WO2019239913A1 - Procédé de fabrication de stratifié biodégradable - Google Patents

Procédé de fabrication de stratifié biodégradable Download PDF

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Publication number
WO2019239913A1
WO2019239913A1 PCT/JP2019/021569 JP2019021569W WO2019239913A1 WO 2019239913 A1 WO2019239913 A1 WO 2019239913A1 JP 2019021569 W JP2019021569 W JP 2019021569W WO 2019239913 A1 WO2019239913 A1 WO 2019239913A1
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weight
pressure
resin material
resin
parts
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PCT/JP2019/021569
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English (en)
Japanese (ja)
Inventor
宏司 刀禰
大倉　徹雄
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株式会社カネカ
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Priority to JP2020525433A priority Critical patent/JP7353280B2/ja
Publication of WO2019239913A1 publication Critical patent/WO2019239913A1/fr

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Classifications

    • 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
    • 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
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • 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
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
    • 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
    • B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
    • B29C63/02—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor using sheet or web-like material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/08—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the cooling method
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

  • the present invention relates to a method for producing a biodegradable laminate comprising a paper base and a resin layer, a method for improving the surface state of the resin layer, and a biodegradable laminate.
  • Poly (3-hydroxyalkanoate) resin (Poly (3-hydroxyalkanoate); hereinafter abbreviated as “P3HA”) is a heat produced and stored as an energy storage substance in cells of many microbial species. It is a plastic polyester. P3HA is completely biodegraded by microorganisms in the soil and water, and is easily biodegraded in the natural environment such as the ocean and is taken into the natural carbon cycle process. Therefore, it can be said that P3HA is an environmentally friendly plastic that has almost no adverse effect on the ecosystem.
  • Such a laminated paper produced by laminating P3HA on a paper base material is an extremely promising laminated paper from the viewpoint of environmental protection because both paper and P3HA are environmentally degradable materials.
  • laminated paper is manufactured by laminating a paper base material and a resin material by extrusion lamination or heat lamination.
  • P3HA tends to adhere to the cooling roll during laminating, and a large force is applied when peeling from the roll to form fine irregularities on the surface of the resin layer, resulting in white turbidity and deterioration of the appearance of the resin layer. was there.
  • the peelability from the roll is poor, there is also a problem that continuous lamination over a long time becomes difficult.
  • a P3HA and a polyolefin resin are coextruded on a paper base material to form a three-layer laminate
  • a method for producing a laminated paper composed of a paper base material and a P3HA layer by peeling a polyolefin resin layer from a laminate is known.
  • this method since the polyolefin resin film peeled from the laminate is discarded, there is a problem in terms of waste treatment.
  • cooling is achieved by producing a three-layer biodegradable laminate by coextruding P3HA, a polycondensation polyester of dicarboxylic acid and glycol having good processability on a paper base material. It describes preventing blocking to rolls. Patent Document 2 describes that a blocking of a cooling roll is prevented by extruding a mixture of P3HA and a polycondensation polyester or polylactic acid on a paper base material.
  • Patent Document 1 and Patent Document 2 are resins having low environmental degradability, they were undesirable components for providing laminated paper having environmental degradability. .
  • the present invention can produce a biodegradable laminate by laminating a paper base material and P3HA, without using a resin material with low environmental degradability.
  • An object of the present invention is to produce a biodegradable laminate that improves the peelability of the resin layer, has a good surface condition, and has high environmental degradability.
  • the inventors of the present invention blended a predetermined amount of glycerin ester compound with P3HA, and constituted a resin layer with this blend, so that from a pressure bonding surface such as a cooling roll. It has been found that a biodegradable laminate having a good surface state can be produced by improving the peelability of the resin layer of the present invention.
  • the present invention provides a biodegradable laminate composed of the paper base material and the resin layer by pressure-bonding the resin material to the paper base material using the pressure-bonding surface and then peeling the resin material from the pressure-bonding surface.
  • the resin material has the formula (A): [—CHR—CH 2 —CO—O—] (wherein R is an alkyl group represented by C n H 2n + 1 , n Is a resin material containing 100 parts by weight of a polyhydroxyalkanoate containing a repeating unit represented by (1) to 15 parts by weight, and (B) 1 to 20 parts by weight of a glycerin ester compound.
