Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
• • 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
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/098—Metal salts of carboxylic acids
• • 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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

• the present invention relates to a resin composition and molded article containing a poly(3-hydroxyalkanoate) resin.
• Poly(3-hydroxyalkanoate) resins are thermoplastic polyesters that are produced and accumulated as energy storage substances within the cells of many microbial species, and are attracting attention as materials that can biodegrade not only in soil but also in seawater.
• Patent Document 1 discloses the use of such resins in calendar molding to produce sheets.
• fatty acid amides such as behenamide and erucamide can be added as lubricants to impart lubricity to molded bodies of poly(3-hydroxyalkanoate) resins (see, for example, Patent Document 2).
• a lubricant suppresses adhesion of the molten resin to the calendar roll during, for example, calendar molding, and the formed sheet can be easily peeled off from the roll.
• a sheet made of poly(3-hydroxyalkanoate) resin is subjected to secondary molding using a mold to give it a specific shape.
• a release agent e.g., a silicone-based release agent
• a silicone-based release agent is often applied to the surface of the sheet in advance so that the sheet can be easily removed from the mold after molding.
• conventional sheets made of poly(3-hydroxyalkanoate) resin can repel the release agent, making it difficult to apply it evenly.
• the sheet surface may repel the printing ink, and improvements in this regard were also necessary.
• the inventors have investigated the above problems and have found that the behenamide and/or erucamide contained as lubricants in a sheet made of poly(3-hydroxyalkanoate) resin causes the sheet to repel release agents and ink.
• the present invention aims to provide a poly(3-hydroxyalkanoate)-based resin-containing composition that has slip properties and allows for uniform application of a release agent to the surface of a molded article and good printing.
• the present invention relates to a resin composition containing a poly(3-hydroxyalkanoate) copolymer (A) and a lubricant (B), wherein the lubricant (B) contains at least one selected from the group consisting of a diester compound constituted by a dihydric alcohol and two molecules of a monovalent carboxylic acid, and a triester compound constituted by a trihydric alcohol and three molecules of a monovalent carboxylic acid, and the monovalent carboxylic acid contains a carboxylic acid having 15 or more carbon atoms.
• the present invention also relates to a molded article comprising the resin composition.
• a poly(3-hydroxyalkanoate) resin-containing composition that has lubricity and enables uniform application of a release agent to the surface of a molded article and favorable printing.
• the resin composition according to the present invention has lubricity, and therefore the resin composition can be easily peeled off from members that come into contact with the molten resin composition, such as rolls used during melt molding.
• a molded article made of the resin composition according to the present invention can preferably have a vapor-deposited layer containing an inorganic material on its surface, since the adhesion of the vapor-deposited layer to the surface of the molded article is good.
• This embodiment relates to a resin composition containing a poly(3-hydroxyalkanoate) copolymer (A) and a lubricant (B).
• the resin composition contains a poly(3-hydroxyalkanoate) copolymer (A) as a constituent resin.
• the copolymer (A) is a copolymer having at least one or two or more kinds of 3-hydroxyalkanoate units.
• the 3-hydroxyalkanoate unit is preferably represented by the following general formula (1). [-CHR-CH 2 -CO-O-] (1)
• R represents an alkyl group represented by C p H 2p+1 , and p represents an integer of 1 to 15.
• R include linear or branched alkyl groups such as methyl, ethyl, propyl, methylpropyl, butyl, isobutyl, t-butyl, pentyl, and hexyl.
• p is preferably 1 to 10, and more preferably 1 to 8.
• poly(3-hydroxyalkanoate) copolymer a poly(3-hydroxyalkanoate) copolymer produced from a microorganism is particularly preferred.
• a poly(3-hydroxyalkanoate) copolymer produced from a microorganism all of the 3-hydroxyalkanoate units are contained as (R)-3-hydroxyalkanoate units.
• the poly(3-hydroxyalkanoate) copolymer preferably contains 3-hydroxyalkanoate units (particularly units represented by general formula (1)) in an amount of 50 mol% or more of all constituent units (monomer units), more preferably 60 mol% or more, and even more preferably 70 mol% or more.
