 to 90% by mass with respect to the total mass of the crystalline thermoplastic resin A and the crystalline thermoplastic resin B.
  • the above-mentioned various resins can be mentioned, and the combination can be arbitrary. Above all, it is preferable that the difference between the melting point of the crystalline thermoplastic resin A and the melting point of the crystalline thermoplastic resin B is 0 to 50 ° C. in absolute value. In this case, the crystalline thermoplastic resin A and the crystalline thermoplastic resin B are mixed more uniformly (that is, the compatibility between the two becomes higher), and the stretching ratio can be easily adjusted.
  • the difference between the melting point of the crystalline thermoplastic resin A and the melting point of the crystalline thermoplastic resin B is more preferably 0 to 40 ° C, further preferably 0 to 30 ° C, and 0 to 20 ° C. It is more preferable to have.
  • the crystalline thermoplastic resin A contained in the layer a has a glass transition temperature of 50 ° C. or lower and is crystalline. It is also preferable that the glass transition temperature of the thermoplastic resin B is ⁇ 40 ° C. to 70 ° C. In this case, the crystalline thermoplastic resin A and the crystalline thermoplastic resin B are mixed more uniformly (that is, the compatibility between the two becomes higher), the stretching ratio can be adjusted more easily, and the draw ratio can be adjusted more easily. It also tends to have the desired transparency. In this combination, the glass transition temperature of the crystalline thermoplastic resin A is more preferably ⁇ 30 ° C. to 30 ° C. Further, in this combination, the glass transition temperature of the crystalline thermoplastic resin B is more preferably 0 ° C. to 60 ° C.
  • the resin component forming the layer a may further contain the thermoplastic resin C.
  • the layer a contains the thermoplastic resin C
  • the layer a contains 96 to 30% by mass of the crystalline thermoplastic resin A and 3 to 60% by mass of the crystalline thermoplastic resin B based on the total mass of the resin components. It is preferable that the thermoplastic resin C is contained in an amount of 1 to 20% by mass.
  • the crystalline thermoplastic resin A and the crystalline thermoplastic resin B are mixed particularly uniformly (that is, the compatibility between the two becomes particularly high), the stretching ratio can be adjusted particularly easily, and the draw ratio can be adjusted.
  • the desired transparency is particularly easy to obtain.
  • the content ratio of the crystalline thermoplastic resin A is preferably 95 to 40% by mass, more preferably 90 to 50% by mass, based on the total mass of the resin components.
  • the content ratio of the crystalline thermoplastic resin B is preferably 4 to 50% by mass, more preferably 9 to 40% by mass, based on the total mass of the resin components.
  • the content ratio of the thermoplastic resin C can be appropriately set according to the content ratios of the crystalline thermoplastic resin A and the crystalline thermoplastic resin B, and for example, based on the total mass of the resin components.
  • the content ratio of the thermoplastic resin C is more preferably 1 to 15% by mass, and particularly preferably 1 to 10% by mass.
  • the resin component constituting the layer a may be composed of only the crystalline thermoplastic resin A, the crystalline thermoplastic resin B, and the thermoplastic resin C. However, in this case, even the component unavoidably contained in the resin component is not excluded. Further, as long as the effect of the present invention is not impaired, the resin component constituting the layer a may contain a resin other than the crystalline thermoplastic resin A, the crystalline thermoplastic resin B and the thermoplastic resin C.
  • Examples of the resin other than the crystalline thermoplastic resin A, the crystalline thermoplastic resin B, and the thermoplastic resin C include polyethylene, polypropylene, poly (1-butene), polyisobutene, poly (1-pentene), and polymethylpentene (for example, poly). (4-Methyl-1-pentene)) or the like, or a copolymer resin thereof, for example, an ethylene-propylene copolymer, a propylene-butene copolymer, an ethylene-butene copolymer. And the like, a copolymer of ⁇ -olefins and the like can be exemplified.
  • polyolefin-based resins may be graft-modified with an unsaturated carboxylic acid such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride, or an anhydride thereof.
  • unsaturated carboxylic acid such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride, or an anhydride thereof.
  • styrene-based resin, vinyl-based resin, polyester-based resin, polyurethane-based resin, nylon-based resin and their copolymers for example, vinyl monomer-diene monomer copolymer such as styrene-butadiene copolymer and the like.
  • Vinyl monomer such as styrene-butadiene-styrene copolymer-diene monomer-vinyl monomer copolymer and the like.
  • the content of the other resin is preferably 15% by mass or less, more preferably 10% by mass or less, based on the total mass of the resin components contained in the layer a.
  • the lower limit of the content of the other resin is not particularly limited, but is, for example, 0% by mass, 1% by mass, or the like.