  • the present invention relates to a method for manufacturing a laminate.
  • the resin composition further contains 0.1 to 5 parts by weight of (C) an aliphatic amide compound.
  • the polyhydroxyalkanoate is a copolymer of 3-hydroxybutyric acid and 3-hydroxyhexanoic acid.
  • the step of pressure-bonding the resin material to the paper substrate using the pressure-bonding surface is performed by extruding the molten resin material into a film shape by an extrusion laminating method and then cooling and pressure-bonding to the separately-rolled paper substrate with a cooling roller. It is a process.
  • the take-off force when peeling the resin material from the pressure-bonding surface is 25 N or less.
  • the pressure-bonding surface is used to select [—CHR—CH 2 —CO—O—] (wherein R is an alkyl group represented by C n H 2n + 1 , and n is an integer of 1 or more and 15 or less.
  • the paper substrate and the resin produced by peeling the resin material from the pressure-bonding surface after pressure-bonding the resin material containing the polyhydroxyalkanoate containing the repeating unit represented by A method for improving the surface state of the resin layer in a biodegradable laminate composed of layers, comprising 1 to 20 parts by weight of glycerin ester per 100 parts by weight of the polyhydroxyalkanoate relative to the resin material
  • the present invention also relates to a method for improving the surface state of a resin layer, which comprises blending a compound.
  • the present invention is a biodegradable laminate in which a resin layer is laminated on one side or both sides of a paper substrate, wherein the resin layer is represented by the formula (A): [—CHR—CH 2 —CO—O—] ( In the formula, R is an alkyl group represented by C n H 2n + 1 , and n is an integer of 1 or more and 15 or less.) 100 parts by weight of a polyhydroxyalkanoate including a repeating unit represented by: and (B) glycerin
  • the present invention also relates to a biodegradable laminate containing 1 to 20 parts by weight of an ester compound.
  • the biodegradable laminate has a form wound in a roll shape.
  • the resin layer when a biodegradable laminate is produced by laminating a paper base material and P3HA, the resin layer can be peeled from the pressure-bonding surface such as a cooling roll without using other resin materials. It is possible to produce a biodegradable laminate that is improved and has a good surface condition and high environmental degradability. Furthermore, according to the present invention, it is possible to stably carry out a continuous laminating process for a long time.
  • the main resin material constituting the resin layer is a poly (3-hydroxyalkanoate) resin, specifically, a formula : Containing a repeating unit represented by [—CHR—CH 2 —CO—O—] (wherein R is an alkyl group represented by C n H 2n + 1 , and n is an integer of 1 or more and 15 or less).
  • Polyhydroxyalkanoate is a poly (3-hydroxyalkanoate) resin, specifically, a formula : Containing a repeating unit represented by [—CHR—CH 2 —CO—O—] (wherein R is an alkyl group represented by C n H 2n + 1 , and n is an integer of 1 or more and 15 or less).
  • the repeating unit represented by the formula contained in the P3HA may be only one type or two or more types.
  • the type of copolymerization is not particularly limited and may be random copolymerization, alternating copolymerization, block copolymerization, graft copolymerization, or the like, but random copolymerization is preferred because it is easily available.
  • the repeating unit constituting the P3HA may be only the repeating unit represented by the above formula, or may contain other repeating units in addition to the repeating unit represented by the above formula.
  • Other repeating units include 4-hydroxyalkanoate units such as 4-hydroxybutyrate units.
  • P3HA examples include poly (3-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate), poly (3-hydroxybutyrate-co-3-hydroxyvalerate) Poly (3-hydroxybutyrate-co-4-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxyoctanoate), poly (3-hydroxybutyrate-co-3-hydroxyoctanoate) Decanoate) and the like.
  • poly (3-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate), poly (3-hydroxybutyrate-co-) 3-hydroxyvalerate) and poly (3-hydroxybutyrate-co-4-hydroxybutyrate) are preferred.
