WO2021075412A1 - 水分散液およびその利用 - Google Patents

水分散液およびその利用 Download PDF

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Publication number
WO2021075412A1
WO2021075412A1 PCT/JP2020/038555 JP2020038555W WO2021075412A1 WO 2021075412 A1 WO2021075412 A1 WO 2021075412A1 JP 2020038555 W JP2020038555 W JP 2020038555W WO 2021075412 A1 WO2021075412 A1 WO 2021075412A1
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Prior art keywords
aqueous dispersion
phbh
copolymer
laminate
base material
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English (en)
French (fr)
Japanese (ja)
Inventor
明日香 福留
康則 岡田
大倉　徹雄
和紀 西山
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Kaneka Corp
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Kaneka Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes

Definitions

  • the present invention relates to an aqueous dispersion containing a copolymer of 3-hydroxybutyrate and 3-hydroxyhexanoate and its use.
  • Water dispersions of resins are widely used in paints, adhesives, fiber processing, sheet / film processing, paper processing, etc., and are superior in ease of handling and safety in the work environment compared to solvent solutions. ..
  • Patent Document 1 The above-mentioned technique of Patent Document 1 is excellent, but there is room for further improvement.
  • one aspect of the present invention is a water dispersion containing PHBH and water, which can be formed at a low temperature and has excellent peel strength at a low heat seal temperature when a laminate is formed.
  • the purpose is to provide and the technology for using it.
  • one aspect of the present invention is an aqueous dispersion containing PHBH and water and having a weight average molecular weight of the copolymer of 50,000 to 550,000.
  • one aspect of the present invention is a laminate containing a coating layer containing a copolymer of 3-hydroxybutyrate and 3-hydroxyhexanoate, an intermediate layer, and a base material layer.
  • the weight average molecular weight of the polymer is 50,000 to 550,000
  • the coating layer, the intermediate layer, and the base material layer are laminated in this order, and the intermediate layer is derived from the coating layer.
  • It is a laminate containing a part of the above-mentioned copolymer and a part of the base material derived from the base material layer.
  • a water dispersion containing PHBH and water which can be formed at a low temperature and has excellent peel strength at a low heat seal temperature when a laminate is formed. Etc. can be provided.
  • the aqueous dispersion according to an embodiment of the present invention contains PHBH and is characterized in that the weight average molecular weight of the copolymer is 50,000 to 550,000. To do.
  • the present inventors have found that high-temperature treatment is required in order to form a film using the aqueous dispersion and obtain a smooth film. ..
  • high-temperature treatment is required in order to form a film using the aqueous dispersion and obtain a smooth film. ..
  • the productivity is impaired because the solidification (crystallization) of PHBH is relatively slow.
  • the present inventors have made it possible to form a film at a low temperature by using PHBH having a specific molecular weight, and when a laminate is formed. It has been found that an aqueous dispersion having excellent peel strength can be obtained at a low heat sealing temperature.
  • the present invention is the first to disclose an aqueous dispersion liquid which can form a film at a low temperature and has excellent peel strength at a low heat seal temperature when a laminate is formed. It is extremely useful in applications in various fields where coating is required.
  • the term "capable of forming a film at a low temperature” as used herein can be cited as an example of the fact that the smoothness of the coating film surface is good at 140 ° C., as shown in Examples described later. .. Further, “having excellent peel strength at a low heat seal temperature” is excellent, for example, when heated at 130 ° C. or 140 ° C. for 0.1 Mpa for 3 seconds, as shown in Examples described later. Having peel strength can be mentioned as an example.
  • This aqueous dispersion contains PHBH and water.
  • PHBH is a copolymer having 3-hydroxybutyrate (also referred to as “3HB”) and 3-hydroxyhexanoate (also referred to as “3HH”) as repeating units.
  • PHBH may be obtained by either a method produced from a microorganism or a chemical synthesis method, and is not particularly limited. Above all, PHBH obtained by a method produced from a microorganism is preferable in that it is fine particles.
  • the microorganism that produces PHBH is not particularly limited as long as it is a microorganism that can accumulate PHBH in the cell.
