WO2023171565A1 - Resin composition - Google Patents

Resin composition Download PDF

Info

Publication number
WO2023171565A1
WO2023171565A1 PCT/JP2023/008067 JP2023008067W WO2023171565A1 WO 2023171565 A1 WO2023171565 A1 WO 2023171565A1 JP 2023008067 W JP2023008067 W JP 2023008067W WO 2023171565 A1 WO2023171565 A1 WO 2023171565A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
resin composition
aliphatic
acid
composition according
Prior art date
Application number
PCT/JP2023/008067
Other languages
French (fr)
Japanese (ja)
Inventor
純己 福田
紀人 酒井
Original Assignee
三菱ケミカル株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三菱ケミカル株式会社 filed Critical 三菱ケミカル株式会社
Publication of WO2023171565A1 publication Critical patent/WO2023171565A1/en

Links

Classifications

    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • 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
    • 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

Definitions

  • the present invention relates to a resin composition containing a biodegradable resin.
  • the present invention relates to a resin composition that contains a specific aliphatic polyester resin and cellulose fibers, has excellent moldability, and has excellent tensile elongation properties after molding.
  • biodegradable resins for example, polylactic acid, polybutylene succinate, polybutylene succinate adipate, polybutylene adipate terephthalate, etc. are known.
  • Biodegradable resins usually do not have sufficient mechanical strength compared to general-purpose resins such as polyethylene and polypropylene, so when processing them into molded products, etc., it is important to increase the mechanical strength of the resulting molded product.
  • Various reinforcing components may be added.
  • Patent Documents 1 to 3 describe molding compositions in which a cellulose-based raw material is blended with polybutylene succinate or polybutylene succinate adipate.
  • the present invention has been made in view of the above problems, and provides a resin composition that has excellent moldability and excellent tensile elongation properties.
  • the present inventors surprisingly found that in a resin composition containing a polyester resin and a cellulose fiber, an aliphatic polyester resin and an aliphatic-aromatic polyester It has been found that by combining with resin, it is possible to provide a resin composition that has excellent moldability and excellent tensile elongation properties after molding.
  • A1 An aliphatic polyester resin having an aliphatic polyhydric alcohol unit and an aliphatic polycarboxylic acid unit.
  • A2) An aliphatic-aromatic polyester resin having an aliphatic polyhydric alcohol unit, an aliphatic polycarboxylic acid unit, and an aromatic polycarboxylic acid unit.
  • B Cellulose fiber.
  • the polyester resin in a resin composition containing a polyester resin and a cellulose fiber, is (A1) an aliphatic polyester having an aliphatic polyhydric alcohol unit and an aliphatic polycarboxylic acid unit.
  • the resin By combining the resin and (A2) an aliphatic-aromatic polyester resin having an aliphatic polyhydric alcohol unit, an aliphatic polycarboxylic acid unit, and an aromatic polycarboxylic acid unit, moldability can be improved. It is possible to provide a resin composition that is excellent in both properties and tensile elongation properties after molding.
  • a resin composition according to an embodiment of the present invention (hereinafter sometimes referred to as "the present resin composition") is characterized by containing the following components (A1), (A2), and (B). shall be.
  • (A1) An aliphatic polyester resin having an aliphatic polyhydric alcohol unit and an aliphatic polycarboxylic acid unit.
  • (A2) An aliphatic-aromatic polyester resin having an aliphatic polyhydric alcohol unit, an aliphatic polycarboxylic acid unit, and an aromatic polycarboxylic acid unit.
  • B Cellulose fiber.
  • the present resin composition is useful in that it has excellent moldability as well as excellent tensile elongation properties after molding and tensile strength properties after molding.
  • this resin composition has excellent moldability even though it contains a relatively large amount of cellulose fibers, so the content of aliphatic polyester resin can be reduced, making it effective as a technology for environmental conservation. It can be used for
  • Component (A1) is, for example, an aliphatic polyester resin having an aliphatic polyhydric alcohol unit and an aliphatic polycarboxylic acid unit as main constituent units. Specifically, it is an aliphatic polyester resin having an aliphatic polyhydric alcohol unit represented by the following formula (1) and an aliphatic polycarboxylic acid unit represented by the following formula (2) as main constituent units. (However, in this specification, the concept of component (A1) does not include component (A2)).
  • R 11 represents a divalent chain aliphatic hydrocarbon group which may have an oxygen atom in the chain, and is not limited to one type when copolymerized.
  • R 21 represents a direct bond or represents a divalent chain aliphatic hydrocarbon group, and is not limited to one type when copolymerized.
  • the above-mentioned “unit” means a structural unit contained in the aliphatic polyester resin derived from the monomer component used in the production of the aliphatic polyester resin, and the "main structural unit” is It means that the aliphatic polyester resin contains 50 mol% or more of structural units derived from the target monomer component in all structural units of the aliphatic polyester resin.
  • the content of structural units derived from the target monomer is preferably 60 mol% or more, more preferably 70 mol% or more, and still more preferably 80 to 100 mol%.
  • the aliphatic polyhydric alcohol and the aliphatic polycarboxylic acid component are contained in the total monomer components used in the polymerization reaction of the aliphatic polyester resin at 50 mol% or more, preferably 60 mol% or more, more preferably It is preferably produced by polymerizing raw materials containing 70 mol% or more, more preferably 80 to 100 mol%.
  • the aliphatic polyhydric alcohol that provides the polyhydric alcohol unit of formula (1) is not particularly limited, but for example, aliphatic polyhydric alcohols having 2 to 10 carbon atoms are preferred, and more preferably aliphatic polyhydric alcohols having 4 to 6 carbon atoms. It is a family of polyhydric alcohols.
  • Examples include diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like.
  • 1,4-butanediol is preferred.
  • the aliphatic polyhydric alcohols may be used alone or in combination of two or more.
  • the aliphatic polycarboxylic acid component providing the aliphatic polycarboxylic acid unit of formula (2) is an aliphatic polycarboxylic acid or an aliphatic polycarboxylic acid derivative such as an alkyl ester thereof;
  • the carboxylic acid is not particularly limited, but for example, an aliphatic polycarboxylic acid having 2 to 40 carbon atoms is preferable, and an aliphatic polycarboxylic acid having 4 to 10 carbon atoms is more preferable.
  • Specific examples include succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, and the like.
  • succinic acid, adipic acid, and sebacic acid are preferred, succinic acid and adipic acid are more preferred, and succinic acid is particularly preferred.
  • the aforementioned aliphatic polycarboxylic acid components may be used alone or in combination of two or more.
  • component (A1) include, for example, an aliphatic polyester resin containing 1,4-butanediol and succinic acid, an aliphatic polyester resin containing 1,4-butanediol, adipic acid, and succinic acid, etc. can be mentioned.
  • component (A1) includes, for example, an aliphatic polyester resin containing 1,4-butanediol and succinic acid, an aliphatic polyester resin containing 1,4-butanediol, adipic acid, and succinic acid, etc.
  • one or more selected from the group consisting of polybutylene succinate and polybutylene succinate adipate are preferred.
  • component (A1) when the aliphatic polycarboxylic acid is succinic acid, the proportion of structural units derived from succinic acid in the total polycarboxylic acid units of the aliphatic polyester resin is usually 50 to 100 mol%, Preferably it is 80 to 100 mol%, more preferably 90 to 100 mol%.
  • component (A1) when the aliphatic polycarboxylic acids are succinic acid and adipic acid, the proportion of structural units derived from succinic acid in the total polycarboxylic acid units of the aliphatic polyester resin is usually 50 -95 mol%, preferably 60-93 mol%, more preferably 70-90 mol%, and the proportion of adipic acid-derived structural units in the total polycarboxylic acid units is usually 5-50 mol%, preferably is 7 to 40 mol%, more preferably 10 to 30 mol%.
  • the component (A1) preferably has the following physical properties.
  • the melt flow rate (MFR) of component (A1) is preferably 1 to 150 g/10 minutes, more preferably 3 to 125 g/10 minutes, when measured at 190 ° C. and 2.16 kg according to JIS K7210. Even more preferably 4 to 100 g/10 minutes, particularly preferably 5 to 50 g/10 minutes.
  • MFR melt flow rate
  • the melting point of component (A1) is preferably 70 to 250°C, more preferably 75 to 200°C, and even more preferably 80 to 150°C. When there are multiple melting points, it is preferable that at least one melting point is within the above range.
  • the weight average molecular weight (Mw) of component (A1) is preferably 10,000 to 1,000,000, more preferably 20,000 to 500,000, and even more preferably 50,000 to 400,000. Note that the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
  • component (A1) only one type of component (A1) may be used, or two or more types may be used in combination.
  • two or more types of components (A1) having different polyhydric alcohol units and polyhydric carboxylic acid units may be used in combination.
  • the content of component (A1) is preferably, for example, 5 to 55% by mass, more preferably 10 to 50% by mass, and even more preferably 15 to 45% by mass, based on the total amount (100% by mass) of the resin composition. %.
  • Component (A2) is, for example, an aliphatic-aromatic polyester resin having an aliphatic polyhydric alcohol unit, an aliphatic polycarboxylic acid unit, and an aromatic polycarboxylic acid unit as main constituent units.
  • an aliphatic polyhydric alcohol unit represented by the above formula (1), an aliphatic polyhydric carboxylic acid unit represented by the above formula (2), and an aromatic represented by the following formula (3) It has a group polyhydric carboxylic acid unit as a main structural unit.
  • Component (A2) may further have an oxycarboxylic acid unit.
  • R 31 represents a divalent aromatic hydrocarbon group, and is not limited to one type when copolymerized.
  • the aromatic polycarboxylic acid component that provides the aromatic polycarboxylic acid unit of formula (3) is not particularly limited, and examples thereof include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyldicarboxylic acid, and the like. These may be acid anhydrides. Furthermore, examples of derivatives of aromatic polycarboxylic acids include lower alkyl esters of these aromatic polycarboxylic acids. Among these, terephthalic acid, isophthalic acid, or lower alkyl (eg, alkyl having 1 to 4 carbon atoms) ester derivatives thereof are preferred. These may be used alone or in combination of two or more.
  • terephthalic acid and/or methyl ester of terephthalic acid are particularly preferred, or mixtures containing terephthalic acid and/or methyl ester of terephthalic acid and isophthalic acid and/or methyl ester of isophthalic acid.
  • polybutylene alkylate terephthalate is preferable from the viewpoint of further improving the moldability of the resin composition, particularly from the viewpoint of achieving both moldability and tensile elongation properties, and polybutylene adipate terephthalate or polybutylene adipate terephthalate is preferred.
  • Butylene succinate terephthalate is more preferred, and polybutylene adipate terephthalate is particularly preferred.
  • the component (A2) preferably has the following physical properties.
  • the melt flow rate (MFR) of component (A2) is preferably 1 to 150 g/10 min, more preferably 1.5 to 125 g/10 min, when measured at 190°C and 2.16 kg according to JIS K7210. minutes, even more preferably 2 to 100 g/10 minutes, particularly preferably 2 to 50 g/10 minutes.
  • MFR melt flow rate
  • the melting point of component (A2) is preferably 70 to 250°C, more preferably 75 to 200°C, even more preferably 80 to 150°C. When there are multiple melting points, it is preferable that at least one melting point is within the above range.
  • the weight average molecular weight (Mw) of component (A2) is preferably 10,000 to 1,000,000, more preferably 20,000 to 500,000, even more preferably 50,000 to 400,000. Note that the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
  • component (A2) only one type of component (A2) may be used, or two or more types may be used in combination.
  • two or more types of components (A2) having different polyhydric alcohol units and polyhydric carboxylic acid units may be used in combination.
  • the content of component (A2) is preferably 1 to 35% by mass, more preferably 2.5 to 30% by mass, even more preferably 3.5 to 30% by mass, based on the total amount (100% by mass) of the resin composition. It is 25% by mass.
  • the total content of components (A1) and (A2) [(A1)+(A2)] is determined from the viewpoint of further improving the moldability of the resin composition, especially from the viewpoint of achieving both moldability and tensile elongation properties.
  • the amount is preferably 20 to 59% by weight, more preferably 30 to 52% by weight, and even more preferably 35 to 50% by weight based on the total amount of the resin composition (100% by weight).
  • the mass ratio of component (A2) to component (A1) [(A2)/(A1)] is set to 0 from the viewpoint of further improving the moldability of the resin composition, especially from the viewpoint of achieving both moldability and tensile elongation properties. It is preferably from .05 to 1.5, more preferably from 0.075 to 1.3, even more preferably from 0.1 to 1.1.
  • component (B) known general cellulose fibers that are blended into resin compositions can be used, for example, selected from the group consisting of cellulose, cellulose derivatives obtained by partially modifying cellulose, and salts thereof.
  • cellulose cellulose
  • hydroxyalkylcelluloses such as hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose
  • alkylcelluloses such as methylcellulose and ethylcellulose
  • carboxyalkylcelluloses such as carboxymethylcellulose.
  • the component (B) is obtained from known cellulose-containing raw materials, and examples of such cellulose-containing raw materials include wood fibers such as wood pulp from coniferous and hardwood trees, cotton such as linters, Bombax cotton, kapok, etc. Examples include seed hair fibers of hemp, flax, jute, ramie, paper mulberry, mitsumata, etc., and leaf fibers of Manila hemp, New Zealand hemp, etc. These can be used alone or in combination of two or more.
  • the average fiber length of the cellulose fiber (B) is, for example, 2,000 ⁇ m or less, preferably 10 to 1,000 ⁇ m, and more preferably 10 to 500 ⁇ m, from the viewpoint of obtaining a resin composition with excellent moldability. Further, the average diameter of the cellulose fiber (B) is, for example, 400 ⁇ m or less, preferably 10 to 300 ⁇ m, and more preferably 10 to 200 ⁇ m.
  • Powdered cellulose fibers are not particularly limited as long as they are cellulose processed into powder, but examples include powdered cellulose obtained by mechanically crushing wood pulp, etc.; Powdered cellulose (crystalline cellulose) obtained by crushing and sieving after removal by hydrolysis treatment; Examples include powdered cellulose (cellulose nanofiber). These can be used alone or in combination of two or more.
  • the average particle diameter of the powdered component (B) is preferably 10 to 100 ⁇ m, more preferably 15 to 80 ⁇ m, even more preferably 18 to 60 ⁇ m, particularly preferably 20 to 50 ⁇ m. When the average particle diameter of component (B) is outside the above range, the moldability of the resin composition tends to be impaired.
  • the average particle diameter is a median diameter (d50) corresponding to 50% of the cumulative particle diameter distribution on a volume basis, and is, for example, a laser diffraction particle diameter measuring device (for example, product number LA-950V2, manufactured by Horiba, Ltd.). It can be measured by
  • the average degree of polymerization of component (B) is not particularly limited, but is preferably from 50 to 1,500, more preferably from 100 to 1,000, even more preferably from 150 to 800, particularly preferably from 200 to 600.
  • the crystallinity of component (B) as measured by X-ray diffraction is not particularly limited, but is preferably 70% or more, more preferably 75 to 95%, and even more preferably 80 to 95%.
  • component (B) can be suitably used as component (B).
  • the KC flock series manufactured by Nippon Paper Industries W-400G/Y, W-300G/Y, W-250, W-200, W-200W/G/Y, W-100W/G/Y, W-50 ), KC Flock GK series (W-50GK, W-100GK, etc.), NP Micros series (W-200M, W-400M, etc.), NP fiber series (W-100F, W-300F, W-10MG2, etc.) etc.
  • the content of component (B) is preferably 41 to 64% by mass, more preferably 41 to 62% by mass, based on the total amount of the resin composition (100% by mass), from the viewpoint of further improving the moldability of the resin composition. %, even more preferably 43 to 60% by weight, particularly preferably 45 to 58% by weight.
  • the mass ratio of component (B) to the total amount of components (A1) and (A2) [(B)/[(A1)+(A2)]] is determined from the viewpoint of further improving the moldability of the resin composition. It is preferably from 0.68 to 2.0, more preferably from 0.75 to 1.8, even more preferably from 0.8 to 1.6, particularly preferably from 1 to 1.5.
  • this resin composition contains (C) inorganic filler (hereinafter referred to as component (C)) from the viewpoint of further improving the moldability of the resin composition. It is preferable to contain the following.
  • component (C) commonly used inorganic fillers commonly used can be used, and the shape thereof is not particularly limited, and for example, fibrous, spherical, plate-like, and needle-like inorganic fillers can be used.
  • component (C) include talc, anhydrous silica, mica, titanium oxide, calcium carbonate, diatomaceous earth, allophane, bentonite, potassium titanate, zeolite, sepiolite, smectite, kaolin, kaolinite, glass, Limestone, carbon, wollastenite, calcined pearlite, calcium silicate, sodium silicate, aluminum silicate, aluminum oxide, magnesium carbonate, calcium hydroxide, ferric carbonate, zinc oxide, iron oxide, aluminum phosphate, barium sulfate, etc. . These may be used alone or in combination of two or more. Among these, talc is preferred from the viewpoint of further improving the moldability of the resin composition.
  • the average particle diameter of component (C) is not particularly limited, but is preferably 0.5 to 30 ⁇ m, more preferably 0.6 to 20 ⁇ m, even more preferably 0.7 to 10 ⁇ m, particularly preferably 1 to 5 ⁇ m. When the average particle diameter of component (C) is within the above range, the resin composition tends to have excellent moldability.
  • the average particle diameter of component (C) is the median diameter (d50) corresponding to 50% of the cumulative particle diameter distribution on a volume basis. (manufactured by Horiba, Ltd.).
  • the specific surface area of component (C) is not particularly limited, but is usually 1 to 200 m 2 /g, preferably 3 to 150 m 2 /g, more preferably 5 to 100 m 2 /g, and even more preferably 10 to 50 m 2 /g. 2 /g. Note that the specific surface area of component (C) can be measured by a known method, for example, by the BET method.
  • the content of component (C) is not particularly limited, but is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, and even more preferably It is 1.5 to 6% by mass. When the content of component (C) is outside the above range, the moldability of the resin composition tends to be impaired.
  • the present resin composition can further contain (D) a plasticizer (hereinafter sometimes referred to as (D) component) in addition to component (A1), component (A2), and component (B).
  • a plasticizer hereinafter sometimes referred to as (D) component
  • component (D) commonly used plasticizers can be used.
  • component (D) include, but are not limited to, aliphatic dibasic acid ester plasticizers such as adipic acid ester plasticizers, sebacic acid ester plasticizers, and azelaic acid ester plasticizers; Phthalate ester plasticizers, phosphate ester plasticizers, citric acid ester plasticizers, glycolate ester plasticizers, trimellitic ester plasticizers, ricinoleate ester plasticizers, benzoate ester plasticizers, Examples include plasticizers having an ester bond in the molecule, such as acetate-based plasticizers. These can be used alone or in combination of two or more.
  • aliphatic dibasic acid ester plasticizers such as adipic acid ester plasticizers, sebacic acid ester plasticizers, and azelaic acid ester plasticizers
  • Phthalate ester plasticizers phosphate ester plasticizers, citric acid ester plasticizers, glycolate ester plasticizers, trimellitic
  • adipate ester plasticizers include dimethyl adipate, dibutyl adipate, dioctyl adipate, isobutyl adipate, isodecyl adipate, diisononyl adipate, divinyl adipate, dibenzyl adipate, adipic acid and aromatic alcohol, and Examples include mixed esters with aliphatic alcohols.
  • Examples of the mixed group ester of adipic acid and aromatic alcohol and aliphatic alcohol include benzyl alkyl diglycol adipate.
  • the alkyl group in the benzyl alkyl diglycol adipate may be linear or branched, and the number of carbon atoms in the alkyl group is not particularly limited, but is usually about 1 to 20.
  • linear alkyl groups are preferred, more preferably linear alkyl groups having 1 to 8 carbon atoms, even more preferably linear alkyl groups having 1 to 4 carbon atoms.
  • examples include benzylmethyl diglycol adipate, benzylethyl diglycol adipate, benzylpropyl diglycol adipate, and benzyl butyl diglycol adipate.
  • sebacate ester plasticizers include dimethyl sebacate, dibutyl sebacate, di-2-ethylhexyl sebacate, dioctyl sebacate, diisooctyl sebacate, and the like.
  • azelate ester plasticizers include dioctyl azelate, 2-ethylhexyl azelate, isobutyl azelate, isodecyl azelate, diisononyl azelate, dihexyl azelate, divinyl azelate, dibenzyl azelate, and the like.
  • phthalate ester plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diisooctyl phthalate, di2-ethylhexyl phthalate, and di-2 isophthalate.
  • phosphate ester plasticizers include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, 2-ethylhexyldiphenyl phosphate, triphenyl phosphate, tricresyl phosphate, and diphenylethyl phosphate. etc.
  • citric acid ester plasticizer examples include triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate, and tri-2-ethylhexyl acetyl citrate.
  • glycolic acid ester plasticizer examples include triacetin, tributyrin, methyl phthalyl ethyl glycolate, ethyl phthalyl ethyl glycolate, butylphthalyl butyl glycolate, and the like.
  • trimellitic acid ester plasticizers examples include trioctyl trimellitate, tri2-ethylhexyl trimellitate, diisooctyl monoisodecyl trimellitate, triisononyl trimellitate, and the like.
  • ricinoleic acid ester plasticizer examples include methylacetyl ricinoleate, butylacetyl ricinoleate, and the like.
  • benzoic acid ester plasticizers include diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, polyethylene glycol dibenzoate, and the like.
  • aliphatic dibasic acid ester plasticizers are preferred, adipic acid ester plasticizers are more preferred, and benzyl alkyl Diglycol adipate.
  • the weight average molecular weight (Mw) of component (D) is not particularly limited, but is preferably, for example, 100 to 2,000, more preferably 200 to 1,500, and even more preferably 300 to 1,000. Note that the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
  • the content of component (D) is not particularly limited, but from the viewpoint of further improving the moldability of the resin composition, it is preferably 0.5 to 20% by mass based on the total amount of the resin composition (100% by mass). More preferably 1 to 15% by weight, even more preferably 2 to 12% by weight.
  • the melt flow rate (MFR) of the composition composed of the (A1) component and (A2) component contained in the present resin composition, or the (A1) component, (A2) component and ( The melt flow rate (MFR) of the composition composed of component D) is preferably 1 to 1250 g/10 minutes, more preferably 3 to 200 g/10 minutes, even more preferably 4 to 180 g/10 minutes, particularly preferably 5 to 160 g/10 minutes.
  • MFR melt flow rate
  • the present resin composition does not contain any other components other than the (A1) component, (A2) component, (B) component, and furthermore the (C) component and (D) component, the effects of the present invention As long as it does not impair the properties of the resin composition, it may contain components that have been commonly used in resin compositions. Examples include, but are not limited to, polyester resins other than (A1) and (A2), organic fillers, lubricants, antistatic agents, antioxidants, light stabilizers, ultraviolet absorbers, dyes, pigments, and hydrolysis inhibitors.
  • crystal nucleating agent such as crystal nucleating agent, anti-blocking agent, light stabilizer, heat stabilizer, flame retardant, mold release agent, antifogging agent, surface wetting improver, incineration aid, dispersion aid, various surfactants, slip agent, freshness preservation agent Agents, antibacterial agents, etc. can also be added. These can be used alone or in combination of two or more.
  • polyester resins other than (A1) and (A2) include aliphatic polyester resins having an aliphatic oxycarboxylic acid unit as a main structural unit.
  • Specific examples of the aliphatic oxycarboxylic acid component that provides the aliphatic oxycarboxylic acid units of the aliphatic polyester resin include lactic acid, glycolic acid, 2-hydroxy-n-butyric acid, 3-hydroxybutyric acid, and 4-hydroxy Butyric acid, 2-hydroxycaproic acid, 6-hydroxycaproic acid, 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, 2-hydroxyisocaproic acid, 3-hydroxyvaleric acid, malic acid, Examples include citric acid, lower alkyl esters or intramolecular esters thereof, and the like.
  • lactone compounds such as ⁇ -caprolactone are also included in the aliphatic oxycarboxylic acids in the present invention. If these have optical isomers, they may be D-form, L-form or racemic, and may be in the form of solid, liquid or aqueous solution. Among these, lactic acid, glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 6-hydroxycaproic acid, and 3-hydroxyvaleric acid are preferred. These aliphatic oxycarboxylic acids may be used alone or in combination of two or more.
  • aliphatic polyester resins having aliphatic oxycarboxylic acid units as main constituent units include polylactic acid, polyglycolic acid, poly3-hydroxybutyrate, poly4-hydroxybutyrate, poly(3- Hydroxybutyrate-co-3-hydroxyvalerate), polycaprolactone, and the like.
  • the polylactic acid may be a copolymer of the above-mentioned polylactic acid and another oxycarboxylic acid, and may also contain a small amount of units derived from a chain extender.
  • Other oxycarboxylic acids include optical isomers of lactic acid (D-lactic acid for L-lactic acid, L-lactic acid for D-lactic acid), glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, Bifunctional aliphatic oxycarboxylic acids such as 2-hydroxy-n-butyric acid, 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, 2-methyllactic acid, 2-hydroxycaproic acid, and caprolactone , butyrolactone, valerolactone, and other lactones.
  • Such units derived from other oxycarboxylic acids can be used in an amount of less than 15 mol% of the total constituent units of polylactic acid.
  • the weight average molecular weight (Mw) of the aliphatic polyester resin having an aliphatic oxycarboxylic acid unit as a main structural unit is preferably 60,000 to 700,000, more preferably 80,000 to 400,000, and even more preferably is between 100,000 and 300,000.
  • the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
  • the present resin composition can be obtained by kneading using a single-screw or twin-screw extruder, a Banbury mixer, a mixing roll, etc., in the same manner as in known manufacturing methods for various resin compositions.
  • the present resin composition can be produced by kneading component (A1), component (A2), component (B), and the like.
  • component (C) inorganic filler
  • the temperature conditions in the method for producing the present resin composition are usually 120 to 160°C, preferably 130 to 150°C.
  • the melt flow rate (MFR) of the resin composition obtained as described above is preferably 0.05 to 20 g/10 min when measured at 140°C and 2.16 kg according to JIS K7210. More preferably 0.1 to 15 g/10 minutes, even more preferably 0.15 to 10 g/10 minutes.
  • the tensile strength (MPa) of the present resin composition is preferably 5 to 50 MPa, more preferably 7 to 40 MPa, and even more preferably 10 to 30 MPa, according to JIS7161-1, 2.
  • the tensile elongation (%) of the resin composition is preferably 6% or more, more preferably 6.4% or more, according to JIS7161-1, 2. Further, the tensile elongation (%) is preferably 6 to 20%, more preferably 6.4 to 15%, even more preferably 6.4 to 10%.
  • the method for molding a molded article using the present resin composition is not particularly limited, and known methods such as injection molding, extrusion molding, compression molding, lamination molding, vacuum molding, pressure molding, and blow molding can be used. However, injection molding and extrusion molding are preferred.
  • the applications of molded products obtained from this resin composition are not limited, and examples include various films, sheets, foams, plates, fibers, containers, etc. More specifically, food films, fresh food products, etc. Trays and fast food containers, outdoor leisure products, fishing lines, fishing nets, vegetation nets, water retention sheets, coating materials, agricultural mulch films, coating materials for fertilizers, striped tapes, split yarns, composite fibers, shopping bags, garbage bags, It can be used for compost bags, cosmetic containers, detergent containers, bleach containers, ropes, binding materials, surgical thread, sanitary cover stock materials, cold boxes, cushioning materials, synthetic paper, etc.
  • Adipic acid ester plasticizer “DAIFATTY-101 (mixed group dibasic acid ester, adipate ester-containing compound)” manufactured by Daihachi Kagaku Kogyo Co., Ltd., weight average molecular weight of adipic acid ester 338]
  • the tensile strength (MPa) and tensile elongation (%) of the obtained test piece were measured using a tensile tester [Strograph API II, manufactured by Toyo Seiki Seisakusho Co., Ltd.] according to the following test conditions. The results are shown in Table 1.
  • ⁇ Test conditions Test speed 50mm/min Distance between marked lines 50mm Distance between grips 115mm
  • ⁇ (poor) less than 5 MPa.
  • melt flow rate (MFR) The melt flow rate (MFR) of the base resins included in Examples 1 to 8 and Comparative Examples 1 and 3 to 7 was measured at a temperature of 190° C. and a load of 2.16 kg in accordance with JIS K7210. The results are shown in Table 1.
  • the base resin means the component contained in each resin composition among component (A1), component (A2), and component (D), or a mixed composition consisting of these components.
  • the base resin means a mixed composition consisting of component (A1), component (A2), and component (D), and in Example 2, component (A1), It means a mixed composition consisting of component (A2) and (A2).
  • the base resin in Comparative Example 7 means a mixed composition consisting of polylactic acid and component (A2), for example.
  • melt flow rate (MFR) of each resin composition according to Examples 1 to 8 and Comparative Examples 1 and 3 to 7 was measured at a temperature of 140° C. and a load of 2.16 kg in accordance with JIS K7210. The results are shown in Table 1.
  • Examples 1 to 8 of the present invention can be pelletized and injection molded, and the surface shape of the obtained pellets is smooth, so it is confirmed that they have excellent moldability. Ta. Furthermore, it was confirmed that Examples 1 to 8 of the present invention were also excellent in tensile elongation properties and tensile strength properties after molding.
  • the resin composition of the present invention has excellent moldability and tensile properties, it can be widely and effectively used as a raw material for various molded products.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Provided is a resin composition having excellent moldability and tensile elongation characteristics.　The resin composition contains the following component (A1), component (A2), and component (B): (A1) an aliphatic polyester-based resin having an aliphatic polyhydric alcohol unit and an aliphatic polycarboxylic acid unit; (A2) an aliphatic-aromatic polyester-based resin having an aliphatic polyhydric alcohol unit, an aliphatic polyvalent carboxylic acid unit, and an aromatic polyvalent carboxylic acid unit; and (B) a cellulose-based fiber.　