  • the melting point and crystallinity can be changed, and physical properties such as Young's modulus and heat resistance can be changed, and physical properties between polypropylene and polyethylene can be imparted.
  • poly (3) which is a copolymer of 3-hydroxybutyric acid and 3-hydroxyhexanoic acid is used. 3-hydroxybutyrate-co-3-hydroxyhexanoate) is preferred.
  • the poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) has poor peelability from the pressure-bonding surface at the time of laminating among P3HA, and the surface state of the resin layer of the resulting laminated paper is deteriorated. Although the problem of being easy is remarkable, the application of the present invention can improve the surface condition of a laminated paper using poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) as a resin material. it can.
  • a specific method for producing poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) is described in, for example, International Publication No. 2010/013483.
  • Examples of commercially available products of poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) include Kaneka Corporation “Kaneka Biodegradable Polymer PHBH” (registered trademark).
  • composition ratio of the repeating unit of poly is determined from the viewpoint of the balance between flexibility and strength, 3-hydroxybutyrate unit / 3-hydroxyhexanoate
  • the composition ratio of units is preferably 80/20 to 99/1 (mol / mol), and more preferably 85/15 to 97/3 (mo1 / mo1). The reason is that 99/1 or less is preferable from the viewpoint of flexibility, and 80/20 or more is preferable in that the resin has an appropriate hardness.
  • the weight average molecular weight of P3HA used in the present invention (hereinafter sometimes referred to as Mw) is not particularly limited, but is preferably 100,000 to 2.5 million, more preferably 150,000 to 2 million, and further preferably 200,000 to 1 million. preferable. If the weight average molecular weight is less than 100,000, the mechanical properties and the like may be inferior, and if it exceeds 2.5 million, molding may be difficult.
  • the weight average molecular weight of P3HA is determined by gel permeation chromatography (GPC) (“Shodex GPC-101” manufactured by Showa Denko KK) and polystyrene gel (“Shodex K-804” manufactured by Showa Denko KK) as a column. It can be determined as the molecular weight when converted to polystyrene using chloroform as the mobile phase.
  • GPC gel permeation chromatography
  • P3HA in the resin layer constituting the biodegradable laminate of the present invention, P3HA can be used alone or in combination of two or more.
  • an aliphatic polyester resin such as polybutylene succinate adipate, polybutylene succinate, and polylactic acid, and an aliphatic aromatic polyester type such as polybutylene adipate terephthalate, as long as the effects of the present invention are not impaired.
  • One or more biodegradable resins other than P3HA, such as a resin, may be contained.
  • the content of the resin other than P3HA is preferably as small as possible so as not to inhibit the environmental degradability of P3HA.
  • the content of the resin other than P3HA is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, and still more preferably 10 parts by weight or less with respect to 100 parts by weight of P3HA.
  • the resin layer which comprises the biodegradable laminated body of this invention may contain only P3HA as a resin component, ie, may not contain resin other than P3HA at all.
  • the resin layer constituting the biodegradable laminate is composed of a resin composition in which a glycerin ester compound is blended with P3HA, thereby improving the peelability from the pressure-bonding surface such as a cooling roll in lamination.
  • the resin layer hardly adheres to the pressure-bonding surface, and the resin layer can be smoothly peeled off from the pressure-bonding surface, so that a biodegradable laminate having a good surface condition can be produced.
  • the glycerin ester compound is a compound in which a hydroxyl group of glycerin forms an ester bond with a compound having a carboxyl group, for example.
  • the ester compound may be a glycerol monoester, a glycerol diester, or a glycerol triester. From the viewpoint of improving peelability from the pressure-bonding surface, a triester of glycerin is preferred, and glycerin diacetate monoester is more preferred.
  • glycerol diacetomonoester examples include glycerol diacetomonolaurate, glycerol diacetomonooleate, glycerol diacetomonostearate, glycerol diacetomonocaprylate, glycerol diacetomonodecanoate and the like. Only one type of glycerin ester compound may be used, or a plurality may be used in combination.
  • the blending amount of the glycerin ester compound in the resin composition is 1 to 20 parts by weight with respect to 100 parts by weight of P3HA.
