WO2011158884A1 - Composition d'acide polylactique, et article moulé formé à partir de cette composition - Google Patents

Composition d'acide polylactique, et article moulé formé à partir de cette composition Download PDF

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WO2011158884A1
WO2011158884A1 PCT/JP2011/063750 JP2011063750W WO2011158884A1 WO 2011158884 A1 WO2011158884 A1 WO 2011158884A1 JP 2011063750 W JP2011063750 W JP 2011063750W WO 2011158884 A1 WO2011158884 A1 WO 2011158884A1
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group
polylactic acid
carbon atoms
acid composition
acid
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PCT/JP2011/063750
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English (en)
Japanese (ja)
Inventor
竜司 野々川
顕通 小田
信一郎 庄司
俊介 兼松
淳一 石丸
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帝人株式会社
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Priority claimed from JP2010135096A external-priority patent/JP6059417B2/ja
Priority claimed from JP2010136130A external-priority patent/JP6087487B2/ja
Priority claimed from JP2010136128A external-priority patent/JP6087486B2/ja
Priority claimed from JP2010136129A external-priority patent/JP2012001594A/ja
Priority claimed from JP2010137328A external-priority patent/JP2012001620A/ja
Application filed by 帝人株式会社 filed Critical 帝人株式会社
Publication of WO2011158884A1 publication Critical patent/WO2011158884A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds

Definitions

  • the present invention relates to a polylactic acid composition, and more specifically, it is composed of a polylactic acid component and an ⁇ -hydroxycarboxylic acid component other than lactic acid, and has good heat resistance and moldability and is suitable for industrial production.
  • the present invention relates to a polylactic acid composition and fibers, films, and resin molded articles comprising the same.
  • biodegradable polymers that are decomposed in a natural environment have attracted attention and are being studied all over the world.
  • aliphatic polyesters such as polylactic acid, polyhydroxybutyrate and polycaprolactone are known.
  • Polylactic acid is a polymer material that has high biological safety and is environmentally friendly because it uses lactic acid or its derivatives obtained from biological raw materials as raw materials. Therefore, the use as a general-purpose polymer is examined, and the use as a stretched film, a fiber, an injection molded product, etc. is examined.
  • polylactic acid has a low glass transition point of 58 ° C.
  • a method of adding a crystallization accelerating agent such as a crystallization nucleating agent for example, Patent Document 1
  • a method in which a phosphoric acid ester metal salt of a crystallization nucleating agent and a fatty acid amide are used in combination.
  • stereocomplex polylactic acid is formed by mixing (Patent Document 4).
  • This stereocomplex polylactic acid has a crystal melting temperature of 200 to 230 ° C., a higher melting point than PLLA and PDLA, and an interesting phenomenon showing high crystallinity has been discovered.
  • formation of stereocomplex polylactic acid is not easy, and the difficulty becomes even more pronounced especially when the weight average molecular weight of PLLA or PDLA exceeds 150,000 (Patent Document 4).
  • the stereocomplex polylactic acid usually does not show a single phase, but a PLLA phase and a PDLA phase (hereinafter sometimes referred to as a homo phase) and a polylactic acid stereocomplex phase (hereinafter sometimes referred to as a complex phase).
  • the mixed phase composition becomes.
  • a carbodiimide compound to polylactic acid and use it as a carboxyl group-terminal sealing agent to suppress hydrolysis of polylactic acid (for example, Patent Document 5).
  • the carbodiimide compound used in this proposal is a linear carbodiimide compound.
  • An object of the present invention is to provide a polylactic acid composition suitable for industrial production, which has excellent molding processability, improves hydrolysis resistance, and does not generate free isocyanate during the process. is there. It is another object of the present invention to provide a polylactic acid composition containing stereocomplex polylactic acid and having the above properties and excellent heat resistance. Means for Solving the Problems The inventors of the present invention have completed the present invention as a result of intensive studies in order to solve the above problems. That is, the object of the present invention is to 1.
  • a polylactic acid composition comprising a polylactic acid (A) component as a main component, wherein the polylactic acid (A) component is 95 wt% or more and 99.99 wt% or less, and ⁇ - other than lactic acid based on the resin composition.
  • the hydroxycarboxylic acid (B) component is 0.01% by weight or more and 5% by weight or less, and the carbodiimide compound (C) represented by the following structural formula is added to 100 parts by weight of the total amount of the component (A) and the component (B). This is achieved by a polylactic acid composition containing 0.01 to 10 parts by weight.
  • Q represents an aliphatic group, an alicyclic group, an aromatic group, or a divalent to tetravalent linking group that is a combination thereof.
  • this invention includes the following. 2.
  • 2. The polylactic acid composition according to 1 above, wherein the ⁇ -hydroxycarboxylic acid (B) component other than lactic acid is a component derived from a compound represented by the following structural formula.
  • R ′ represents a hydrogen atom or an aliphatic alkyl group.
  • 3. The polylactic acid composition according to 1 above, comprising a poly L-lactic acid component and a poly D-lactic acid component as the polylactic acid (A) component. 4). 4.