• the poly(3-hydroxyalkanoate) copolymer may contain only two or more types of 3-hydroxyalkanoate units as the constituent units of the polymer, or may contain other units (e.g., 4-hydroxyalkanoate units, etc.) in addition to one or more types of 3-hydroxyalkanoate units.
• the poly(3-hydroxyalkanoate) copolymer is preferably a copolymer containing 3-hydroxybutyrate (hereinafter sometimes referred to as 3HB) units and other hydroxyalkanoate units. It is preferable that all of the 3-hydroxybutyrate units are (R)-3-hydroxybutyrate units.
• the other hydroxyalkanoate units may be 3-hydroxyalkanoate units other than 3HB units, or may be hydroxyalkanoate units other than 3-hydroxyalkanoate units (e.g., 4-hydroxyalkanoate units).
• the other hydroxyalkanoate units may include only one type, or may include two or more types.
• poly(3-hydroxyalkanoate) copolymers include, for example, poly(3-hydroxybutyrate-co-3-hydroxypropionate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (abbreviation: P3HB3HV), poly(3-hydroxybutyrate-co-3-hydroxyvalerate-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (abbreviation: P3HB3HH), poly(3- Examples of such poly(3-hydroxybutyrate-co-3-hydroxyheptanoate), poly(3-hydroxybutyrate-co-3-hydroxyoctanoate), poly(3-hydroxybutyrate-co-3-hydroxynonanoate), poly(3-hydroxybutyrate-co-3-hydroxydecanoate), poly(3-hydroxybutyrate-co-3-hydroxyundecanoate), poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (abbreviation: P3HB4HB
• poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) or poly(3-hydroxybutyrate-co-4-hydroxybutyrate) is preferred, with poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) being particularly preferred.
• the poly(3-hydroxyalkanoate) copolymer may contain at least two types of poly(3-hydroxyalkanoate) copolymers having different crystallinity from each other, from the viewpoint of productivity and mechanical properties of the resin composition.
• the poly(3-hydroxyalkanoate) copolymer may contain at least two types of poly(3-hydroxyalkanoate) copolymers having different types of constituent monomers and/or different content ratios of the constituent monomers.
• the poly(3-hydroxyalkanoate)-based copolymer may include a copolymer (A1) of 3-hydroxybutyrate units and other hydroxyalkanoate units, in which the content of other hydroxyalkanoate units is 1 to 5 mol%, and a copolymer (A2) of 3-hydroxybutyrate units and other hydroxyalkanoate units, in which the content of other hydroxyalkanoate units is 24 mol% or more.
• copolymer (A1) and the copolymer (A2) it is preferable to further include a copolymer (A3) of 3-hydroxybutyrate units and other hydroxyalkanoate units, in which the content of other hydroxyalkanoate units is 6 mol% or more and less than 24 mol%.
• the average content ratio of each monomer unit in all monomer units constituting the entire poly(3-hydroxyalkanoate)-based copolymer can be determined by a method known to those skilled in the art, for example, the method described in paragraph [0047] of WO 2013/147139.
• the average content ratio means the molar ratio of each monomer unit in all monomer units constituting the entire poly(3-hydroxyalkanoate)-based copolymer.
• the weight average molecular weight of the poly(3-hydroxyalkanoate) copolymer is not particularly limited, but from the viewpoint of achieving both strength and productivity of the resin composition, it is preferably 100,000 to 2,000,000, more preferably 250,000 to 1,500,000, and even more preferably 300,000 to 1,000,000.
• the weight-average molecular weight of poly(3-hydroxyalkanoate) copolymers can be measured in terms of polystyrene using gel permeation chromatography (Shimadzu Corporation HPLC GPC system) with a chloroform solution.
• a column suitable for measuring the weight-average molecular weight should be used as the column for the gel permeation chromatography.
• the method for producing poly(3-hydroxyalkanoate) copolymers is not particularly limited, and may be a production method by chemical synthesis or a production method using microorganisms. Among these, a production method using microorganisms is preferable. For the production method using microorganisms, known methods can be applied. For example, known bacteria that produce copolymers of 3-hydroxybutyrate and other hydroxyalkanoates include Aeromonas caviae, which produces P3HB3HV and P3HB3HH, and Alcaligenes eutrophus, which produces P3HB4HB.