  • the blending amount of the glycerin ester compound is less than 1 part by weight, it becomes difficult to obtain the effect of improving the peelability from the crimping surface.
  • the blending amount is more than 20 parts by weight, the glycerin ester compound bleeds during crimping, and the cooling roll There is a problem that it becomes difficult to perform continuous processing for a long time because it adheres to the pressure-bonding surface.
  • the blending amount of the glycerin ester compound is preferably 1 to 10 parts by weight, more preferably 2 to 5 parts by weight.
  • the resin composition constituting the biodegradable laminate of the present invention may contain an aliphatic amide compound in addition to P3HA and a glycerin ester compound.
  • the aliphatic amide compound is an optional component, and the resin composition may not contain an aliphatic amide compound.
  • An aliphatic amide compound is a kind of additive conventionally known as a lubricant added to a resin.
  • the aliphatic amide compound is not particularly limited, and examples thereof 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, and erucic acid amide.
  • alkylene fatty acid amides such as methylene bis stearic acid amide and methylene bis stearic acid amide. Of these, fatty acid amides are preferred from the viewpoint of improving the peelability from the crimping surface. Only one type of aliphatic amide compound may be used, or a plurality of types may be used in combination.
  • the blending amount of the aliphatic amide compound in the resin layer is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of P3HA.
  • the blending amount of the aliphatic amide compound is more preferably 0.3 to 4 parts by weight, still more preferably 0.5 to 3 parts by weight.
  • the resin layer constituting the biodegradable laminate of the present invention may contain pentaerythritol in addition to P3HA and a glycerin ester compound. By blending pentaerythritol, the peelability from the pressure-bonded surface can be further improved. However, pentaerythritol is an optional component, and the resin layer may not contain pentaerythritol.
  • the blend amount of pentaerythritol in the resin layer is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of P3HA.
  • the blending amount of pentaerythritol is more preferably 0.3 to 4 parts by weight, still more preferably 0.5 to 3 parts by weight.
  • the resin layer in addition to the glycerin ester compound, the optional component aliphatic amide compound, and the optional component pentaerythritol, other additives usually added to the resin material as long as the effects of the present invention are not impaired.
  • 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, weather resistance improvers, ultraviolet absorbers
  • one or more kinds of crystal nucleating agents, lubricants, mold release agents, water repellents, antibacterial agents, slidability improving agents, and other secondary additives may be added. The content of these additives can be set as appropriate.
  • the thickness of the resin layer in the biodegradable laminate of the present invention is not particularly limited, but prevents water absorption to paper. However, from the viewpoint of ensuring sufficient flexibility, the thickness is preferably 5 to 300 ⁇ m, more preferably 10 to 200 ⁇ m.
  • the paper base material which comprises the biodegradable laminated body of this invention is not specifically limited, What is necessary is just to be able to form the resin layer in the single side
  • a surface treatment such as a corona treatment, a frame treatment, or an anchor coat treatment.
  • surface or both surfaces is manufactured by the lamination method.
  • the laminating method is a method in which a resin material is pressure-bonded to a paper substrate using a pressure-bonding surface such as a cooling roll, and then a resin layer composed of the resin material is peeled off from the pressure-bonding surface, whereby a biodegradable laminate is obtained. It is a manufacturing method.
  • the laminating method is not particularly limited as long as it is a method in which a resin material and a paper base material are pressure-bonded using a pressure-bonding surface.
  • the molten resin material is extruded from a T-die into a film shape, it is separately fed out.
  • examples thereof include an extrusion laminating method in which a paper base is cooled and pressure-bonded using a cooling roll, and a heat laminating method in which a resin film prepared in advance is heated and pressure-bonded to the paper base.
  • the pressure-bonding surface is not particularly limited as long as the resin and the paper base material can be pressure-bonded, and examples thereof include a plate-shaped surface and a roll surface.