  • R 1 and R 2 are each Independently, an aliphatic group having 1 to 20 carbon atoms having 2 to 4 carbon atoms, an alicyclic group having 3 to 20 carbon atoms having 2 to 4 carbon atoms, a combination thereof, or these aliphatic groups, alicyclic groups and 2 It is a combination of a tetravalent aromatic group having 5 to 15 carbon atoms and may contain a hetero atom or a substituent, and X 1 and X 2 are each independently a divalent to tetravalent carbon number 1 to 20 An aliphatic group, a divalent to tetravalent alicyclic group having 3 to 20 carbon atoms, a divalent to tetravalent aromatic group having 5 to 15 carbon atoms, or a combination thereof, including a heteroatom and a substituent the Idei good .s can be an integer from 0 to 10 .k is an integer of 0 to 10.
  • X 1 as repeating units Or X 2 is other X 1 or may .
  • X 3 be different from X 2, is a divalent to tetravalent aliphatic group having 1 to 20 carbon atoms, a divalent to tetravalent carbon atoms 3-20 It is an alicyclic group, a divalent to tetravalent aromatic group having 5 to 15 carbon atoms, or a combination thereof, and may contain a hetero atom or a substituent, and Q is a divalent linking group.
  • Q a is a divalent linking group that is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may contain a hetero atom or a substituent.
  • Q a is represented by the following formula (2-1), (2-2) or the polylactic acid composition according to the above 7 is a divalent linking group represented by (2-3).
  • Ar a 1 , Ar a 2 , R a 1 , R a 2 , X a 1 , X a 2 , X a 3 , s and k are respectively represented by the formulas (1-1) to (1-3).
  • R q and R r each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • X a 1 is an alkylene group having 1 to 20 carbon atoms.
  • C carbodiimide compound
  • Q b is a trivalent linking group which is an aliphatic group, an alicyclic group, an aromatic group or a combination thereof, and may contain a hetero atom or a substituent.
  • Y is cyclic.
  • Q b is represented by the following formula (3-1), (3-2) or the polylactic acid composition according to the above 11 which is a trivalent linking group represented by (3-3).
  • Ar b 1 , Ar b 2 , R b 1 , R b 2 , X b 1 , X b 2 , X b 3 , s and k are represented by the formulas (1-1) to (1-3), respectively.
  • Ar 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 , X 3 , s and k are represented by the formulas (1-1) to (1-3), respectively.
  • Ar 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 , X 3 , s and k are represented by the formulas (1-1) to (1-3), respectively.
  • Ar 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 , X 3 , s and k with one of these
  • Q c is a tetravalent linking group which is an aliphatic group, an aromatic group, an alicyclic group or a combination thereof, and may contain a hetero atom or a substituent.
  • Z 1 and Z 2 is a carrier carrying a ring structure.
  • Q c is a tetravalent linking group represented by the following formula (4-1), (4-2), or (4-3).
  • Ar c 1 , Ar c 2 , R c 1 , R c 2 , X c 1 , X c 2 , X c 3 , s and k are represented by the formulas (1-1) to (1-3), respectively.
  • Ar 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 , X 3 , s and k are represented by the formulas (1-1) to (1-3), respectively.
  • Ar 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 , X 3 , s and k are represented by the formulas (1-1) to (1-3), respectively.
  • Z 1 and Z 2 are each independently a single bond, a double bond, an atom, an atomic group or a polymer.
  • R q , R r , R s and R t are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. .) 19.
  • 20. A structure including at least the molded body according to claim 19. Effect of the Invention According to the present invention, a polylactic acid composition suitable for industrial production is provided, which has excellent molding processability, improves hydrolysis resistance, and does not generate free isocyanate during the process. can do.
  • the end of the polymer compound is sealed with the cyclic carbodiimide compound, an isocyanate group is formed at the end of the polymer compound, and the polymer compound can have a high molecular weight by the reaction of the isocyanate group.
  • the cyclic carbodiimide compound also has an action of capturing a free monomer or other compound having an acidic group in the polymer compound.
  • the cyclic carbodiimide compound since the cyclic carbodiimide compound has a cyclic structure, the cyclic carbodiimide compound has an advantage that it can be end-capped under milder conditions than the linear carbodiimide compound.
  • the difference between the linear carbodiimide compound and the cyclic carbodiimide compound in the end-capping reaction mechanism is as described below.
  • a linear carbodiimide compound (R 1 —N ⁇ C ⁇ N—R 2 ) is used as an end-capping agent for a polymer compound having a carboxy group terminal
  • the reaction is represented by the following formula.
  • W is the main chain of the polymer compound.
  • a cyclic carbodiimide compound when used as a terminal blocking agent for a polymer compound having a carboxy group terminal, the reaction is represented by the following formula. It can be seen that when the cyclic carbodiimide compound reacts with a carboxy group, an isocyanate group (—NCO) is formed at the terminal of the polymer compound via an amide group, and the isocyanate compound is not liberated.