• genetically modified microorganisms into which various poly(3-hydroxyalkanoate) resin synthesis-related genes have been introduced may be used according to the poly(3-hydroxyalkanoate) resin to be produced, and the culture conditions, including the type of substrate, may be optimized.
• the resin composition according to this embodiment contains a lubricant (B), which is an ester compound having a specific structure.
• the lubricant (B) includes a diester compound composed of a dihydric alcohol and two molecules of a monovalent carboxylic acid, or a triester compound composed of a trihydric alcohol and three molecules of a monovalent carboxylic acid.
• the monovalent carboxylic acid includes a carboxylic acid having at least 15 carbon atoms.
• the lubricant (B) two or more of the diester compounds may be used in combination, or two or more of the triester compounds may be used in combination, or only the diester compound may be used, or only the triester compound may be used, or the diester compound and the triester compound may be used in combination. Since the diester compound is more excellent in the effect of imparting lubricity than the triester compound, it is preferable that the lubricant (B) contains at least the diester compound.
• the dihydric alcohol or trihydric alcohol constituting the diester compound or the triester compound refers to an organic compound having two hydroxyl groups or three hydroxyl groups.
• the number of carbon atoms in the alcohol is not particularly limited, but may be, for example, about 2 to 18, preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 to 4.
• the minimum number of carbon atoms in the trihydric alcohol is 3.
• dihydric alcohol examples include ethylene glycol, propylene glycol, butylene glycol, and pentylene glycol.
• trihydric alcohol examples include glycerin.
• the carboxylic acid constituting the diester compound or the triester compound is a monovalent carboxylic acid, that is, an organic compound having one carboxyl group.
• the carboxylic acid may be either an aliphatic carboxylic acid or an aromatic carboxylic acid, but is preferably an aliphatic carboxylic acid.
• the aliphatic carboxylic acid may be either a saturated fatty acid or an unsaturated fatty acid, but is preferably a saturated fatty acid.
• the saturated fatty acid is preferably a fatty acid having a linear carbon chain.
• the carboxylic acid includes a carboxylic acid having 15 or more carbon atoms.
• the number of carbon atoms is preferably 16 or more, more preferably 18 or more, even more preferably 20 or more, even more preferably 22 or more, particularly preferably 24 or more, and most preferably 25 or more.
• carboxylic acids with 15 or more carbon atoms include pentadecylic acid (15 carbon atoms), palmitic acid (16 carbon atoms), stearic acid (18 carbon atoms), arachidic acid (20 carbon atoms), behenic acid (22 carbon atoms), lignoceric acid (24 carbon atoms), and montanic acid (28 carbon atoms).
• pentadecylic acid (15 carbon atoms)
• palmitic acid (16 carbon atoms
• stearic acid (18 carbon atoms)
• behenic acid 22 carbon atoms
• lignoceric acid 24 carbon atoms
• montanic acid 28 carbon atoms.
• montanic acid is preferred because of its particularly excellent ability to impart lubricity.
• the carboxylic acid constituting the diester compound or the triester compound may be only the carboxylic acid having 15 or more carbon atoms as described above, but may also include a carboxylic acid having 14 or less carbon atoms in addition to the carboxylic acid having 15 or more carbon atoms.
• Examples of the carboxylic acid having 14 or less carbon atoms include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, and myristic acid.
• the monovalent carboxylic acid constituting the diester compound or the triester compound is composed only of a carboxylic acid having 15 or more carbon atoms.
• diester compound examples include ethylene glycol dimontanate, butylene glycol dimontanate, etc.
• triester compound examples include glycerin tristearate and glycerin trimontanate.
• the lubricant (B) may be composed only of the diester compound and/or the triester compound, but may also be a partial saponification product of these ester compounds. That is, the lubricant (B) may contain, in addition to the diester compound and/or the triester compound, a salt of the monovalent carboxylic acid having 15 or more carbon atoms. Such salts are preferably alkali metal salts or alkaline earth metal salts, and specific examples include potassium salts, sodium salts, calcium salts, and the like. However, since the effect of imparting lubricating property is particularly excellent, it is preferable that the lubricant (B) is composed only of the diester compound and/or the triester compound.