Description

樹脂組成物resin composition
　本発明は、生分解性樹脂を含有する樹脂組成物に関する。詳細には、特定の脂肪族ポリエステル系樹脂、及びセルロース系繊維を含有し、成形性に優れると共に、成形後の引張伸び特性等に優れる樹脂組成物に関する。 The present invention relates to a resin composition containing a biodegradable resin. In particular, the present invention relates to a resin composition that contains a specific aliphatic polyester resin and cellulose fibers, has excellent moldability, and has excellent tensile elongation properties after molding.
　近年、環境負担の軽減要請を背景に、各種の生分解性樹脂に関する研究開発が進んでいる。生分解性樹脂としては、例えば、ポリ乳酸、ポリブチレンサクシネート、ポリブチレンサクシネートアジペート、ポリブチレンアジペートテレフタレート等が知られている。 In recent years, research and development on various biodegradable resins has been progressing against the backdrop of requests to reduce environmental burden. As biodegradable resins, for example, polylactic acid, polybutylene succinate, polybutylene succinate adipate, polybutylene adipate terephthalate, etc. are known.
　生分解性樹脂は、通常、ポリエチレンやポリプロピレン等の汎用樹脂に比べ、機械的強度が十分でない場合が多いため、成形品等に加工して使用する場合、得られる成形品の機械強度を高める観点等から、各種の補強成分が配合される場合がある。 Biodegradable resins usually do not have sufficient mechanical strength compared to general-purpose resins such as polyethylene and polypropylene, so when processing them into molded products, etc., it is important to increase the mechanical strength of the resulting molded product. Various reinforcing components may be added.
　例えば、特許文献１～３には、ポリブチレンサクシネートやポリブチレンサクシネートアジペートに対し、セルロース系原料を配合した成形用組成物が記載されている。 For example, Patent Documents 1 to 3 describe molding compositions in which a cellulose-based raw material is blended with polybutylene succinate or polybutylene succinate adipate.
国際公開第２０２１／０５４０１３号公報International Publication No. 2021/054013 国際公開第２０１４／１１９６５７号公報International Publication No. 2014/119657 国際公開第２０１１／０７８２７２号公報International Publication No. 2011/078272
　しかしながら、前記各特許文献に記載の樹脂組成物は、機械強度の改善は期待できるものの、成形性が不十分であって改善の余地がある。また、成形性と、成形後における引張伸び特性とを両立させることについての検討は不十分である。 However, although the resin compositions described in each of the above-mentioned patent documents can be expected to improve mechanical strength, their moldability is insufficient and there is room for improvement. Furthermore, studies on achieving both moldability and tensile elongation properties after molding have not been sufficiently conducted.
　本発明は、前記課題に鑑みなされたものであり、成形性に優れ、引張伸び特性にも優れる樹脂組成物を提供する。 The present invention has been made in view of the above problems, and provides a resin composition that has excellent moldability and excellent tensile elongation properties.
　本発明者等は、かかる事情に鑑み鋭意研究を重ねた結果、意外にも、ポリエステル系樹脂とセルロース系繊維とを含有する樹脂組成物において、脂肪族ポリエステル系樹脂と脂肪族－芳香族ポリエステル系樹脂とを組み合わせることによって、成形性に優れ、成形後の引張伸び特性にも優れる樹脂組成物を提供し得ることを見出した。 As a result of extensive research in view of the above circumstances, the present inventors surprisingly found that in a resin composition containing a polyester resin and a cellulose fiber, an aliphatic polyester resin and an aliphatic-aromatic polyester It has been found that by combining with resin, it is possible to provide a resin composition that has excellent moldability and excellent tensile elongation properties after molding.
　本発明は、以下の［１］～［１１］を提供する。
［１］
　下記（Ａ１）成分、（Ａ２）成分、及び、（Ｂ）成分を含有する樹脂組成物。
　（Ａ１）脂肪族多価アルコール単位と脂肪族多価カルボン酸単位とを有する脂肪族ポリエステル系樹脂。
　（Ａ２）脂肪族多価アルコール単位と、脂肪族多価カルボン酸単位と、芳香族多価カルボン酸単位とを有する脂肪族－芳香族ポリエステル系樹脂。
　（Ｂ）セルロース系繊維。
［２］
　前記樹脂組成物全量に対する、前記（Ａ１）成分と前記（Ａ２）成分との合計含有量が、２０～５９質量％である［１］記載の樹脂組成物。
［３］
　ＪＩＳ７１６１－１，２に準拠して測定した引張伸びが６．４％以上である、［１］又は［２］に記載の樹脂組成物。
［４］
　前記樹脂組成物全量に対する、前記（Ｂ）成分の含有量が、４１～６４質量％である、［１］～［３］のいずれかに記載の樹脂組成物。
［５］
　前記（Ａ１）成分に対する前記（Ａ２）成分の質量比（Ａ２）／（Ａ１）が、０．０５～１．５である、［１］～［４］のいずれかに記載の樹脂組成物。
［６］
　更に、（Ｃ）無機フィラーを含有する、［１］～［５］のいずれかに記載の樹脂組成物。
［７］
　前記（Ａ１）成分の温度１９０℃、荷重２．１６ｋｇにおけるメルトフローレートが、１～１５０ｇ／１０分である、［１］～［６］のいずれかに記載の樹脂組成物。
［８］
　前記（Ａ１）成分が、ポリブチレンサクシネート及びポリブチレンサクシネートアジペートからなる群より選択される１種以上である、［１］～［７］のいずれかに記載の樹脂組成物。
［９］
　前記（Ａ２）成分が、ポリブチレンアルキレートテレフタレートである、［１］～［８］のいずれかに記載の樹脂組成物。
［１０］
　前記（Ｂ）成分が、粉末状である、［１］～［９］のいずれかに記載の樹脂組成物。
［１１］
　前記（Ｂ）成分の平均粒子径が、１０～１００μｍである、［１０］に記載の樹脂組成物。 The present invention provides the following [1] to [11].
[1]
A resin composition containing the following components (A1), (A2), and (B).
(A1) An aliphatic polyester resin having an aliphatic polyhydric alcohol unit and an aliphatic polycarboxylic acid unit.
(A2) An aliphatic-aromatic polyester resin having an aliphatic polyhydric alcohol unit, an aliphatic polycarboxylic acid unit, and an aromatic polycarboxylic acid unit.
(B) Cellulose fiber.
[2]
The resin composition according to [1], wherein the total content of the component (A1) and the component (A2) based on the total amount of the resin composition is 20 to 59% by mass.
[3]
The resin composition according to [1] or [2], which has a tensile elongation of 6.4% or more as measured in accordance with JIS7161-1, 2.
[4]
The resin composition according to any one of [1] to [3], wherein the content of the component (B) is 41 to 64% by mass based on the total amount of the resin composition.
[5]
The resin composition according to any one of [1] to [4], wherein the mass ratio (A2)/(A1) of the component (A2) to the component (A1) is 0.05 to 1.5.
[6]
The resin composition according to any one of [1] to [5], further containing (C) an inorganic filler.
[7]
The resin composition according to any one of [1] to [6], wherein the component (A1) has a melt flow rate of 1 to 150 g/10 minutes at a temperature of 190° C. and a load of 2.16 kg.
[8]
The resin composition according to any one of [1] to [7], wherein the component (A1) is one or more selected from the group consisting of polybutylene succinate and polybutylene succinate adipate.
[9]
The resin composition according to any one of [1] to [8], wherein the component (A2) is polybutylene alkylate terephthalate.
[10]
The resin composition according to any one of [1] to [9], wherein the component (B) is in powder form.
[11]
The resin composition according to [10], wherein the component (B) has an average particle diameter of 10 to 100 μm.
　本発明によれば、ポリエステル系樹脂とセルロース系繊維とを含有する樹脂組成物において、ポリエステル系樹脂として、（Ａ１）脂肪族多価アルコール単位と脂肪族多価カルボン酸単位とを有する脂肪族ポリエステル系樹脂と、（Ａ２）脂肪族多価アルコール単位と、脂肪族多価カルボン酸単位と、芳香族多価カルボン酸単位とを有する脂肪族－芳香族ポリエステル系樹脂とを組み合わせることによって、成形性に優れると共に、成形後の引張伸び特性にも優れる樹脂組成物を提供できる。 According to the present invention, in a resin composition containing a polyester resin and a cellulose fiber, the polyester resin is (A1) an aliphatic polyester having an aliphatic polyhydric alcohol unit and an aliphatic polycarboxylic acid unit. By combining the resin and (A2) an aliphatic-aromatic polyester resin having an aliphatic polyhydric alcohol unit, an aliphatic polycarboxylic acid unit, and an aromatic polycarboxylic acid unit, moldability can be improved. It is possible to provide a resin composition that is excellent in both properties and tensile elongation properties after molding.
　以下、本発明の実施形態に基づいて本発明をより詳細に説明するが、本発明はこれらの実施形態に限定されない。
　なお、本明細書において「Ｘ～Ｙ」（Ｘ，Ｙは任意の数字）と表現する場合、特にことわらない限り「Ｘ以上Ｙ以下」の意と共に、「好ましくはＸより大きい」又は「好ましくはＹより小さい」の意も包含する。
　更に、「Ｘ及び／又はＹ（Ｘ，Ｙは任意の構成）」とは、Ｘ及びＹの少なくとも一方を意味するものであって、Ｘのみ、Ｙのみ、Ｘ及びＹ、の３通りを意味するものである。 Hereinafter, the present invention will be described in more detail based on embodiments of the present invention, but the present invention is not limited to these embodiments.
In this specification, when expressed as "X to Y" (X, Y are arbitrary numbers), unless otherwise specified, it means "more than or equal to X and less than or equal to Y", and also means "preferably greater than X" or "preferably is less than Y.
Furthermore, "X and/or Y (X, Y are arbitrary configurations)" means at least one of X and Y, and means three ways: X only, Y only, and X and Y. It is something to do.
　本発明の一実施形態に係る樹脂組成物（以下、「本樹脂組成物」という場合がある）は、下記（Ａ１）成分、（Ａ２）成分、及び、（Ｂ）成分を含有することを特徴とする。
　（Ａ１）脂肪族多価アルコール単位と脂肪族多価カルボン酸単位とを有する脂肪族ポリエステル系樹脂。
　（Ａ２）脂肪族多価アルコール単位と、脂肪族多価カルボン酸単位と、芳香族多価カルボン酸単位とを有する脂肪族－芳香族ポリエステル系樹脂。
　（Ｂ）セルロース系繊維。 A resin composition according to an embodiment of the present invention (hereinafter sometimes referred to as "the present resin composition") is characterized by containing the following components (A1), (A2), and (B). shall be.
(A1) An aliphatic polyester resin having an aliphatic polyhydric alcohol unit and an aliphatic polycarboxylic acid unit.
(A2) An aliphatic-aromatic polyester resin having an aliphatic polyhydric alcohol unit, an aliphatic polycarboxylic acid unit, and an aromatic polycarboxylic acid unit.
(B) Cellulose fiber.
　本樹脂組成物は、成形性に優れると共に、成形後の引張伸び特性や、成形後の引張強度特性にも優れる点で有用である。 The present resin composition is useful in that it has excellent moldability as well as excellent tensile elongation properties after molding and tensile strength properties after molding.
　また、本樹脂組成物は、セルロース系繊維を比較的多く含みながらも成形性に優れることから、脂肪族ポリエステル系樹脂の含有量を低減することができ、環境を保全するための技術としても有効に活用できる。 In addition, this resin composition has excellent moldability even though it contains a relatively large amount of cellulose fibers, so the content of aliphatic polyester resin can be reduced, making it effective as a technology for environmental conservation. It can be used for
　以下、まず、本樹脂組成物に用いられる（Ａ１）成分、（Ａ２）成分及び（Ｂ）成分について説明する。 Hereinafter, first, the (A1) component, (A2) component, and (B) component used in the present resin composition will be explained.
［（Ａ１）脂肪族多価アルコール単位と脂肪族多価カルボン酸単位を有する脂肪族ポリエステル系樹脂］
　（Ａ１）成分は、例えば、脂肪族多価アルコール単位及び脂肪族多価カルボン酸単位を主たる構成単位として有する脂肪族ポリエステル系樹脂である。具体的には、下記式（１）で表される脂肪族多価アルコール単位及び下記式（２）で表される脂肪族多価カルボン酸単位を主たる構成単位として有する脂肪族ポリエステル系樹脂である（但し、本明細書において、（Ａ１）成分の概念には（Ａ２）成分は含まれないものとする)。 [(A1) Aliphatic polyester resin having an aliphatic polyhydric alcohol unit and an aliphatic polycarboxylic acid unit]
Component (A1) is, for example, an aliphatic polyester resin having an aliphatic polyhydric alcohol unit and an aliphatic polycarboxylic acid unit as main constituent units. Specifically, it is an aliphatic polyester resin having an aliphatic polyhydric alcohol unit represented by the following formula (1) and an aliphatic polycarboxylic acid unit represented by the following formula (2) as main constituent units. (However, in this specification, the concept of component (A1) does not include component (A2)).
　－Ｏ－Ｒ11－Ｏ－　　　（１）
［式（１）中、Ｒ11は、鎖中に酸素原子を有していてもよい２価の鎖状脂肪族炭化水素基を示し、共重合されている場合には１種に限定されない。］ -O-R 11 -O- (1)
[In formula (1), R 11 represents a divalent chain aliphatic hydrocarbon group which may have an oxygen atom in the chain, and is not limited to one type when copolymerized. ]
　－ＯＣ－Ｒ21－ＣＯ－　　　（２）
［式（２）中、Ｒ21は、直接結合を示すか、２価の鎖状脂肪族炭化水素基を示し、共重合されている場合には１種に限定されない。］ -OC-R 21 -CO- (2)
[In formula (2), R 21 represents a direct bond or represents a divalent chain aliphatic hydrocarbon group, and is not limited to one type when copolymerized. ]
　なお、前記「単位」とは、脂肪族ポリエステル系樹脂の製造に用いた単量体成分に由来して脂肪族ポリエステル系樹脂中に含まれる構成単位を意味し、「主たる構成単位」とは、対象とする単量体成分に由来する構成単位を、脂肪族ポリエステル系樹脂の全構成単位中に５０モル％以上含むことを意味する。この対象とする単量体に由来する構成単位の含有量は、好ましくは６０モル％以上、より好ましくは７０モル％以上、更に好ましくは８０～１００モル％である。例えば、脂肪族多価アルコールと脂肪族多価カルボン酸成分とを、脂肪族ポリエステル系樹脂の重合反応に用いる全単量体成分中に５０モル％以上、好ましくは６０モル％以上、より好ましくは７０モル％以上、更に好ましくは８０～１００モル％含む原料を重合反応して製造されたものであることが好ましい。 The above-mentioned "unit" means a structural unit contained in the aliphatic polyester resin derived from the monomer component used in the production of the aliphatic polyester resin, and the "main structural unit" is It means that the aliphatic polyester resin contains 50 mol% or more of structural units derived from the target monomer component in all structural units of the aliphatic polyester resin. The content of structural units derived from the target monomer is preferably 60 mol% or more, more preferably 70 mol% or more, and still more preferably 80 to 100 mol%. For example, the aliphatic polyhydric alcohol and the aliphatic polycarboxylic acid component are contained in the total monomer components used in the polymerization reaction of the aliphatic polyester resin at 50 mol% or more, preferably 60 mol% or more, more preferably It is preferably produced by polymerizing raw materials containing 70 mol% or more, more preferably 80 to 100 mol%.
