Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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 laminate containing a laminate layer containing a poly (3-hydroxybutyrate) resin and its use.
• biodegradable plastics examples include starch, polylactic acid, polyvinyl alcohol, poly (3-hydroxybutyrate), polybutylene succinate, polybutylene succinate adipate, polyethylene succinate, polyethylene succinate adipate, and poly. Butylene adipate terephthalate, polycaprolactone and the like are present.
• poly (3-hydroxybutyrate) -based resin is a material having a high melting point and heat resistance, so that it is useful in applications requiring heat resistance and has the property that biodegradation proceeds even in seawater. Therefore, it is attracting attention as a material for solving the problem of marine pollution (Patent Documents 1 and 2).
• the poly (3-hydroxybutyrate) resin has a high melting point, so that it does not melt unless it is at a high temperature, and there is a problem in heat-sealing property at a low temperature when it is formed into a laminate. I understood it. That is, a laminate containing a poly (3-hydroxybutyrate) resin that has both heat-sealing properties and heat resistance at low temperatures has not existed so far, and it is considered that there is a need for it.
• one aspect of the present invention is to provide a laminate containing a poly (3-hydroxybutyrate) resin having both heat-sealing properties and heat resistance at low temperatures, and a technique for utilizing the same. is there.
• the present inventors have identified a specific resin in the laminate layer of a laminate containing a poly (3-hydroxybutyrate) resin which is a material that biodegrades in seawater.
• the present invention has been completed by finding a new finding that a laminate having excellent heat-sealing properties at low temperatures and also having good heat resistance can be obtained by including the above-mentioned compounding ratio.
• one aspect of the present invention is a laminate including a base material layer and a laminate layer laminated on at least one surface of the base material layer, and is a poly (3-hydroxybutylate) -based resin by weight 25 to 85.
• the laminate according to the embodiment of the present invention (hereinafter, referred to as "the present laminate") is a laminate including a base material layer and a laminate layer laminated on at least one surface of the base material layer.
• the laminate layer is characterized by containing 25 to 85 parts by weight of a poly (3-hydroxybutyrate) resin and 75 to 15 parts by weight of a polybutylene succinate adipate resin.
• a poly (3-hydroxybutyrate) resin has a high melting point and is therefore a useful material especially for applications having heat resistance.
• it since it has a high melting point, it is heated at a low temperature. It turned out to have a problem that it is not suitable for sealing.
• adhesion between resin layers containing a poly (3-hydroxybutyrate) resin there has been a problem regarding adhesion between resin layers containing a poly (3-hydroxybutyrate) resin.
• the laminate according to the embodiment of the present invention includes a base material layer and a laminate layer laminated on at least one surface of the base material layer, and the laminate layer is a poly (3-hydroxybutylate) resin. It is characterized by containing 25 to 85 parts by weight and 75 to 15 parts by weight of a polybutylene succinate adipate-based resin. This laminate has heat-sealing properties and heat resistance at low temperatures, and is therefore advantageous in various applications.
• the laminate layer may be laminated on only one side of the base material layer, or may be laminated on both sides.
• the laminated layer may be laminated on the base material layer via another layer, or may be directly laminated on the base material layer without interposing another layer.
• another laminated layer or the like may be laminated on the laminated layer.
• Laminate layer The laminate layer in this laminate contains a resin composition described later.
• the "laminate layer” can also be expressed as a "resin layer” from the viewpoint of the components constituting the layer.
• the resin composition according to one embodiment of the present invention (hereinafter, referred to as “the present resin composition”) is a specific amount of a poly (3-hydroxybutyrate) resin and a specific amount of polybutylene succinate adipate. Contains with resin.
• the present resin composition contains a poly (3-hydroxybutyrate) resin.
• poly (3-hydroxybutyrate) -based resin may be abbreviated as “P3HB-based resin”.
• the P3HB-based resin is an aliphatic polyester resin that can be produced from a microorganism and has 3-hydroxybutyrate as a repeating unit.