  • —NCO isocyanate group
  • Q is a divalent to tetravalent linking group which is an aliphatic group, alicyclic group, aromatic group or a combination thereof, and may contain a hetero atom or a substituent.
  • Q is a divalent to tetravalent linking group which is an aliphatic group, alicyclic group, aromatic group or a combination thereof, and may contain a hetero atom or a substituent.
  • the polylactic acid composition of the present invention is a polylactic acid composition mainly comprising a polylactic acid (A) component, and the polylactic acid (A) component is 95 wt% or more and 99.99 based on the resin composition.
  • ⁇ -hydroxycarboxylic acid (B) component other than lactic acid is 0.01 wt% or more and 5 wt% or less
  • carbodiimide compound (C) represented by the following structural formula, (A) component and (B) This is achieved by including 0.01 to 10 parts by weight per 100 parts by weight in total with the components.
  • the polylactic acid composition of the present invention is excellent in heat resistance and molding processability, which are the objects of the present invention, and can be suitably produced industrially by adopting such a composition.
  • each component in the polylactic acid composition of the present invention will be described.
  • the polylactic acid (A) component of the present invention may be a poly L-lactic acid component or a poly D-lactic acid component.
  • each of the poly L-lactic acid and poly D-lactic acid was measured by differential scanning calorimetry (DSC), and the crystal melting peak (Tm) between 150 ° C. and 190 ° C. h ), Having a glass transition point (Tg) of 60 ° C. or higher, and the heat of crystal melting ( ⁇ Hm).
  • sc Is preferably 10 J / g or more. This is because the heat resistance of the polylactic acid (A) can be suitably enhanced by satisfying the ranges of the crystal melting point and the heat of crystal fusion.
  • stereocomplex polylactic acid composed of poly L lactic acid and poly D lactic acid is also included from the viewpoint of heat resistance.
  • the polylactic acid used here is a poly-L-lactic acid copolymer having a poly-L-lactic acid component of 95% by weight or more and an ⁇ -hydroxycarboxylic acid component other than lactic acid described later of 5% by weight or less, and a poly-D-lactic acid.
  • a stereocomplex polylactic acid is prepared by mixing 95% by weight or more of the component with a poly D-lactic acid copolymer containing 5% by weight or less of an ⁇ -hydroxycarboxylic acid component other than lactic acid, which will be described later.
  • the stereocomplex crystallinity defined in i) is preferably selected in the range of 90% to 100%, more preferably 95% to 100%. Particularly preferred is when the stereocomplex crystallinity is 100%.
  • the crystal melting point of the stereocomplex phase polylactic acid is suitably selected in the range of 190 to 250 ° C., more preferably 200 to 230 ° C., and the crystal melting enthalpy by DSC measurement is 20 J / g or more, preferably A range of 20 to 80 J / g, more preferably 30 to 80 J / g is selected. If the crystal melting point of the stereocomplex phase polylactic acid is less than 190 ° C., the significance of the formation of the stereocomplex phase, and thus the significance of the present invention will be small.
  • the weight ratio of the poly L-lactic acid component to the poly D-lactic acid component Is preferably 90/10 to 10/90.
  • the poly-D-lactic acid component is represented by the following formula (iv), and is composed of D-lactic acid units, preferably 90 to 100 mol% D-lactic acid units and 0 to 10 mol% D-. Consists of copolymer units other than lactic acid units. A range of 95 to 100 mol% is more preferable, and a range of 98 to 100 mol% is more preferable.
  • the poly L-lactic acid component is represented by the following formula (iv), and is composed of L-lactic acid units, preferably 90 to 100 mol% L-lactic acid units and 0 to 10 mol% L-lactic acid units. It consists of copolymerized units other than. A range of 95 to 100 mol% is more preferable, and a range of 98 to 100 mol% is more preferable.
  • the copolymer unit is composed of units derived from dicarboxylic acid, polyhydric alcohol, lactone and the like having a functional group capable of forming two or more ester bonds and these various constituent components.
  • Units derived from various polyesters, various polyethers, various polycarbonates and the like are exemplified.
  • the dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid.
  • the polyhydric alcohol include aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol.
  • the weight average molecular weights of the poly L-lactic acid and poly D-lactic acid components of the present invention are preferably 100,000 to 500,000, more preferably 110,000, in order to achieve both the mechanical properties and moldability of the molded product of the present invention. A range of 350,000, more preferably 120,000 to 250,000 is selected.
  • Poly L-lactic acid and poly D-lactic acid can be produced by a conventionally known method.
  • the low molecular weight polylactic acid containing a metal-containing catalyst is optionally crystallized or without crystallization, under reduced pressure or from normal pressure to increased pressure, in the presence or absence of an inert gas stream. It can also be produced by solid phase polymerization. Furthermore, it can be produced by a direct polymerization method in which lactic acid is subjected to dehydration condensation in the presence or absence of an organic solvent. The polymerization reaction can be carried out in a conventionally known reaction vessel.
  • a vertical reactor or a horizontal reactor equipped with a stirring blade for high viscosity such as a helical ribbon blade, is used alone, or Can be used in parallel.