  • the stretched film of the present invention comprises at least the layer a and has a haze of 0.5 to 30%. If the haze is less than 0.5%, it is necessary to make the film extremely thin, which causes a problem that it cannot withstand practical strength. If the haze exceeds 30%, the transparency is impaired and the desired stretched film cannot be obtained.
  • the haze of the stretched film of the present invention is preferably 0.5 to 20%, more preferably 1 to 15%, still more preferably 1 to 10%.
  • the haze of the stretched film is a value measured according to JIS-K7361 using a haze meter NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd.
  • the stretched film of the present invention is preferably transparent or translucent, and is preferably transparent, that is, a transparent stretched film.
  • the stretched film of the present invention may have a single-layer structure including only layer a (that is, a core layer), or may have a so-called laminated structure including layers other than layer a.
  • the stretched film of the present invention has a laminated structure
  • a laminated body formed by laminating another layer on one side or both sides of the layer a can be mentioned.
  • other layers include a layer b formed of a resin.
  • the resin contained in such a layer b include a crystalline polyolefin resin D having a melting point of 100 to 175 ° C.
  • the layer b is provided on one side or both sides of the layer a, and the layer b contains a crystalline polyolefin resin D having a melting point of 100 to 175 ° C. Can be mentioned.
  • the layer b can serve as a so-called skin layer, which can make the stretched film smoother, make the haze smaller, and increase transparency.
  • the crystalline polyolefin resin D having a melting point of 100 to 175 ° C. is, for example, a polymer obtained by polymerizing an olefin, like the crystalline thermoplastic resin A, and preferably has 2 to 20 carbon atoms.
  • a polymer formed by polymerizing an olefin having 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms can be mentioned.
  • crystalline polyolefin resin crystalline polyethylene resin, polypropylene resin, poly (1-butene) resin, polyisobutene resin, poly (1-pentene) resin, poly (4-methylpentene-1)
  • ⁇ -olefin copolymers such as ethylene-propylene copolymer, propylene-butene copolymer, ethylene-butene copolymer, and propylene-ethylene-butene copolymer can be exemplified. ..
  • the crystalline polyolefin resin D can be one kind alone or a mixture of two or more kinds.
  • the crystalline polyolefin resin D contained in the layer b may be the same as the crystalline thermoplastic resin A contained in the layer a.
  • the resin contained in the layer b may be only the crystalline thermoplastic resin D.
  • the resin contained in the layer b includes the crystalline thermoplastic resin D and at least one selected from the group consisting of the crystalline thermoplastic resin A, the crystalline thermoplastic resin B, and the thermoplastic resin C. You can also do it.
  • the resin contained in the layer b can include other resins described above. That is, the resin contained in the layer b requires the crystalline thermoplastic resin D, and in addition to the crystalline thermoplastic resin A, the crystalline thermoplastic resin B, the thermoplastic resin C, and the other resin. Can include at least one selected from the group of
  • the resin contained in the layer b is only the crystalline thermoplastic resin D in that the haze of the stretched film can be made smaller.
  • the content ratio of the crystalline thermoplastic resin D with respect to the total mass of the layer b is 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass. Above, more preferably 99% by mass or more.
  • the layer b can also have a heat seal function.
  • the crystalline thermoplastic resin D contained in the layer b is a polyethylene resin, an ethylene-propylene copolymer, an ethylene-butene copolymer, or a propylene-ethylene-butene copolymer. It is preferable to have.
  • the heat-sealing function means that the layers b have a property of being fused when they are overlapped and thermocompression-bonded so as to face each other.
  • Whether or not it has a heat-sealing function can be determined by, for example, heat-sealing with a heat-sealing tester TP-701-B (manufactured by Tester Sangyo) at 130 ° C., 0.5 MPa, and 30 seconds. can.
  • TP-701-B manufactured by Tester Sangyo
  • the layer b may be directly bonded to the layer a and laminated, or may have another layer interposed between the layer a and the layer b. good.
  • the layer b is preferably laminated by being directly bonded to the layer a in that the haze of the stretched film can be made smaller.
  • the layers b When the layers b are formed on both sides of the layer a, the layers b may be formed of the same component, or the layers of each other may be formed of different components.
  • the method for forming the layer a, the method for laminating the layer b, and the like will be described later in the section of the method for producing a stretched film.
  • the stretched film of the present invention may include a layer other than the layer b together with the layer b or in place of the layer b.
  • a heat seal layer can be mentioned. That is, the stretched film of the present invention can have a heat seal layer on at least one side. This makes it possible to improve the heat sealability of the stretched film.
  • the heat seal layer referred to here means a layer other than the layer b.
  • the type of the heat seal layer is not particularly limited, and for example, a known heat seal layer applied to a stretched film can be widely applied.
  • the heat seal layer can be formed of, for example, various resins (resins other than the crystalline thermoplastic resin D).