  • examples include bacteria such as the genus (Bacillus), the genus Azotobacter, the genus Nocardia, and the genus Aeromonas.
  • strains such as Aeromonas cavier are particularly preferable in terms of PHBH productivity, and Alkaline Genes eutrophas AC32 strain (accession number FERM BP-6038 (August 12, 1996) into which the gene of the PHA synthase group has been introduced is preferable.
  • the carbon source and culture conditions used for culturing may follow, for example, the methods described in JP-A-5-93049, JP-A-2001-3400078, etc., but are not limited thereto.
  • the microorganism-produced PHBH obtained by the above method is a random copolymer.
  • the composition of 3HH can be adjusted, for example, by selecting cells, selecting a carbon source as a raw material, blending PHBHs having different 3HH compositions, blending 3HB homopolymers, and the like.
  • the weight average molecular weight of PHBH in the aqueous dispersion is 50,000 to 550,000, preferably 100,000 to 500,000, and more preferably 150,000 to 450,000. More preferably, it is 150,000 to 250,000.
  • the main water dispersion containing the PHBH can be formed at a low temperature and when a laminate is formed. It has the effect of having excellent peel strength at a low heat seal temperature.
  • the weight average molecular weight of PHBH in this aqueous dispersion was determined by gel permeation chromatography (GPC) (“Shodex GPC-101” manufactured by Showa Denko Co., Ltd.) on a polystyrene gel (“Shodex K-804” manufactured by Showa Denko Co., Ltd.). ”) Is used to use chloroform as the mobile phase, and it can be determined as the molecular weight when converted to polystyrene.
  • GPC gel permeation chromatography
  • a powder obtained by centrifuging the aqueous dispersion containing PHBH and then drying it is used.
  • the solid content concentration of PHBH in the aqueous dispersion is preferably 25 to 65% by weight, more preferably 30 to 55% by weight, and particularly preferably 35 to 35% by weight. It is 50% by weight.
  • the solid content concentration of PHBH in the present aqueous dispersion is within the above range, the viscosity of the solution is not too high, so that uniform coating is possible, and the required coating film thickness can be maintained. It has the effect of being less likely to cause defects.
  • the solid content concentration of PHBH in the present water dispersion is measured and evaluated by the method described in Examples.
  • the average particle size of PHBH in the aqueous dispersion is, for example, 0.1 to 50 ⁇ m, preferably 0.5 to 30 ⁇ m, and more preferably 0.8 to. It is 20 ⁇ m. If the average particle size is less than 0.1 ⁇ m, it is difficult to produce PHBH by microbial production, and when PHBH is obtained by a chemical synthesis method, it is necessary to make fine particles. That is, when the average particle size is 0.1 ⁇ m or more, PHBH can be easily obtained by either the microbial production method or the chemical synthesis method.
  • the average particle size of PHBH in this aqueous dispersion is normally distributed by adjusting the aqueous suspension containing PHBH to a predetermined concentration using a general-purpose particle size meter such as a Microtrac particle size meter (FRA, manufactured by Nikkiso). It can be calculated as the particle size corresponding to the 50% accumulation amount of all the particles of.
  • the melt flow rate (MFR) of PHBH in the aqueous dispersion at 150 ° C. and 2.16 kgF is, for example, 10 to 500 g / 10 minutes, preferably 15 to 400 g. It is / 10 minutes, more preferably 50 to 200 g / 10 minutes, and particularly preferably 80 to 150 g / 10 minutes.
  • MFR melt flow rate
  • the melt flow rate of PHBH in the present aqueous dispersion is measured and evaluated by the method described in Examples.
  • the dispersion liquid is preferably used for coating a base material layer or the like.
  • the aqueous dispersion may contain one or more biodegradable resins other than PHBH as long as the effects of the present invention are exhibited.
  • biodegradable resins include aliphatic polyester resins such as polybutylene succinate, polycaprolactone, and polylactic acid, and aliphatic polyesters such as polybutylene adipate terephthalate, polybutylene succinate terephthalate, and polybutylene azelate terephthalate.