• the amount of the lubricant (B) to be blended can be appropriately determined taking into consideration the lubrication, the coatability of the release agent, and the printability, but it is preferably 0.01 parts by weight or more and 2 parts by weight or less relative to 100 parts by weight of the poly(3-hydroxyalkanoate)-based copolymer (A).
• the lower limit is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, even more preferably 0.2 parts by weight or more, even more preferably 0.3 parts by weight or more, and particularly preferably 0.4 parts by weight or more.
• the upper limit is preferably 1.5 parts by weight or less, more preferably 1 part by weight or less, even more preferably 0.8 parts by weight or less, and particularly preferably 0.6 parts by weight or less, from the viewpoint of suppressing the effect of the lubricant (B) on the appearance of the obtained molded article.
• the resin composition according to this embodiment may contain other resins besides the poly(3-hydroxyalkanoate) copolymer, provided that the effect of the invention is not impaired.
• other resins include aliphatic polyester resins such as polybutylene succinate adipate, polybutylene succinate, polycaprolactone, and polylactic acid, and aliphatic aromatic polyester resins such as polybutylene adipate terephthalate, polybutylene sebate terephthalate, and polybutylene azelate terephthalate. Only one type of other resin may be contained, or two or more types may be contained.
• the content of the other resin is not particularly limited, but is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, even more preferably 15 parts by weight or less, and even more preferably 10 parts by weight or less, relative to 100 parts by weight of the total amount of poly(3-hydroxyalkanoate)-based copolymer (A).
• the lower limit of the content of the other resin is not particularly limited, and may be 0 parts by weight or more.
• the resin composition according to this embodiment may contain additives that can be used together with the poly(3-hydroxyalkanoate) copolymer (A) to the extent that the effects of the invention are not impaired.
• additives include crystallization nucleating agents, fillers, plasticizers, colorants such as pigments and dyes, odor absorbents such as activated carbon and zeolite, fragrances such as vanillin and dextrin, antioxidants, weather resistance improvers, UV absorbers, release agents, water repellents, antibacterial agents, and sliding property improvers. Only one type of additive may be contained, or two or more types may be contained. The content of these additives can be appropriately set by a person skilled in the art depending on the purpose of use.
• crystallization nucleating agent examples include pentaerythritol, orotic acid, aspartame, cyanuric acid, glycine, zinc phenylphosphonate, boron nitride, etc.
• pentaerythritol is preferred because of its particularly excellent effect of promoting the crystallization of the poly(3-hydroxyalkanoate)-based copolymer (A).
• the amount used is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, and even more preferably 0.7 to 1.5 parts by weight, per 100 parts by weight of the total amount of poly(3-hydroxyalkanoate) copolymer (A).
• one type of crystallization nucleating agent or two or more types may be used, and the usage ratio can be appropriately adjusted depending on the purpose.
• the filler may be either an inorganic filler or an organic filler, or both may be used in combination.
• the inorganic filler includes silicates, carbonates, sulfates, phosphates, oxides, hydroxides, nitrides, and carbon black. Only one type of filler may be used, or two or more types may be used in combination.
• the filler is preferably one or more types selected from the group consisting of talc, silica, mica, kaolinite, montmorillonite, and smectite.
• the content is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the total amount of poly(3-hydroxyalkanoate)-based copolymer (A).
• the plasticizer is not particularly limited, but from the viewpoint of compatibility with the poly(3-hydroxyalkanoate) copolymer (A), it is preferable to use an ester compound having an ester bond in the molecule.
• modified glycerin ester compounds, dibasic acid ester compounds, adipate compounds, polyether ester compounds, and isosorbide ester compounds are preferred.
• the ester compounds can be used alone or in combination of two or more. When using in combination of two or more, the mixing ratio of the ester compounds can be adjusted as appropriate.
• Glycerin ester compounds are preferred as modified glycerin compounds.
• any of glycerin monoesters, diesters, and triesters can be used, but from the viewpoint of compatibility with the poly(3-hydroxyalkanoate) copolymer (A), glycerin triesters are preferred. However, compounds that may be considered as lubricants (B) are excluded.
• glycerin triesters glycerin diacetomonoesters are particularly preferred.
• glycerin diacetomonoesters include glycerin diacetomonolaurate, glycerin diacetomonocaprylate, and glycerin diacetomonodecanoate.