  • examples of the resin used for the heat seal layer include thermoplastic resins having a melting point of 150 ° C. or lower (resins other than the crystalline thermoplastic resin D), and as long as such resins are used, known heat seals are used.
  • a wide range of resins can be mentioned for forming the layer.
  • examples of the resin used for the heat seal layer include crystalline propylene- ⁇ -olefin random copolymers, and examples of ⁇ -olefins include ethylene and ⁇ -olefins having 4 to 20 carbon atoms, such as ethylene and butene-1. , Hexen-1, octene-1, etc.
  • the heat seal layer may contain an anti-blocking agent such as acrylic resin-based fine particles or silica within a range that does not impair the effects of the present invention.
  • the heat seal layer may be directly bonded to the layer a and laminated, or another layer (for example, the layer b) may be interposed between the layer a and the heat seal layer.
  • the heat seal layers may be formed of the same component, or the layers may be formed of different components.
  • the stretched film of the present invention may further include a layer c other than the layer b and the heat seal layer as long as the effect of the present invention is not impaired.
  • the layer c includes, for example, antifogging property, antibacterial property, adhesiveness, non-adhesiveness, smoothness, glossiness, printability, blocking resistance, slipperiness, strength-imparting property, flexibility-imparting property, oxygen gas, and ethylene.
  • a layer having one or more functions such as gas barrier property such as gas, water vapor barrier property, barrier property of odor component, prevention of component transfer of package contents, antibacterial property, antifungal property, and one or more of these various functions.
  • a layer having heat-sealing property such as gas, water vapor barrier property, barrier property of odor component, prevention of component transfer of package contents, antibacterial property, antifungal property, and one or more of these various functions.
  • the layer c may be directly bonded to the layer a and laminated, or another layer (for example, the layer b and / or the heat seal layer) is interposed between the layer a and the layer c. May be good.
  • the layers c may be formed on both sides of the layer a, the layers c may be formed of the same component, or the layers c of each other may be formed of different components.
  • the stretched film of the present invention even if layer a is used as a core layer and at least one layer selected from the group consisting of layer b, a heat seal layer and layer c is laminated, if necessary. good. More specifically, the stretched film of the present invention can include a laminate (that is, b / a / b) in which the layer a is used as a core layer and the layer b is directly bonded to one side or both sides thereof.
  • a laminated body that is, b
  • a layer a is used as a core layer
  • a layer b is directly bonded to one surface thereof
  • a heat seal layer or a layer c is bonded to the opposite surface.
  • the stretched film of the present invention can include a laminated body (that is, a heat seal layer / a / heat seal layer) in which a layer a is used as a core layer and heat seal layers are directly bonded to both sides thereof.
  • the stretched film of the present invention can include a laminated body (that is, c / a / c) in which the layer a is used as a core layer and the c layer is directly bonded to both sides thereof. Further, the stretched film of the present invention has a layer a as a core layer, and a heat seal layer is directly bonded to one side thereof, and a layer c is bonded to the opposite surface (that is, a heat seal layer). / A / c) can be included.
  • the stretched film of the present invention is preferably a laminate in which the layer a is used as the core layer and the layers b and / or the heat seal layer are directly bonded to one or both sides thereof, and more preferably the layer a is used as the core layer.
  • This is a laminated body in which the layer b is directly bonded to one side or both sides.
  • the stretched film of the present invention may have a laminated structure with the layer c as the core layer.
  • the layer c is used as a core layer, and the layer a is directly bonded to both surfaces thereof, and the layer b is directly bonded to at least one surface opposite to the layer c side of the layer a. ..
  • the stretched film of the present invention may contain an additive as an optional component, if necessary.
  • an additive for example, known additives applied to stretched films can be widely mentioned, and examples thereof include heat stabilizers, antioxidants, organic and inorganic lubricants, chlorine trapping agents, antistatic agents, and antifogging agents. , Hydrolysis inhibitor and the like.
  • heat stabilizers and antioxidants include phenol-based, hindered amine-based, phosphite-based, lactone-based, and tocopherol-based heat stabilizers and antioxidants.
  • dibutylhydroxytoluene, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (“Irganox® 1010” manufactured by BASF Japan Ltd.)
  • Irganox® 1330 manufactured by BASF Japan Ltd.
  • Tris (2,4) -Di-t-butylphenyl) phosphite (“Irgafos (registered trademark) 168" manufactured by BASF Japan Ltd.) and the like can be mentioned.
  • lubricants examples include stearic acid amides, erucic acid amides and other aliphatic amides, lauric acid diethanolamides, alkyldiethanolamines, aliphatic monoglycerides, aliphatic diglycerides, silicone crosslinked polymers, and silica as inorganic lubricants. , Alumina and the like, but an organic lubricant having less stain on the printing plate for printing purposes is preferable.
  • chlorine trapping agents examples include calcium stearate, metal soaps, hydrotalcite, and the like.