• the P3HB-based resin may be a poly (3-hydroxybutyrate) having only 3-hydroxybutyrate as a repeating unit, or 3-hydroxybutyrate and other hydroxyalkanoates. It may be a copolymer with.
• the P3HB-based resin may be a mixture of a homopolymer and one or more copolymers, or a mixture of two or more copolymers. Good.
• the type of copolymerization is not particularly limited, and may be random copolymerization, alternate copolymerization, block copolymerization, graft copolymerization, or the like.
• examples of the P3HB-based resin include poly (3-hydroxybutyrate) (P3HB), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (P3HB3HH), and poly.
• P3HB3HV poly (3-hydroxybutyrate-co-4-hydroxybutyrate)
• P3HB4HB poly (3-hydroxybutyrate-co-3) -Hydroxyoctanoate)
• P3HB3HO poly (3-hydroxybutyrate-co-3-hydroxyoctanoate)
• P3HB3HOD poly (3-hydroxybutyrate-co-3-hydroxyoctanoate)
• P3HB3HD poly (3-hydroxybutyrate-co-3-hydroxyvariate-co-3-hydroxyhexanoate
• P3HB3HV3HH poly 3-hydroxybutyrate-co-3-hydroxyhexanoate
• the melting point and crystallinity can be changed, and as a result, the physical properties such as Young's modulus and heat resistance can be changed, and the physical properties between polypropylene and polyethylene can be changed.
• a copolymer of 3-hydroxybutyric acid and 3-hydroxyhexanoic acid from the viewpoint that it can be imparted and that it is a plastic that is industrially easy to produce and is physically useful as described above. Certain P3HB3HH is more preferred.
• P3HB3HV The melting point, Young's modulus, etc. of the above P3HB3HV change depending on the ratio of the 3-hydroxybutyrate component and the 3-hydroxyvalerate component, but the crystallinity is 50% or more because both components co-crystallize. high. Therefore, P3HB3HV is more flexible than P3HB, but the improvement in brittleness is insufficient.
• the P3HB-based resin can be produced by, for example, a microorganism.
• the microorganism that produces the P3HB-based resin is not particularly limited as long as it is a microorganism that has the ability to produce the P3HB-based resin.
• a P3HB-producing bacterium Bacillus megaterium discovered in 1925 is the first, and in addition, Cupriavidus necator (former classification: Alcaligenes eutrophos, Ralstonia eutropha) (Ralstonia eutropha) Examples include natural microorganisms such as Alcaligenes lattice. It is known that P3HB is accumulated in the cells of these microorganisms.
• Examples of the bacterium that produces a copolymer of hydroxybutyrate and other hydroxyalkanoates include Aeromonas caviae, which is a P3HB3HV and P3HB3HH-producing bacterium, and Alcaligenes, which is a P3HB4HB-producing bacterium. It has been known.
• P3HB3HH in order to increase the productivity of P3HB3HH, Alcaligenes utrophas AC32 strain (Alcaligenes europhos AC32, FERM BP-6038) (T. Fukui, Y. Doi, J. Baeri) into which a gene of the P3HA synthase group was introduced was introduced.
• microbial cells in which P3HB3HH is accumulated in the cells by culturing these microorganisms under appropriate conditions are used.
• a genetically modified microorganism into which various P3HB resin synthesis-related genes have been introduced may be used according to the P3HB resin to be produced, or the culture conditions including the type of substrate may be optimized. ..
• P3HB3HH can also be produced, for example, by the method described in International Publication No. 2010/0134883.
• Examples of commercially available products of P3HB3HH include Kaneka Corporation "Kaneka Biodegradable Polymer PHBH (registered trademark)".
• the composition ratio of the repeating unit of P3HB3HH is such that the composition ratio of 3-hydroxybutyrate unit / 3-hydroxyhexanoate unit is 80/20 or more from the viewpoint of the balance between flexibility and strength. It is preferably 99/1 (mol / mol), more preferably 85/15 to 97/3 (mo1 / mo1).