　式（１）の多価アルコール単位を与える脂肪族多価アルコールとしては、特に限定されないが、例えば、炭素数２～１０の脂肪族多価アルコールが好ましく、より好ましくは炭素数４～６の脂肪族多価アルコールである。具体的には、例えば、エチレングリコール、１，２－プロパンジオール、１，３－プロパンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、１，７－ヘプタンジオール、１，８－オクタンジオール、１，９－ノナンジオール、１，１０－デカンジオール、ネオペンチルグリコール、ジエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレンエーテルグリコール等が挙げられる。なかでも、１，４－ブタンジオールが好ましい。前記脂肪族多価アルコールは、１種を単独で用いても、２種以上を併用してもよい。 The aliphatic polyhydric alcohol that provides the polyhydric alcohol unit of formula (1) is not particularly limited, but for example, aliphatic polyhydric alcohols having 2 to 10 carbon atoms are preferred, and more preferably aliphatic polyhydric alcohols having 4 to 6 carbon atoms. It is a family of polyhydric alcohols. Specifically, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol Examples include diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like. Among them, 1,4-butanediol is preferred. The aliphatic polyhydric alcohols may be used alone or in combination of two or more.
　式（２）の脂肪族多価カルボン酸単位を与える脂肪族多価カルボン酸成分は、脂肪族多価カルボン酸或いはそのアルキルエステル等の脂肪族多価カルボン酸誘導体であり、その脂肪族多価カルボン酸としては、特に限定されないが、例えば、炭素数２～４０の脂肪族多価カルボン酸が好ましく、より好ましくは炭素数４～１０の脂肪族多価カルボン酸である。具体的には、例えば、コハク酸、アジピン酸、スベリン酸、セバシン酸、ドデカン二酸等が挙げられる。なかでも、コハク酸、アジピン酸、セバシン酸が好ましく、コハク酸、アジピン酸がより好ましく、コハク酸が特に好ましい。前記の脂肪族多価カルボン酸成分は、１種を単独で用いても、２種以上を併用してもよい。 The aliphatic polycarboxylic acid component providing the aliphatic polycarboxylic acid unit of formula (2) is an aliphatic polycarboxylic acid or an aliphatic polycarboxylic acid derivative such as an alkyl ester thereof; The carboxylic acid is not particularly limited, but for example, an aliphatic polycarboxylic acid having 2 to 40 carbon atoms is preferable, and an aliphatic polycarboxylic acid having 4 to 10 carbon atoms is more preferable. Specific examples include succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, and the like. Among these, succinic acid, adipic acid, and sebacic acid are preferred, succinic acid and adipic acid are more preferred, and succinic acid is particularly preferred. The aforementioned aliphatic polycarboxylic acid components may be used alone or in combination of two or more.
　（Ａ１）成分の具体例としては、例えば、１，４－ブタンジオールとコハク酸を含む脂肪族ポリエステル系樹脂、１，４－ブタンジオール、アジピン酸、及びコハク酸を含む脂肪族ポリエステル系樹脂等が挙げられる。これらのなかでも、樹脂組成物の成形性をより向上させる観点から、ポリブチレンサクシネート及びポリブチレンサクシネートアジペートからなる群より選択される１種以上が好ましい。 Specific examples of component (A1) include, for example, an aliphatic polyester resin containing 1,4-butanediol and succinic acid, an aliphatic polyester resin containing 1,4-butanediol, adipic acid, and succinic acid, etc. can be mentioned. Among these, from the viewpoint of further improving the moldability of the resin composition, one or more selected from the group consisting of polybutylene succinate and polybutylene succinate adipate are preferred.
　（Ａ１）成分において、脂肪族多価カルボン酸がコハク酸である場合、脂肪族ポリエステル系樹脂の全多価カルボン酸単位中のコハク酸由来の構成単位の割合は、通常５０～１００モル％、好ましくは８０～１００モル％、より好ましくは９０～１００モル％である。 In component (A1), when the aliphatic polycarboxylic acid is succinic acid, the proportion of structural units derived from succinic acid in the total polycarboxylic acid units of the aliphatic polyester resin is usually 50 to 100 mol%, Preferably it is 80 to 100 mol%, more preferably 90 to 100 mol%.
　また、（Ａ１）成分において、脂肪族多価カルボン酸がコハク酸とアジピン酸である場合、脂肪族ポリエステル系樹脂の全多価カルボン酸単位中のコハク酸由来の構成単位の割合は、通常５０～９５モル％、好ましくは６０～９３モル％、より好ましくは７０～９０モル％であり、全多価カルボン酸単位中のアジピン酸由来の構成単位の割合は、通常５～５０モル％、好ましくは７～４０モル％、より好ましくは１０～３０モル％である。 In addition, in component (A1), when the aliphatic polycarboxylic acids are succinic acid and adipic acid, the proportion of structural units derived from succinic acid in the total polycarboxylic acid units of the aliphatic polyester resin is usually 50 -95 mol%, preferably 60-93 mol%, more preferably 70-90 mol%, and the proportion of adipic acid-derived structural units in the total polycarboxylic acid units is usually 5-50 mol%, preferably is 7 to 40 mol%, more preferably 10 to 30 mol%.
　（Ａ１）成分は、以下の物性を有するものが好ましい。 The component (A1) preferably has the following physical properties.
　（Ａ１）成分のメルトフローレート（ＭＦＲ）は、ＪＩＳ　Ｋ７２１０に準拠して、１９０℃、２．１６ｋｇで測定した場合、好ましくは１～１５０ｇ／１０分、より好ましくは３～１２５ｇ／１０分、更により好ましくは４～１００ｇ／１０分、特に好ましくは５～５０ｇ／１０分である。メルトフローレート（ＭＦＲ）が前記範囲外になると、樹脂組成物の成形性が損なわれる傾向がある。 The melt flow rate (MFR) of component (A1) is preferably 1 to 150 g/10 minutes, more preferably 3 to 125 g/10 minutes, when measured at 190 ° C. and 2.16 kg according to JIS K7210. Even more preferably 4 to 100 g/10 minutes, particularly preferably 5 to 50 g/10 minutes. When the melt flow rate (MFR) is outside the above range, the moldability of the resin composition tends to be impaired.
　（Ａ１）成分の融点は、好ましくは７０～２５０℃、より好ましくは７５～２００℃、更により好ましくは８０～１５０℃である。融点が複数存在する場合には、少なくとも１つの融点が前記範囲内にあることが好ましい。 The melting point of component (A1) is preferably 70 to 250°C, more preferably 75 to 200°C, and even more preferably 80 to 150°C. When there are multiple melting points, it is preferable that at least one melting point is within the above range.
　（Ａ１）成分の重量平均分子量（Ｍｗ）は、好ましくは１０，０００～１，０００，０００、より好ましくは２０，０００～５００，０００、更に好ましくは５０，０００～４００，０００である。
　なお、前記重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により、ポリスチレンを標準物質として測定した値である。 The weight average molecular weight (Mw) of component (A1) is preferably 10,000 to 1,000,000, more preferably 20,000 to 500,000, and even more preferably 50,000 to 400,000.
Note that the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
　本樹脂組成物において、（Ａ１）成分は、１種のみを用いてもよく、２種以上を併用してもよい。例えば、多価アルコール単位や多価カルボン酸単位の異なる（Ａ１）成分の２種以上を混合して用いてもよい。 In the present resin composition, only one type of component (A1) may be used, or two or more types may be used in combination. For example, two or more types of components (A1) having different polyhydric alcohol units and polyhydric carboxylic acid units may be used in combination.
　（Ａ１）成分の含有量は、本樹脂組成物全量（１００質量％）に対して、例えば、５～５５質量％が好ましく、より好ましくは１０～５０質量％、更により好ましくは１５～４５質量％である。 The content of component (A1) is preferably, for example, 5 to 55% by mass, more preferably 10 to 50% by mass, and even more preferably 15 to 45% by mass, based on the total amount (100% by mass) of the resin composition. %.
［（Ａ２）脂肪族多価アルコール単位、脂肪族多価カルボン酸単位、及び芳香族多価カルボン酸単位を有する脂肪族－芳香族ポリエステル系樹脂］
　（Ａ２）成分は、例えば、脂肪族多価アルコール単位、脂肪族多価カルボン酸単位、及び芳香族多価カルボン酸単位を主たる構成単位として有する脂肪族－芳香族ポリエステル系樹脂である。具体的には、前記式（１）で表される脂肪族多価アルコール単位、前記式（２）で表される脂肪族多価カルボン酸単位、及び、下記式（３）で表される芳香族多価カルボン酸単位を主たる構成単位として有するものである。（Ａ２）成分は、更に、オキシカルボン酸単位を有していてもよい。 [(A2) Aliphatic-aromatic polyester resin having an aliphatic polyhydric alcohol unit, an aliphatic polycarboxylic acid unit, and an aromatic polycarboxylic acid unit]
Component (A2) is, for example, an aliphatic-aromatic polyester resin having an aliphatic polyhydric alcohol unit, an aliphatic polycarboxylic acid unit, and an aromatic polycarboxylic acid unit as main constituent units. Specifically, an aliphatic polyhydric alcohol unit represented by the above formula (1), an aliphatic polyhydric carboxylic acid unit represented by the above formula (2), and an aromatic represented by the following formula (3) It has a group polyhydric carboxylic acid unit as a main structural unit. Component (A2) may further have an oxycarboxylic acid unit.
　－ＯＣ－Ｒ31－ＣＯ－　　　（３）
［式（３）中、Ｒ31は２価の芳香族炭化水素基を示し、共重合されている場合には１種に限定されない。］ -OC-R 31 -CO- (3)
[In formula (3), R 31 represents a divalent aromatic hydrocarbon group, and is not limited to one type when copolymerized. ]
　式（１）の多価アルコール単位を与える脂肪族多価アルコール及び式（２）の脂肪族多価カルボン酸単位を与える脂肪族多価カルボン酸成分については、前記［（Ａ１）脂肪族多価アルコール単位と脂肪族多価カルボン酸単位を有する脂肪族ポリエステル系樹脂］の説明で例示したものと同様であり、好ましいものも同様である。 Regarding the aliphatic polyhydric alcohol that provides the polyhydric alcohol unit of formula (1) and the aliphatic polycarboxylic acid component that provides the aliphatic polycarboxylic acid unit of formula (2), [Aliphatic polyester resin having alcohol unit and aliphatic polycarboxylic acid unit]], and preferred examples are also the same.
　式（３）の芳香族多価カルボン酸単位を与える芳香族多価カルボン酸成分としては、特に限定されないが、例えば、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸、ジフェニルジカルボン酸等が挙げられる。これらは酸無水物であってもよい。また、芳香族多価カルボン酸の誘導体として、これらの芳香族多価カルボン酸の低級アルキルエステル等も挙げられる。これらのなかで、テレフタル酸、イソフタル酸、又はそれらの低級アルキル（例えば、炭素数１～４のアルキル）エステル誘導体が好ましい。これらは１種を単独で用いてもよく、２種以上を混合して使用してもよい。特にテレフタル酸及び／又はテレフタル酸のメチルエステルか、テレフタル酸及び／又はテレフタル酸のメチルエステルとイソフタル酸及び／又はイソフタル酸のメチルエステルとを含有する混合物が好ましい。 The aromatic polycarboxylic acid component that provides the aromatic polycarboxylic acid unit of formula (3) is not particularly limited, and examples thereof include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyldicarboxylic acid, and the like. These may be acid anhydrides. Furthermore, examples of derivatives of aromatic polycarboxylic acids include lower alkyl esters of these aromatic polycarboxylic acids. Among these, terephthalic acid, isophthalic acid, or lower alkyl (eg, alkyl having 1 to 4 carbon atoms) ester derivatives thereof are preferred. These may be used alone or in combination of two or more. Particularly preferred are terephthalic acid and/or methyl ester of terephthalic acid, or mixtures containing terephthalic acid and/or methyl ester of terephthalic acid and isophthalic acid and/or methyl ester of isophthalic acid.
　（Ａ２）成分の具体例としては、樹脂組成物の成形性をより向上させる観点から、特に成形性と引張伸び特性を両立させる観点から、ポリブチレンアルキレートテレフタレートが好ましく、ポリブチレンアジペートテレフタレート又はポリブチレンサクシネートテレフタレートがより好ましく、ポリブチレンアジペートテレフタレートが特に好ましい。 As a specific example of component (A2), polybutylene alkylate terephthalate is preferable from the viewpoint of further improving the moldability of the resin composition, particularly from the viewpoint of achieving both moldability and tensile elongation properties, and polybutylene adipate terephthalate or polybutylene adipate terephthalate is preferred. Butylene succinate terephthalate is more preferred, and polybutylene adipate terephthalate is particularly preferred.
　（Ａ２）成分は、以下の物性を有するものが好ましい。 The component (A2) preferably has the following physical properties.
　（Ａ２）成分のメルトフローレート（ＭＦＲ）は、ＪＩＳ　Ｋ７２１０に準拠して、１９０℃、２．１６ｋｇで測定した場合、好ましくは１～１５０ｇ／１０分、より好ましくは１．５～１２５ｇ／１０分、更により好ましくは２～１００ｇ／１０分、特に好ましくは２～５０ｇ／１０分である。メルトフローレート（ＭＦＲ）が前記範囲外になると、樹脂組成物の成形性が損なわれる傾向がある。 The melt flow rate (MFR) of component (A2) is preferably 1 to 150 g/10 min, more preferably 1.5 to 125 g/10 min, when measured at 190°C and 2.16 kg according to JIS K7210. minutes, even more preferably 2 to 100 g/10 minutes, particularly preferably 2 to 50 g/10 minutes. When the melt flow rate (MFR) is outside the above range, the moldability of the resin composition tends to be impaired.
　（Ａ２）成分の融点は、好ましくは７０～２５０℃、より好ましくは７５～２００℃、更により好ましく８０～１５０℃である。融点が複数存在する場合には、少なくとも１つの融点が前記範囲内にあることが好ましい。 The melting point of component (A2) is preferably 70 to 250°C, more preferably 75 to 200°C, even more preferably 80 to 150°C. When there are multiple melting points, it is preferable that at least one melting point is within the above range.
　（Ａ２）成分の重量平均分子量（Ｍｗ）は、好ましくは１０，０００～１，０００，０００、より好ましくは２０，０００～５００，０００、更に好ましくは５０，０００～４００，０００である。
　なお、前記重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により、ポリスチレンを標準物質として測定した値である。 The weight average molecular weight (Mw) of component (A2) is preferably 10,000 to 1,000,000, more preferably 20,000 to 500,000, even more preferably 50,000 to 400,000.
Note that the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
　本樹脂組成物において、（Ａ２）成分は、１種のみを用いてもよく、２種以上を併用してもよい。例えば、多価アルコール単位や多価カルボン酸単位の異なる（Ａ２）成分の２種以上を混合して用いてもよい。 In the present resin composition, only one type of component (A2) may be used, or two or more types may be used in combination. For example, two or more types of components (A2) having different polyhydric alcohol units and polyhydric carboxylic acid units may be used in combination.
　（Ａ２）成分の含有量は、本樹脂組成物全量（１００質量％）に対して、１～３５質量％が好ましく、より好ましくは２．５～３０質量％、更により好ましくは３．５～２５質量％である。 The content of component (A2) is preferably 1 to 35% by mass, more preferably 2.5 to 30% by mass, even more preferably 3.5 to 30% by mass, based on the total amount (100% by mass) of the resin composition. It is 25% by mass.
　（Ａ１）成分及び（Ａ２）成分の合計含有量［（Ａ１）＋（Ａ２）]は、樹脂組成物の成形性をより向上させる観点から、特に成形性と引張伸び特性を両立させる観点から、本樹脂組成物全量（１００質量％）に対して、２０～５９質量％が好ましく、より好ましくは３０～５２質量％、更により好ましくは３５～５０質量％である。 The total content of components (A1) and (A2) [(A1)+(A2)] is determined from the viewpoint of further improving the moldability of the resin composition, especially from the viewpoint of achieving both moldability and tensile elongation properties. The amount is preferably 20 to 59% by weight, more preferably 30 to 52% by weight, and even more preferably 35 to 50% by weight based on the total amount of the resin composition (100% by weight).
　（Ａ１）成分に対する（Ａ２）成分の質量比[（Ａ２）／（Ａ１）]は、樹脂組成物の成形性をより向上させる観点から、特に成形性と引張伸び特性を両立させる観点から、０．０５～１．５が好ましく、より好ましくは０．０７５～１．３、更により好ましくは０．１～１．１である。 The mass ratio of component (A2) to component (A1) [(A2)/(A1)] is set to 0 from the viewpoint of further improving the moldability of the resin composition, especially from the viewpoint of achieving both moldability and tensile elongation properties. It is preferably from .05 to 1.5, more preferably from 0.075 to 1.3, even more preferably from 0.1 to 1.1.
