WO2023228736A1 - 積層体、その製造方法、および成形体 - Google Patents

積層体、その製造方法、および成形体 Download PDF

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Publication number
WO2023228736A1
WO2023228736A1 PCT/JP2023/017540 JP2023017540W WO2023228736A1 WO 2023228736 A1 WO2023228736 A1 WO 2023228736A1 JP 2023017540 W JP2023017540 W JP 2023017540W WO 2023228736 A1 WO2023228736 A1 WO 2023228736A1
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Prior art keywords
resin
layer
adhesive layer
styrene
laminate
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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
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PCT/JP2023/017540
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English (en)
French (fr)
Japanese (ja)
Inventor
健介 村島
五樹 日下部
雅幸 藤田
康則 岡田
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Kaneka Corp
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Kaneka Corp
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Publication date
Application filed by Kaneka Corp filed Critical Kaneka Corp
Priority to EP23811611.5A priority Critical patent/EP4530065A1/en
Priority to CN202380041024.9A priority patent/CN119212866A/zh
Priority to JP2024523021A priority patent/JPWO2023228736A1/ja
Publication of WO2023228736A1 publication Critical patent/WO2023228736A1/ja
Priority to US18/955,030 priority patent/US20250083426A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • B32B27/10—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 paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
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    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
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    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2425/00—Presence of styrenic polymer

Definitions

  • the present invention relates to a laminate in which a resin layer is laminated on at least one side of a base material layer such as paper, a method for manufacturing the same, and a molded product.
  • Poly(3-hydroxyalkanoate) copolymer (hereinafter sometimes referred to as "P3HA”) is a thermoplastic polyester that is produced and accumulated as an energy storage substance in the cells of many microbial species. It is a material that can biodegrade not only in soil but also in seawater. Therefore, it is attracting attention as a material that can solve the above problems.
  • P3HA Poly(3-hydroxyalkanoate) copolymer
  • 3HB 3-hydroxybutyrate
  • 3HH 3-hydroxyhexanoate
  • PHBH/paper composite material which is made by integrating a copolymer with PHBH (hereinafter sometimes referred to as "PHBH") with a base material such as paper, is suitable for food contact containers etc. with low environmental impact. It is of particular interest to society because of its applicability.
  • Examples of methods for integrating PHBH and paper include extrusion lamination and aqueous slurry coating, but extrusion lamination is preferred because it is difficult to obtain sufficient mechanical strength of the resin layer with coating. It will be done.
  • PHBH generally has a high melt viscosity and does not easily penetrate paper, it has not been easy to bond melt-extruded PHBH and paper with sufficient strength. As a result, the laminate layer peels off from the paper during the manufacturing process of cup molded bodies such as drinking cups, resulting in a problem of leakage when the contents are filled.
  • PHBH is not disclosed in Patent Document 1
  • 10 g of polycaprolactone dispersion or emulsion is placed on paper for the purpose of improving the penetration of biodegradable resin into paper and improving the lamination strength.
  • a method is disclosed in which a 3-hydroxybutyric acid/3-hydroxyvaleric acid copolymer (PHBV) is laminated by extrusion lamination after coating and drying at a basis weight (dry weight of the layer) of /m 2 .
  • Patent Document 1 Although the method of Patent Document 1 tends to improve the adhesion between the paper and the resin layer, it is difficult to apply the dispersion or emulsion of polycaprolactone at a large basis weight of 10 g/m 2 and then dry it. There have been problems such as drying takes a long time and productivity is not high, and the paper base material deteriorates due to the drying, and the paper becomes too dry, causing warpage in the laminate.
  • the present invention provides a laminate including a base layer, an adhesive layer, and a resin layer containing a poly(3-hydroxyalkanoate) copolymer in this order, the adhesive layer forming the adhesive layer. It is an object of the present invention to provide a laminate that has good drying properties when drying and has high adhesive strength between a base layer and a resin layer.
  • the present inventors have discovered a laminate including a base material layer, an adhesive layer, and a resin layer containing a poly(3-hydroxyalkanoate) copolymer in this order.
  • the above problem can be solved by adjusting the glass transition temperature of the entire resin contained in the adhesive layer within a specific range and setting the thickness of the resin layer within a specific range while making the basis weight of the adhesive layer sufficiently small.
  • the inventors have discovered that the problem can be solved, and have completed the present invention.
  • the present invention provides a laminate including a base material layer (A), an adhesive layer (B), and a resin layer (D) containing a poly(3-hydroxyalkanoate) copolymer (C) in this order.
  • the glass transition temperature of the entire resin contained in the adhesive layer (B) is 20°C or more and less than 90°C
  • the adhesive layer (B) has a basis weight of 0.1 g/m 2 or more and less than 5.0 g/m 2
  • the resin layer (D) relates to a laminate having a thickness of 5 ⁇ m or more and 100 ⁇ m or less.
  • the present invention also provides a method for manufacturing the laminate, comprising: forming the adhesive layer (B) on at least one side of the base layer (A);
  • the present invention also relates to a method for manufacturing a laminate, which includes a step of forming the resin layer (D) on the surface of the adhesive layer (B) by an extrusion lamination method or a thermal lamination method.
  • the present invention also relates to a molded article containing the laminate.
  • a laminate including a base material layer, an adhesive layer, and a resin layer containing a poly(3-hydroxyalkanoate) copolymer in this order, wherein It is possible to provide a laminate that has good drying properties and high adhesive strength between the base layer and the resin layer. By using the laminate, it is possible to improve the production efficiency and quality of the molded body.
  • FIG. 2 is a schematic diagram showing a laminated structure of a laminated body according to the present embodiment.
  • the laminate according to one embodiment of the present invention includes an adhesive layer (B) and a resin layer (C) containing a poly(3-hydroxyalkanoate) copolymer (C) on at least one side of the base layer (A). D).