• the composition ratio of 3-hydroxybutyrate unit / 3-hydroxyhexanoate unit is 99/1 (mol / mol) or less, sufficient flexibility is obtained, and when it is 80/20 (mol / mol) or more. If there is, sufficient hardness can be obtained.
• the weight average molecular weight of the P3HB-based resin (hereinafter, may be referred to as “Mw”) is not particularly limited, but is preferably 100,000 to 1,000,000, more preferably 120,000 to 600,000. It is preferable, and more preferably 150,000 to 400,000.
• Mw the weight average molecular weight of the P3HB-based resin
• the weight average molecular weight is 100,000 or more, sufficient mechanical properties and the like can be obtained, and when it is 600,000 or less, sufficient molding processability is guaranteed.
• the weight average molecular weight of the P3HB resin is determined by gel permeation chromatography (GPC) (“Shodex GPC-101” manufactured by Showa Denko Co., Ltd.), using polystyrene gel (“Shodex K-804” manufactured by Showa Denko Co., Ltd.) on the column, and chloroform. Is used as the mobile phase, and can be obtained as the molecular weight when converted to polystyrene.
• GPC gel permeation chromatography
• the present resin composition contains a polybutylene succinate adipate-based resin.
• the "polybutylene succinate adipate resin” is an aliphatic polyester polymer having 1,4-butanediol, succinic acid and adipic acid as structural units.
• the polybutylene succinate adipate resin includes 1,4-butanediol, any diol other than succinic acid and adipic acid, dicarboxylic acid, or hydroxyalkano as long as the biodegradability is not impaired. It may have an ate as a structural unit, for example, polybutylene succinate adipate, polybutylene succinate adipate and lactic acid copolymer, polybutylene succinate adipate and terephthalic acid copolymer, polybutylene succi.
• Examples thereof include a copolymer of nate adipate and malic acid, a copolymer of polybutylene succinate adipate and sebacic acid, and a copolymer of polybutylene succinate adipate and azelaic acid.
• polybutylene succinate adipate is preferable from the viewpoint of industrial availability, heat resistance, and marine degradability.
• the polybutylene succinate adipate-based resin may contain a diol other than the above, a dicarboxylic acid other than the above, and the like as long as the effects of the present invention are exhibited.
• diols include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,4.
• -Cyclohexanediol, 1,4-cyclohexanedimethanol and the like can be mentioned.
• dicarboxylic acids include sperrinic acid, sebacic acid, dodecanoic acid, succinic anhydride, adipic anhydride and the like.
• the flexural modulus of the polybutylene succinate adipate resin is, for example, 100 to 700 MPa, preferably 150 to 650 MPa, and more preferably 200 to 600 MPa.
• the drawability during secondary processing into a soft container, bag, etc. when blended with a P3HB resin having a high elastic modulus is improved, resulting in poor shape. It is possible to obtain a laminated body in which
• the melting point of the polybutylene succinate adipate resin is, for example, 60 ° C. or higher and 110 ° C. or lower, preferably 70 ° C. or higher and 100 ° C. or lower, and more preferably 75 ° C. or higher and 95 ° C. or higher. It is below ° C.
• the processing temperature at the time of melt-kneading with the P3HB resin is set to 150 to 160 ° C, which is significantly lowered from the thermal decomposition temperature of the P3HB resin of 180 ° C. It is possible to suppress the deterioration of the mechanical properties of the resin composition due to the thermal decomposition of the P3HB-based resin and the deterioration of the working environment due to the odor.
• the fluidity of the polybutylene succinate adipate resin is, for example, a melt flow rate of 5 g / 10 minutes or more and 50 g / 10 minutes or less at 190 ° C. and a load of 2.16 kg, preferably. It is 10 g / 10 minutes or more and 40 g / 10 minutes or less, and more preferably 15 g / 10 minutes or more and 35 g / 10 minutes or less.