  • a stirring blade for high viscosity such as a helical ribbon blade
  • any of a batch type, a continuous type, a semibatch type may be sufficient, and these may be combined.
  • Alcohol may be used as a polymerization initiator.
  • Such alcohol is preferably non-volatile without inhibiting the polymerization of polylactic acid, such as decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, ethylene glycol, trimethylolpropane, pentaerythritol, etc. Can be suitably used. It can be said that the polylactic acid prepolymer used in the solid phase polymerization method is preferably crystallized in advance from the viewpoint of preventing pellet fusion.
  • the prepolymer is polymerized in a solid state in a fixed vertical or horizontal reaction vessel, or in a reaction vessel (such as a rotary kiln) in which the vessel itself rotates, such as a tumbler or kiln, in the temperature range above the glass transition temperature of the prepolymer and below the melting point. Is done. If it is above the glass transition temperature, the degree of polymerization will be improved. On the other hand, when the melting point is exceeded, the composition does not maintain a solid phase, the melt viscosity becomes too high as the molecular weight increases, and a composition having a high degree of polymerization cannot be obtained.
  • the shape of the polylactic acid composition containing the cyclic carbodiimide compound is not particularly limited, and any of a lump, a film, a pellet, and a powder may be used. From the viewpoint of efficiently improving the degree of polymerization in the heat treatment in, it is preferable to use pellets or powder.
  • a method for making pellets there are a method of making a polylactic acid composition containing a cyclic carbodiimide compound into a molten state, extruding it into a strand shape, pelletizing with a strand cutter, a method of making it molten and then extruding it into water and cutting it. Can be mentioned.
  • pulverizing using grinders such as a mixer, a blender, a ball mill, a hammer mill, etc. are mentioned.
  • the method for performing the heat treatment step in the solid phase is not particularly limited, and may be a batch method or a continuous method.
  • the reaction vessel is a stirred tank reactor, a mixer reactor, or a column reactor. These reactors can be used alone or in combination of two or more.
  • the polylactic acid composition containing the cyclic carbodiimide compound is crystallized.
  • the method for crystallization is not particularly limited, and a known method can be used.
  • a method of holding at a crystallization temperature in a gas phase or a liquid phase a method of volatilizing a solvent from a polylactic acid composition containing a cyclic carbodiimide compound, and a polyester resin composition containing a cyclic carbodiimide compound are melted and stretched
  • a method of cooling and solidifying while performing a shearing operation is exemplified, and from the viewpoint that the operation is simple, a method of holding at a crystallization temperature in a gas phase or a liquid phase is preferable.
  • the crystallization temperature here is not particularly limited as long as it is higher than the glass transition temperature and lower than the melting point, but it is a temperature rising crystallization temperature measured in advance by a differential scanning calorimeter (DSC). It is more preferable that the temperature falls within the range of the cooling crystallization temperature.
  • DSC differential scanning calorimeter
  • any of reduced pressure, normal pressure, and increased pressure may be used.
  • the time for crystallization is not particularly limited.
  • the temperature condition for carrying out this heat treatment step is not particularly limited as long as the degree of polymerization is improved as long as it is less than the melting point of the polylactic acid composition containing the cyclic carbodiimide compound, but usually polylactic acid (component A) If it is more than the glass transition temperature, the degree of polymerization can be improved without any problem. Moreover, in order to shorten heat processing time, you may raise temperature in steps with progress of reaction. Further, when this heat treatment step is carried out, it is preferably carried out under a vacuum or an inert gas stream such as dry nitrogen. In particular, for the purpose of removing the residual monomer contained in the polylactic acid, it is preferable to perform a heat treatment under a vacuum or a dry nitrogen stream.
  • Metal-containing catalysts include alkali metals, alkaline earth metals, rare earths, transition metals, fatty acid salts such as aluminum, germanium, tin, antimony, titanium, carbonates, sulfates, phosphates, oxides, hydroxides , Halides, alcoholates and the like.
  • fatty acid salts, carbonates, sulfates, phosphates, oxides, hydroxides containing at least one metal selected from tin, aluminum, zinc, calcium, titanium, germanium, manganese, magnesium and rare earth elements Products, halides, and alcoholates are preferred.
  • Tin compounds due to low catalytic activity and side reactions specifically stannous chloride, stannous bromide, stannous iodide, stannous sulfate, stannic oxide, tin myristate, tin octylate Tin-containing compounds such as tin stearate and tetraphenyltin are exemplified as preferred catalysts.
  • tin (II) compounds specifically, diethoxytin, dinonyloxytin, tin (II) myristate, tin (II) octylate, tin (II) stearate, tin (II) chloride and the like are suitable. Illustrated.
  • the amount of catalyst used is 0.42 x 10 per kg of lactide -4 To 100 ⁇ 10 -4 (Mole) and further considering the reactivity, color tone and stability of the resulting polylactides, 1.68 ⁇ 10 -4 To 42.1 ⁇ 10 -4 (Mole), particularly preferably 2.53 ⁇ 10 -4 To 16.8 ⁇ 10 -4 (Mol) range.