  • a base material layer (A) indicated by numeral 2 an adhesive layer (B) indicated by numeral 3, and a resin layer (D) indicated by numeral 4 are arranged in this order. It is laminated with
  • the adhesive layer (B) may be laminated directly on the base material layer (A), or the adhesive layer (B) and the base material layer (A) may be laminated directly on top of the base material layer (A), as long as the adhesion is not inhibited. Another layer may be further included in between.
  • the resin layer (D) may be the outermost layer exposed on the surface of the laminate, or may be a separate layer on the resin layer (D) for the purpose of imparting water resistance or gloss.
  • the layers may be laminated.
  • the base layer (A) Only one side of the base layer (A) may have an adhesive layer (B) and a resin layer (D), or both sides of the base layer (A) may have an adhesive layer (B) and a resin layer ( D) may also be included.
  • the base layer (A) has an adhesive layer (B) and a resin layer (D) on only one side, no other layer is formed on the other side, and the base layer (A) is a laminate. It may be the outermost layer exposed on the surface, or another layer may be laminated for the purpose of imparting water resistance, gloss, or adhesiveness.
  • the base material layer (A) has an adhesive layer (B) and a resin layer (D) on both sides, the materials constituting the adhesive layer (B) on the front side and the adhesive layer (B) on the back side, and the basis weight , the thicknesses may be the same or different. The same applies to the resin layer (D) on the front side and the resin layer (D) on the back side.
  • the basis weight (g/m 2 ) in this application refers to the dry weight (solid content) of the layer.
  • the material constituting the base layer (A) is not particularly limited, but is preferably biodegradable.
  • Examples include paper (mainly composed of cellulose), cellophane, cellulose ester; polyvinyl alcohol, polyamino acids, polyglycolic acid, pullulan, and materials obtained by vapor-depositing inorganic substances such as aluminum and silica on these substrates. Among them, paper is preferred because it has excellent heat resistance and is inexpensive.
  • the type of paper is not particularly limited and can be appropriately selected depending on the use of the laminate, and examples thereof include cup base paper, kraft paper, high-quality paper, coated paper, thin paper, glassine paper, paperboard, etc.
  • the paper may be added with a water resistant agent, a water repellent, an inorganic substance, etc. as necessary, and may be subjected to a surface treatment such as an oxygen barrier layer coating or a water vapor barrier coating.
  • the base layer (A) may be subjected to surface treatment such as corona treatment, ozone treatment, plasma treatment, flame treatment, anchor coat treatment, oxygen barrier layer coating, water vapor barrier coating, etc. These surface treatments may be performed alone or in combination with a plurality of surface treatments.
  • the adhesive layer (B) is a layer mainly composed of resin.
  • the main resin contained in the adhesive layer (B) is not particularly limited, but resins commonly used in the coated paper field or resin film field can be suitably used. Resins that have high affinity with base materials such as paper and P3HA are preferred, and examples of such resins include acrylic resins, vinyl chloride resins, styrene-acrylic resins, styrene-butadiene resins, and styrene-isoprene resins.
  • Examples thereof include polycarbonate resins, urea resins, melamine resins, epoxy resins, phenol resins, urethane resins, diallylphthalate resins, and imine resins. Only one type of these resins can be used, or two or more types of resins can be used in a mixture at an arbitrary ratio.
  • the adhesive layer (B) contains at least one of an acrylic resin or a styrene-acrylic resin, since it has particularly good affinity with P3HA.
  • the adhesive layer (B) preferably contains the above-mentioned main resins in a total amount of 50% by weight or more, more preferably 60% by weight or more, and preferably 70% by weight or more of the total amount of the adhesive layer (B). More preferably, it is particularly preferably contained in an amount of 80% by weight or more.
  • the upper limit may be 100% by weight or less, and may be 99% by weight or less.
  • the proportion of styrene units in the entire acrylic resin or styrene-acrylic resin is 0 mol% or more and less than 50 mol%. It is preferable that When the styrene unit content is less than 50 mol%, the glass transition temperature (hereinafter sometimes referred to as "Tg") of the resin can be easily adjusted to less than 90°C, and the affinity between the adhesive layer (B) and P3HA is improved. By improving the properties, the adhesive strength of the laminate can be further improved.
  • the proportion of the styrene units is more preferably 40 mol% or less, even more preferably 30 mol% or less, and particularly preferably 20 mol% or less.
  • the adhesive layer (B) contains either an acrylic resin or a styrene-acrylic resin
  • the proportion of methyl (hereinafter sometimes referred to as "MMA") units is preferably 50 mol% or more and less than 95 mol%.
  • the (meth)acrylic unit refers to an acrylic monomer unit and a methacrylic monomer unit that constitute the resin.
  • the proportion of MMA units is 50 mol % or more, the Tg of the resin can be easily adjusted to 20° C. or more, and the adhesive strength of the laminate can be further improved.
  • the proportion of the MMA unit is more preferably 60 mol% or more, even more preferably 70 mol% or more, and particularly preferably 80 mol% or more.
  • the proportion of MMA units is less than 95 mol %, the Tg of the resin can be easily adjusted to less than 90° C., and the adhesive strength of the laminate can be improved.
  • the monomer component of the structural unit other than the styrene unit and MMA unit contained in the acrylic resin or styrene-acrylic resin is not particularly limited, but a monomer component having good affinity with P3HA is preferable, and specifically, , acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, and the like.
  • methacrylic acid and/or methacrylic ester it is preferable to use methacrylic acid and methacrylic ester, and it is particularly preferable to use methacrylic acid and methacrylic ester in combination.
  • methacrylic esters other than MMA include ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and methacrylic acid.
  • the Tg of the main resin contained in the adhesive layer (B) is not particularly limited, it is preferably within a range that satisfies the Tg (described later) of the entire resin contained in the adhesive layer (B). From that viewpoint, the Tg of the main resin contained in the adhesive layer (B) is preferably 20°C or more and less than 90°C, more preferably 25°C or more and less than 85°C, and even more preferably 30°C or more and less than 80°C.