• the fluidity of the polybutylene succinate adipate-based resin is within the above range, the fluidity can be kept good even in the above-mentioned melt-kneading at a relatively low temperature of 150 to 160 ° C., and the phase with the P3HB-based resin.
• the solubility can be made good.
• a commercially available product may be used as the polybutylene succinate adipate resin, for example, BiO-PBS® FD series manufactured by Mitsubishi Chemical Corporation and Bionore (registered) manufactured by Showa Denko Corporation. Trademark) etc. can be used.
• the present resin composition is a resin composition for a laminate layer containing the above-mentioned poly (3-hydroxybutyrate) -based resin and the above-mentioned polybutylene succinate adipate-based resin in a specific blending ratio.
• Form laminate layer is intended to be used as a layer for laminating a base material layer.
• for a laminated layer is intended to be used as a resin layer used by laminating a base material layer.
• the blending ratio of the poly (3-hydroxybutyrate) -based resin and the polybutylene succinate adipate-based resin in the resin composition is, for example, the poly (3-hydroxybutyrate) -based resin.
• the ratio includes 25 to 85 parts by weight and 75 to 15 parts by weight of the polybutylene succinate adipate resin, preferably 30 to 80 parts by weight of the poly (3-hydroxybutyrate) resin and polybutylene succinate.
• the ratio includes 70 to 20 parts by weight of the adipate resin, and more preferably 35 to 75 parts by weight of the poly (3-hydroxybutyrate) resin and 65 to 25 parts by weight of the polybutylene succinate adipate resin.
• the laminate containing the present resin composition and the laminate containing the base material layer will be: It has the effect of having excellent heat-sealing properties at low temperatures and good heat resistance. The heat sealability and heat resistance of the laminate are measured and evaluated by the method described in Examples.
• the present resin composition may use one kind of P3HB-based resin alone, or may use two or more kinds of P3HB-based resins in combination.
• the resin described in the above section ⁇ Poly (3-hydroxybutyrate) -based resin> is used.
• the present resin composition contains a biodegradable resin other than the poly (3-hydroxybutyrate) resin and the polybutylene succinate adipate resin within the range in which the effect of the present invention is exhibited. It may contain one kind or two or more kinds.
• examples of such other 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 present resin composition.
• the viscosity of the resin composition is, for example, 100 to 500 Pa ⁇ s, preferably 130 to 470 Pa ⁇ s, and more preferably 130 to 470 Pa ⁇ s at 175 ° C. and a shear rate of 122 s-1. , 150-450 Pa ⁇ s.
• the viscosity of the present resin composition is within the above range, good adhesiveness can be obtained when laminated on a base material.
• the melting point of the present resin composition has a melting point derived from a polybutylene succinate adipate-based resin and a melting point derived from a P3HB-based resin.
• the melting point range of the polybutylene succinate adipate-based resin described in 1 above is 75 ° C. or higher and 95 ° C. or lower, whereas the melting point range of the P3HB-based resin is, for example, 120 to 160 ° C., preferably 125 to 155 ° C. Yes, more preferably 130-150 ° C.
• the melting point of the P3HB-based resin is within the above range, it has sufficient heat resistance when formed into a laminated body and has heat sealability at a low temperature.
• the laminate layer in the present laminate is formed by the present resin composition described in the above-mentioned (resin composition).
• the laminate layer in the present laminate may contain components other than the above resin composition as long as the effects of the present invention are not impaired.
• the content of these additives can be appropriately set by those skilled in the art according to the purpose of use.
• the laminate layer in the present laminate may contain additives usually used in the art as long as the effects of the present invention are exhibited.
• additives include waste paper such as fir tree, wood flour and newspaper, organic fillers such as various starches and cellulose, colorants such as pigments and dyes, odor absorbers such as activated charcoal and zeolite, vanillin, and the like. Fragrances such as dextrin, plasticizers, antioxidants, antioxidants, weather resistance improvers, ultraviolet absorbers, crystal nucleating agents, lubricants, mold release agents, water repellents, antibacterial agents, slidability improving agents, etc. Be done.