• modified glycerin compounds include the "Rikemal” PL series and "BIOCIZER” from Riken Vitamin Co., Ltd.
• dibasic acid ester compounds include dibutyl adipate, diisobutyl adipate, bis(2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, bis[2-(2-butoxyethoxy)ethyl]adipate, bis[2-(2-butoxyethoxy)ethyl]adipate, bis(2-ethylhexyl)azelate, dibutyl sebacate, bis(2-ethylhexyl)sebacate, diethyl succinate, and mixed-group dibasic acid ester compounds.
• adipate ester compounds examples include diethylhexyl adipate, dioctyl adipate, and diisononyl adipate.
• polyether ester compounds examples include polyethylene glycol dibenzoate, polyethylene glycol dicaprylate, and polyethylene glycol diisostearate.
• a plasticizer When a plasticizer is used, its amount can be set appropriately taking into consideration the moldability and strength of the resin composition, but it is preferably 0.1 to 10 parts by weight, more preferably 1 to 8 parts by weight, and even more preferably 3 to 6 parts by weight, per 100 parts by weight of the total amount of poly(3-hydroxyalkanoate) copolymer (A).
• the resin composition according to the present embodiment can be heated to a temperature equal to or higher than the melting point of the resin composition, melted, and then formed into a molded article having a predetermined shape.
• molding method there are no particular limitations on the molding method that can be used, and any commonly used molding method can be applied, including, specifically, calendar molding, blow molding, injection molding, extrusion molding, inflation molding, and the like.
• Calender molding is a method in which a molten resin composition is kneaded between heated rolls and rolled into a sheet to obtain a film or sheet.
• Blow molding is a molding method that can produce a molded body having a hollow part, such as a bottle, by blowing air into the inside of a molten and plasticized resin material. Any of extrusion blow molding, multilayer extrusion blow molding, injection blow molding, stretch blow molding, etc. can be used.
• Injection molding is a method in which a molten resin composition is injected into a mold, the resin composition is cooled and solidified inside the mold, the mold is opened, and the molded body is demolded to obtain a molded body.
• other injection molding methods such as gas-assisted molding and injection compression molding can be used.
• In-mold molding, gas press molding, two-color molding, sandwich molding, PUSH-PULL, SCORIM, etc. can also be used.
• the injection molding methods that can be used are not limited to the above methods.
• Extrusion molding is a method for obtaining a long molded product by extruding a molten resin composition through a mold of a specific shape.
• a film or sheet is obtained by using a T-die as the mold, and a tube or pipe is obtained by using a double cylindrical mold.
• the inflation molding is a method in which a molten resin composition is extruded into a cylindrical shape while inflating it with air, thereby obtaining a tubular film.
• a molded article can be obtained that can be easily peeled off from a member that comes into contact with the molten resin composition using various molding methods and has good applicability and printability of a release agent.
• Preferred molded articles include films, sheets, injection molded articles, and blow molded articles.
• blow molded articles include extrusion blow molded articles and injection blow molded articles.
• the thickness of the film or sheet is not particularly limited, but may be, for example, about 10 ⁇ m or more and about 1 mm or less.
• the thickness of the film or sheet is preferably about 0.1 to 1 mm, more preferably 0.15 to 0.8 mm, and even more preferably 0.20 to 0.6 mm.
• the uses of the film or sheet are not particularly limited, but for example, it can be preferably used in the fields of agriculture, fishing, forestry, horticulture, medicine, sanitary products, the food industry, clothing, non-clothing, packaging, automobiles, building materials, and other fields. More specifically, it can be used for applications such as agricultural mulch film, forestry fumigation sheet, binding tape including flat yarn, film for wrapping plant roots, diaper back sheets, packaging sheets, shopping bags, garbage bags, draining bags, and other compost bags.
• blow molded or injection molded articles are not particularly limited, but examples include bottles, containers, cases for beverages, liquid foods, liquid detergents, etc., toys, entertainment items, tableware, agricultural materials, office automation parts, home appliance parts, body parts for ships and aircraft, automobile parts, daily necessities, stationery products, etc.
• the molded article made from the resin composition according to this embodiment has good printability, and can therefore preferably have a printed layer on its surface.