  • antistatic agent examples include alkylmethyldibetaine, alkylamine diethanol and / or alkylamine ethanol ester and / or alkylamine diethanol diester. Of these, two or more kinds of antistatic agents may be used in combination, and an aliphatic alcohol may be used in combination. Among them, the combined use of stearyldiethanolamine monostearic acid ester and stearyldiethanolamine is preferable because it has excellent antistatic performance and improves printability. Examples of typical commercially available antistatic agents include the Electro Stripper (registered trademark) series manufactured by Kao Corporation.
  • the type of anti-fog agent is not particularly limited, and for example, an anti-fog agent used for a general polyolefin film can be widely exemplified.
  • an antifogging agent an ester of a polyhydric alcohol such as glycerin, polyethylene glycol, pentaerythritol, sorbitol, polypropylene glycol and a higher fatty acid such as lauric acid, stearic acid, and oleic acid, and an ethylene oxide adduct of a higher aliphatic amine.
  • the type of hydrolysis stabilizer inhibitor is not particularly limited, and for example, those having a function of preventing or suppressing hydrolysis can be widely mentioned.
  • the hydrolysis stabilizer inhibitor for example, at least one conventionally known appropriate hydrolysis-resistant stabilizer selected from carbodiimide compounds, epoxy compounds and the like can be used.
  • the carbodiimide compound means one or more carbodiimides in the molecule.
  • the hydrolysis inhibitor in the present invention preferably has a functional group reactive with the hydroxyl group and / or the carboxyl group of the above-mentioned crystalline thermoplastic resin B, and examples of such a functional group include.
  • Examples thereof include an epoxy group, a carbodiimide group, an amino group, an isocyanate group, an oxazoline group, an anhydrous carboxylic acid group and an anhydrous phthalic acid.
  • a carbodiimide group is preferable from the viewpoint of high reactivity with a hydroxyl group and / or a carboxyl group constituting a part of the aliphatic polyester resin, and a carbodiimide compound which is a compound having one or more carbodiimide groups in the molecule is used. It is preferably used as a hydrolysis inhibitor.
  • carbodiimide compound examples include isopropylcarbodiimide, dicyclohexylcarbodiimide, and dioctylcarbodiimide as carbodiimide compounds having one carbodiimide group in the molecule, and carbodiimide having two or more carbodiimide groups in the molecule.
  • the compound examples include 1,3-phenylenedi isocyanate, 1,4-phenylenedi isocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, tetramethylxylylene diisocyanate, 4,4.
  • the additive may be contained in the layer a, and when the stretched film of the present invention includes a layer other than the layer a (layer b, heat seal layer, layer c, etc.), the other layer may be included. Additives can also be included.
  • the content ratio of the additive can be arbitrarily adjusted to the extent that the effect of the present invention is not impaired, and for example, it can be 1% by mass or less based on the total mass of the stretched film, and is 0.5% by mass. It is preferably less than or equal to, more preferably 0.1% by mass or less, and even more preferably 0.01% by mass or less.
  • the thickness of the stretched film of the present invention is not particularly limited and can be appropriately set according to the intended use.
  • the thickness of the stretched film is, for example, preferably 10 to 150 ⁇ m, more preferably 15 to 100 ⁇ m, and even more preferably 20 to 60 ⁇ m.
  • the stretched film of the present invention is used for fusing seal bags, packaging, food packaging, chemical packaging, decoration (including fashion), labels, tape base materials, printing base materials, stationery, home appliances, etc. It can be suitably used for poster paper, heat-sensitive paper base material, recording paper base material, interior and exterior of houses, automobiles, containers and the like.
  • the method for fusing the stretched film is not particularly limited, and a known method can be widely adopted, and for example, various fusing seal bags can be obtained.
  • the fusing seal bag formed by fusing the above-mentioned stretched film has high transparency and also has high fusing seal strength. Therefore, the stretched film of the present invention is particularly suitable for use in a fusing seal bag.
  • the stretched film of the present invention is preferably used as a laminate having a stretched film and a base material. That is, the present invention also includes the laminated body.
  • the stretched film and the base material are provided with an adhesive layer or an adhesive resin layer between them, and are subjected to surface treatment such as corona treatment, if necessary, by a known laminating process such as a dry lamination method or a melt extrusion lamination method. It can be pasted together.
  • the base material examples include polyethylene resin, polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), and polychloride.
  • the substrate preferably contains biomass plastic.
  • the method for producing the stretched film of the present invention is not particularly limited, and for example, a known production method can be widely adopted.
  • a resin raw material containing at least the crystalline thermoplastic resin A and the crystalline thermoplastic resin B is extruded to obtain a resin sheet, and the resin sheet is stretched to produce the stretched film of the present invention. can do.
  • Such a manufacturing method is abbreviated as "manufacturing method A”.