  • the main resin contained in the adhesive layer (B) may be water-soluble or may be soluble in an organic solvent.
  • water-insoluble resins other additives can also be added to improve dispersibility and coatability in water.
  • the solid content concentration of the resin is not particularly limited, but it is preferably 30% by weight or more, and 40% by weight or more in order to keep the amount of heat required for drying low. is more preferable, and even more preferably 50% by weight or more. Further, from the viewpoint of avoiding sedimentation of the dispersed resin and achieving good coating properties, the solid content concentration is preferably 60% by weight or less.
  • the adhesive layer (B) may contain only the main resin as a resin component, or may further contain a tackifying resin in addition to the main resin.
  • a tackifying resin By using the tackifier resin, the Tg of the entire resin contained in the adhesive layer (B) can be reduced, and the adhesive strength of the laminate can be further improved.
  • the tackifying resin is not particularly limited, and commonly used resins can be used. It may be either solid or liquid at room temperature. Specifically, rosin resin, terpene resin, ethylene resin, vinyl acetate resin, alkylphenol-formaldehyde resin, alkylphenol-acetylene resin, coumaron-indene resin, styrene resin, xylene-formaldehyde resin. It can be preferably used. These may be used alone or in combination of two or more. Particularly preferred are rosin resins.
  • the weight average molecular weight (Mw) of the tackifying resin can be selected as appropriate, but from the viewpoint of improving adhesive strength, it is preferably 100 or more and less than 5,000, more preferably 200 or more and less than 3,000. It is preferably 300 to 2,000, more preferably 400 to 1,000.
  • the weight average molecular weight of the tackifying resin can be measured in terms of polystyrene using gel permeation chromatography (HPLC GPC system manufactured by Shimadzu Corporation) using a chloroform solution.
  • gel permeation chromatography HPLC GPC system manufactured by Shimadzu Corporation
  • a column suitable for measuring the weight average molecular weight may be used.
  • the content of the tackifying resin is 1% by weight or more and less than 30% by weight of the total weight of the adhesive layer (B) from the viewpoint of improving adhesive strength. It is preferably 3 to 25% by weight, and even more preferably 5 to 20% by weight. In particular, when the content of the tackifying resin is 10% by weight or more, the adhesive strength of the laminate can be particularly good.
  • the Tg of the entire resin contained in the adhesive layer (B) is controlled within the range of 20°C or more and less than 90°C from the viewpoint of ensuring adhesive strength between the base layer (A) and the resin layer (D). If the Tg of the entire resin contained in the adhesive layer (B) is less than 20° C., the adhesion strength may be insufficient at around room temperature due to strong tackiness. Moreover, if the temperature is 90° C. or higher, depending on the resin temperature when laminating the resin layer (D), the amount of heat may be insufficient and the lamination strength may become insufficient.
  • the Tg of the entire resin contained in the adhesive layer (B) is preferably 25°C or more and less than 85°C, more preferably 30°C or more and less than 80°C. Moreover, the upper limit may be 75°C or less, 70°C or less, or 65°C or less. The lower limit may be 40°C or higher, 50°C or higher, or 60°C or higher.
  • the Tg of the entire resin contained in the adhesive layer (B) refers to the Tg of the main resin when the adhesive layer (B) contains only the above-mentioned main resin as a resin component, and the Tg of the entire resin contained in the adhesive layer (B) When contains the main resin and the tackifier resin, it refers to the Tg shown by the main resin and the tackifier resin as a whole.
  • the Tg of the entire resin contained in the adhesive layer (B) can be measured by differential thermal analysis.
  • the basis weight of the adhesive layer (B) is adjusted to a range of 0.1 g/m 2 or more and less than 5.0 g/m 2 . If the basis weight is less than 0.1 g/m 2 , the adhesiveness with the resin layer (D) may decrease. On the other hand, if it exceeds 5.0 g/m 2 , a large amount of heat is required during drying, resulting in a heavy load on the equipment, or, for example, blocking during winding of the original fabric may become a problem due to insufficient drying.
  • the basis weight is preferably 0.5 g/m 2 or more and 4.0 g/m 2 or less, more preferably 0.8 g/m 2 or more and 3.0 g/m 2 or less, and 1.0 g/m 2 or more and 3.0 g/m 2 or less. More preferably, it is .5 g/m 2 or less.
  • the resin layer (D) contains a poly(3-hydroxyalkanoate) copolymer (hereinafter sometimes referred to as "P3HA") (C).
  • P3HA poly(3-hydroxyalkanoate) copolymer
  • the resin layer (D) may be the outermost layer in the laminate according to the present embodiment, and in that case, the resin layer (D) can be used for heat sealing (described later). .
  • the poly(3-hydroxyalkanoate) copolymer (C) is a biodegradable aliphatic polyester (preferably a polyester containing no aromatic ring), and contains at least one or more 3-hydroxy It is a copolymer with alkanoate units.
  • the 3-hydroxyalkanoate unit is preferably represented by the following general formula (1). [-CHR-CH 2 -CO-O-] (1)
  • R represents an alkyl group represented by C p H 2p+1 , and p represents an integer of 1 to 15.
  • R include linear or branched alkyl groups such as methyl, ethyl, propyl, methylpropyl, butyl, isobutyl, t-butyl, pentyl, and hexyl.
  • p is preferably 1 to 10, more preferably 1 to 8.
  • the poly(3-hydroxyalkanoate) copolymer (C) contains 3-hydroxyalkanoate units (particularly units represented by general formula (1)) in an amount of 50 mol% of the total structural units (monomer units).
  • the content is preferably 60 mol% or more, more preferably 60 mol% or more, and even more preferably 70 mol% or more.
  • the poly(3-hydroxyalkanoate) copolymer may contain only two or more types of 3-hydroxyalkanoate units, or may contain one or two or more types of 3-hydroxyalkanoate units as constituent units of the polymer. -In addition to the hydroxyalkanoate unit, it may contain other units (eg, 4-hydroxyalkanoate unit, etc.).