〔（Ｂ）セルロース系繊維〕
　（Ｂ）成分としては、樹脂組成物に配合される公知一般のセルロース系繊維を用いることができ、例えば、セルロース、セルロースを部分的に変性したセルロース系誘導体、及びこれらの塩からなる群より選択される１種以上を挙げることができる。
　具体的には、セルロース；ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース等のヒドロキシアルキルセルロース；メチルセルロース、エチルセルロース等のアルキルセルロース；カルボキシメチルセルロース等のカルボキシアルキルセルロース等が挙げられる。これらは単独でもしくは２種以上併せて用いることができる。 [(B) Cellulose fiber]
As component (B), known general cellulose fibers that are blended into resin compositions can be used, for example, selected from the group consisting of cellulose, cellulose derivatives obtained by partially modifying cellulose, and salts thereof. One or more types can be mentioned.
Specifically, cellulose; hydroxyalkylcelluloses such as hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose; alkylcelluloses such as methylcellulose and ethylcellulose; and carboxyalkylcelluloses such as carboxymethylcellulose. These can be used alone or in combination of two or more.
　前記（Ｂ）成分は公知のセルロース含有原料から得られるものであり、かかるセルロース含有原料としては、例えば、針葉樹、広葉樹等の木材パルプ等の木材繊維、リンター等の綿花、ボンバックス綿、カポック等の種子毛繊維、麻、亜麻、黄麻、ラミー、コウゾ、ミツマタ等のジン皮繊維、マニラ麻、ニュージーランド麻等の葉繊維等が挙げられる。これらは単独でもしくは２種以上併せて用いることができる。 The component (B) is obtained from known cellulose-containing raw materials, and examples of such cellulose-containing raw materials include wood fibers such as wood pulp from coniferous and hardwood trees, cotton such as linters, Bombax cotton, kapok, etc. Examples include seed hair fibers of hemp, flax, jute, ramie, paper mulberry, mitsumata, etc., and leaf fibers of Manila hemp, New Zealand hemp, etc. These can be used alone or in combination of two or more.
　（Ｂ）セルロース系繊維の平均繊維長は、成形性に優れる樹脂組成物を得る観点から、例えば２，０００μｍ以下であり、１０～１，０００μｍが好ましく、１０～５００μｍがより好ましい。また、（Ｂ）セルロース系繊維の平均径は、例えば４００μｍ以下であり、１０～３００μｍが好ましく、１０～２００μｍがより好ましい。 The average fiber length of the cellulose fiber (B) is, for example, 2,000 μm or less, preferably 10 to 1,000 μm, and more preferably 10 to 500 μm, from the viewpoint of obtaining a resin composition with excellent moldability. Further, the average diameter of the cellulose fiber (B) is, for example, 400 μm or less, preferably 10 to 300 μm, and more preferably 10 to 200 μm.
　これらのなかでも、成形性に優れる樹脂組成物を得る観点から、粉末状のセルロース系繊維を用いることが好ましい。粉末状のセルロース系繊維としては、粉末状に加工されたセルロースであれば特に制限されないが、例えば、木材パルプ等を機械的に粉砕して得られる粉末セルロース；木材パルプ等の非結晶部分を酸加水分解処理等で除去した後、粉砕・篩い分けすることで得られる粉末セルロース（結晶性セルロース）；化学変性セルロースの水懸濁液等を機械的な磨砕等のより解繊する方法によって得られる粉末セルロース（セルロースナノファイバー）等が挙げられる。これらは単独でもしくは２種以上併せて用いることができる。 Among these, from the viewpoint of obtaining a resin composition with excellent moldability, it is preferable to use powdered cellulose fibers. Powdered cellulose fibers are not particularly limited as long as they are cellulose processed into powder, but examples include powdered cellulose obtained by mechanically crushing wood pulp, etc.; Powdered cellulose (crystalline cellulose) obtained by crushing and sieving after removal by hydrolysis treatment; Examples include powdered cellulose (cellulose nanofiber). These can be used alone or in combination of two or more.
　粉末状の（Ｂ）成分の平均粒子径は、１０～１００μｍが好ましく、より好ましくは１５～８０μｍ、更により好ましくは１８～６０μｍ、特に好ましくは２０～５０μｍである。（Ｂ）成分の平均粒子径が前記範囲外になると、樹脂組成物の成形性が損なわれる傾向がある。
　前記平均粒子径は、体積基準で積算粒子径分布の値が５０％に相当するメジアン径（ｄ５０）であり、例えば、レーザー回折粒子径測定装置（例えば、品番ＬＡ－９５０Ｖ２、堀場製作所社製）で測定することができる。 The average particle diameter of the powdered component (B) is preferably 10 to 100 μm, more preferably 15 to 80 μm, even more preferably 18 to 60 μm, particularly preferably 20 to 50 μm. When the average particle diameter of component (B) is outside the above range, the moldability of the resin composition tends to be impaired.
The average particle diameter is a median diameter (d50) corresponding to 50% of the cumulative particle diameter distribution on a volume basis, and is, for example, a laser diffraction particle diameter measuring device (for example, product number LA-950V2, manufactured by Horiba, Ltd.). It can be measured by
　（Ｂ）成分の平均重合度は、特に制限されないが、５０～１５００が好ましく、より好ましくは１００～１０００、更により好ましくは１５０～８００、特に好ましくは２００～６００である。 The average degree of polymerization of component (B) is not particularly limited, but is preferably from 50 to 1,500, more preferably from 100 to 1,000, even more preferably from 150 to 800, particularly preferably from 200 to 600.
　（Ｂ）成分のＸ線回折法による結晶化度は、特に制限されないが、７０％以上が好ましく、より好ましくは７５～９５％、更により好ましくは８０～９５％である。 The crystallinity of component (B) as measured by X-ray diffraction is not particularly limited, but is preferably 70% or more, more preferably 75 to 95%, and even more preferably 80 to 95%.
　（Ｂ）成分としては市販品を好適に用いることができる。例えば、日本製紙社製のＫＣフロックシリーズ（Ｗ－４００Ｇ／Ｙ、Ｗ－３００Ｇ／Ｙ、Ｗ－２５０、Ｗ－２００、Ｗ－２００Ｗ／Ｇ／Ｙ、Ｗ－１００Ｗ／Ｇ／Ｙ、Ｗ－５０等）、ＫＣフロックＧＫシリーズ（Ｗ－５０ＧＫ、Ｗ－１００ＧＫ等）、ＮＰミクローズシリーズ（Ｗ－２００Ｍ、Ｗ－４００Ｍ等）、ＮＰファイバーシリーズ（Ｗ－１００Ｆ、Ｗ－３００Ｆ、Ｗ－１０ＭＧ２等）等が挙げられる。 Commercially available products can be suitably used as component (B). For example, the KC flock series manufactured by Nippon Paper Industries (W-400G/Y, W-300G/Y, W-250, W-200, W-200W/G/Y, W-100W/G/Y, W-50 ), KC Flock GK series (W-50GK, W-100GK, etc.), NP Micros series (W-200M, W-400M, etc.), NP fiber series (W-100F, W-300F, W-10MG2, etc.) etc.
　（Ｂ）成分の含有量は、樹脂組成物の成形性をより向上させる観点から、樹脂組成物全量（１００質量％）に対して、４１～６４質量％が好ましく、より好ましくは４１～６２質量％、更により好ましくは４３～６０質量％、特に好ましくは４５～５８質量％である。 The content of component (B) is preferably 41 to 64% by mass, more preferably 41 to 62% by mass, based on the total amount of the resin composition (100% by mass), from the viewpoint of further improving the moldability of the resin composition. %, even more preferably 43 to 60% by weight, particularly preferably 45 to 58% by weight.
　（Ａ１）成分及び（Ａ２）成分の合計量に対する（Ｂ）成分の質量比〔（Ｂ）／[（Ａ１）＋（Ａ２）]〕は、樹脂組成物の成形性をより向上させる観点から、０．６８～２．０が好ましく、より好ましくは０．７５～１．８、更により好ましくは０．８～１．６、特に好ましくは１～１．５である。 The mass ratio of component (B) to the total amount of components (A1) and (A2) [(B)/[(A1)+(A2)]] is determined from the viewpoint of further improving the moldability of the resin composition. It is preferably from 0.68 to 2.0, more preferably from 0.75 to 1.8, even more preferably from 0.8 to 1.6, particularly preferably from 1 to 1.5.
〔（Ｃ）無機フィラー〕
　本樹脂組成物は、（Ａ１）成分、（Ａ２）成分及び（Ｂ）成分のほか、樹脂組成物の成形性をより向上させる観点から、（Ｃ）無機フィラー（以下、（Ｃ）成分という場合がある）を含有することが好ましい。（Ｃ）成分としては、通常用いられる公知一般の無機フィラーを用いることができ、その形状は特に制限されず、例えば、繊維状、球状、板状、針状の無機フィラーを用いることができる。 [(C) Inorganic filler]
In addition to component (A1), component (A2), and component (B), this resin composition contains (C) inorganic filler (hereinafter referred to as component (C)) from the viewpoint of further improving the moldability of the resin composition. It is preferable to contain the following. As component (C), commonly used inorganic fillers commonly used can be used, and the shape thereof is not particularly limited, and for example, fibrous, spherical, plate-like, and needle-like inorganic fillers can be used.
　（Ｃ）成分の具体例としては、例えば、タルク、無水シリカ、雲母、酸化チタン、炭酸カルシウム、ケイ藻土、アロフェン、ベントナイト、チタン酸カリウム、ゼオライト、セピオライト、スメクタイト、カオリン、カオリナイト、ガラス、石灰石、カーボン、ワラステナイト、焼成パーライト、珪酸カルシウム、珪酸ナトリウム、珪酸アルミニウム、酸化アルミニウム、炭酸マグネシウム、水酸化カルシウム、炭酸第二鉄、酸化亜鉛、酸化鉄、リン酸アルミニウム、硫酸バリウム等が挙げられる。これらは単独で用いてもよく、２種類以上を併用してもよい。これらのなかでも、樹脂組成物の成形性をより向上させる観点から、タルクが好ましい。 Specific examples of component (C) include talc, anhydrous silica, mica, titanium oxide, calcium carbonate, diatomaceous earth, allophane, bentonite, potassium titanate, zeolite, sepiolite, smectite, kaolin, kaolinite, glass, Limestone, carbon, wollastenite, calcined pearlite, calcium silicate, sodium silicate, aluminum silicate, aluminum oxide, magnesium carbonate, calcium hydroxide, ferric carbonate, zinc oxide, iron oxide, aluminum phosphate, barium sulfate, etc. . These may be used alone or in combination of two or more. Among these, talc is preferred from the viewpoint of further improving the moldability of the resin composition.
　（Ｃ）成分の平均粒子径は、特に制限されないが、０．５～３０μｍが好ましく、より好ましくは０．６～２０μｍ、更に好ましくは０．７～１０μｍ、特に好ましくは１～５μｍである。（Ｃ）成分の平均粒子径が前記範囲内であると、樹脂組成物の成形性に優れる傾向がある。なお、（Ｃ）成分の平均粒子径は、体積基準で積算粒子径分布の値が５０％に相当するメジアン径（ｄ５０）であり、例えば、レーザー回折粒子径測定装置（例えば、品番ＬＡ－９５０Ｖ２、堀場製作所社製）で測定することができる。 The average particle diameter of component (C) is not particularly limited, but is preferably 0.5 to 30 μm, more preferably 0.6 to 20 μm, even more preferably 0.7 to 10 μm, particularly preferably 1 to 5 μm. When the average particle diameter of component (C) is within the above range, the resin composition tends to have excellent moldability. The average particle diameter of component (C) is the median diameter (d50) corresponding to 50% of the cumulative particle diameter distribution on a volume basis. (manufactured by Horiba, Ltd.).
　（Ｃ）成分の比表面積は、特に制限されないが、通常１～２００ｍ2／ｇであり、３～１５０ｍ2／ｇが好ましく、より好ましくは５～１００ｍ2／ｇ、更により好ましくは１０～５０ｍ2／ｇである。なお、（Ｃ）成分の比表面積は、公知の方法により測定することができ、例えばＢＥＴ法により測定できる。 The specific surface area of component (C) is not particularly limited, but is usually 1 to 200 m 2 /g, preferably 3 to 150 m 2 /g, more preferably 5 to 100 m 2 /g, and even more preferably 10 to 50 m 2 /g. 2 /g. Note that the specific surface area of component (C) can be measured by a known method, for example, by the BET method.
　（Ｃ）成分の含有量は、特に制限されないが、樹脂組成物全量（１００質量％）に対して、０．５～１５質量％が好ましく、より好ましくは１～１０質量％、更により好ましくは１．５～６質量％である。（Ｃ）成分の含有量が前記範囲外になると、樹脂組成物の成形性が損なわれる傾向がある。 The content of component (C) is not particularly limited, but is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, and even more preferably It is 1.5 to 6% by mass. When the content of component (C) is outside the above range, the moldability of the resin composition tends to be impaired.
〔（Ｄ）可塑剤〕
　本樹脂組成物は、（Ａ１）成分、（Ａ２）成分及び（Ｂ）成分のほか、更に（Ｄ）可塑剤（以下、（Ｄ）成分という場合がある）を含有させることができる。（Ｄ）成分としては、通常用いられる公知一般の可塑剤を用いることができる。
　（Ｄ）成分の具体例としては、以下に制限されないが、例えば、アジピン酸エステル系可塑剤、セバシン酸エステル系可塑剤、アゼライン酸エステル系可塑剤等の脂肪族二塩基酸エステル系可塑剤、フタル酸エステル系可塑剤、リン酸エステル系可塑剤、クエン酸エステル系可塑剤、グリコール酸エステル系可塑剤、トリメリット酸エステル系可塑剤、リシノール酸エステル系可塑剤、安息香酸エステル系可塑剤、酢酸エステル系可塑剤等の分子内にエステル結合を有する可塑剤が挙げられる。これらは単独でもしくは２種以上併せて用いることができる。 [(D) Plasticizer]
The present resin composition can further contain (D) a plasticizer (hereinafter sometimes referred to as (D) component) in addition to component (A1), component (A2), and component (B). As component (D), commonly used plasticizers can be used.
Specific examples of component (D) include, but are not limited to, aliphatic dibasic acid ester plasticizers such as adipic acid ester plasticizers, sebacic acid ester plasticizers, and azelaic acid ester plasticizers; Phthalate ester plasticizers, phosphate ester plasticizers, citric acid ester plasticizers, glycolate ester plasticizers, trimellitic ester plasticizers, ricinoleate ester plasticizers, benzoate ester plasticizers, Examples include plasticizers having an ester bond in the molecule, such as acetate-based plasticizers. These can be used alone or in combination of two or more.
　アジピン酸エステル系可塑剤としては、例えば、アジピン酸ジメチル、アジピン酸ジブチル、アジピン酸ジオクチル、アジピン酸イソブチル、アジピン酸イソデシル、アジピン酸ジイソノニル、アジピン酸ジビニル、アジピン酸ジベンジル、アジピン酸と芳香族アルコール及び脂肪族アルコールとの混基エステル等が挙げられる。 Examples of adipate ester plasticizers include dimethyl adipate, dibutyl adipate, dioctyl adipate, isobutyl adipate, isodecyl adipate, diisononyl adipate, divinyl adipate, dibenzyl adipate, adipic acid and aromatic alcohol, and Examples include mixed esters with aliphatic alcohols.
　アジピン酸と芳香族アルコール及び脂肪族アルコールとの混基エステルとしては、例えば、ベンジルアルキルジグリコールアジペート等が挙げられる。ベンジルアルキルジグリコールアジペートにおけるアルキル基は直鎖状又は分岐鎖状のいずれでもよく、当該アルキル基の炭素数は特に制限されないが、通常１～２０程度である。これらのなかでも、直鎖状アルキル基が好ましく、より好ましくは炭素数１～８の直鎖状アルキル基、更により好ましくは炭素数１～４の直鎖状アルキル基である。より具体的には、例えば、ベンジルメチルジグリコールアジペート、ベンジルエチルジグリコールアジペート、ベンジルプロピルジグリコールアジペート、及びベンジルブチルジグリコールアジペート等が挙げられる。 Examples of the mixed group ester of adipic acid and aromatic alcohol and aliphatic alcohol include benzyl alkyl diglycol adipate. The alkyl group in the benzyl alkyl diglycol adipate may be linear or branched, and the number of carbon atoms in the alkyl group is not particularly limited, but is usually about 1 to 20. Among these, linear alkyl groups are preferred, more preferably linear alkyl groups having 1 to 8 carbon atoms, even more preferably linear alkyl groups having 1 to 4 carbon atoms. More specifically, examples include benzylmethyl diglycol adipate, benzylethyl diglycol adipate, benzylpropyl diglycol adipate, and benzyl butyl diglycol adipate.
　セバシン酸エステル系可塑剤としては、例えば、セバシン酸ジメチル、セバシン酸ジブチル、セバシン酸ジ－２－エチルヘキシル、セバシン酸ジオクチル、セバシン酸ジイソオクチル等が挙げられる。 Examples of sebacate ester plasticizers include dimethyl sebacate, dibutyl sebacate, di-2-ethylhexyl sebacate, dioctyl sebacate, diisooctyl sebacate, and the like.