  • the resin raw material used in the production method A preferably contains the thermoplastic resin C, if necessary. Further, the resin raw material used in the production method A may contain other resins and / or additives, if necessary.
  • the content ratio of each component in the resin raw material is the same as the content ratio of each resin in the resin component contained in the above-mentioned layer a. Therefore, for example, based on the total mass of the resin raw material used in the method for producing a stretched film, the crystalline thermoplastic resin A is 96 to 30% by mass, the crystalline thermoplastic resin B is 3 to 60% by mass, and the like. , Thermoplastic resin C can be contained in an amount of 1 to 20% by mass.
  • the method for preparing the resin raw material can be, for example, the same as a known preparation method, and a batch type mixing device such as a tumbler or a mixer, or a continuous weighing type mixing device is used for resin pellets, powders, and the like. Dry blending method; Alternatively, the resin pellets, powders, etc. are supplied to a kneader together with other resin pellets, powders, and / or additives as needed, and melt-kneaded to form a melt-blended resin composition. How to obtain; etc. Above all, it is preferable to prepare a resin raw material by melt-kneading. In this case, the crystalline thermoplastic resin A and the crystalline thermoplastic resin B are easily mixed uniformly, and a stretched film having a desired haze can be obtained. Easy to obtain.
  • a known kneader can be used as the kneader used for melt kneading, and a single-screw screw type, a double-screw screw type, or a multi-screw screw type having more than two shafts may be used, and in the case of a screw type having two or more shafts. , Either the same direction rotation or the different direction rotation may be used.
  • a biaxial screw type kneader that rotates in the same direction is preferable because the crystalline thermoplastic resin A and the crystalline thermoplastic resin B can be easily mixed uniformly.
  • the kneading temperature for melt kneading is preferably in the range of 200 ° C to 300 ° C, more preferably 220 ° C to 280 ° C.
  • the crystalline thermoplastic resin A and the crystalline thermoplastic resin B can be mixed more uniformly.
  • an inert gas such as nitrogen can be purged.
  • the melt-kneaded resin can be pelletized to an appropriate size using a generally known granulator to obtain melt-blended resin composition pellets.
  • a resin sheet can be obtained by using the resin raw material obtained as described above. Specifically, the resin raw material is supplied to an extruder, heated and melted, and if necessary, fine foreign substances and the like are removed by a filter or the like, and then melt-extruded into a sheet from a T-die to form a resin sheet. Obtainable.
  • the extruder used to obtain the resin sheet for example, a known extruder can be widely used.
  • the screw type of the extruder There is no limitation on the screw type of the extruder, and a single-screw screw type, a double-screw screw type, or a multi-screw screw type may be used. If a multi-axis screw type having or more than that is used, it is easy to excel in mixing and dispersibility.
  • the extrusion temperature is preferably in the range of 200 ° C to 300 ° C, more preferably 220 ° C to 280 ° C.
  • an inert gas such as nitrogen can be purged.
  • the melt-extruded resin sheet is formed into a sheet by, for example, a known method such as bringing it into close contact with at least one metal drum set at a temperature of 25 to 120 ° C. by an air knife, another roll, static electricity, or the like.
  • the resin sheet is obtained as a so-called raw sheet.
  • a more preferred temperature for the metal drum is 30-80 ° C.
  • the manufacturing method A can further include, for example, a laminating step, whereby a resin sheet having a laminated structure can be obtained.
  • a laminating step whereby a resin sheet having a laminated structure can be obtained.
  • the manufacturing method A is laminated. Can be equipped with a process.
  • a conventionally adopted laminating method can be widely used, and examples thereof include a film obtained by laminating using a coextrusion method, a laminating method, a heat sealing method, or the like.
  • a stretched film having a laminated structure when producing a stretched film having a laminated structure, two or more dry blend and / or melt blend resin compositions (the composition of each resin composition may be different or the same) are used together.
  • a resin sheet having a laminated structure can be obtained by extrusion, and the resin sheet having such a laminated structure can be stretched.
  • a stretched film having a laminated structure can be produced by laminating a stretched film having a single-layer structure with another film.
  • a multilayer non-stretched film (the composition of the resin composition constituting each layer may be different or the same) obtained by laminating two or more non-stretched films extruded as a single layer with each other is stretched. This also makes it possible to produce a stretched film having a laminated structure.
  • the coextrusion method includes a pre-die laminating method in which the molten resin is brought into contact in the feed block in front of the mold, an in-die laminating method in which the molten resin is brought into contact with the inner path of the mold, for example, a multi-manifold die, and concentric multiple lips.
  • examples thereof include a die outer lamination method of discharging and contacting.
  • a multi-layer die such as a three-layer multi-manifold die is used, and the layer b / layer a / composed of a surface layer (skin layer: layer b) and a core layer (intermediate layer: layer a). It can be a three-layer structure of layer b or the like.