  • the extrusion laminating method is carried out continuously, and a melted resin material is cooled and pressure-bonded to a paper substrate, and immediately thereafter, the resin layer is peeled off from the cooling roll. Therefore, in the conventional method, when P3HA is used as the resin material, the resin layer is not easily peeled off from the cooling roll, and the phenomenon that the resin layer is temporarily attached to the cooling roll is likely to occur. As a result, the problem that the force applied when the adhesion location peeled from the roll and the cloudy nonuniformity (fine unevenness
  • the present invention even in the extrusion laminating method, it is possible to improve the peelability from the cooling roll and produce a biodegradable laminate having a good surface state of the resin layer. According to the present invention, it is possible to reduce the take-up force when peeling a resin material containing P3HA from a pressure-bonding surface such as a cooling roll, preferably to 25 N or less, more preferably to 20 N or less.
  • the surface temperature of the cooling roll is not particularly limited as long as it is a temperature at which the resin layer can be cooled and pressure-bonded, and can be appropriately determined, but may be in the range of 10 to 60 ° C., for example.
  • this invention is also a biodegradable laminated body containing the paper base material and the resin layer formed in the single side
  • the resin layer is a resin layer containing the above-described P3HA and a glycerin ester compound as essential components.
  • the biodegradable laminate of the present invention is laminated so that the resin layer is in contact with the paper substrate, and an adhesive layer and other resin layers are interposed between the resin layer and the paper substrate. It is preferable that it is not.
  • the biodegradable laminate of the present invention has a resin layer other than the resin layer mainly composed of P3HA in the present invention (for example, a polyolefin resin layer or a layer composed of a polycondensation polyester of dicarboxylic acid and glycol). It is preferable that it does not contain.
  • the biodegradable laminate of the present invention is preferably a long biodegradable laminate continuously produced by the above-described laminating method, and is wound around a winding roll after pressure bonding and peeling by the laminating method. It is preferable that it is a biodegradable laminated body which has the form wound by roll shape which can be manufactured by.
  • biodegradable laminate of the present invention is not particularly limited, and examples thereof include paper cups, paper bags, cartons, trays, and interior wallpaper.
  • Tanehaha medium 1w / v% Meat-extract, 1w / v% Bacto-Tryptone, 0.2w / v% Yeast-extract, 0.9w / v% Na 2 HPO 4 ⁇ 12H 2 O, 0.15w / V% KH 2 PO 4 (pH 6.8).
  • the composition of the preculture medium is 1.1 w / v% Na 2 HPO 4 ⁇ 12H 2 O, 0.19 w / v% KH 2 PO 4 , 1.29 w / v% (NH 4 ) 2 SO 4 , 0.1 w / v% MgSO 4 ⁇ 7H 2 O , 0.5v / v% trace metal salt solution (1.6 w in 0.1N HCl / v% FeCl 3 ⁇ 6H 2 O, 1w / v% CaCl 2 ⁇ 2H 2 O, 0 0.02 w / v% CoCl 2 .6H 2 O, 0.016 w / v% CuSO 4 .5H 2 O, 0.012 w / v% NiCl 2 .6H 2 O).
  • palm kernel oil was added all at a concentration of 10 g / L.
  • the composition of the P3HA production medium is 0.385 w / v% Na 2 HPO 4 ⁇ 12H 2 O, 0.067 w / v% KH 2 PO 4 , 0.291 w / v% (NH 4 ) 2 SO 4 , 0.1 w / v% MgSO 4 .7H 2 O, 0.5 v / v% trace metal salt solution (1.6 W / v% FeCl 3 .6H 2 O in 0.1N hydrochloric acid, 1 w / v% CaCl 2 .2H 2 O, 0 0.02 w / v% CoCl 2 ⁇ 6H 2 O, 0.016 w / v% CuSO 4 ⁇ 5H 2 O, 0.012 w / v% NiCl 2 ⁇ 6H 2 O), 0.05 w / v% BIOSPUREX 200K (Antifoamer: manufactured by Cognis Japan).
  • a glycerol stock (50 ⁇ l) of KNK-631 strain was inoculated into a seed medium (10 ml) and cultured for 24 hours to perform seed culture.
  • 1.0 v / v% of the seed mother culture solution was inoculated into a 3 L jar fermenter (MDL-300 type, manufactured by Maruhishi Bioengine) containing 1.8 L of a preculture medium.