  • examples include aromatic polyester-based resins. The amount of these resins added is preferably 10 parts by weight or less in order to ensure the biodegradability of the aqueous dispersion.
  • the aqueous dispersion may contain additives usually used in the art as long as the effects of the present invention are exhibited.
  • additives include inorganic fillers such as talc, calcium carbonate, mica, silica, titanium oxide, and alumina, used paper such as fir tree, wood flour, and newspaper, and organic fillers such as various starches and cellulose.
  • Colorants such as pigments and dyes, odor absorbers such as activated charcoal and zeolite, fragrances such as vanillin and dextrin, plasticizers, antioxidants, antioxidants, weather resistance improvers, ultraviolet absorbers, crystal nucleating agents, lubricants, etc.
  • Examples thereof include mold release agents, water repellents, antibacterial agents, slidability improvers, tackifiers, fillers, and chemicals.
  • As an additive only one kind may be contained. Two or more kinds may be included. The content of these additives can be appropriately set by those skilled in the art according to the purpose of use.
  • the emulsifier can be said to be a dispersant or anti-sedimentant.
  • the emulsifier include anionic surfactants such as sodium lauryl sulfate and sodium oleate, cationic surfactants such as lauryltrimethylammonium chloride, nonionic surfactants such as glycerin fatty acid ester and sorbitan fatty acid ester, and polyvinyl.
  • Examples thereof include water-soluble polymers such as alcohol and polyvinylpyrrolidone, modified celluloses and alkylene oxides.
  • modified cellulose include methyl cellulose (MC), ethyl cellulose, propyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose (HEC), hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxyethyl ethyl cellulose, hydroxypropyl methyl cellulose (HPMC), and carboxymethyl cellulose (CMC).
  • alkylene oxide examples include compounds represented by the following formula (1), and commercially available products include Pluronic 10400 (manufactured by BASF), Pluronic 10500 (manufactured by BASF), and Genapol PF80 (manufactured by Clariant).
  • the amount of the emulsifier added is not particularly limited, but is preferably 1 to 10% by weight based on the solid content of PHBH.
  • the amount of the emulsifier added is 1% by weight or more, the stabilizing effect of the emulsifier tends to be obtained, and when it is 10% by weight or less, deterioration of physical properties and coloring due to excessive mixing of the emulsifier in PHBH are avoided. be able to.
  • the emulsifier can be added to the aqueous dispersion after crushing and alkali-treating the microbial cells, centrifuging and washing with water.
  • it can be added after washing with methanol before or after adjusting the solid content concentration of PHBH by adding an appropriate amount of water.
  • the shear viscosity of the aqueous dispersion at 23 ° C. is preferably 0.01 to 2 Pa ⁇ s, more preferably 0.03 to 1 Pa ⁇ s, and particularly preferably 0.03 to 1 Pa ⁇ s. , 0.05 to 0.5 Pa ⁇ s.
  • the shear viscosity of this aqueous dispersion at 23 ° C. is within the above range, the viscosity is not too high, so that when coating the liquid, there is little frictional force with the base material and coater, and coating is possible smoothly. The penetration of particles into the unevenness of the paper is also good.
  • the viscosity is not too low, and it is possible to obtain a uniform coating film by suppressing non-uniformity due to the flow of the coating liquid (aqueous dispersion liquid) on the substrate.
  • the shear viscosity of this aqueous dispersion at 23 ° C. is measured and evaluated by the method described in Examples.
  • the laminate according to the embodiment of the present invention (hereinafter, referred to as “the present laminate”) includes a coating layer formed by the present aqueous dispersion and a base material layer.
  • the coating layer in this laminate is formed of an aqueous dispersion containing PHBH, which can be formed at a low temperature and has excellent peel strength at a low heat seal temperature when the laminate is formed. Therefore, it is advantageous in various applications.
  • the laminate includes a coating layer.
  • the coating layer may be laminated on only one side of the base material layer, or may be laminated on both sides. Further, the coating layer may be laminated on the base material layer with another layer, or may be directly laminated on the base material layer without interposing the other layer.