  • Examples of the laminating method include an extrusion laminating method in which a molten resin film is directly extruded onto another film to form a laminated film by using the equipment of the melt extrusion molding method used in the T-die method.
  • the heat-sealing method includes an external heating method in which a heated metal body is pressed against a plurality of bonded films from the outside of the film, and the conducted heat melts and adheres the films, and heat is applied to the film by high-frequency radio waves or ultrasonic waves.
  • An internal heat generation method or the like in which the above-mentioned is generated and joined is mentioned.
  • the above laminating methods can be used alone or in combination of two or more.
  • the resin sheet when the manufacturing method A has a laminating step, the resin sheet can have a laminating structure, and when the manufacturing method A does not have a laminating step, the resin sheet has a single-layer structure.
  • a stretched film made of layer a can be obtained by stretching later using a resin sheet having a single-layer structure.
  • a multilayer stretched film having at least layer a can be obtained.
  • the resin sheet (raw sheet) having the above-mentioned single layer or laminated structure is stretched.
  • the stretching method known methods such as a method of stretching between rolls provided with a peripheral speed difference, a tenter method, and a tubular method can be used.
  • the stretching direction uniaxial stretching, biaxial stretching, biaxial stretching in the diagonal direction and the like are possible, and in biaxial or more stretching, sequential stretching and simultaneous stretching are all applicable. From the viewpoint that the desired stretched film can be easily obtained, the simultaneous biaxial stretching method by the tenter method, the sequential biaxial stretching method by the tenter method, and the longitudinal (flow, MD) stretching between the rolls provided with the peripheral speed difference are performed.
  • a sequential biaxial stretching method of laterally (width, TD) stretching by the post-tenter method is preferable.
  • TD laterally
  • a method for obtaining a stretched film of the present invention by a sequential biaxial stretching method will be described, but the present invention is not limited thereto.
  • the resin sheet (raw sheet) is kept at a temperature of preferably 100 to 180 ° C, more preferably 120 to 170 ° C, passed between rolls provided with a peripheral speed difference, or in the vertical direction by the tenter method. It is preferably stretched 2 to 10 times, more preferably 2.5 to 8 times, and even more preferably 3 to 6 times. Subsequently, the stretched film is subjected to a tenter method at a temperature of preferably 100 to 180 ° C., more preferably 120 to 175 ° C., preferably 2 to 12 times, more preferably 2.5 to 11.5 times in the transverse direction. More preferably, after stretching 3 to 11 times, relaxation, heat setting is applied and the film is wound.
  • the wound film can be cut to a desired product width after being aged, preferably in an atmosphere of about 20 to 45 ° C. In this way, a stretched film having excellent stretchability, transparency, mechanical strength and the like can be obtained.
  • a step of providing the layer b on one side or both sides of the layer a is provided, the layer a and the layer b are laminated, and the crystalline thermoplastic resin A is formed at both ends in the lateral direction.
  • Examples thereof include a method in which a single-layer portion is provided to form a resin sheet, and at least the single-layer portions at both ends are gripped and stretched. According to such a method, a single-layer portion having low adhesiveness can be provided at both ends in the lateral direction by using a feed block and a single-layer T-die, and at least the single-layer portion is gripped by a clip by the tenter method.
  • the width (one side) of the single layer portion is not particularly limited, and is preferably about 1 to 30% with respect to the total width of the unstretched resin sheet, and more preferably about 2 to 30%.
  • a step of providing the layer b on one side or both sides of the layer a is provided, the layer a is provided on both sides of the layer c made of the crystalline thermoplastic resin A, and the layer c of the layer a is provided.
  • a layer b is provided on at least one surface opposite to the side, and a single layer portion composed of the layer c is provided on both ends in the lateral direction to form a resin sheet, and at least the single layer portions on both ends are gripped.
  • a method of stretching may be mentioned.
  • a feed block, a deckle, and a multi-layer T-die can be used to provide a single-layer portion having low adhesiveness at both ends in the lateral direction, and the single-layer portion is gripped by a clip by the tenter method.
  • a multilayer stretched film having at least the layer a can be obtained.
  • the width (one side) of the single layer portion is not particularly limited, and is preferably about 1 to 30% with respect to the total width of the unstretched resin sheet, and more preferably about 2 to 30%.
  • the resins used in the examples and comparative examples are as follows.