  • the poly(3-hydroxyalkanoate) copolymer (C) is preferably a copolymer containing 3-hydroxybutyrate (hereinafter sometimes referred to as 3HB) units and other hydroxyalkanoate units. .
  • 3HB 3-hydroxybutyrate
  • the other hydroxyalkanoate unit may be a 3-hydroxyalkanoate unit other than the 3HB unit, or a hydroxyalkanoate unit other than the 3-hydroxyalkanoate unit (for example, a 4-hydroxyalkanoate unit). Good too. Only one type of the other hydroxyalkanoate units may be included, or two or more types may be included.
  • poly(3-hydroxyalkanoate) copolymer (C) examples include poly(3-hydroxybutyrate-co-3-hydroxypropionate), poly(3-hydroxybutyrate-co-3-hydroxypropionate), and poly(3-hydroxybutyrate-co-3-hydroxypropionate).
  • PHBV poly(3-hydroxybutyrate-co-3-hydroxyvalerate-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-3-hydroxy hexanoate)
  • PHBH poly(3-hydroxybutyrate-co-3-hydroxyheptanoate), poly(3-hydroxybutyrate-co-3-hydroxyoctanoate), poly(3-hydroxybutyrate-co-3-hydroxyoctanoate), hydroxybutyrate-co-3-hydroxynonanoate), poly(3-hydroxybutyrate-co-3-hydroxydecanoate), poly(3-hydroxybutyrate-co-3-hydroxyundecanoate), poly (3-hydroxybutyrate-co-4-hydroxybutyrate) (abbreviation: P3HB4HB) and the like.
  • P3HB4HB poly(3-hydroxybutyrate-co-4-hydroxybutyrate)
  • PHBH changes the melting point and degree of crystallinity by changing the composition ratio of repeating units, and as a result, physical properties such as Young's modulus and heat resistance can be easily adjusted. It is a particularly useful plastic industrially because it can impart physical properties.
  • PHBH A specific method for producing PHBH is described, for example, in International Publication No. 2010/013483.
  • commercially available PHBHs include Kaneka Biodegradable Polymer Green Planet (registered trademark) by Kaneka Corporation.
  • the average content ratio of 3HH in PHBH is 3 mol% or more, the adhesive strength of the laminate can be further improved.
  • the average content ratio of 3HH is 20 mol % or less, the crystallization rate of PHBH does not become too slow, and production is relatively easy.
  • the average content ratio of each constituent monomer in PHBH means the molar ratio of 3HB and 3HH contained in PHBH.
  • PHBH is a mixture of at least two types of PHBH with different content ratios of constituent monomers, or when it is a mixture containing at least one type of PHBH and PHB, the mole of each constituent monomer contained in the entire mixture means ratio.
  • the average content ratio of the constituent monomers can be determined by a method known to those skilled in the art, for example, the method described in paragraph [0047] of International Publication No. 2013/147139, or by NMR measurement.
  • the resin layer (D) may contain at least two types of PHBH with different content ratios of constituent monomers, and in addition to at least one type of PHBH, PHB (3-hydroxybutyl
  • the polymer may further contain a homopolymer of esters.
  • a highly crystalline and high melting point PHBH with a 3HH content ratio of less than 6 mol%, and a low crystalline and low melting point PHBH with a 3HH content ratio of 15 mol% or more is preferable to include.
  • the resin layer (D) is preferably a resin layer containing PHBH as a main component.
  • the content of PHBH in the resin layer (D) is preferably 50 to 100% by weight, more preferably 70 to 100% by weight, and even more preferably 80 to 100% by weight.
  • the lower limit may be 90% by weight or more, or 95% by weight or more.
  • the resin layer (D) may contain only PHBH or only PHBH and PHB as a resin component, or may further contain a resin other than PHBH and PHB.
  • PHBH and resins other than PHB are preferably biodegradable resins, specifically poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHB3HV), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHB3HV), poly(3-hydroxybutyrate-co-3-hydroxyoctanoate) (PHB3HO), poly(3-hydroxybutyrate-co-3-hydroxyoctadeca) (PHB3HOD), poly(3-hydroxybutyrate-co-3-hydroxydecanoate) (PHB3HD), poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexa Poly(3-hydroxyalkanoates) such as (PHB3HV3HH); Aliphatic polyester resins such as polycaprolactone, polybutylene succ
  • the resin layer (D) may contain additives that are normally added to resin materials within a range that does not impede the effects of the invention.
  • additives include, for example, inorganic fillers, colorants such as pigments and dyes, odor absorbers such as activated carbon and zeolite, fragrances such as vanillin and dextrin, plasticizers, antioxidants, antioxidants, and weatherproofing agents. Examples include properties improvers, ultraviolet absorbers, crystal nucleating agents, lubricants, mold release agents, water repellents, antibacterial agents, sliding properties improvers, and the like. As these additives, only one type may be used, or two or more types may be used in combination. However, the additive is an arbitrary component, and the resin layer (D) may not contain these additives. As the additive, it is preferable to use a lubricant and/or an inorganic filler from the viewpoint of improving the releasability from the pressure bonding surface such as a cooling roll during lamination of the resin layer (D).
  • the lubricant examples include saturated or unsaturated fatty acid amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, and methylene bisstearic acid amide. , aliphatic amide compounds such as alkylene fatty acid amide such as methylene bisstearic acid amide, pentaerythritol, and the like.
  • saturated or unsaturated fatty acid amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, and methylene bisstearic acid amide.
  • aliphatic amide compounds such as alkylene fatty acid amide such as methylene bisstearic acid amide, pentaerythritol, and the like
  • the blending amount of the lubricant in the resin layer (D) is preferably 0.1 to 2 parts by weight, and preferably 0.2 to 2 parts by weight, based on 100 parts by weight of the total amount of resin components contained in the resin layer (D). 1 part by weight is more preferred.