  • the metal-containing catalyst used in the polylactic acid polymerization is preferably deactivated with a conventionally known deactivator prior to the use of polylactic acid (application to polylactic acid spinning, film formation, molding, etc.).
  • a deactivator include an organic ligand consisting of a group of chelate ligands having an imino group and capable of coordinating to a polymerized metal catalyst, dihydridooxoline (I) acid, dihydridotetraoxodilin (II, II) Acid, hydridotrioxoline (III) acid, dihydridopentaoxodiphosphorus (III) acid, hydridopentaoxodi (II, IV) acid, dodecaoxohexaphosphorus (III) acid, hydridooctaoxotriphosphate (III, IV, IV) acid, octaoxotriphosphoric acid (IV, III, IV), hydrido
  • the metaphosphoric acid compound used in the present invention is a cyclic metaphosphoric acid in which about 3 to 200 phosphoric acid units are condensed, an ultra-regional metaphosphoric acid having a three-dimensional network structure, or their (alkal metal salt, alkaline earth metal salt, Onium salts).
  • cyclic sodium metaphosphate, ultra-region sodium metaphosphate, phosphono-substituted lower aliphatic carboxylic acid derivative dihexylphosphonoethyl acetate (hereinafter sometimes abbreviated as DHPA) and the like are preferably used.
  • the ⁇ -hydroxycarboxylic acid (B) component other than lactic acid of the present invention is a component derived from a compound in which R ′ is hydrogen or an aliphatic alkyl group, as shown by the following formula. (Wherein R 'represents a hydrogen atom or an aliphatic alkyl group.)
  • “derived component” means that an ⁇ -hydroxycarboxylic acid compound other than lactic acid represented by the above formula can be introduced into polylactic acid as a repeating unit.
  • the ⁇ -hydroxycarboxylic acid (B) component other than lactic acid is contained in an amount of 0.01 to 5% by weight per 100% by weight of the polylactic acid composition.
  • the content is selected in the range of preferably 0.01 to 5% by weight, more preferably 0.01 to 4% by weight, particularly preferably 0.02 to 3% by weight.
  • ⁇ -hydroxycarboxylic acid (B) component other than lactic acid examples include a glycolic acid component, a 2-hydroxybutyric acid component, a 2-hydroxyvaleric acid component, a 2-hydroxyisovaleric acid component, and 2-hydroxy-4.
  • examples thereof include ⁇ -hydroxycarboxylic acid components (B) other than lactic acid, wherein R ′ in the above formula is an aliphatic group, such as a methyl-valeric acid component.
  • the number of carbon atoms of the aliphatic group is preferably in the range of 1 to 20, more preferably in the range of 1 to 10, and particularly preferably in the range of 2 to 5. .
  • the ⁇ -hydroxylcarboxylic acid other than these lactic acids is produced from a cyclic dimer containing these components in the production of the aforementioned poly L-lactic acid and poly D-lactic acid.
  • a cyclic dimer containing these components in the production of the aforementioned poly L-lactic acid and poly D-lactic acid.
  • 2-hydroxybutyric acid cyclic dimer, 2-hydroxyvaleric acid cyclic dimer, 2-hydroxyisovaleric acid cyclic dimer, 2-hydroxy-4-methyl-valeric acid In addition to the cyclic dimer, a combination in which one of these components is different, or a cyclic dimer of 2-hydroxybutyric acid and lactic acid, one of which is composed of lactic acid, can be used.
  • ⁇ / RTI> By using such starting materials, the glass transition point is improved, the thermal decomposability is lowered, the moldability and the dyeability are improved.
  • ⁇ Carbodiimide compound (C)> In order to achieve the object of the present invention, it is necessary to contain a carbodiimide compound (C) described later in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the total amount of the component (A) and the component (B). is there. If the content is less than 0.01 parts by weight, the effect of adding a carbodiimide compound cannot be obtained as expected, while if it exceeds 10 parts by weight, no further effect of addition can be obtained.
  • the content is preferably selected in the range of 0.01 to 5 parts by weight, more preferably 0.01 to 4 parts by weight, particularly preferably 0.02 to 3 parts by weight.
  • the cyclic carbodiimide compound used as the carbodiimide compound (C) has a cyclic structure.
  • the cyclic carbodiimide compound may have a plurality of cyclic structures.
  • the cyclic structure has one carbodiimide group (—N ⁇ C ⁇ N—), and the first nitrogen and the second nitrogen are bonded by a bonding group.
  • One cyclic structure has only one carbodiimide group.
  • the compound when there are a plurality of cyclic structures in the molecule, such as a spiro ring, one cyclic structure bonded to a spiro atom is included in each cyclic structure.
  • the compound may have a plurality of carbodiimide groups as long as it has a carbodiimide group.
  • the number of atoms in the cyclic structure is preferably 8 to 50, more preferably 10 to 30, further preferably 10 to 20, and particularly preferably 10 to 15.