　アゼライン酸エステル系可塑剤としては、例えば、アゼライン酸ジオクチル、アゼライン酸２－エチルヘキシル、アゼライン酸イソブチル、アゼライン酸イソデシル、アゼライン酸ジイソノニル、アゼライン酸ジヘキシル、アゼライン酸ジビニル、アゼライン酸ジベンジル等が挙げられる。 Examples of azelate ester plasticizers include dioctyl azelate, 2-ethylhexyl azelate, isobutyl azelate, isodecyl azelate, diisononyl azelate, dihexyl azelate, divinyl azelate, dibenzyl azelate, and the like.
　フタル酸エステル系可塑剤としては、例えば、フタル酸ジメチル、フタル酸ジエチル、フタル酸ジブチル、フタル酸ジへプチル、フタル酸ジオクチル、フタル酸ジイソオクチル、フタル酸ジ２－エチルへキシル、イソフタル酸ジ２－エチルヘキシル、フタル酸ジノニル、フタル酸ジイソノニル、フタル酸ジイソデシル、フタル酸ジトリデシル、フタル酸ジブチルペンチル、フタル酸ジシクロヘキシル、フタル酸ジウンデシル、フタル酸ジフェニル等が挙げられる。 Examples of phthalate ester plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diisooctyl phthalate, di2-ethylhexyl phthalate, and di-2 isophthalate. - Ethylhexyl, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, ditridecyl phthalate, dibutylpentyl phthalate, dicyclohexyl phthalate, diundecyl phthalate, diphenyl phthalate, and the like.
　リン酸エステル系可塑剤としては、例えば、リン酸トリメチル、リン酸トリエチル、リン酸トリブチル、リン酸トリ２－エチルヘキシル、リン酸２－エチルヘキシルジフェニル、リン酸トリフェニル、リン酸トリクレジル、リン酸ジフェニルエチル等が挙げられる。 Examples of phosphate ester plasticizers include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, 2-ethylhexyldiphenyl phosphate, triphenyl phosphate, tricresyl phosphate, and diphenylethyl phosphate. etc.
　クエン酸エステル系可塑剤としては、例えば、クエン酸トリエチル、アセチルクエン酸トリエチル、クエン酸トリブチル、アセチルクエン酸トリブチル、アセチルクエン酸トリ２－エチルヘキシル等が挙げられる。 Examples of the citric acid ester plasticizer include triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate, and tri-2-ethylhexyl acetyl citrate.
　グリコール酸エステル系可塑剤としては、例えば、トリアセチン、トリブチリン、エチルグリコール酸メチルフタリル、エチルグリコール酸エチルフタリル、ブチルグリコール酸ブチルフタリル等が挙げられる。 Examples of the glycolic acid ester plasticizer include triacetin, tributyrin, methyl phthalyl ethyl glycolate, ethyl phthalyl ethyl glycolate, butylphthalyl butyl glycolate, and the like.
　トリメリット酸エステル系可塑剤としては、例えば、トリメリット酸トリオクチル、トリメリット酸トリ２－エチルヘキシル、トリメリット酸ジイソオクチルモノイソデシル、トリメリット酸トリイソノニル等が挙げられる。 Examples of trimellitic acid ester plasticizers include trioctyl trimellitate, tri2-ethylhexyl trimellitate, diisooctyl monoisodecyl trimellitate, triisononyl trimellitate, and the like.
　リシノール酸エステル系可塑剤としては、例えば、リシノール酸メチルアセチル、リシノール酸ブチルアセチル等が挙げられる。 Examples of the ricinoleic acid ester plasticizer include methylacetyl ricinoleate, butylacetyl ricinoleate, and the like.
　安息香酸エステル系可塑剤としては、例えば、ジエチレングリコールジベンゾエート、ジプロピレングリコールジベンゾエート、トリエチレングリコールジベンゾエート、ポリエチレングリコールジベンゾエート等が挙げられる。 Examples of benzoic acid ester plasticizers include diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, polyethylene glycol dibenzoate, and the like.
　これら（Ｄ）成分のなかでも、樹脂組成物の成形性をより向上させる観点から、脂肪族二塩基酸エステル系可塑剤が好ましく、より好ましくはアジピン酸エステル系可塑剤、更により好ましくはベンジルアルキルジグリコールアジペートである。 Among these components (D), from the viewpoint of further improving the moldability of the resin composition, aliphatic dibasic acid ester plasticizers are preferred, adipic acid ester plasticizers are more preferred, and benzyl alkyl Diglycol adipate.
　（Ｄ）成分の重量平均分子量（Ｍｗ）は、特に制限されないが、例えば、１００～２０００が好ましく、より好ましくは２００～１５００、更により好ましくは３００～１０００である。なお、前記重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により、ポリスチレンを標準物質として測定した値である。 The weight average molecular weight (Mw) of component (D) is not particularly limited, but is preferably, for example, 100 to 2,000, more preferably 200 to 1,500, and even more preferably 300 to 1,000. Note that the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
　（Ｄ）成分の含有量は、特に制限されないが、樹脂組成物の成形性をより向上させる観点から、樹脂組成物全量（１００質量％）に対して、０．５～２０質量％が好ましく、より好ましくは１～１５質量％、更により好ましくは２～１２質量％である。 The content of component (D) is not particularly limited, but from the viewpoint of further improving the moldability of the resin composition, it is preferably 0.5 to 20% by mass based on the total amount of the resin composition (100% by mass). More preferably 1 to 15% by weight, even more preferably 2 to 12% by weight.
　本樹脂組成物に含まれる（Ａ１）成分及び（Ａ２）成分から構成される組成物のメルトフローレート（ＭＦＲ）、又は、本樹脂組成物に含まれる（Ａ１）成分、（Ａ２）成分及び（Ｄ）成分から構成される組成物のメルトフローレート（ＭＦＲ）は、ＪＩＳ　Ｋ７２１０に準拠して、１９０℃、２．１６ｋｇで測定した場合、好ましくは１～１２５０ｇ／１０分、より好ましくは３～２００ｇ／１０分、更により好ましくは４～１８０ｇ／１０分、特に好ましくは５～１６０ｇ／１０分である。メルトフローレート（ＭＦＲ）が前記範囲外になると、樹脂組成物の成形性が損なわれる傾向がある。 The melt flow rate (MFR) of the composition composed of the (A1) component and (A2) component contained in the present resin composition, or the (A1) component, (A2) component and ( The melt flow rate (MFR) of the composition composed of component D) is preferably 1 to 1250 g/10 minutes, more preferably 3 to 200 g/10 minutes, even more preferably 4 to 180 g/10 minutes, particularly preferably 5 to 160 g/10 minutes. When the melt flow rate (MFR) is outside the above range, the moldability of the resin composition tends to be impaired.
〔その他の成分〕
　本樹脂組成物には、（Ａ１）成分、（Ａ２）成分、（Ｂ）成分、更に（Ｃ）成分や（Ｄ）成分以外に、その他の成分を含まないことが好ましいが、本発明の効果を損なわない範囲であれば、従来から、一般的に樹脂組成物に常用されている成分を含んでいても差し支えない。例えば、以下に限定されないが、（Ａ１）及び（Ａ２）以外のポリエステル系樹脂、有機フィラー、滑剤、帯電防止剤、酸化防止剤、光安定剤、紫外線吸収剤、染料、顔料、加水分解防止剤、結晶核剤、アンチブロッキング剤、耐光剤、熱安定剤、難燃剤、離型剤、防曇剤、表面ぬれ改善剤、焼却補助剤、分散助剤、各種界面活性剤、スリップ剤、鮮度保持剤、抗菌剤等を配合することもできる。これらは単独でもしくは２種以上併せて用いることができる。 [Other ingredients]
Although it is preferable that the present resin composition does not contain any other components other than the (A1) component, (A2) component, (B) component, and furthermore the (C) component and (D) component, the effects of the present invention As long as it does not impair the properties of the resin composition, it may contain components that have been commonly used in resin compositions. Examples include, but are not limited to, polyester resins other than (A1) and (A2), organic fillers, lubricants, antistatic agents, antioxidants, light stabilizers, ultraviolet absorbers, dyes, pigments, and hydrolysis inhibitors. , crystal nucleating agent, anti-blocking agent, light stabilizer, heat stabilizer, flame retardant, mold release agent, antifogging agent, surface wetting improver, incineration aid, dispersion aid, various surfactants, slip agent, freshness preservation agent Agents, antibacterial agents, etc. can also be added. These can be used alone or in combination of two or more.
　前記（Ａ１）及び（Ａ２）以外のポリエステル系樹脂としては、例えば、脂肪族オキシカルボン酸単位を主たる構成単位として有する脂肪族ポリエステル系樹脂が挙げられる。
　前記脂肪族ポリエステル系樹脂の脂肪族オキシカルボン酸単位を与える脂肪族オキシカルボン酸成分の具体例としては、例えば、乳酸、グリコール酸、２－ヒドロキシ－ｎ－酪酸、３－ヒドロキシ酪酸、４－ヒドロキシ酪酸、２－ヒドロキシカプロン酸、６－ヒドロキシカプロン酸、２－ヒドロキシ－３，３－ジメチル酪酸、２－ヒドロキシ－３－メチル酪酸、２－ヒドロキシイソカプロン酸、３－ヒドロキシ吉草酸、リンゴ酸、クエン酸等、又はこれらの低級アルキルエステル若しくは分子内エステル等が挙げられる。また、ε－カプロラクトン等のラクトン化合物も本発明において脂肪族オキシカルボン酸に包含される。これらに光学異性体が存在する場合には、Ｄ体、Ｌ体又はラセミ体のいずれでもよく、形態としては固体、液体又は水溶液であってもよい。これらのなかでも、乳酸、グリコール酸、３－ヒドロキシ酪酸、４－ヒドロキシ酪酸、６－ヒドロキシカプロン酸、３－ヒドロキシ吉草酸が好ましい。これら脂肪族オキシカルボン酸は、１種を単独で用いても、２種以上を併用してもよい。 Examples of polyester resins other than (A1) and (A2) include aliphatic polyester resins having an aliphatic oxycarboxylic acid unit as a main structural unit.
Specific examples of the aliphatic oxycarboxylic acid component that provides the aliphatic oxycarboxylic acid units of the aliphatic polyester resin include lactic acid, glycolic acid, 2-hydroxy-n-butyric acid, 3-hydroxybutyric acid, and 4-hydroxy Butyric acid, 2-hydroxycaproic acid, 6-hydroxycaproic acid, 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, 2-hydroxyisocaproic acid, 3-hydroxyvaleric acid, malic acid, Examples include citric acid, lower alkyl esters or intramolecular esters thereof, and the like. Furthermore, lactone compounds such as ε-caprolactone are also included in the aliphatic oxycarboxylic acids in the present invention. If these have optical isomers, they may be D-form, L-form or racemic, and may be in the form of solid, liquid or aqueous solution. Among these, lactic acid, glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 6-hydroxycaproic acid, and 3-hydroxyvaleric acid are preferred. These aliphatic oxycarboxylic acids may be used alone or in combination of two or more.
　脂肪族オキシカルボン酸単位を主たる構成単位として有する脂肪族ポリエステル系樹脂の具体例としては、例えば、ポリ乳酸、ポリグリコール酸、ポリ３－ヒドロキシブチレート、ポリ４－ヒドロキシブチレート、ポリ（３－ヒドロキシブチレート－ｃｏ－３－ヒドロキシバレエート）、ポリカプロラクトン等が挙げられる。 Specific examples of aliphatic polyester resins having aliphatic oxycarboxylic acid units as main constituent units include polylactic acid, polyglycolic acid, poly3-hydroxybutyrate, poly4-hydroxybutyrate, poly(3- Hydroxybutyrate-co-3-hydroxyvalerate), polycaprolactone, and the like.
　ポリ乳酸に含まれる乳酸の構成としては、例えば、モル比で、Ｄ－乳酸：Ｌ－乳酸＝１００：０～８５：１５、又は、０：１００～１５：８５である。また、Ｄ－乳酸とＬ－乳酸との構成割合が異なった他のポリ乳酸をブレンドすることも可能である。 The composition of lactic acid contained in polylactic acid is, for example, a molar ratio of D-lactic acid:L-lactic acid=100:0 to 85:15, or 0:100 to 15:85. It is also possible to blend other polylactic acids with different composition ratios of D-lactic acid and L-lactic acid.
　更には、ポリ乳酸は、前述のポリ乳酸と、他のオキシカルボン酸との共重合体であってもよく、また少量の鎖延長剤に由来する単位を含んでいてもよい。他のオキシカルボン酸としては、乳酸の光学異性体（Ｌ－乳酸に対してはＤ－乳酸、Ｄ－乳酸に対してはＬ－乳酸）、グリコール酸、３－ヒドロキシ酪酸、４－ヒドロキシ酪酸、２－ヒドロキシ－ｎ－酪酸、２－ヒドロキシ－３，３－ジメチル酪酸、２－ヒドロキシ－３－メチル酪酸、２－メチル乳酸、２－ヒドロキシカプロン酸等の２官能脂肪族オキシカルボン酸類、及びカプロラクトン、ブチロラクトン、バレロラクトン等のラクトン類が挙げられる。このような他のオキシカルボン酸に由来する単位は、ポリ乳酸の全構成単位中１５モル％未満で使用することができる。 Furthermore, the polylactic acid may be a copolymer of the above-mentioned polylactic acid and another oxycarboxylic acid, and may also contain a small amount of units derived from a chain extender. Other oxycarboxylic acids include optical isomers of lactic acid (D-lactic acid for L-lactic acid, L-lactic acid for D-lactic acid), glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, Bifunctional aliphatic oxycarboxylic acids such as 2-hydroxy-n-butyric acid, 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, 2-methyllactic acid, 2-hydroxycaproic acid, and caprolactone , butyrolactone, valerolactone, and other lactones. Such units derived from other oxycarboxylic acids can be used in an amount of less than 15 mol% of the total constituent units of polylactic acid.
　脂肪族オキシカルボン酸単位を主たる構成単位として有する脂肪族ポリエステル系樹脂の重量平均分子量（Ｍｗ）は、好ましくは６０，０００～７００，０００、より好ましくは８０，０００～４００，０００、更により好ましくは１００，０００～３００，０００である。
　なお、前記重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により、ポリスチレンを標準物質として測定した値である。 The weight average molecular weight (Mw) of the aliphatic polyester resin having an aliphatic oxycarboxylic acid unit as a main structural unit is preferably 60,000 to 700,000, more preferably 80,000 to 400,000, and even more preferably is between 100,000 and 300,000.
Note that the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
〔樹脂組成物の製造方法〕
　本樹脂組成物は、各種樹脂組成物の公知の製造方法と同様、単軸もしくは二軸押出機、バンバリーミキサー、ミキシングロール等を用いて混練することにより得ることができる。 [Method for manufacturing resin composition]
The present resin composition can be obtained by kneading using a single-screw or twin-screw extruder, a Banbury mixer, a mixing roll, etc., in the same manner as in known manufacturing methods for various resin compositions.
　具体的には、本樹脂組成物は、（Ａ１）成分、（Ａ２）成分及び（Ｂ）成分等を混練することにより製造することができる。また、樹脂組成物の成形性をより向上させる観点から、更に（Ｃ）成分（無機フィラー）を添加し、（Ａ１）成分、（Ａ２）成分及び（Ｂ）成分と共に混練して製造することが好ましい。 Specifically, the present resin composition can be produced by kneading component (A1), component (A2), component (B), and the like. In addition, from the viewpoint of further improving the moldability of the resin composition, it is possible to further add component (C) (inorganic filler) and knead it with component (A1), component (A2), and component (B). preferable.
　本樹脂組成物の製造方法における温度条件は、通常、１２０～１６０℃であり、好ましくは１３０～１５０℃である。 The temperature conditions in the method for producing the present resin composition are usually 120 to 160°C, preferably 130 to 150°C.
〔樹脂組成物の物性〕
　前記のようにして得られた本樹脂組成物のメルトフローレート（ＭＦＲ）は、ＪＩＳ　Ｋ７２１０に準拠して、１４０℃、２．１６ｋｇで測定した場合、好ましくは０．０５～２０ｇ／１０分、より好ましくは０．１～１５ｇ／１０分、更により好ましくは０．１５～１０ｇ／１０分である。 [Physical properties of resin composition]
The melt flow rate (MFR) of the resin composition obtained as described above is preferably 0.05 to 20 g/10 min when measured at 140°C and 2.16 kg according to JIS K7210. More preferably 0.1 to 15 g/10 minutes, even more preferably 0.15 to 10 g/10 minutes.
　本樹脂組成物の引張強度（ＭＰａ）は、ＪＩＳ７１６１－１，２に準拠して、５～５０ＭＰａが好ましく、より好ましくは７～４０ＭＰａ、更により好ましくは１０～３０ＭＰａである。 The tensile strength (MPa) of the present resin composition is preferably 5 to 50 MPa, more preferably 7 to 40 MPa, and even more preferably 10 to 30 MPa, according to JIS7161-1, 2.
　本樹脂組成物の引張伸び（％）は、ＪＩＳ７１６１－１，２に準拠して、６％以上が好ましく、より好ましくは６．４％以上である。
　また、前記引張伸び（％）は、６～２０％が好ましく、より好ましくは６．４～１５％、更により好ましくは６．４～１０％である。 The tensile elongation (%) of the resin composition is preferably 6% or more, more preferably 6.4% or more, according to JIS7161-1, 2.
Further, the tensile elongation (%) is preferably 6 to 20%, more preferably 6.4 to 15%, even more preferably 6.4 to 10%.