• a printed layer There are no particular limitations on the printed layer, so long as it is a layer that contains a pigment or dye.
• the ink used for printing may be either an oil-based ink or a water-based ink.
• the molded body made of the resin composition according to the present embodiment can have a release agent layer on the surface because the release agent can be uniformly applied to the surface.
• the release agent is, for example, a chemical that is applied to the surface of the molded body before secondary molding so that the molded body can be smoothly removed from the mold after secondary molding when the molded body is placed in a mold and a predetermined shape is given to the mold. After application, the agent is appropriately dried to form a film, which can prevent the molded body from adhering to the mold. Specific examples include silicone-based release agents, wax-based release agents, and fluorine-based release agents.
• the method for applying the release agent is not particularly limited and may be a known method.
• the thickness of the formed release agent layer is also not particularly limited and may be appropriately determined by a person skilled in the art.
• the aforementioned secondary molding also known as thermoforming, refers to giving a predetermined shape to a molded body such as a film or sheet while heating and softening it; for example, a container with a recess can be obtained from a sheet. More specifically, it can be performed by fixing the ends of the molded body such as a film or sheet with clamps or pins, heating and softening the molded body using a far-infrared heater or the like, and then shaping the film into the mold using vacuum or compressed air.
• thermoforming method examples include vacuum forming, pressure forming, vacuum pressure forming, matched mold forming, plug assist forming, and TOM forming, but vacuum forming and pressure forming are preferred because they are simple and require low mold costs.
• the device used to heat the molded body during the thermoforming process is not particularly limited, and examples include far-infrared heaters, hot-wire heaters, and hot-air heaters. Among these, far-infrared heaters are preferred because they provide quick and uniform heating.
• the molded products obtained by thermoforming are not particularly limited, but examples include containers with a recess in the center, containers with a partition, containers with a folded portion around the opening, lids with a recess or protrusion in the center, and lids with curved or stepped structures around part or the entire circumference of the edge.
• the molded article made from the resin composition according to this embodiment can have a release agent evenly applied to its surface, so by forming a release agent layer in advance, the molded article can be easily removed from the mold after thermoforming.
• the molded article made of the resin composition according to this embodiment has good adhesion to the deposition layer, so that it can preferably have a deposition layer containing an inorganic material on the surface.
• the deposition layer may contain an inorganic material, but may also be composed of only inorganic materials.
• the inorganic material in the deposition layer may be, for example, a metal or an inorganic oxide, and is not particularly limited.
• a metal or an inorganic oxide aluminum, aluminum oxide, silicon oxide (e.g., silicon monoxide, silicon dioxide, silicon oxynitride, etc.), cerium oxide, calcium oxide, diamond-like carbon film, or a mixture thereof, etc., can be preferably used.
• aluminum or silicon dioxide can be particularly preferably used.
• the thickness of the deposition layer is not particularly limited, but from the viewpoints of productivity, handling, appearance, etc., it is preferably 5 nm to 100 nm, and more preferably 5 nm to 60 nm. When the thickness of the deposition layer is within the above range, the adhesion between the deposition layer and the molded body and the barrier property of the deposition layer (non-permeability of the molded body to water vapor and oxygen) can be improved.
• the vapor deposition layer may be formed on only one side of the molded body, or on both sides. From the viewpoint of ensuring the biodegradability of the molded body, it is preferable that the vapor deposition layer is formed on only one side of the molded body. It is also preferable that the vapor deposition layer is formed directly on the surface of the molded body without any other layers in between.
• the molded article having a vapor deposition layer may further have a resin layer or the like laminated thereon.
• a resin layer may be laminated on top of the vapor deposition layer.
• the molded article having a vapor deposition layer containing an inorganic material formed on its surface can be preferably used for, for example, paper, film, sheet, tube, plate, rod, container (e.g., bottle container), bag, parts, etc., and is particularly preferably used for film or bottle container from the viewpoint of marine pollution countermeasures.
• Methods for forming the deposition layer include, for example, vacuum deposition, sputtering, chemical vapor deposition, ion plating, etc.
• the surface of the molded body before deposition is preferably a corona treatment or plasma treatment.