• As an additive only one kind may be contained. Two or more types 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 laminate layer in the present laminate may contain an inorganic filler as an additive, but it is preferable that the laminate layer does not substantially contain the inorganic filler.
• substantially free of inorganic filler means that the content of the inorganic filler is 5 parts by weight or less when the entire laminated layer is 100 parts by weight.
• the content of the inorganic filler is preferably 1 part by weight or less, and more preferably not contained at all.
• the laminate when the laminate is secondarily processed into a molded product, there may be a problem that sufficient heat seal strength cannot be obtained due to a decrease in the adhesiveness of the laminate layer during the heat seal process. Further, the deterioration of the bending characteristics of the laminate layer may cause the laminate layer to be easily cracked, and the decrease in transparency may cause problems such as insufficient visibility of printing and the contents of the container.
• inorganic filler examples include talc, calcium carbonate, mica, silica, clay, kaolin, titanium oxide, alumina, and zeolite having an average particle size of 0.5 ⁇ m or more.
• This laminate includes a base material layer.
• the base material layer in the present laminate is not particularly limited as long as it is a layer on which the laminate 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 laminated layer has biodegradability, which is more advantageous as a material for solving the problem of marine pollution.
• 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. , The one obtained by depositing an inorganic substance such as silica. 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, single gloss paper, kraft paper, high-quality 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.
• the adhesion strength between the P3HB resin and the base material layer can be increased by applying the corona treatment to the base material layer in the in-line of the lamination processing and laminating the laminate layer on the base material layer.
• the present laminate can be produced, for example, by heat-sealing the resin composition on one side or both sides of the base material layer by a lamination method.
• a lamination method a known method can be appropriately carried out, and the method is not particularly limited.
• a cooling roll is applied to a separately drawn base material layer (for example, paper).
• Extrusion laminating method in which a resin film prepared in advance is heated and pressure-bonded to a base material layer, or a resin film prepared in advance is applied to a base material layer via an adhesive.
• a dry laminating method or the like in which laminating is performed can be mentioned. Among them, extrusion laminating is preferable in that the number of steps is small and the productivity is excellent.
• the heating temperature when the resin composition is pressure-bonded to the base material layer is preferably adjusted so that the temperature of the resin to be heat-sealed is 150 to 175 ° C., and 160 to 170 ° C. It is more preferable to adjust to.
• the temperature is 150 ° C. or higher, the adhesion between the laminate layer containing the resin composition and the base material layer tends to be good, and when the temperature is 175 ° C. or lower, thermal decomposition of the P3HB-based resin is suppressed. , The mechanical strength of the laminated layer can be guaranteed.
• the surface temperature of the cooling roll in the extrusion laminating method is not particularly limited as long as it can cool and crimp the laminated layer, and can be appropriately determined.
• the surface temperature of the cooling roll can be, for example, in the range of 10-60 ° C.
• the thickness of the laminate layer (each laminate layer when the present laminate has two or more laminate layers) in the present laminate is not particularly limited, but is sufficiently flexible while preventing water absorption to the base material layer. From the viewpoint of ensuring the properties, 5 to 300 ⁇ m is preferable, and 10 to 200 ⁇ m is more preferable. When the thickness of the laminate layer is 5 ⁇ m or more, sufficient heat seal strength can be obtained. Further, when the thickness of the laminate layer is 300 ⁇ m or less, the amount of heat required for heat sealing can be suppressed low, and the productivity is high.
• the thickness of the laminate layer may be 20 to 100 ⁇ m. It is preferably 30 to 70 ⁇ m, more preferably 30 to 70 ⁇ m. By setting the thickness within the above range, it is possible to maintain good secondary workability such as punching property and heat sealing property.
• the thickness of the laminate layer Is preferably 20 to 50 ⁇ m, and more preferably 30 to 40 ⁇ m.