  • the blending amount is 2 parts by weight or less, the problem of the lubricant bleeding during pressure bonding and adhering to the pressure bonding surface of the cooling roll or the like can be suppressed, and continuous processing for a long time can be carried out.
  • examples of the inorganic filler include talc, calcium carbonate, mica, silica, clay, kaolin, titanium oxide, alumina, and zeolite.
  • the average particle diameter of these inorganic fillers is preferably 0.5 ⁇ m or more.
  • the blending amount of the inorganic filler in the resin layer (D) is preferably 0.5 to 5 parts by weight, and 1 to 5 parts by weight, based on 100 parts by weight of the total amount of resin components contained in the resin layer (D). 3 parts by weight is more preferred.
  • the blending amount is preferably 0.5 to 5 parts by weight or more, it is possible to obtain the effect of improving peelability by blending the inorganic filler.
  • the blending amount is 5 parts by weight or less, it is possible to suppress the occurrence of cracks in the resin layer (D).
  • the thickness of the resin layer (D) is set in a range of 5 ⁇ m or more and 100 ⁇ m or less. If the thickness is less than 5 ⁇ m, the resin is cooled too quickly during lamination of the resin layer (D), so that the adhesion with the base layer (A) on which the adhesive layer (B) is formed may decrease. Furthermore, cracks are likely to occur in the resin layer (D) when processing the laminate into a molded body.
  • the lower limit of the thickness is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more.
  • the thickness of the resin layer (D) exceeds 100 ⁇ m, unevenness in resin temperature becomes large during formation of the resin layer (D), which may cause unevenness in thickness or poor appearance due to melt fracture. Furthermore, the laminate may become too hard, resulting in molding defects.
  • the upper limit of the thickness is preferably 80 ⁇ m or less, more preferably 60 ⁇ m or less.
  • an adhesive layer (B) is formed on at least one side of the base layer (A) (first step), and a resin layer (D) is formed on the surface of the formed adhesive layer (B). ) (second step).
  • a solution or aqueous slurry containing the components constituting the adhesive layer (B) is applied to one or both sides of the base layer (A). It is preferable to apply an aqueous dispersion such as the like and heat it to dry and form a film.
  • the method for applying the solution or aqueous dispersion onto the substrate is not particularly limited, and any known method capable of forming a resin layer on the substrate can be used as appropriate. Specifically, a spraying method, a scattering method, a slit coater method, an air knife coater method, a roll coater method, a bar coater method, a comma coater method, a blade coater method, a screen printing method, a gravure printing method, etc. can be used. . Before applying the solution or aqueous dispersion, the substrate may be subjected to a surface treatment such as the above-mentioned corona treatment.
  • a surface treatment such as the above-mentioned corona treatment.
  • the drying treatment after coating can be performed using a known heating method.
  • Examples include hot air heating, infrared heating, microwave heating, roll heating, hot plate heating, etc., and these can be used alone or in combination of two or more types.
  • a second step of forming a resin layer (D) on the surface of the formed adhesive layer (B) is performed.
  • the method for forming the resin layer (D) is to apply a solution or aqueous dispersion containing the components constituting the resin layer (D) onto the surface of the adhesive layer (B), and dry it by heating to form a film. You can. However, from the viewpoint of adhesion with the adhesive layer (B), productivity, or quality to suppress thermal deterioration, a resin layer ( D) is preferably formed.
  • a general extrusion lamination method can be used. Specifically, a molten resin material is extruded into a film from a T-shaped die, and is pressed onto the surface of the adhesive layer (B) while being cooled using a cooling roll. Immediately thereafter, the resin material is extruded from a cooling roll. By peeling, a resin layer (D) can be formed and a laminate can be manufactured.
  • the temperature of the resin immediately after being melted and extruded from the tip of the T-shaped die must be higher than the melting point of the component contained in the resin layer (D) and lower than 165 ° C. preferable.
  • a general thermal lamination method can be used. Specifically, first, a molten resin material is extruded from, for example, a T-shaped die, and a film containing the resin material is formed while being cooled using a cooling roll. Next, a molded article can be produced by pressing the obtained film onto the surface of the adhesive layer (B) using a hot roll or the like.
  • the temperature of the resin immediately after being melted and extruded from the tip of the T-shaped die is higher than that of the resin layer (D).
  • ) is preferably higher than or equal to the melting point of the components contained in (165° C.) and lower than 165° C.
  • the surface of the adhesive layer (B) is subjected to corona treatment or flame treatment. , ozone treatment, etc. may be performed.
  • the first step and the second step are preferably performed sequentially and continuously from the viewpoint of adhesion and processability (balance between melting and crystallization).
  • the molded article according to one aspect of the present embodiment includes the above-described laminate and has a desired size and shape. Since the molded body is formed from a laminate including a resin layer (D) containing P3HA, it is advantageous in various uses.
  • the molded body is not particularly limited as long as it contains the laminate, and examples thereof include paper, film, sheet, tube, plate, rod, container (eg, bottle container), bag, parts, and the like.
  • the molded body is preferably a bag or a bottle container from the viewpoint of measures against marine pollution.
  • the molded body may be the laminate itself, or may be obtained by secondary processing of the laminate.
  • the molded body can be used as various packaging container materials such as shopping bags, various bag making materials, food/confectionery packaging materials, cups, trays, cartons, etc. (in other words, food, It can be suitably used in various fields such as cosmetics, electronics, medical care, pharmaceuticals, etc.).
  • the molded body contains the resin layer (D) that has high adhesion to the base material and good heat resistance, it can be used as a container for storing liquids, especially instant noodles, instant soup, coffee cups, etc., and side dishes. It can be more suitably used as a container for holding warm contents, such as a tray used for lunch boxes, microwave foods, etc.