  • the operating conditions were a culture temperature of 33 ° C., a stirring speed of 500 rpm, an aeration rate of 1.8 L / min, and the culture was performed for 28 hours while controlling the pH between 6.7 and 6.8.
  • a 14% aqueous ammonium hydroxide solution was used for pH control.
  • the preculture solution was inoculated at 1.0 v / v% into a 10 L jar fermenter (MDS-1000, manufactured by Marubishi Bioengineer) containing 6 L of P3HA production medium.
  • the operating conditions were a culture temperature of 28 ° C., a stirring speed of 400 rpm, an aeration rate of 6.0 L / min, and a pH controlled between 6.7 and 6.8.
  • a 14% aqueous ammonium hydroxide solution was used for pH control. Palm kernel oil was used as the carbon source. Culturing was carried out for 64 hours. After completion of the cultivation, the cells were collected by centrifugation, washed with methanol, freeze-dried, and the weight of the obtained dried cells was measured.
  • the 3HH composition analysis of the obtained P3HA was measured by gas chromatography as follows. To 20 mg of dry P3HA, 2 ml of a sulfuric acid-methanol mixture (15:85) and 2 ml of chloroform were added and sealed, and heated at 100 ° C. for 140 minutes to obtain a methyl ester of a P3HA decomposition product. After cooling, 1.5 g of sodium bicarbonate was added little by little to neutralize it, and the mixture was allowed to stand until the generation of carbon dioxide gas stopped. After adding 4 ml of diisopropyl ether and mixing well, the mixture was centrifuged and the monomer unit composition of the polyester degradation product in the supernatant was analyzed by capillary gas chromatography.
  • the gas chromatograph used was Shimadzu GC-17A, and the capillary column used was GL Science's Neutra Bond-1 (column length 25 m, column inner diameter 0.25 mm, liquid film thickness 0.4 ⁇ m). He was used as the carrier gas, the column inlet pressure was set to 100 kPa, and 1 ⁇ l of the sample was injected. As temperature conditions, the temperature was raised from an initial temperature of 100 to 200 ° C. at a rate of 8 ° C./min, and further from 200 to 290 ° C. at a rate of 30 ° C./min.
  • P3HA A1 was poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (P (3HB-co-3HH)).
  • the weight average molecular weight Mw measured by GPC was 740,000.
  • the 3-hydroxyhexanoate (3HH) composition was 11.4 mol%.
  • P3HA A1 obtained in Production Example 1 was treated at 120 ° C. and 100% humidity for 2 hours using a highly accelerated life test apparatus (PC-422R5E manufactured by Hirayama Seisakusho), so that P3HA A2 was treated as P (3HB-co -3HH).
  • the weight average molecular weight Mw of P3HA A2 was 540,000, and the 3HH composition was 11.4 mol%.
  • P (3HB-co-3HH) was obtained as P3HA A3 in the same manner as in Production Example 1, except that KNK-005 strain (see US Pat. No. 7,384,766) and palm oil were used as the carbon source.
  • the weight average molecular weight Mw of P3HA A3 was 570,000, and the 3HH composition was 5.6 mol%.
  • P3HA A3 obtained in Production Example 3 was treated at 120 ° C. and 100% humidity for 2 hours using a high acceleration life test apparatus (PC-422R5E manufactured by Hirayama Seisakusho), so that P (3HB- co-3HH) was obtained.
  • the weight average molecular weight Mw of P3HA A4 was 440,000, and the 3HH composition was 5.6 mol%.
  • a single-screw extruder (Toyo Seiki Seisakusho Co., Ltd.) equipped with a T-type die having a width of 150 mm and a lip width of 0.25 mm
  • a laminator roll diameter: 100 mm
  • screw rotation speed 30 rpm
  • the temperature of the cooling roll was adjusted to 30 ° C.
  • a biodegradable laminate was obtained by laminating at a thickness of 100 ⁇ m on one side of unbleached kraft paper having a basis weight of 150 g / m 2 .
  • glycerin ester compound B1 glycerin diacetomonolaurate (manufactured by Riken Vitamin Co., Ltd., “Riquemar PL012”) was used.