• the molded body according to one embodiment of the present invention includes the present laminated body. Since this molded product is formed of a laminate having heat-sealing properties and heat resistance at low temperatures, it is advantageous in various applications.
• the molded product is not particularly limited as long as it includes the laminated product, and is, for example, paper, film, sheet, tube, plate, rod, container (for example, bottle container, cup (also referred to as cup), tray). , Bags, parts, etc.
• the molded product is preferably a bag or container (for example, a bottle container, a cup, a tray) from the viewpoint of measures against marine pollution.
• the molded body may be the laminated body itself.
• 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.
• this laminate has a container for liquids, especially instant noodles, instant soup, food and drink cups such as coffee, side dishes, lunch boxes, and microwave ovens. It is more preferable as a container for storing warm contents such as trays used for microwave oven foods and the like.
• the above-mentioned various secondary processes can be performed by using the same method as the conventional resin laminated paper, that is, using various bag making machines, filling and wrapping 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 heat seal temperature of the laminated body or the molded body differs depending on the bonding method.
• the heat-sealing temperature of the laminated body or the molded body is usually 200 ° C. or lower, preferably 160 ° C. or lower, and more preferably 140 ° C. or lower when a heating type heat-sealing tester having a seal bar is used.
• the lower limit value when a heating type heat seal tester having a seal bar is used is usually 100 ° C. or higher, preferably 110 ° C. or higher, and more preferably 120 ° C. or higher.
• appropriate adhesion at the seal portion can be ensured.
• the heat sealing pressure of the laminated body or the molded body differs depending on the bonding method.
• the heat-sealing pressure of the laminated body or the molded product is usually 0.05 MPa or more, preferably 0.1 MPa or more when a heating type heat-sealing tester having a seal bar is used. Within the above range, appropriate adhesion at the seal portion can be ensured. Further, when a heating type heat seal tester having a seal bar is used, the upper limit value is usually 0.5 MPa or less, preferably 0.4 MPa or less. When it is within the above range, it is possible to avoid thinning the film thickness of the seal end portion and secure the seal strength.
• the molded body for example, fiber, thread, rope, woven fabric, knitted fabric, non-woven fabric
• a material different from the present molded body is used.
• Paper, film, sheet, tube, board, rod, container, bag, part, foam, etc. are also preferably biodegradable.
• one embodiment of the present invention is as follows.
• a laminate including a base material layer and a laminate layer laminated on at least one surface of the base material layer, wherein the laminate layer is a poly (3-hydroxybutylate) resin 25 to 85 weight by weight.
• the laminate layer does not substantially contain an inorganic filler.
• ⁇ 4> The laminate according to any one of ⁇ 1> to ⁇ 3>, wherein the thickness of the laminate layer is 5 to 300 ⁇ m.
• ⁇ 5> The laminate according to any one of ⁇ 1> to ⁇ 4>, wherein the base material layer is a biodegradable layer.
• ⁇ 6> The laminate according to any one of ⁇ 1> to ⁇ 5>, wherein the base material layer is paper.
• ⁇ 7> A molded product containing the laminate according to any one of ⁇ 1> to ⁇ 6>.
• Poly (3-hydroxybutyrate) resin (A): Kaneka's biodegradable polymer PHBH® X331N [Poly (3-hydroxybutyrate-co-3-hydroxyhexanoate)] Polybutylene succinate adipate resin (B): Mitsubishi Chemical Corporation, BiO-PBS (registered trademark) FD72PB [polybutylene succinate adipate] Polybutylene succinate resin (C): Mitsubishi Chemical Corporation, BiO-PBS (registered trademark) FZ71PB [Polybutylene succinate adipate] Polylactic acid (D): Made by Nature Works, Ingeo (registered trademark) 10361D [Polylactic acid] [Measurement and evaluation method] Evaluation in Examples and Comparative Examples was carried out by the following method.