• the treatment intensity when performing the corona treatment is preferably 5 to 80 W ⁇ min/ m2 , more preferably 10 to 60 W ⁇ min/ m2 .
• a resin composition comprising a poly(3-hydroxyalkanoate) copolymer (A) and a lubricant (B), the lubricant (B) contains at least one selected from the group consisting of a diester compound constituted by a dihydric alcohol and two molecules of a monovalent carboxylic acid, and a triester compound constituted by a trihydric alcohol and three molecules of a monovalent carboxylic acid,
• the resin composition, wherein the monovalent carboxylic acid contains a carboxylic acid having 15 or more carbon atoms.
• the blending amount of the lubricant (B) is 0.01 parts by weight or more and 2 parts by weight or less per 100 parts by weight of the poly(3-hydroxyalkanoate)-based copolymer (A).
• the poly(3-hydroxyalkanoate)-based copolymer (A) is a copolymer containing 3-hydroxybutyrate units and other hydroxyalkanoate units.
• a molded article comprising the resin composition according to any one of items 1 to 10.
• Item 12 Item 12.
• the molded article according to item 11, wherein the molded article is a film or a sheet.
• Item 13 Item 12.
• the molded article according to item 11, wherein the molded article is an extrusion blow molded article or an injection blow molded article.
• Item 14 Item 14.
• Item 15 Item 15.
• PHBH (1) Powder obtained by blending 70 parts by weight of PHBH (1'), 30 parts by weight of PHBH (1"), and 5 parts by weight of filler.
• PHBH (2) Powder obtained by blending 70 parts by weight of PHBH (2'), 30 parts by weight of PHBH (1"), and 5 parts by weight of filler.
• PHBH (3) Powder obtained by blending 60 parts by weight of PHBH (3'), 40 parts by weight of PHBH (1"), and 15 parts by weight of filler.
• Lubricant (B) Ethylene glycol dimontanate Mixture of butylene glycol dimontanate and calcium montanate Glycerin tristearate
• the weight average molecular weight of the poly(3-hydroxyalkanoate) copolymer was measured by first dissolving the poly(3-hydroxyalkanoate) copolymer to be measured in chloroform and heating the solution in a hot water bath at 60° C. for 0.5 hours, filtering the soluble matter through a disposable PTFE filter having a pore size of 0.45 ⁇ m, and then using the filtrate to perform GPC measurement under the following conditions.
• GPC measuring device Hitachi RI monitor (L-3000) Columns: Showa Denko K-G (1 column), K-806L (2 columns) Sample concentration: 3 mg/ml Free solution: chloroform solution Free solution flow rate: 1.0 ml/min Sample injection volume: 100 ⁇ L Analysis time: 30 minutes Standard sample: Standard polystyrene
• a vapor-deposited layer (thickness: 100 nm) containing aluminum as an inorganic material was formed.
• the deposition layer was formed on a sheet cut into a 30 mm square using a film-forming device (UHSP-T2040H, manufactured by Shimadzu Industrial Machinery Systems Co., Ltd.) in an argon gas atmosphere.
• the obtained sheet having the vapor-deposited layer was subjected to a cross-cut method (JIS-K5600-6), and the adhesion of the vapor-deposited layer was evaluated based on the area ratio (%) of the area where the vapor-deposited layer had peeled off to the surface to be evaluated.
• ⁇ The area where the vapor-deposited layer has peeled off is less than 25%.
• ⁇ The area where the vapor-deposited layer has peeled off is 25% or more and 75% or less.
• ⁇ The area where the vapor-deposited layer has peeled off is more than 75%.
• Example 1 100 parts by weight of PHBH (2) and 0.05 parts by weight of ethylene glycol dimontanate were added, and a sheet was obtained by the method described in Processing Method 1. The obtained sheet was used to evaluate roll releasability, sheet appearance, release agent applicability, and printability, and the results are shown in Table 1.
• Example 2 100 parts by weight of PHBH (2) and 0.07 parts by weight of ethylene glycol dimontanate were added, and a sheet was obtained by the method described in Processing Method 1. The obtained sheet was used to evaluate roll releasability, sheet appearance, release agent applicability, and printability, and the results are shown in Table 1.