  • the secondary processing can be carried out in the same manner as conventional resin-laminated paper or coated paper, that is, using various bag-making machines, filling and packaging machines, etc. It can also be processed using equipment such as a paper cup molding machine, punching machine, box machine, etc. In these processing machines, a known technique can be used to bond the laminate, such as a heat sealing method, an impulse sealing method, an ultrasonic sealing method, a high frequency sealing method, a hot air sealing method, a flame sealing method, etc. can be used.
  • the heat-sealing temperature of the laminate varies depending on the adhesion method, but for example, when using a heated heat-sealing tester with a seal bar, the resin temperature is usually 180°C or lower, preferably 170°C or lower, and more preferably 160°C or lower. Set it so that it is below °C. Within the above range, melting of the resin near the sealing portion can be avoided, and an appropriate thickness of the resin layer and sealing strength can be ensured. Further, the lower limit of the resin temperature when using a heating type heat seal tester having a seal bar is usually 100°C or higher, preferably 110°C or higher, and more preferably 120°C or higher. Within the above range, appropriate adhesion at the seal portion can be ensured.
  • the heat sealing pressure of the laminate varies depending on the adhesion method, but for example, when a heating heat sealing tester having a seal bar is used, it is usually 0.1 MPa or more, preferably 0.5 MPa or more. Within the above range, appropriate adhesion at the seal portion can be ensured. Further, the upper limit of the heat sealing pressure when using a heating type heat sealing tester having a seal bar is usually 1.0 MPa or less, preferably 0.75 MPa or less. Within the above range, thinning of the film thickness at the end of the seal can be avoided and seal strength can be ensured.
  • the molded body is made of a material different from the molded body (for example, fiber, thread, rope, woven fabric, knitted fabric, nonwoven fabric, paper, film, sheet, tube, plate, etc.) in order to improve its physical properties. , rods, containers, bags, parts, foams, etc.). Preferably, these materials are also biodegradable.
  • a laminate comprising a base layer (A), an adhesive layer (B), and a resin layer (D) containing a poly(3-hydroxyalkanoate) copolymer (C) in this order,
  • the glass transition temperature of the entire resin contained in the adhesive layer (B) is 20°C or more and less than 90°C
  • the adhesive layer (B) has a basis weight of 0.1 g/m 2 or more and less than 5.0 g/m 2
  • the resin layer (D) is a laminate having a thickness of 5 ⁇ m or more and 100 ⁇ m or less.
  • the adhesive layer (B) is made of acrylic resin, vinyl chloride resin, styrene-acrylic resin, styrene-butadiene resin, styrene-isoprene resin, polycarbonate resin, urea resin, melamine resin, epoxy resin,
  • the laminate according to item 1, comprising at least one resin selected from the group consisting of phenolic resin, urethane resin, diallyl phthalate resin, and imine resin.
  • the adhesive layer (B) contains at least one of an acrylic resin or a styrene-acrylic resin, and the proportion of styrene units in the entire acrylic resin or styrene-acrylic resin is 0 mol% or more and less than 50 mol%.
  • the adhesive layer (B) contains at least one of an acrylic resin or a styrene-acrylic resin, and contains methyl methacrylate units in (meth)acrylic units contained in the acrylic resin or styrene-acrylic resin as a whole.
  • the tackifying resin includes rosin resin, terpene resin, ethylene resin, vinyl acetate resin, alkylphenol-formaldehyde resin, alkylphenol-acetylene resin, coumaron-indene resin, styrene resin, and xylene-based resin.
  • [Item 7] The laminate according to item 5 or 6, wherein the tackifying resin has a weight average molecular weight of 100 or more and less than 5,000.
  • [Item 8] The laminate according to item 1 or 2, wherein the poly(3-hydroxyalkanoate) copolymer (C) is poly(3-hydroxybutyrate-co-3-hydroxyhexanoate).
  • [Item 9] A method for producing a laminate according to any one of items 1 to 8, comprising: forming the adhesive layer (B) on at least one side of the base layer (A); A method for producing a laminate, comprising a step of forming the resin layer (D) on the surface of the adhesive layer (B) by an extrusion lamination method or a thermal lamination method.
  • the temperature of the resin immediately after being melted and extruded from the tip of the T-shaped die is higher than or equal to the melting point of the component contained in the resin layer (D) and lower than 165°C.
  • a method for producing a laminate according to item 9. In the thermal lamination method, a film constituting the resin layer (D) is used, and the resin temperature immediately after being melted and extruded from the tip of the T-shaped die is such that the components contained in the resin layer (D)
  • a molded article comprising the laminate according to any one of items 1 to 8.
  • Coating liquid 1 Styrene/methyl methacrylate/2-ethylhexyl methacrylate/methacrylic acid (all manufactured by Tokyo Chemical Industry Co., Ltd.) After polymerization to a molar ratio of 10/81/3/6, solid content concentration Coating liquid 1 was obtained by diluting with a water/isopropanol mixture so that the amount was 5%. The glass transition temperature of the obtained styrene-acrylic resin was 79°C.
  • Coating liquid 2 Styrene/methyl methacrylate/2-ethylhexyl methacrylate/methacrylic acid (all manufactured by Tokyo Chemical Industry Co., Ltd.) After polymerization to a molar ratio of 5/86/3/6, solid content concentration Coating liquid 2 was obtained by diluting with a water/isopropanol mixture so that the amount was 5%. The glass transition temperature of the obtained styrene-acrylic resin was 68°C.
  • Coating liquid 3 Styrene/methyl methacrylate/2-ethylhexyl methacrylate/methacrylic acid (all manufactured by Tokyo Chemical Industry Co., Ltd.) After polymerization to a molar ratio of 10/63/21/6, solid content concentration Coating liquid 3 was obtained by diluting with a water/isopropanol mixture so that the amount was 5%. The glass transition temperature of the obtained styrene-acrylic resin was 48°C.