• the laminated resin surface of the laminate obtained by laminating the resin composition for the laminate layer on the base material is superposed, and using HEATSEALTESTER TP-701-B manufactured by Tester Sangyo Co., Ltd., in a heating bar set at 130 ° C. Heat fusion was performed from both substrate sides under the conditions of a sealing surface pressure of 0.4 MPa and a time of 2 seconds.
• the heat-sealed 15 mm wide laminate was peeled off at a tensile speed of 300 mm / min using an Autograph EZ-LX manufactured by Shimadzu Corporation, and the state of the peeled surface was visually observed.
• the evaluation criteria are as follows.
• Paper peeling occurs uniformly and there is no interface peeling part ⁇ : Paper peeling and interface peeling are mixed and the area of the interface peeling part is less than 50% ⁇ : Paper peeling and interface peeling are mixed and the interface is peeled off The area of the peeled portion is 50% or more. “Paper peeling” refers to a state in which the surface layer of the paper is transferred to the laminate layer side and is torn.
• Example 1 The poly (3-hydroxybutyrate) resin (A) and the polybutylene succinate adipate resin (B) were dry-blended at the compounding ratio (part by weight) shown in Table 1.
• the obtained mixture is melt-kneaded at a set temperature of 150 ° C. (the temperature of the resin from which the die came out is 160 ° C.) and a screw rotation speed of 100 rpm using a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd .: TEM26SS) in the same direction. It was extruded into water in a strand shape and cut to obtain resin composition pellets for a laminate layer.
• a twin-screw extruder manufactured by Toshiba Machine Co., Ltd .: TEM26SS
• the obtained resin composition pellets for the laminate layer were subjected to a single-screw extruder (“20C200 type” lab plast mill manufactured by 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 cylinder set temperature was set to 140 to 170 ° C.
• a chill roll set temperature was set to 50 ° C.
• a laminate was obtained by laminating on one side of a cup base paper having a basis weight of 200 g / m 2 with a thickness of 50 ⁇ m.
• the laminated layer of the above-mentioned laminate did not contain an inorganic filler.
• pellets of the resin composition were heat-pressed at 170 ° C. and 5 MPa to obtain a press sheet having a thickness of 2 mm, a width of 80 mm and a length of 60 mm, which was cut into a width of 10 mm to prepare a sample for heat resistance evaluation.
• Example 2 and 3 Laminates in the same manner as in Example 1 except that the amounts of the poly (3-hydroxybutyrate) resin (A) and the polybutylene succinate adipate resin (B) were changed as shown in Table 1, respectively. And manufactured press sheets. The results are shown in Table 1.
• Example 1 A laminate and a press sheet were produced in the same manner as in Example 1 except that the polybutylene succinate adipate resin (B) was removed. The results are shown in Table 1.
• Example 5 A laminate and a press sheet were produced in the same manner as in Example 2 except that the polybutylene succinate resin (C) was used instead of the polybutylene succinate adipate resin (B). The results are shown in Table 1.
• Example 6 A laminate and a press sheet were produced in the same manner as in Example 2 except that polylactic acid (D) was used instead of the polybutylene succinate adipate resin (B). The results are shown in Table 1.
• Example 7 A laminate and a press sheet were produced in the same manner as in Example 2 except that polycaprolactone (E) was used instead of the polybutylene succinate adipate resin (B). The results are shown in Table 1.
• the laminate of the present invention has excellent heat-sealing properties at low temperatures and also has good heat resistance.
• the laminate of the present invention has excellent heat-sealing properties at low temperatures and also has good heat resistance. Therefore, agriculture, fisheries, forestry, horticulture, medicine, sanitary goods, clothing, non-clothing, packaging, automobiles, building materials , Can be suitably used in other fields.

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• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Laminated Bodies (AREA)

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• 2020
  • 2020-11-18 JP JP2021558409A patent/JPWO2021100732A1/ja active Pending
  • 2020-11-18 WO PCT/JP2020/042894 patent/WO2021100732A1/ja not_active Ceased

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