  • the coating layer is intended to be obtained by applying the above-mentioned aqueous dispersion to the base material layer, drying the aqueous dispersion, and forming a film.
  • another coating layer or the like may be laminated on the coating layer.
  • This laminate includes a base material layer.
  • the base material layer in this laminate is not particularly limited as long as it is a layer on which a coating layer can be laminated.
  • the base material layer is preferably a biodegradable layer. Since the base material layer is a biodegradable layer, the entire laminate including the coating layer has biodegradability, which is more advantageous as a material for solving the problem of marine pollution.
  • the base material layer is water-absorbent from the viewpoint of preventing the coating liquid (aqueous dispersion liquid) from flowing on the surface and forming a coating film having an uneven thickness. Is preferable.
  • the biodegradable base material layer is not particularly limited, but for example, paper (main component is cellulose), cellophane, cellulose ester; polyvinyl alcohol, polyamino acid, polyglycolic acid, purulan, or aluminum on these base materials. , Those in which an inorganic substance such as silica is vapor-deposited, and the like. Of these, paper is preferable because it has excellent heat resistance and is inexpensive.
  • the type of paper is not particularly limited, and examples thereof include cup base paper, kraft paper, woodfree paper, coated paper, thin leaf paper, glassin paper, and paperboard. The type of paper can be appropriately selected according to the use of the laminated body. If necessary, a water resistant agent, a water repellent agent, an inorganic substance, or the like may be added to the paper, or the paper may be surface-treated such as an oxygen barrier layer coating and a water vapor barrier coating.
  • the base material layer may be subjected to surface treatment such as corona treatment, frame treatment, and anchor coating treatment. These surface treatments may be performed alone or in combination with a plurality of surface treatments. Further, the anchoring agent may be added to the aqueous dispersion.
  • the laminate comprises a coating layer containing a copolymer of 3-hydroxybutyrate and 3-hydroxyhexanoate, an intermediate layer, and a substrate layer.
  • the weight average molecular weight of the copolymer is 50,000 to 550,000
  • the coating layer, the intermediate layer, and the base material layer are laminated in this order, and the intermediate layer is the coating.
  • a part of the copolymer derived from the layer and a part of the base material derived from the base material layer are included.
  • the coating layer of the laminate is formed by applying the aqueous dispersion to the substrate layer, drying, and forming a film, as described later (4-2. Method for producing the laminate). .. Therefore, a part of this aqueous dispersion penetrates into the base material layer in the process of manufacturing the laminate, and a part of PHBH derived from the coating layer and the base material derived from the base material layer are between the coating layer and the base material layer.
  • Such an intermediate layer is not found in a laminated body manufactured by extrusion molding such as a laminating method, and has a structure characteristic of this laminated body.
  • the morphology of the intermediate layer in this laminate can be easily observed using, for example, a scanning electron microscope (SEM) or the like.
  • the weight (weight) per unit of PHBH in the coating layer of the present laminate is preferably 10 to 500 g / m 2 , and more preferably 15 to 250 g / m 2 . Particularly preferably, it is 18 to 100 g / m 2 .
  • the weight per unit of PHBH in the coating layer of this laminate is within the above range, defects such as pinholes can be prevented, the strength can be increased to withstand use, and functions such as water resistance can be efficiently performed. It has an effect that is manifested.
  • the weight per unit of PHBH in the coating layer of this laminate is measured and evaluated by the method described in Examples.
  • the thickness of the coating layer (each coating layer when the present laminate has two or more coating layers) in the present laminate is not particularly limited, but water absorption into the base material layer is limited. 5 to 300 ⁇ m is preferable, and 10 to 200 ⁇ m is more preferable, from the viewpoint of ensuring sufficient flexibility while preventing the above.
  • the heat seal temperature in the laminate is, for example, 120 to 160 ° C, preferably 125 to 155 ° C, more preferably 128 to 150 ° C, and particularly preferably. , 130-150 ° C. Since the present laminate contains a coating layer formed by the present aqueous dispersion, it has an advantage of having excellent peel strength even at a low temperature such as 130 ° C.