  • Coating liquid 4 Styrene/methyl methacrylate/2-ethylhexyl methacrylate/methacrylic acid (all manufactured by Tokyo Chemical Industry Co., Ltd.) After polymerization to a molar ratio of 10/81/3/6, solid content concentration A coating solution was obtained by diluting the solution with a water/isopropanol mixture to a concentration of 5%. Then, a solution in which rosin ester (RE-650 manufactured by Arakawa Chemical Co., Ltd., weight average molecular weight 600) was dissolved in a toluene/isopropanol mixture was added to The coating liquid 4 was obtained by mixing the components in a proportion of % by weight. The glass transition temperature of the entire mixture of styrene-acrylic resin and rosin ester obtained was 66°C.
  • Coating liquid 5 Styrene/methyl methacrylate/2-ethylhexyl methacrylate/methacrylic acid (all manufactured by Tokyo Chemical Industry Co., Ltd.) After polymerization to a molar ratio of 10/81/3/6, solid content concentration A coating solution was obtained by diluting the solution with a water/isopropanol mixture to a concentration of 5%.
  • the coating liquid 5 was obtained by mixing the components in such a manner as to achieve the same weight percentage.
  • the glass transition temperature of the entire mixture of styrene-acrylic resin and rosin ester obtained was 62°C.
  • Coating liquid 6 Styrene/methyl methacrylate/2-ethylhexyl methacrylate/methacrylic acid (all manufactured by Tokyo Chemical Industry Co., Ltd.) After polymerization to a molar ratio of 10/81/3/6, solid content concentration A coating solution was obtained by diluting the solution with a water/isopropanol mixture to a concentration of 5%. Then, a solution in which rosin ester (RE-2160 manufactured by Arakawa Chemical Co., Ltd., weight average molecular weight 2160) was dissolved in a toluene/isopropanol mixture was added to The coating liquid 6 was obtained by mixing the components in a proportion of % by weight. The glass transition temperature of the entire mixture of styrene-acrylic resin and rosin ester obtained was 71°C.
  • Coating liquid 7 Methyl methacrylate/2-ethylhexyl methacrylate/methacrylic acid (all manufactured by Tokyo Chemical Industry Co., Ltd.) After polymerization to a molar ratio of 91/3/6, the solid content concentration was 5%. Coating liquid 7 was obtained by diluting with water/isopropanol mixture so as to have the following properties. The glass transition temperature of the obtained acrylic resin was 87°C.
  • Coating liquid 8 Styrene/methyl methacrylate/2-ethylhexyl methacrylate/methacrylic acid (all manufactured by Tokyo Chemical Industry Co., Ltd.) After polymerization to a molar ratio of 10/45/39/6, solid content concentration Coating liquid 8 was obtained by diluting with a water/isopropanol mixture so that the amount was 5%. The glass transition temperature of the obtained styrene-acrylic resin was 16°C.
  • Coating solution 9 Styrene/methyl methacrylate/methacrylic acid (all manufactured by Tokyo Chemical Industry Co., Ltd.) After polymerization to a molar ratio of 40/54/6, add water to a solid concentration of 5%. /isopropanol mixture to obtain coating liquid 9. The glass transition temperature of the obtained styrene-acrylic resin was 94°C.
  • PHBH powder As the PHBH powder, one manufactured according to the method described in International Publication No. 2019-142845 was used. The specific prescription is as follows. PHBH powder: PHBH powder with a weight average molecular weight of 590,000 and a ratio of 3HH to the total of 3HB and 3HH in PHBH is 15 mol%
  • PHBH pellets Dry blend behenic acid amide (0.5 parts by weight) and pentaerythritol (1.0 parts by weight) with the PHBH powder (100 parts by weight), and use a twin-screw extruder to dry at a set temperature of 150 parts by weight. The mixture was melt-kneaded at 100 rpm and extruded into a strand, passed through hot water at 40°C to solidify, and cut into pellets. The weight average molecular weight was 550,000.
  • Example 1 ⁇ Manufacture of laminate by extrusion lamination method> (Example 1) Coating liquid 1 was applied to A4 size base paper with a basis weight of 210 g/m 2 using a bar coater No. Immediately after coating with No. 10, the paper was dried by placing it in a hot air oven heated to 100° C. for 30 seconds to form an adhesive layer (B) on the paper base material. The area weight of the obtained adhesive layer (B) was 1.0 g/m 2 .
  • the PHBH pellets were put into a single screw extruder equipped with a T-shaped die, extruded from the T-shaped die under conditions such that the resin temperature immediately after extrusion was 163 ° C., and taken off with a cooling roll set at 60 ° C. It was molded into a film with a thickness of 30 ⁇ m.
  • the paper base material with the adhesive layer (B) obtained above and the PHBH film are sandwiched so that the heating roll is in contact with the paper side and the cooling roll is in contact with the PHBH film side, so that the surface temperature of the PHBH film is 170 ° C.
  • the conditions were adjusted as follows, and a laminate containing a paper base material, an adhesive layer (B), and a resin layer (D) in this order was obtained.
  • Example 2 Apply coating liquid 1 to bar coater No. A laminate was obtained in the same manner as in Example 1, except that it was coated with No. 2.
  • the adhesive layer (B) had a basis weight of 0.2 g/m 2 .
  • Example 3 Apply coating liquid 1 to bar coater No. A laminate was obtained in the same manner as in Example 1, except that it was coated with No. 45.
  • the adhesive layer (B) had a basis weight of 4.5 g/m 2 .
  • Example 4 A laminate was obtained in the same manner as in Example 1 except that the thickness of the PHBH film for the resin layer (D) was changed to 10 ⁇ m.
  • Example 5 A laminate was obtained in the same manner as in Example 1 except that the thickness of the PHBH film for the resin layer (D) was changed to 70 ⁇ m.
  • Example 6 A laminate was obtained in the same manner as in Example 1, except that coating liquid 2 was used to prepare the adhesive layer (B).