　なお、前記引張強度（ＭＰａ）、引張伸び（％）のより具体的な測定方法は、後記の実施例のとおりである。 Note that more specific methods for measuring the tensile strength (MPa) and tensile elongation (%) are as described in Examples below.
〔成形方法〕
　本樹脂組成物を用いた成形品の成形方法としては、特に制限されず、射出成形、押出成形、圧縮成形、積層成形、真空成形、圧空成形、ブロー成形等の公知の方法を用いることができるが、射出成形及び押出成形が好適である。 [Forming method]
The method for molding a molded article using the present resin composition is not particularly limited, and known methods such as injection molding, extrusion molding, compression molding, lamination molding, vacuum molding, pressure molding, and blow molding can be used. However, injection molding and extrusion molding are preferred.
〔成形品の用途〕
　本樹脂組成物から得られる成形品の用途は限定されず、例えば、各種のフィルム、シート、発泡体、板、繊維、容器等が挙げられ、より具体的には、食品用フィルム、生鮮食品のトレーやファーストフードの容器、野外レジャー製品、釣り糸、漁網、植生ネット、保水シート、コーティング資材、農業量マルチフィルム、肥料用コーティング材、筋付きテープ、スプリットヤーン、複合繊維、ショッピングバッグ、ゴミ袋、コンポスト袋、化粧品容器、洗剤容器、漂白剤容器、ロープ、結束材、手術糸、衛生用カバーストック材、保冷箱、クッション材及び合成紙等の用途に利用可能である。 [Applications of molded products]
The applications of molded products obtained from this resin composition are not limited, and examples include various films, sheets, foams, plates, fibers, containers, etc. More specifically, food films, fresh food products, etc. Trays and fast food containers, outdoor leisure products, fishing lines, fishing nets, vegetation nets, water retention sheets, coating materials, agricultural mulch films, coating materials for fertilizers, striped tapes, split yarns, composite fibers, shopping bags, garbage bags, It can be used for compost bags, cosmetic containers, detergent containers, bleach containers, ropes, binding materials, surgical thread, sanitary cover stock materials, cold boxes, cushioning materials, synthetic paper, etc.
　以下、実施例により本発明を更に具体的に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。なお、例中、「部」、「％」とあるのは、質量基準を意味する。 Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof. In addition, in the examples, "parts" and "%" mean mass standards.
　まず、（Ａ１）成分、（Ａ２）成分、（Ｂ）成分、（Ｃ）成分、（Ｄ）成分等として、以下のものを用意した。 First, the following were prepared as the (A1) component, (A2) component, (B) component, (C) component, (D) component, etc.
＜（Ａ１）成分＞
・（ａ１－１）ポリブチレンサクシネート１〔ＰＴＴ　ＭＣＣ　Ｂｉｏｃｈｅｍ社製の「ＢｉＯＰＢＳ（ＦＺ７１ＰＭ）」、メルトフローレート（ＭＦＲ）２２ｇ／１０分（１９０℃、２．１６ｋｇ）、融点１１５℃〕 <(A1) component>
・(a1-1) Polybutylene succinate 1 [“BiOPBS (FZ71PM)” manufactured by PTT MCC Biochem, melt flow rate (MFR) 22 g/10 minutes (190°C, 2.16 kg), melting point 115°C]
・（ａ１－２）ポリブチレンサクシネートアジペート〔ＰＴＴ　ＭＣＣ　Ｂｉｏｃｈｅｍ社製の「ＢｉＯＰＢＳ（ＦＤ９２ＰＭ）」、メルトフローレート（ＭＦＲ）４ｇ／１０分（１９０℃、２．１６ｋｇ）、融点８４℃〕 ・(a1-2) Polybutylene succinate adipate [PTT MCC "BiOPBS (FD92PM)" manufactured by Biochem, melt flow rate (MFR) 4 g / 10 minutes (190 ° C, 2.16 kg), melting point 84 ° C]
・（ａ１－３）ポリブチレンサクシネート２〔ＰＴＴ　ＭＣＣ　Ｂｉｏｃｈｅｍ社製の「ＢｉＯＰＢＳ（ＦＺ９１ＰＭ）」、メルトフローレート（ＭＦＲ）５ｇ／１０分（１９０℃、２．１６ｋｇ）、融点１１５℃〕 ・(a1-3) Polybutylene succinate 2 [PTT MCC "BiOPBS (FZ91PM)" manufactured by Biochem, melt flow rate (MFR) 5 g / 10 minutes (190 ° C, 2.16 kg), melting point 115 ° C]
＜（Ａ２）成分＞
・（ａ２－１）ポリブチレンアジペートテレフタレート〔ＢＡＳＦ社製の「ｅｃｏｆｌｅｘ」、メルトフローレート（ＭＦＲ）３ｇ／１０分（１９０℃、２．１６ｋｇ）、融点１２０℃〕 <(A2) component>
・(a2-1) Polybutylene adipate terephthalate [“ecoflex” manufactured by BASF, melt flow rate (MFR) 3 g/10 minutes (190°C, 2.16 kg), melting point 120°C]
・ポリ乳酸〔Ｎａｔｕｒｅｗｏｒｋｓ社製の「Ｉｎｇｅｏ３２５１Ｄ」〕 ・Polylactic acid [“Ingeo3251D” manufactured by Natureworks]
＜（Ｂ）成分＞
・（ｂ１）粉末セルロース〔日本製紙社製の「ＫＣフロック（Ｗ－４００Ｇ）」、平均粒子径２４μｍ〕 <(B) component>
・(b1) Powdered cellulose [“KC Flock (W-400G)” manufactured by Nippon Paper Industries, average particle size 24 μm]
＜（Ｃ）成分＞
・（ｃ１）タルク〔日本タルク社製の「ＳＧ－９５」、平均粒子径：２．１μｍ〕 <(C) component>
・(c1) Talc [“SG-95” manufactured by Nippon Talc Co., Ltd., average particle size: 2.1 μm]
＜（Ｄ）成分＞
・（ｄ１）アジピン酸エステル系可塑剤〔大八化学工業社製の「ＤＡＩＦＡＴＴＹ－１０１（混基二塩基酸エステル、アジピン酸エステル含有化合物）」、アジピン酸エステルの重量平均分子量３３８〕 <(D) component>
・(d1) Adipic acid ester plasticizer [“DAIFATTY-101 (mixed group dibasic acid ester, adipate ester-containing compound)” manufactured by Daihachi Kagaku Kogyo Co., Ltd., weight average molecular weight of adipic acid ester 338]
［実施例１～８、比較例１～７］
＜成形性評価試験１（ペレット化）＞
　二軸押出機〔ＫＺＷ１５－４５／６０ＭＧ、テクノベル社製〕を用い、下記試験条件に従い、表１に示す組成を有する実施例１～８及び比較例１～７に係る樹脂組成物のペレット化を試み、下記評価基準に従い評価した。その結果を表１に示す。
〔試験条件〕
　スクリューパターン：フルフライト
　加工温度：C1/C2/C3/C4/C5/C6/C7/C8/D3=80℃/140℃/150℃/150℃/140℃/140℃/140℃/140℃/140℃
　回転数：２００ｒｐｍ
　ベント：全閉
　Ｍｅｓｈ：無
　吐出量：１．５ｋｇ／ｈｒ
　なお、比較例７の試験条件における加工温度は、「C1/C2/C3/C4/C5/C6/C7/C8/D3=80℃/140℃/170℃/190℃/190℃/190℃/190℃/190℃/190℃」である。
〔評価基準〕
　〇（very good）：ペレット化可能。表面形状は平滑。
　△（good）：ペレット化可能。表面形状は粗く、平滑ではない。
　×（poor）：ペレット化不可（押出機内で詰まりが発生）。 [Examples 1 to 8, Comparative Examples 1 to 7]
<Moldability evaluation test 1 (pelletization)>
Using a twin-screw extruder [KZW15-45/60MG, manufactured by Technovel Co., Ltd.], the resin compositions of Examples 1 to 8 and Comparative Examples 1 to 7 having the compositions shown in Table 1 were pelletized according to the following test conditions. We tried it and evaluated it according to the following evaluation criteria. The results are shown in Table 1.
〔Test conditions〕
Screw pattern: Full flight Processing temperature: C1/C2/C3/C4/C5/C6/C7/C8/D3=80℃/140℃/150℃/150℃/140℃/140℃/140℃/140℃/ 140℃
Rotation speed: 200rpm
Vent: Fully closed Mesh: None Discharge rate: 1.5kg/hr
In addition, the processing temperature under the test conditions of Comparative Example 7 is "C1/C2/C3/C4/C5/C6/C7/C8/D3=80℃/140℃/170℃/190℃/190℃/190℃/ 190℃/190℃/190℃".
〔Evaluation criteria〕
〇(very good): Can be made into pellets. The surface shape is smooth.
△ (good): Can be made into pellets. The surface shape is rough and not smooth.
× (poor): Cannot be pelletized (clog occurs in the extruder).
＜成形性評価試験２（射出成形）＞
　射出成型機〔品番ＦＥ８０Ｓ１２ＡＳ、日精樹脂工業社製〕を用い、下記試験条件に従い、表１に示す組成を有する実施例１～８及び比較例１、３～７に係る樹脂組成物の射出成形を試み、下記評価基準に従い評価した。その結果を表１に示す。
〔試験条件〕
　金型:ＩＳＯ多目的タイプＡ
　予備乾燥:実施せず
　シリンダー設定温度:１４０℃／１４０℃／１３０℃／１２０℃
　金型設定温度:２０℃
　射出時間:１．８秒
　保圧時間:２０秒
　冷却時間:３０秒
　全サイクル時間:６０士５秒
　なお、比較例７の試験条件におけるシリンダー設定温度は「１９０℃／１８０℃／１７０℃／１６０℃」である。
〔評価基準〕
　〇（very good）：射出成形可能。全サイクル時間は６０秒未満。表面形状は平滑。
　△（good）：射出成形可能だが、全サイクル時間は６０秒以上。表面形状は平滑。
　×（poor）：射出成形不可（射出成型機内で詰まりが発生）。 <Moldability evaluation test 2 (injection molding)>
Using an injection molding machine [product number FE80S12AS, manufactured by Nissei Jushi Kogyo Co., Ltd.], injection molding of the resin compositions according to Examples 1 to 8 and Comparative Examples 1 and 3 to 7 having the compositions shown in Table 1 was carried out according to the following test conditions. We tried it and evaluated it according to the following evaluation criteria. The results are shown in Table 1.
〔Test conditions〕
Mold: ISO multi-purpose type A
Pre-drying: Not performed Cylinder setting temperature: 140℃/140℃/130℃/120℃
Mold setting temperature: 20℃
Injection time: 1.8 seconds Holding pressure time: 20 seconds Cooling time: 30 seconds Total cycle time: 60 seconds 5 seconds The cylinder temperature settings under the test conditions of Comparative Example 7 were 190℃/180℃/170℃/160℃. ℃”.
〔Evaluation criteria〕
〇(very good): Injection molding possible. Total cycle time is less than 60 seconds. The surface shape is smooth.
△ (good): Injection molding is possible, but the total cycle time is 60 seconds or more. The surface shape is smooth.
× (poor): Injection molding is not possible (clog occurs in the injection molding machine).
　次に、下記のとおり、表１に示す組成を有する実施例１～８、比較例３～７に係る樹脂組成物から得られた試験片に基づいて、「引張強度試験」、「引張伸び試験」、を実施した。
＜引張強度試験・引張伸び試験＞
　ＪＩＳ　Ｋ７１６１－１，２に準拠して、引張強度及び引張伸び試験を実施した。具体的には、まず、前記「成形性評価試験２（射出成形）」における試験条件に基づいて射出成形を行い、１Ａ型試験片（厚さ４ｍｍ）を作製した。得られた試験片の引張強度（ＭＰａ）及び引張伸び（％）を、引張試験機〔ストログラフＡＰII、東洋精機製作所社製〕により、下記試験条件に従い測定した。その結果を表１に示す。
〔試験条件〕
　試験速度５０ｍｍ／分
　標線間距離５０ｍｍ
　つかみ具間距離１１５ｍｍ
〔評価基準（引張強度）〕
　〇（very good）：５ＭＰａ以上。
　×（poor）：５ＭＰａ未満。
〔評価基準（引張伸び）〕
　〇（very good）：６．４％以上。
　△（good）：５％以上６．４％未満。
　×（poor）：５％未満。 Next, as described below, based on the test pieces obtained from the resin compositions of Examples 1 to 8 and Comparative Examples 3 to 7 having the compositions shown in Table 1, "Tensile strength test" and "Tensile elongation test" were conducted. ”, was carried out.
<Tensile strength test/Tensile elongation test>
Tensile strength and tensile elongation tests were conducted in accordance with JIS K7161-1, 2. Specifically, first, injection molding was performed based on the test conditions in the above-mentioned "Moldability Evaluation Test 2 (Injection Molding)" to produce a type 1A test piece (thickness: 4 mm). The tensile strength (MPa) and tensile elongation (%) of the obtained test piece were measured using a tensile tester [Strograph API II, manufactured by Toyo Seiki Seisakusho Co., Ltd.] according to the following test conditions. The results are shown in Table 1.
〔Test conditions〕
Test speed 50mm/min Distance between marked lines 50mm
Distance between grips 115mm
[Evaluation criteria (tensile strength)]
〇(very good): 5MPa or more.
× (poor): less than 5 MPa.
[Evaluation criteria (tensile elongation)]
〇(very good): 6.4% or more.
△ (good): 5% or more and less than 6.4%.
× (poor): less than 5%.
＜メルトフローレート（ＭＦＲ）の測定＞
　実施例１～８及び比較例１、３～７に含まれるベース樹脂について、ＪＩＳ　Ｋ７２１０に準拠して、温度１９０℃、荷重２．１６ｋｇにおけるメルトフローレート（ＭＦＲ）を測定した。その結果を表１に示す。
　なお、ベース樹脂とは、（Ａ１）成分、（Ａ２）成分、（Ｄ）成分のうち、各樹脂組成物に含まれる成分又はそれらからなる混合組成物を意味する。例えば、実施例１では、ベース樹脂とは、（Ａ１）成分、（Ａ２）成分、及び（Ｄ）成分からなる混合組成物を意味するものであり、実施例２においては、（Ａ１）成分、及び（Ａ２）成分からなる混合組成物を意味する。
　また、ベース樹脂とは、例えば、比較例７においては、ポリ乳酸、及び（Ａ２）成分からなる混合組成物を意味する。 <Measurement of melt flow rate (MFR)>
The melt flow rate (MFR) of the base resins included in Examples 1 to 8 and Comparative Examples 1 and 3 to 7 was measured at a temperature of 190° C. and a load of 2.16 kg in accordance with JIS K7210. The results are shown in Table 1.
In addition, the base resin means the component contained in each resin composition among component (A1), component (A2), and component (D), or a mixed composition consisting of these components. For example, in Example 1, the base resin means a mixed composition consisting of component (A1), component (A2), and component (D), and in Example 2, component (A1), It means a mixed composition consisting of component (A2) and (A2).
Moreover, the base resin in Comparative Example 7 means a mixed composition consisting of polylactic acid and component (A2), for example.
　実施例１～８及び比較例１、３～７に係る各樹脂組成物について、ＪＩＳ　Ｋ７２１０に準拠して、温度１４０℃、荷重２．１６ｋｇにおけるメルトフローレート（ＭＦＲ）を測定した。その結果を表１に示す。 The melt flow rate (MFR) of each resin composition according to Examples 1 to 8 and Comparative Examples 1 and 3 to 7 was measured at a temperature of 140° C. and a load of 2.16 kg in accordance with JIS K7210. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すとおり、本発明の実施例１～８は、ペレット化及び射出成形が可能であって、得られたペレットの表面形状も平滑であるから、成形性に優れていることが確認された。また、本発明の実施例１～８は、成形後の引張伸び特性や引張強度特性においても優れていることが確認された。 As shown in Table 1, Examples 1 to 8 of the present invention can be pelletized and injection molded, and the surface shape of the obtained pellets is smooth, so it is confirmed that they have excellent moldability. Ta. Furthermore, it was confirmed that Examples 1 to 8 of the present invention were also excellent in tensile elongation properties and tensile strength properties after molding.
　他方、本発明の（Ａ１）成分を含む一方、（Ａ２）成分を含まない比較例１～６は、本発明の実施例１～８に比して、成形性又は引張伸びの少なくとも一方において劣ることが確認された。
　また、本発明の（Ａ２）成分を含む一方、ポリ乳酸を含み、（Ａ１）成分を含まない比較例７は、本発明の実施例１～８に比して、成形性及び引張伸びにおいて劣ることが確認された。 On the other hand, Comparative Examples 1 to 6, which contain the component (A1) of the present invention but do not contain the component (A2), are inferior to Examples 1 to 8 of the present invention in at least one of moldability or tensile elongation. This was confirmed.
Comparative Example 7, which contains component (A2) of the present invention but also contains polylactic acid and does not contain component (A1), is inferior in moldability and tensile elongation compared to Examples 1 to 8 of the present invention. This was confirmed.
　前記実施例においては、本発明における具体的な形態について示したが、前記実施例は単なる例示にすぎず、限定的に解釈されるものではない。当業者に明らかな様々な変形は、本発明の範囲内であることが企図されている。 Although the embodiments described above show specific embodiments of the present invention, the embodiments are merely illustrative and should not be construed as limiting. Various modifications apparent to those skilled in the art are intended to be within the scope of the invention.
　本発明の樹脂組成物は成形性や引張特性に優れているため、各種の成形品の原料として広く有効に活用できる。 Since the resin composition of the present invention has excellent moldability and tensile properties, it can be widely and effectively used as a raw material for various molded products.