  • PHBH is produced from a microorganism, and the PHBH-containing microbial bacterium is produced.
  • the step of crushing the body in the state of an aqueous dispersion to separate PHBH in the cells is included.
  • the advantages of this method are (i) prevention of an increase in the viscosity of the dispersion due to bacterial cell components other than PHBH leaked from the microbial cells, and (ii) prevention of an increase in the viscosity of the bacterial cell dispersion to control the pH.
  • the pH of the bacterial cell dispersion liquid after addition of alkali is preferably 9 to 13.5.
  • the pH is 9 or more, PHBH tends to be easily separated from the cells, and when the pH is 13.5 or less, the decomposition of PHBH tends to be suppressed.
  • PHBH emulsification disperser
  • a high-pressure homogenizer a mill
  • PHBH emulsification disperser
  • an emulsification disperser for example, a Silberson mixer (manufactured by Silberson), a clear mix (manufactured by MTEC), an Ebara milder (manufactured by Ebara), or the like.
  • the temperature conditions for crushing the microbial cells and adding alkali are preferably in the range of room temperature to 50 ° C. If the above temperature condition exceeds 50 ° C., decomposition of PHBH is likely to occur, so that the temperature is preferably around room temperature. In addition, it is not economical because a cooling operation is required to keep the temperature below room temperature.
  • a precipitate is obtained by centrifugation from the dispersion obtained by crushing and alkali-treating the microbial cells, washing the precipitate with water if necessary, washing with methanol if necessary, and finally adding an appropriate amount of water. , An aqueous dispersion containing PHBH having a desired solid content concentration can be obtained.
  • Mechanical shearing of the aqueous dispersion can be performed using, for example, a stirrer, a homogenizer, ultrasonic waves, or the like. At this point, the aggregation of PHBH particles is not so strong, so from the viewpoint of convenience, it is preferable to use a stirrer equipped with a normal stirring blade.
  • the present laminate can be produced, for example, by applying the present water dispersion liquid to one side or both sides of the base material layer, drying and forming a film.
  • a known method can be appropriately implemented and is not particularly limited.
  • the method for producing a laminate is a step of applying the present water dispersion liquid to one side or both sides of the base material layer, and the application. The subsequent step of drying the aqueous dispersion to form a film is included.
  • the method for producing the laminate may include the following steps: (a) a process for producing the present aqueous dispersion, (b) a step for drawing out the base material layer, and (c). A step of applying the aqueous dispersion to the base material layer, and (d) a step of forming a film (including drying of the aqueous dispersion).
  • step (a) is not particularly limited, but can be performed by, for example, the method described in the above (4-1. Method for producing an aqueous dispersion). Further, the above steps (b) to (d) can be performed by any method known in the art without particular limitation.
  • the method for producing the present laminate may further include (e) a step of winding the laminate obtained in the step (d).
  • the step (e) is not particularly limited, and may be performed by any method known in the art.
  • the film formation temperature (heating temperature) in the film formation step of step (d) is, for example, 130 to 160 ° C, preferably 135 to 155 ° C, and more preferably 138 ° C. It is about 150 ° C., particularly preferably 140 to 150 ° C. Since the aqueous dispersion is used in the method for producing the laminated body, there is an advantage that the film can be formed even at a low temperature such as 140 ° C.
  • the drying and film formation in the step (d) may be performed as separate steps.
  • the drying temperature in this case can be, for example, room temperature to 100 ° C.
  • the molded body according to one embodiment of the present invention includes the present laminated body.
  • This molded body has a coating layer formed of an aqueous dispersion containing PHBH, which can be formed at a low temperature and has excellent peel strength at a low heat seal temperature when a laminate is formed. It is advantageous in various applications because it contains a laminate containing.
  • the molded product is not particularly limited as long as it includes the laminate, but for example, paper, film, sheet, tube, plate, rod, packaging material (for example, bag), container (for example, bottle container), and parts. And so on.
  • the molded product is preferably a packaging material or a container from the viewpoint of measures against marine pollution.
  • the molded body may be the laminated body itself. Further, in one embodiment of the present invention, the present laminated body included in the present molded body may be a secondary processed product.