  • the number of atoms in the ring structure means the number of atoms directly constituting the ring structure, for example, 8 for a 8-membered ring and 50 for a 50-membered ring.
  • the number of atoms in the cyclic structure is smaller than 8, the stability of the cyclic carbodiimide compound is lowered, and it may be difficult to store and use. From the viewpoint of reactivity, there is no particular restriction on the upper limit of the number of ring members, but cyclic carbodiimide compounds having more than 50 atoms are difficult to synthesize, and the cost may increase significantly. From this viewpoint, the number of atoms in the cyclic structure is preferably 10 to 30, more preferably 10 to 20, and particularly preferably 10 to 15. The molecular weight of the cyclic carbodiimide compound is preferably 100 to 1,000. If it is lower than 100, the structural stability and volatility of the cyclic carbodiimide compound may be problematic.
  • the ring structure is a structure represented by the following formula.
  • Q is a divalent to tetravalent linking group that is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may contain a hetero atom or a substituent. Two of the valences of this linking group are used to form a cyclic structure.
  • Q is a trivalent or tetravalent linking group, it is bonded to a polymer or other cyclic structure via a single bond, a double bond, an atom, or an atomic group.
  • the linking group is an aliphatic group having 1 to 20 carbon atoms having 2 to 4 carbon atoms, an alicyclic group having 3 to 20 carbon atoms having 2 to 4 carbon atoms, an aromatic group having 5 to 15 carbon atoms having 2 to 4 carbon atoms, or A combination of these is preferred.
  • the linking group one having the necessary number of carbon atoms for forming a cyclic structure is selected. Examples of combinations include structures such as an alkylene-arylene group in which an alkylene group and an arylene group are bonded.
  • the aliphatic group, alicyclic group, and aromatic group constituting the linking group may each include a hetero atom and a substituent.
  • a hetero atom refers to O, N, S, P.
  • the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
  • examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.
  • the linking group (Q) is preferably a divalent to tetravalent linking group represented by the following formula (1-1), (1-2) or (1-3).
  • Ar 1 And Ar 2 are each independently a divalent to tetravalent aromatic group having 5 to 15 carbon atoms, and may contain a heteroatom or a substituent.
  • the aromatic group include an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, and an arenetetrayl group having 5 to 15 carbon atoms.
  • the arylene group (divalent) include a phenylene group and a naphthalenediyl group.
  • Examples of the arenetriyl group include a benzenetriyl group and a naphthalenetriyl group.
  • Examples of the arenetetrayl group include a benzenetetrayl group and a naphthalenetetrayl group.
  • These aromatic groups may be substituted.
  • Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group. These aromatic groups may contain a hetero atom and have a heterocyclic structure.
  • Heteroatoms include O, N, S, and P.
  • R 1 And R 2 are each independently an aliphatic group having 1 to 20 carbon atoms having 2 to 4 carbon atoms, an alicyclic group having 2 to 4 carbon atoms having 3 to 20 carbon atoms, and combinations thereof, or these aliphatic groups and alicyclic Group and a divalent to tetravalent aromatic group having 5 to 15 carbon atoms, and may contain a hetero atom or a substituent.
  • the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms.
  • alkylene group examples include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group.
  • alkanetriyl group methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group
  • alkanetriyl group methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group.
  • Examples include a hexadecantriyl group.
  • alkanetetrayl group methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like.
  • These aliphatic groups may be substituted.
  • substituents examples include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
  • these aliphatic groups may contain a hetero atom. Heteroatoms include O, N, S, and P.
  • the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms.
  • Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group.
  • alkanetriyl group cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group , Cyclododecanetriyl group, cyclohexadecanetriyl group and the like.
  • alkanetetrayl group cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like.
  • These alicyclic groups may be substituted.
  • substituents examples include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
  • these alicyclic groups may include a hetero atom and have a heterocyclic structure.
  • Heteroatoms include O, N, S, and P.
  • aromatic group examples include an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, and an arenetetrayl group having 5 to 15 carbon atoms.
  • Examples of the arylene group include a phenylene group and a naphthalenediyl group.
  • examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group.
  • examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted.
  • substituents examples include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
  • aromatic groups may contain a hetero atom and have a heterocyclic structure. Heteroatoms include O, N, S, and P.
  • X 1 And X 2 are each independently an aliphatic group having 1 to 20 carbon atoms having 2 to 4 carbon atoms, an alicyclic group having 3 to 20 carbon atoms having 2 to 4 carbon atoms, and an aromatic group having 5 to 15 carbon atoms having 2 to 4 carbon atoms. Or a combination thereof, and may contain a heteroatom or a substituent.
  • the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms.
  • alkylene group examples include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group.
  • alkanetriyl group methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group
  • alkanetriyl group methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group.
  • Examples include a hexadecantriyl group.
  • alkanetetrayl group methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like.
  • These aliphatic groups may be substituted.
  • substituents examples include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
  • these aliphatic groups may contain a hetero atom. Heteroatoms include O, N, S, and P.
  • the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms.
  • Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group.