Claims (11)

  1. 　下記（Ａ１）成分、（Ａ２）成分、及び、（Ｂ）成分を含有する樹脂組成物。
    　（Ａ１）脂肪族多価アルコール単位と脂肪族多価カルボン酸単位とを有する脂肪族ポリエステル系樹脂。
    　（Ａ２）脂肪族多価アルコール単位と、脂肪族多価カルボン酸単位と、芳香族多価カルボン酸単位とを有する脂肪族－芳香族ポリエステル系樹脂。
    　（Ｂ）セルロース系繊維。     A resin composition containing the following components (A1), (A2), and (B).
    (A1) An aliphatic polyester resin having an aliphatic polyhydric alcohol unit and an aliphatic polycarboxylic acid unit.
    (A2) An aliphatic-aromatic polyester resin having an aliphatic polyhydric alcohol unit, an aliphatic polycarboxylic acid unit, and an aromatic polycarboxylic acid unit.
    (B) Cellulose fiber.
  2. 　前記樹脂組成物全量に対する、前記（Ａ１）成分と前記（Ａ２）成分との合計含有量が、２０～５９質量％である請求項１記載の樹脂組成物。 The resin composition according to claim 1, wherein the total content of the component (A1) and the component (A2) based on the total amount of the resin composition is 20 to 59% by mass.
  3. 　ＪＩＳ７１６１－１，２に準拠して測定した引張伸びが６．４％以上である、請求項１又は２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, which has a tensile elongation of 6.4% or more as measured in accordance with JIS7161-1, 2.
  4. 　前記樹脂組成物全量に対する、前記（Ｂ）成分の含有量が、４１～６４質量％である、請求項１又は２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the content of the component (B) is 41 to 64% by mass based on the total amount of the resin composition.
  5. 　前記（Ａ１）成分に対する前記（Ａ２）成分の質量比（Ａ２）／（Ａ１）が、０．０５～１．５である、請求項１又は２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the mass ratio (A2)/(A1) of the (A2) component to the (A1) component is 0.05 to 1.5.
  6. 　更に、（Ｃ）無機フィラーを含有する、請求項１又は２記載の樹脂組成物。 The resin composition according to claim 1 or 2, further comprising (C) an inorganic filler.
  7. 　前記（Ａ１）成分の温度１９０℃、荷重２．１６ｋｇにおけるメルトフローレートが、１～１５０ｇ／１０分である、請求項１又は２記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the melt flow rate of the component (A1) at a temperature of 190° C. and a load of 2.16 kg is 1 to 150 g/10 minutes.
  8. 　前記（Ａ１）成分が、ポリブチレンサクシネート及びポリブチレンサクシネートアジペートからなる群より選択される１種以上である、請求項１又は２記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the component (A1) is one or more selected from the group consisting of polybutylene succinate and polybutylene succinate adipate.
  9. 　前記（Ａ２）成分が、ポリブチレンアルキレートテレフタレートである、請求項１又は２記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the component (A2) is polybutylene alkylate terephthalate.
  10. 　前記（Ｂ）成分が、粉末状である、請求項１又は２記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the component (B) is in powder form.
  11. 　前記（Ｂ）成分の平均粒子径が、１０～１００μｍである、請求項１０記載の樹脂組成物。 The resin composition according to claim 10, wherein the average particle diameter of the component (B) is 10 to 100 μm.
PCT/JP2023/008067 2022-03-09 2023-03-03 Resin composition WO2023171565A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-036326 2022-03-09
JP2022036326 2022-03-09