  • the molded product containing the laminate can be used as various packaging container materials such as shopping bags, various bag making materials, food / confectionery packaging materials, cups, trays, and cartons (in other words,). , Food, cosmetics, electronics, medicine, medicine, etc.), can be suitably used.
  • the above-mentioned various secondary processes can be performed by using any method known in the art, for example, various bag making machines, filling and packaging machines, and the like. Further, it can be processed by using an apparatus such as a paper cup molding machine, a punching machine, and a box machine. In these processing machines, known techniques can be used as the bonding method of the laminate, for example, the heat sealing method, the impulse sealing method, the ultrasonic sealing method, the high frequency sealing method, the hot air sealing method, the frame sealing method, and the like. Can be used.
  • the molded product for example, fiber, thread, rope, woven fabric, knitted fabric, non-woven fabric, paper
  • a material different from the present molded product Films, sheets, tubes, plates, rods, containers, bags, parts, foams, etc.
  • These materials are also preferably biodegradable.
  • ⁇ 1> An aqueous dispersion containing a copolymer of 3-hydroxybutyrate and 3-hydroxyhexanoate and water, and the weight average molecular weight of the copolymer is 50,000 to 550,000.
  • ⁇ 2> The aqueous dispersion according to ⁇ 1>, wherein the solid content concentration of the copolymer in the aqueous dispersion is 25 to 65% by weight.
  • ⁇ 3> The aqueous dispersion according to ⁇ 1> or ⁇ 2>, wherein the shear viscosity at 23 ° C. is 0.01 to 2 Pa ⁇ s.
  • the copolymer is produced from a microorganism, and includes a step of crushing the microbial cells containing the copolymer in the state of an aqueous dispersion to separate the copolymer in the cells.
  • ⁇ 5> A laminate comprising a coating layer formed by the aqueous dispersion according to any one of ⁇ 1> to ⁇ 3> and a base material layer.
  • the weight average molecular weight of the copolymer is 50,000 to 550,000, and the copolymer has a weight average molecular weight of 50,000 to 550,000.
  • the coating layer, the intermediate layer, and the base material layer are laminated in this order.
  • a laminate in which the intermediate layer contains a part of the copolymer derived from the coating layer and a part of a base material derived from the base material layer.
  • ⁇ 8> A molded product containing the laminate according to any one of ⁇ 5> to ⁇ 7>.
  • ⁇ 9> A step of applying the aqueous dispersion according to any one of ⁇ 1> to ⁇ 3> on one or both sides of the base material layer, and a step of drying and forming a film of the applied aqueous dispersion.
  • a method for producing a laminate including. ⁇ 10> The method for producing a laminate according to ⁇ 9>, wherein the film forming temperature in the film forming step is 130 ° C. to 160 ° C.
  • Another embodiment of the present invention also includes the following aspects.
  • An aqueous dispersion containing a copolymer of 3-hydroxybutyrate and 3-hydroxyhexanoate and water and having a weight average molecular weight of 50,000 to 550,000 is applied to the material to be coated.
  • a coating method comprising the steps of drying the aqueous dispersion and forming a film.
  • An aqueous dispersion containing a copolymer of 3-hydroxybutyrate and 3-hydroxyhexanoate and water and having a weight average molecular weight of 50,000 to 550,000 is applied to the material to be coated.
  • a method for producing a coating layer which comprises a step of drying the aqueous dispersion to form a film.
  • aqueous dispersion containing a copolymer of 3-hydroxybutyrate and 3-hydroxyhexanoate and water and having a weight average molecular weight of the copolymer of 50,000 to 550,000 for coating.
  • PHBH melt flow rate The melt flow rate of PHBH was measured using a melt flow rate measuring device (No. 120-FWP, manufactured by Yasuda Seiki Seisakusho). The load was 2.16 kgF, and the measurement temperatures were 140 ° C. and 150 ° C.
  • Shear viscosity The shear viscosity of the aqueous dispersion was measured using a B-type viscometer (TVB-15M) manufactured by Toki Sangyo. Using an M3 cone, the viscosity at 23 ° C., 50 mpp, and 3 minutes after the start of measurement was measured.