• Example 3 100 parts by weight of PHBH (2) and 0.1 parts by weight of ethylene glycol dimontanate were added, and a sheet was obtained by the method described in Processing Method 1. The obtained sheet was used to evaluate roll releasability, sheet appearance, release agent applicability, and printability, and the results are shown in Table 1.
• Example 4 100 parts by weight of PHBH (3) and 0.1 parts by weight of ethylene glycol dimontanate were added, and a sheet was obtained by the method described in Processing Method 1. The obtained sheet was used to evaluate roll releasability, sheet appearance, release agent applicability, and printability, and the results are shown in Table 1.
• Example 5 100 parts by weight of PHBH (3) and 0.3 parts by weight of ethylene glycol dimontanate were added, and a sheet was obtained by the method described in Processing Method 1. The obtained sheet was used to evaluate roll releasability, sheet appearance, release agent applicability, and printability, and the results are shown in Table 1.
• Example 6 100 parts by weight of PHBH (1) and 0.1 parts by weight of ethylene glycol dimontanate were added, and a sheet was obtained by the method described in Processing Method 1. The obtained sheet was used to evaluate roll releasability, sheet appearance, release agent applicability, and printability, and the results are shown in Table 1.
• Example 7 100 parts by weight of PHBH (1) and 0.3 parts by weight of ethylene glycol dimontanate were added, and a sheet was obtained by the method described in Processing Method 1. The obtained sheet was used to evaluate roll releasability, sheet appearance, release agent applicability, and printability, and the results are shown in Table 1.
• Example 8 100 parts by weight of PHBH (1) and 0.5 parts by weight of ethylene glycol dimontanate were added, and a sheet was obtained by the method described in Processing Method 1. The obtained sheet was used to evaluate roll releasability, sheet appearance, release agent applicability, and printability, and the results are shown in Table 1.
• Example 9 100 parts by weight of PHBH (3) and 0.5 parts by weight of ethylene glycol dimontanate were added, and a sheet was obtained by the method described in Processing Method 1. The obtained sheet was used to evaluate roll releasability, sheet appearance, release agent applicability, and printability, and the results are shown in Table 1.
• Example 10 100 parts by weight of PHBH (1) and 1.0 part by weight of ethylene glycol dimontanate were added, and a sheet was obtained by the method described in Processing Method 1. The obtained sheet was used to evaluate roll releasability, sheet appearance, release agent applicability, and printability, and the results are shown in Table 1.
• Example 11 100 parts by weight of PHBH (1) and 0.1 parts by weight of a mixture of butylene glycol dimontanate and calcium montanate were added, and a sheet was obtained by the method described in Processing Method 1. Using the obtained sheet, roll peelability, sheet appearance, release agent applicability, and printability were evaluated, and the results are shown in Table 1.
• Example 12 100 parts by weight of PHBH (1) and 0.5 parts by weight of a mixture of butylene glycol dimontanate and calcium montanate were added, and a sheet was obtained by the method described in Processing Method 1. Using the obtained sheet, roll peelability, sheet appearance, release agent applicability, and printability were evaluated, and the results are shown in Table 1.
• Example 13 100 parts by weight of PHBH (1) and 1.0 part by weight of a mixture of butylene glycol dimontanate and calcium montanate were added, and a sheet was obtained by the method described in Processing Method 1. Using the obtained sheet, roll peelability, sheet appearance, release agent applicability, and printability were evaluated, and the results are shown in Table 1.
• Example 14 100 parts by weight of PHBH (1) and 0.5 parts by weight of glycerin tristearate were added, and a sheet was obtained by the method described in Processing method 1. The obtained sheet was used to evaluate roll releasability, sheet appearance, release agent coatability, and printability, and the results are shown in Table 1.
• Example 15 An aluminum-containing vapor-deposited layer was formed on the sheet produced in Example 9, and the adhesion of the vapor-deposited layer was evaluated. The results are shown in Table 2.
• Comparative Example 9 An aluminum-containing vapor deposition layer was formed on the sheet produced in Comparative Example 2, and the results are shown in Table 2.
• Example 15 in which a compound satisfying the definition of lubricant (B) was added, had better adhesion of the vapor-deposited layer than Comparative Example 9, which contained the resin alone, and Comparative Example 10, in which a compound not satisfying the definition of lubricant (B) was added.

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