  • alkanetriyl group cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group , Cyclododecanetriyl group, cyclohexadecanetriyl group and the like.
  • alkanetetrayl group cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like.
  • These alicyclic groups may be substituted.
  • substituents examples include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
  • these alicyclic groups may include a hetero atom and have a heterocyclic structure.
  • Heteroatoms include O, N, S, and P.
  • aromatic group examples include an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, and an arenetetrayl group having 5 to 15 carbon atoms.
  • Examples of the arylene group include a phenylene group and a naphthalenediyl group.
  • examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group.
  • examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted.
  • substituents examples include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
  • aromatic groups may include a hetero atom and have a heterocyclic structure.
  • Heteroatoms include O, N, S, and P.
  • S and k are each independently an integer of 0 to 10, preferably an integer of 0 to 3, more preferably an integer of 0 to 1. When s and k exceed 10, the cyclic carbodiimide compound is difficult to synthesize, and the cost may increase significantly.
  • the integer is preferably selected in the range of 0 to 3.
  • X as a repeating unit 1 Or X 2 But other X 1 Or X 2 And may be different.
  • X 3 Is a divalent to tetravalent aliphatic group having 1 to 20 carbon atoms, 2 to 4 valent aliphatic groups having 3 to 20 carbon atoms, 2 to 4 valent aromatic groups having 5 to 15 carbon atoms, or these And may contain a heteroatom and a substituent.
  • Examples of the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms.
  • Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group.
  • alkanetriyl group methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group
  • alkanetriyl group methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group.
  • Examples include a hexadecantriyl group.
  • alkanetetrayl group methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like.
  • These aliphatic groups may contain a substituent, such as an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, or an ester group. , Ether group, aldehyde group and the like.
  • these aliphatic groups may contain a hetero atom. Heteroatoms include O, N, S, and P.
  • Examples of the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms.
  • Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group.
  • alkanetriyl group cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group , Cyclododecanetriyl group, cyclohexadecanetriyl group and the like.
  • alkanetetrayl group cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like.
  • These alicyclic groups may contain a substituent, such as an alkyl group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester. Group, ether group, aldehyde group and the like.
  • these alicyclic groups may include a hetero atom and have a heterocyclic structure. Heteroatoms include O, N, S, and P.
  • Examples of the aromatic group include an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, and an arenetetrayl group having 5 to 15 carbon atoms.
  • Examples of the arylene group include a phenylene group and a naphthalenediyl group.
  • examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group.
  • examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted.
  • substituents examples include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
  • aromatic groups may include a hetero atom and have a heterocyclic structure. Heteroatoms include O, N, S, and P.
  • Ar 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 And X 3 May contain heteroatoms.
  • Examples of the cyclic carbodiimide used in the present invention include a compound represented by the following formula (2) (hereinafter sometimes referred to as “cyclic carbodiimide (a)”).
  • Q a Is a divalent linking group which is an aliphatic group, an alicyclic group, an aromatic group or a combination thereof, and may contain a hetero atom or a substituent.
  • the aliphatic group, alicyclic group, and aromatic group are the same as those described in Formula (1).
  • the aliphatic group, alicyclic group, and aromatic group are all divalent.
  • Q a Is preferably a divalent linking group represented by the following formula (2-1), (2-2) or (2-3).
  • Ar a 1 , Ar a 2 , R a 1 , R a 2 , X a 1 , X a 2 , X a 3 , S and k are each Ar in the formulas (1-1) to (1-3) 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 , X 3 , S and k.
  • these are all divalent.
  • the cyclic carbodiimide (a) a compound represented by the following formula (2-1-1) is preferable.
  • X in the formula a 1 Is preferably an alkylene group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.
  • the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group.
  • Ar a 1 , Ar a 2 Each independently represents an optionally substituted arylene group having 5 to 15 carbon atoms.
  • the arylene group include a phenylene group and a naphthalenediyl group. The arylene group may be substituted.
  • the substituent include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms.
  • substituents examples include a methyl group, an ethyl group, and a propyl group.
  • a a compound represented by the following formula (2-1-1a) is preferable.
  • X in the formula a 1 Is preferably an alkylene group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 4 carbon atoms.
  • alkylene group include a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group.
  • R q , R r are each independently preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.
  • alkyl group include a methyl group, an ethyl group, and a propyl group.
  • the cyclic carbodiimide compound (a) include the following compounds. ⁇ Cyclic carbodiimide (b)>
  • examples of the cyclic carbodiimide used in the present invention include a compound represented by the following formula (3) (hereinafter sometimes referred to as “cyclic carbodiimide (b)”).
  • Q b Is a trivalent linking group which is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may contain a hetero atom or a substituent.
  • Y is a carrier supporting a cyclic structure.
  • the aliphatic group, alicyclic group, and aromatic group are the same as those described in Formula (1).
  • Q b One of the groups constituting is trivalent.
  • Ar b 1 , Ar b 2 , R b 1 , R b 2 , X b 1 , X b 2 , X b 3 , S and k are each Ar in the formulas (1-1) to (1-3) 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 , X 3 , S and k.