  • Example 1 An A4 size base paper having a basis weight of 210 g / m 2 was coated with an aqueous dispersion having a weight average molecular weight of PHBH of 230,000 using a slit coat of 60 ⁇ m. After drying at room temperature for 5 minutes, the film was formed by heating at each temperature of 120, 130, 140, 150 ° C. for 5 minutes.
  • the basis weights of the resin components were 19 g / m 2 , 11 g / m 2 , 10 g / m 2 , and 30 g / m 2 , respectively.
  • Example 2 The same operation as in Example 1 was carried out except that an aqueous dispersion having a weight average molecular weight of 410,000 was used.
  • the basis weights of the resin components were 23 g / m 2 , 14 g / m 2 , 11 g / m 2 , and 15 g / m 2 , respectively.
  • Example 3 On an A4 size base paper with a basis weight of 210 g / m 2, an aqueous dispersion having a weight average molecular weight of 230,000 of PHBH was applied to the bar coater No. Coated with 80. After drying at room temperature for 5 minutes, the film was formed by heating at 150 ° C. for 5 minutes. The basis weight of the resin content was 60 g / m 2 .
  • the laminate obtained above was heat-sealed at 140 ° C., and a peel strength test was conducted 48 hours later.
  • Example 4 The same operation as in Example 3 was performed.
  • the basis weight of the resin content was 20 g / m 2 .
  • Example 1 The same operation as in Example 1 was carried out except that an aqueous dispersion having a weight average molecular weight of PHBH of 580,000 was used. Each basis weight of the resin component was 10g / m 2, 11g / m 2, 11g / m 2, 11g / m 2.
  • this aqueous dispersion can be formed at a low temperature and has excellent peel strength at a low heat seal temperature when a laminate is formed.
  • this water dispersion can be formed at a low temperature and has excellent peel strength at a low heat seal temperature when a laminate is formed, various fields where coating is required, for example, , Agriculture, fishery, forestry, horticulture, medicine, sanitary goods, clothing, non-clothing, packaging, automobiles, building materials, etc.

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  • Paints Or Removers (AREA)
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WO2021256381A1 (ja) * 2020-06-16 2021-12-23 日本製紙株式会社 塗工紙
WO2023243309A1 (ja) 2022-06-14 2023-12-21 株式会社カネカ 積層体、成形体、及び積層体の製造方法
CN117337235A (zh) * 2021-05-17 2024-01-02 株式会社钟化 层叠体、包装材料及容器
WO2024024504A1 (ja) * 2022-07-29 2024-02-01 株式会社カネカ 積層体の製造方法、及び成形体の製造方法
WO2024043200A1 (ja) * 2022-08-22 2024-02-29 日本製紙株式会社 ヒートシール紙
SE2330129A1 (en) * 2023-03-20 2024-09-21 Stora Enso Oyj Pha dispersion coating composition and coated fiber-based substrate

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WO2010067543A1 (ja) * 2008-12-09 2010-06-17 株式会社カネカ ポリ－３－ヒドロキシアルカン酸の製造方法およびその凝集体
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WO2021256381A1 (ja) * 2020-06-16 2021-12-23 日本製紙株式会社 塗工紙
US12351985B2 (en) 2020-06-16 2025-07-08 Nippon Paper Industries Co., Ltd. Coated paper
CN117337235A (zh) * 2021-05-17 2024-01-02 株式会社钟化 层叠体、包装材料及容器
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WO2024043200A1 (ja) * 2022-08-22 2024-02-29 日本製紙株式会社 ヒートシール紙
SE2330129A1 (en) * 2023-03-20 2024-09-21 Stora Enso Oyj Pha dispersion coating composition and coated fiber-based substrate
WO2024194713A1 (en) * 2023-03-20 2024-09-26 Stora Enso Oyj Pha dispersion coating composition and coated fiber-based substrate
SE547135C2 (en) * 2023-03-20 2025-04-29 Stora Enso Oyj Pha dispersion coated fiber-based substrate and method for creating the same

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