Publications (1)

Publication Number Publication Date
WO2023171565A1 true WO2023171565A1 (en) 2023-09-14

Family

ID=87935018

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/008067 WO2023171565A1 (en) 2022-03-09 2023-03-03 Resin composition

Country Status (1)

Country Link
WO (1) WO2023171565A1 (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008202212A (en) * 1990-11-30 2008-09-04 Eastman Chem Co Aliphatic-aromatic copolyester fibers
JP2009072113A (en) * 2007-09-20 2009-04-09 Mitsubishi Chemicals Corp Agricultural mulching film
JP2018021103A (en) * 2016-08-02 2018-02-08 三菱ケミカル株式会社 Polyester resin composition, film obtained by molding the resin composition, and bag obtained by molding the film
WO2021241712A1 (en) * 2020-05-28 2021-12-02 三菱ケミカル株式会社 Biodegradable resin composition and biodegradable resin molded articles
JP2021191845A (en) * 2020-06-02 2021-12-16 三菱ケミカル株式会社 Biodegradable resin composition, and biodegradable resin molded body
WO2022039282A1 (en) * 2021-03-25 2022-02-24 株式会社Tbm Resin composition and molded article

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008202212A (en) * 1990-11-30 2008-09-04 Eastman Chem Co Aliphatic-aromatic copolyester fibers
JP2009072113A (en) * 2007-09-20 2009-04-09 Mitsubishi Chemicals Corp Agricultural mulching film
JP2018021103A (en) * 2016-08-02 2018-02-08 三菱ケミカル株式会社 Polyester resin composition, film obtained by molding the resin composition, and bag obtained by molding the film
WO2021241712A1 (en) * 2020-05-28 2021-12-02 三菱ケミカル株式会社 Biodegradable resin composition and biodegradable resin molded articles
JP2021191845A (en) * 2020-06-02 2021-12-16 三菱ケミカル株式会社 Biodegradable resin composition, and biodegradable resin molded body
WO2022039282A1 (en) * 2021-03-25 2022-02-24 株式会社Tbm Resin composition and molded article

Similar Documents

Publication Publication Date Title
JP5589377B2 (en) Resin composition, film, bag product, and method for producing resin composition
US8716373B2 (en) Biodegradable resin composition
US8722774B2 (en) Biodegradable resin composition
WO2013099770A1 (en) Polyester resin composition
JP5356593B2 (en) Molded body made of polyester resin composition
JP5200208B2 (en) Aliphatic aromatic polyester and resin composition
JP2002327107A (en) Polylactic acid-based film and method for producing the same
JP2011153296A (en) Biodegradable resin composition
JP4880851B2 (en) Method for reducing the water vapor permeability of a film or coating
JP2018021103A (en) Polyester resin composition, film obtained by molding the resin composition, and bag obtained by molding the film
JP5143374B2 (en) Biodegradable resin composition
JPH11241008A (en) Polylactate resin composition
JP2009155531A (en) Resin composition, preparation method, and film including the resin composition
EP4303266A1 (en) Biodegradable resin composition and molded product thereof
JP5167502B2 (en) Aliphatic aromatic polyester and resin composition thereof
WO2023171565A1 (en) Resin composition
JPH11241009A (en) Polylactate resin composition
WO2020202813A1 (en) Polyester resin composition, production method therefor, and molded body
WO2024024667A1 (en) Resin composition and molding method using resin composition
WO2024048402A1 (en) Resin composition containing biodegradable resin
JP7218650B2 (en) Polyester resin composition and molded article
JP5472502B2 (en) Film containing polyester resin composition
JPH09291164A (en) Biodegradable porous film
JP2007262422A (en) Biodegradable resin composition
JP5218724B2 (en) Film containing polyester resin composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23766741

Country of ref document: EP

Kind code of ref document: A1