  • erucic acid amide manufactured by Nippon Seika Co., Ltd., “Nutron-S” was used.
  • pentaerythritol D pentaerythritol (manufactured by Nippon Synthetic Chemical Co., Ltd., “Neulizer P”) was used.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Laminated Bodies (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

L'invention concerne un procédé dans lequel une surface de liaison par pression est utilisée pour lier par pression un matériau de résine à un substrat de papier, puis le matériau de résine est retiré de la surface de liaison par pression, ce par quoi un stratifié biodégradable conçu à partir du substrat de papier et d'une couche de résine est fabriqué, le matériau de résine contenant (A) 100 parties en poids de polyhydroxyalcanoate qui comprend des unités de répétition représentées par la formule suivante : (-CHR-CH2-CO-O) (dans la formule, R est un groupe alkyle représenté par CnH2n+1 et n est un nombre entier de 1 à 15), et (B) 1 à 20 parties en poids d'un composé d'ester de glycérol.
PCT/JP2019/021569 2018-06-14 2019-05-30 Procédé de fabrication de stratifié biodégradable WO2019239913A1 (fr)

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JP2021161434A (ja) * 2020-04-01 2021-10-11 アイ‐コンポロジー株式会社 海洋資材
WO2022059592A1 (fr) * 2020-09-17 2022-03-24 株式会社カネカ Stratifié et corps moulé
CN115023469A (zh) * 2020-01-29 2022-09-06 株式会社钟化 生物降解性聚酯溶液及其利用
WO2022264944A1 (fr) * 2021-06-16 2022-12-22 株式会社カネカ Stratifié biodégradable et son procédé de fabrication

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JPH10128920A (ja) * 1996-10-29 1998-05-19 Kanegafuchi Chem Ind Co Ltd 生分解性を有する積層体
JP2003535996A (ja) * 2000-06-09 2003-12-02 ザ プロクター アンド ギャンブル カンパニー 生分解性コーティングされた基材
WO2009122673A1 (fr) * 2008-04-02 2009-10-08 株式会社カネカ Composition de résine
WO2013147139A1 (fr) * 2012-03-30 2013-10-03 株式会社カネカ Composition de résine de polyester biodégradable
JP2016049630A (ja) * 2014-08-28 2016-04-11 三菱化学株式会社 積層体の製造方法

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JP6573094B2 (ja) 2012-09-11 2019-09-11 パナソニックＩｐマネジメント株式会社 洗濯機制御システム
US9850376B2 (en) * 2012-10-05 2017-12-26 Kaneka Corporation Polyester resin composition and method for producing same

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Publication number Priority date Publication date Assignee Title
JPH10128920A (ja) * 1996-10-29 1998-05-19 Kanegafuchi Chem Ind Co Ltd 生分解性を有する積層体
JP2003535996A (ja) * 2000-06-09 2003-12-02 ザ プロクター アンド ギャンブル カンパニー 生分解性コーティングされた基材
WO2009122673A1 (fr) * 2008-04-02 2009-10-08 株式会社カネカ Composition de résine
WO2013147139A1 (fr) * 2012-03-30 2013-10-03 株式会社カネカ Composition de résine de polyester biodégradable
JP2016049630A (ja) * 2014-08-28 2016-04-11 三菱化学株式会社 積層体の製造方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115023469A (zh) * 2020-01-29 2022-09-06 株式会社钟化 生物降解性聚酯溶液及其利用
EP4098699A4 (fr) * 2020-01-29 2024-01-24 Kaneka Corp Solution de polyester biodégradable et son utilisation
JP2021161434A (ja) * 2020-04-01 2021-10-11 アイ‐コンポロジー株式会社 海洋資材
JP7030315B2 (ja) 2020-04-01 2022-03-07 アイ‐コンポロジー株式会社 海洋資材
WO2022059592A1 (fr) * 2020-09-17 2022-03-24 株式会社カネカ Stratifié et corps moulé
WO2022264944A1 (fr) * 2021-06-16 2022-12-22 株式会社カネカ Stratifié biodégradable et son procédé de fabrication

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