  • Luminy (registered trademark) LX175 Polylactic acid manufactured by Total Corporation PLA
  • -Resin B-2 Luminy (registered trademark) L175 (Polylactic acid manufactured by Total Corporation PLA)
  • -Resin B-3 Luminy (registered trademark) LX930 (Polylactic acid manufactured by Total Corporation PLA)
  • -Resin B-4 ENMAT (registered trademark) Y1000P (polyhydroxy alkanoate manufactured by Tianan Biological Material)
  • -Resin B-5 BioPBS (registered trademark) FZ91 (polybutylene succinate manufactured by Mitsubishi Chemical Corporation)
  • thermoplastic resin C -Resin C-1: Modiper A4400 (manufactured by NOF CORPORATION, styrene-acrylonitrile copolymer graft ethylene-glycidyl methacrylate copolymer)
  • Resin C-2 Modiper A1100 (manufactured by NOF CORPORATION, styrene graft polyethylene)
  • Resin C-3 Dynaron 9901P (manufactured by JSR Corporation, styrene-ethylene-butylene-styrene block copolymer)
  • -Resin a-1 Toughmer BL3110M (manufactured by Mitsui Chemicals, Inc., melting point 110 ° C)
  • -Resin a-2 TPX MX-002 (manufactured by Mitsui Chemicals, Inc., polymethylpentene melting point 224 ° C)
  • Biomass plastics other than crystalline thermoplastic resin B -Resin b-1: BioPBS (registered trademark) FD82 (polybutylene succinate manufactured by Mitsubishi Chemical Corporation)
  • the melting point and glass transition temperature of the resins used in Examples and Comparative Examples were calculated by the following procedure using an input compensation type DSC and Diamond DSC manufactured by PerkinElmer. Each resin was weighed in 5 mg, packed in an aluminum sample holder, and set in a DSC device. Under nitrogen flow, the temperature was raised from ⁇ 40 ° C. to 300 ° C. at a rate of 20 ° C./min, held at 300 ° C. for 5 minutes, cooled to ⁇ 40 ° C. at 20 ° C./min, and held at ⁇ 40 ° C. for 5 minutes. After that, the melting point and the glass transition temperature were obtained from the DSC curve when the temperature was raised to 300 ° C.
  • the melting peak specified in 9.1 (1) of JIS-K7121 (the maximum melting peak when a plurality of melting peaks are shown) is set as the melting point, and the intermediate point glass transition temperature specified in 9.3 (1) of JIS-K7121 is set. The glass transition temperature was used.
  • the thickness of the stretched film was measured according to JIS-C2330 using a paper thickness measuring instrument MEI-11 manufactured by Citizen Fine Device Co., Ltd.
  • the stretchability was evaluated using a batch type biaxial stretching machine KARO manufactured by Bruckner.
  • KARO a sequential biaxial stretching method was adopted, in which stretching was performed in the vertical direction and then in the horizontal direction.
  • the raw sheet was preheated and the film temperature (Ts) reached 135 ° C., and then the film was stretched in the vertical direction at a stretching speed of 6 times / sec to a stretching ratio of 5 times.
  • the film temperature (Ts) reached 145 ° C. in the same oven, the film was stretched laterally at a stretching speed of 1 times / sec to a stretching ratio of 10 times.
  • the stretchability of the obtained stretched film was evaluated according to the following criteria.
  • the 60-degree glossiness of the stretched films obtained in each Example and Comparative Example was based on JIS Z 8741 (Method 3) using a variable angle gloss meter GM-3D manufactured by Murakami Color Technology Laboratory Co., Ltd. It was measured. In the measurement, the film was measured in the vertical direction and the horizontal direction, and the average value of both was taken as the 60-degree glossiness.
  • the heat seal treatment was performed under the condition of 1 cm, and the heat sealability was evaluated according to the following criteria. ⁇ Criteria for heat sealability> ⁇ : The heat-sealed portion was fused and difficult to peel off, and the heat-sealing property was particularly excellent. ⁇ : The heat-sealing part was fused and had excellent heat-sealing properties. X: The heat-sealed portion did not fuse and was easily peeled off, and the heat-sealing property was inferior.
  • fusing seal strength (fusing property) evaluation method As the fusing seal bag, an automatic bag making machine (manufactured by Kyoei Co., Ltd.) was used, and the centrifugal film was fusing under the conditions that the temperature of the sealing blade was 400 ° C. and the bag making speed was 90 shots / minute. From the obtained fusing seal bag, a sample was cut out in a strip shape having a width of 15 mm in the direction perpendicular to the sealing direction. This strip sample was opened 180 ° so that the fusing seal portion was located in the center, both ends were sandwiched between chucks, and a tensile test was conducted so as to peel off the fusing seal portion. The test was conducted at a tensile speed of 300 mm / min, and the strength at which the fusing seal portion was broken was defined as the fusing seal strength (unit: N / 15 mm).
  • the obtained raw sheet was stretched using a batch type biaxial stretching machine KARO manufactured by Bruckner.
  • the stretching method was a sequential biaxial stretching method in which stretching was performed in the vertical direction and then in the horizontal direction. After preheating the film in an oven at a set temperature of 150 ° C. until the film temperature (Ts) reached 135 ° C., the film was stretched up to 5 times at a stretching speed of 6 times / sec in the vertical direction. Then, the film was preheated in an oven at a set temperature of 165 ° C. until the film temperature reached 145 ° C., and the film was stretched laterally at a stretching speed of 1 times / sec to 10 times.