  • Example 7 A laminate was obtained in the same manner as in Example 1, except that coating liquid 3 was used to prepare the adhesive layer (B).
  • Example 8 A laminate was obtained in the same manner as in Example 1, except that coating liquid 4 was used to prepare the adhesive layer (B).
  • Example 9 A laminate was obtained in the same manner as in Example 1, except that coating liquid 5 was used to prepare the adhesive layer (B).
  • Example 10 A laminate was obtained in the same manner as in Example 1, except that coating liquid 6 was used to prepare the adhesive layer (B).
  • Example 11 A laminate was obtained in the same manner as in Example 1, except that coating liquid 7 was used to prepare the adhesive layer (B).
  • Example 1 The method described in Example 1 was repeated, except that PHBH was extrusion laminated on the base paper without the adhesive layer (B), and the paper base material and the resin layer (D ) was obtained.
  • Example 3 A laminate was obtained in the same manner as in Example 1, except that coating liquid 9 was used to prepare the adhesive layer (B).
  • Example 4 A laminate was obtained in the same manner as in Example 1 except that the thickness of the PHBH film for the resin layer (D) was changed to 3 ⁇ m.
  • the peel tester used was Shimadzu Autograph EZ-LX (manufactured by Shimadzu Corporation).
  • the above evaluation results are ⁇ , If it is ⁇ or ⁇ , it can be said that there is sufficient lamination strength.
  • the glass transition temperature of the entire resin contained in the adhesive layer (B) was measured using differential thermal analysis. More specifically, a portion of each of the coating liquids obtained by the method described in the production example was transferred to a metal container and dried for 30 minutes in a hot air oven set at 100°C. 3 mg of the obtained solid was weighed and heated at a rate of 10°C/min in the range of 0°C to 150°C using a differential scanning calorimeter (NETZSCH Polyma 214) to obtain a temperature dependence curve. . The obtained results were further differentiated with respect to temperature to determine the inflection point, and the temperature at that point was taken as the glass transition temperature.
  • NETZSCH Polyma 2114 differential scanning calorimeter

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
PCT/JP2023/017540 2022-05-23 2023-05-10 積層体、その製造方法、および成形体 Ceased WO2023228736A1 (ja)

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EP23811611.5A EP4530065A1 (en) 2022-05-23 2023-05-10 Layered body, method for producing same, and molded article
CN202380041024.9A CN119212866A (zh) 2022-05-23 2023-05-10 层叠体、其制造方法及成型体
JP2024523021A JPWO2023228736A1 (https=) 2022-05-23 2023-05-10
US18/955,030 US20250083426A1 (en) 2022-05-23 2024-11-21 Laminate, method for producing the same, and molded article

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2026038512A1 (ja) * 2024-08-15 2026-02-19 株式会社カネカ 積層体、及びその製造方法

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JPH06293113A (ja) 1993-04-08 1994-10-21 Toppan Printing Co Ltd 積層体の製造方法
JPH06316042A (ja) * 1993-05-06 1994-11-15 Toppan Printing Co Ltd 積層体
JPH10128920A (ja) * 1996-10-29 1998-05-19 Kanegafuchi Chem Ind Co Ltd 生分解性を有する積層体
JPH11504271A (ja) * 1995-04-24 1999-04-20 テトラ ラバル ホールデイングス エ フイナンス ソシエテ アノニム パッケージ用積層材およびそれによって製造されるパッケージ
JP2003011286A (ja) * 2001-06-28 2003-01-15 Toppan Printing Co Ltd 積層体
WO2010013483A1 (ja) 2008-08-01 2010-02-04 株式会社カネカ 樹脂組成物及びシート
JP2012030547A (ja) * 2010-08-02 2012-02-16 Mitsubishi Chemicals Corp 生分解性樹脂積層体およびその製造方法
WO2013147139A1 (ja) 2012-03-30 2013-10-03 株式会社カネカ 生分解性ポリエステル樹脂組成物
WO2019142845A1 (ja) 2018-01-17 2019-07-25 株式会社カネカ 高組成比率の３ｈｈモノマー単位を含む共重合ｐｈａを生産する形質転換微生物およびそれによるｐｈａの製造方法
WO2023068056A1 (ja) * 2021-10-20 2023-04-27 株式会社カネカ 積層体、その製造方法、および成形体

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JPH06293113A (ja) 1993-04-08 1994-10-21 Toppan Printing Co Ltd 積層体の製造方法
JPH06316042A (ja) * 1993-05-06 1994-11-15 Toppan Printing Co Ltd 積層体
JPH11504271A (ja) * 1995-04-24 1999-04-20 テトラ ラバル ホールデイングス エ フイナンス ソシエテ アノニム パッケージ用積層材およびそれによって製造されるパッケージ
JPH10128920A (ja) * 1996-10-29 1998-05-19 Kanegafuchi Chem Ind Co Ltd 生分解性を有する積層体
JP2003011286A (ja) * 2001-06-28 2003-01-15 Toppan Printing Co Ltd 積層体
WO2010013483A1 (ja) 2008-08-01 2010-02-04 株式会社カネカ 樹脂組成物及びシート
JP2012030547A (ja) * 2010-08-02 2012-02-16 Mitsubishi Chemicals Corp 生分解性樹脂積層体およびその製造方法
WO2013147139A1 (ja) 2012-03-30 2013-10-03 株式会社カネカ 生分解性ポリエステル樹脂組成物
WO2019142845A1 (ja) 2018-01-17 2019-07-25 株式会社カネカ 高組成比率の３ｈｈモノマー単位を含む共重合ｐｈａを生産する形質転換微生物およびそれによるｐｈａの製造方法
WO2023068056A1 (ja) * 2021-10-20 2023-04-27 株式会社カネカ 積層体、その製造方法、および成形体

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Publication number Priority date Publication date Assignee Title
WO2026038512A1 (ja) * 2024-08-15 2026-02-19 株式会社カネカ 積層体、及びその製造方法

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