  • the lateral direction was relaxed to 9.5 times at a relaxation rate of 0.5 times / sec, then heat was set for 10 seconds, then discharged from the oven and cooled to room temperature to a thickness of 25 ⁇ m. A stretched film was obtained.
  • Examples 2 to 7, Comparative Examples 1 to 5 The same as in Example 1 except that the types of the resin of the component A and the resin of the component B for forming the layer a and the ratio of their use were set as shown in Table 1 below to prepare the resin raw material.
  • a stretched film having a thickness of 26.6 ⁇ m was obtained by the above method.
  • Example 8 to 12 A resin raw material was prepared using the component C (thermoplastic resin C) in addition to the component A (crystalline thermoplastic resin A) and the component B (crystalline thermoplastic resin B). Specifically, the types and amounts of the A component resin and the B component resin for forming the layer a are set as shown in Table 1 below, and the C component for forming the layer a is further set. A stretched film having a thickness of 26.6 ⁇ m was obtained by the same method as in Example 1 except that the type and amount used were set as shown in Table 1 to prepare the resin raw material.
  • the pellet a was charged into the uniaxial screw type extruder a from the hopper, and the pellet b was charged into the uniaxial screw type extruder b different from the extruder a from the hopper.
  • the pellet a and the pellet b were each melted, and these were laminated in a three-layer structure of b-ab inside a three-layer multi-manifold die and extruded as a three-layer laminated resin layer.
  • the ratio of the amount of extruded resin between the uniaxial screw type extruder a and the uniaxial screw type extruder b was 2: 1.
  • the extruded resin layer was cooled and solidified while being pneumatically pressed onto a cooling drum controlled at 45 ° C. using an air knife to obtain a raw sheet.
  • the obtained raw sheet was stretched using a batch type biaxial stretching machine KARO manufactured by Bruckner.
  • the stretching method was a sequential biaxial stretching method in which stretching was performed in the vertical direction and then in the horizontal direction.
  • the film temperature (Ts) was preheated in an oven at a set temperature of 150 ° C. until it reached 135 ° C., and then the film was stretched up to 5 times at a stretching speed of 6 times / sec in the vertical direction.
  • the film was preheated in an oven at a set temperature of 165 ° C. until the film temperature reached 145 ° C., and then stretched laterally to 10 times at a stretching speed of 1 time / sec.
  • the lateral direction was relaxed to 9.5 times at a relaxation rate of 0.5 times / sec, then heat was set for 10 seconds, then discharged from the oven and cooled to room temperature to a thickness of 27. A 1 ⁇ m stretched film was obtained.
  • Example 14 to 15 Comparative Examples 6 to 7
  • the types and amounts of the A component resin, the B component resin, and the C component resin for forming the layer a, and the types of the resin for forming the layer b are set as shown in Table 1 below.
  • a stretched film having a thickness of 30.8 ⁇ m was obtained by the same method as in Example 13 except that the resin raw material a and the resin raw material b were prepared respectively.
  • Table 1 shows the production conditions and evaluation results of the stretched films obtained in each Example and Comparative Example.
  • the stretched film obtained in the examples has excellent stretchability because it has a layer a in which a crystalline polyolefin resin having a specific melting point and a biomass plastic having a specific melting point are formed in a predetermined ratio. It was highly transparent. It was also shown that the stretched films of Examples 13 to 15 are suitable for use in a fusing seal bag because they have a high fusing seal strength. In Comparative Examples 1, 2, 4 and 7, a stretched film could not be obtained.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un film étiré présentant une excellente aptitude à l'étirage et une transparence élevée.　Le film étiré selon la présente invention est pourvu d'une couche a comprenant un composant de résine qui contient une résine thermoplastique cristalline A et une résine thermoplastique cristalline B. La résine thermoplastique cristalline A est une résine à base de polyoléfine cristalline ayant un point de fusion de 135 à 175 °C. La résine thermoplastique cristalline B est une matière plastique de biomasse ayant un point de fusion de 110 à 200 °C. La couche a présente un trouble de 0,5 à 30 % et contient de 30 à 96 % en masse de la résine thermoplastique cristalline A par rapport à la masse totale de la résine thermoplastique cristalline A et de la résine thermoplastique cristalline B.
PCT/JP2021/048195 2020-12-28 2021-12-24 Film étiré, sac d'étanchéité découpé par fusion et stratifié WO2022145364A1 (fr)

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JP7512504B1 (ja) 2023-11-16 2024-07-08 デンカ株式会社 熱可塑性離型フィルムの製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7512504B1 (ja) 2023-11-16 2024-07-08 デンカ株式会社 熱可塑性離型フィルムの製造方法

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