  • Y is preferably a single bond, a double bond, an atom, an atomic group or a polymer.
  • Y is a bonding portion, and a plurality of cyclic structures are bonded via Y to form a structure represented by the formula (3).
  • Examples of the cyclic carbodiimide compound (b) include the following compounds.
  • Examples of the cyclic carbodiimide used in the present invention include a compound represented by the following formula (4) (hereinafter sometimes referred to as “cyclic carbodiimide (c)”).
  • Q c Is a tetravalent linking group which is an aliphatic group, an alicyclic group, an aromatic group or a combination thereof, and may contain a hetero atom or a substituent.
  • Z 1 And Z 2 Is a carrier carrying a ring structure.
  • Z 1 And Z 2 May be bonded to each other to form a cyclic structure.
  • the aliphatic group, alicyclic group, and aromatic group are the same as those described in Formula (1).
  • Q c Is tetravalent Accordingly, one of these groups is a tetravalent group or two are trivalent groups.
  • Ar c 1 , Ar c 2 , R c 1 , R c 2 , X c 1 , X c 2 , X c 3 , S and k are each Ar in the formulas (1-1) to (1-3) 1 , Ar 2 , R 1 , R 2 , X 1 , X 2 , X 3 , S and k.
  • One of these is a tetravalent group, or two are trivalent groups.
  • Z 1 And Z 2 are each independently preferably a single bond, a double bond, an atom, an atomic group or a polymer.
  • Z 1 And Z 2 Is a connecting portion, and a plurality of cyclic structures are Z 1 And Z 2 To form a structure represented by the formula (4).
  • a compound represented by the following formula (4-1-1) is preferable.
  • X in the formula c 1 Is preferably an alkanetetrayl group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 6 carbon atoms.
  • alkanetetrayl group examples include an isobutanetetrayl group, an isopentanetetrayl group, and a neopentanetetrayl group.
  • a neopentanetetrayl group represented by the following formula is preferred.
  • Ar c 1 , Ar c 2 , Ar c 3 , Ar c 4 Is an arylene group having 5 to 15 carbon atoms which may be independently substituted.
  • the arylene group examples include a phenylene group and a naphthalenediyl group. The arylene group may be substituted.
  • substituent examples include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms.
  • Examples of the substituent include a methyl group, an ethyl group, and a propyl group.
  • a compound represented by the following formula (2-1-1c) is preferable.
  • X in the formula c 1 Is preferably an alkanetetrayl group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 6 carbon atoms.
  • Examples of the alkanetetrayl group include an isobutanetetrayl group, an isopentanetetrayl group, and a neopentanetetrayl group.
  • a neopentanetetrayl group represented by the following formula is preferred.
  • R q , R r , R s , R t Each independently represents an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.
  • the alkyl group include a methyl group, an ethyl group, and a propyl group.
  • the cyclic carbodiimide compound (c) include the following compounds. ⁇ Method for producing cyclic carbodiimide compound> In the present invention, the production method of the cyclic carbodiimide compound is not particularly limited, and can be produced by a conventionally known method.
  • a method for producing an amine body via an isocyanate body for example, a method for producing an amine body via an isothiocyanate body, a method for producing an amine body via a triphenylphosphine body, a urea body from an amine body
  • the method of manufacturing via a thiourea body, the method of manufacturing via a thiourea body, the method of manufacturing from a carboxylic acid body via an isocyanate body, the method of manufacturing a lactam body, etc. are mentioned.
  • the cyclic carbodiimide compound of the present invention can be produced by combining the methods described in the following documents, or by appropriately modifying and combining them according to the target compound.
  • Ar 1 And Ar 2 are each independently an aromatic group optionally substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group.
  • E 1 And E 2 are each independently a group selected from the group consisting of a halogen atom, a toluenesulfonyloxy group, a methanesulfonyloxy group, a benzenesulfonyloxy group, and a p-bromobenzenesulfonyloxy group.
  • Ar a Is a phenyl group.
  • X is a linking group of the following formulas (i-1) to (i-3).
  • n is an integer of 1 to 6.
  • m and n are each independently an integer of 0 to 3.
  • R 1 And R 2 Each independently represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.
  • the polymer in a molten state is preferably in a melt-kneaded state.
  • the kneading operation can be carried out without dividing the melt-kneading following the addition and the process, which is advantageous from the viewpoint of the thermal history received by the polymer.
  • Polymer melt viscosity is 1 ⁇ 10 5 It is preferably Pa ⁇ s or less. If the melt viscosity is not within this range, the viscosity is too high and the melt-kneading operation itself may be difficult.
  • the polymer temperature at the time of melt-kneading, the shear rate at the time of melt-kneading, the molecular weight of the polymer, etc. may be appropriately set in order to make it within the range of the melt viscosity.
  • the time for the subsequent melt-kneading depends on the temperature of the melt-kneading and the kneading method, but usually it may be set between 0.1 minutes and 2 hours. If it is less than 0.1 minutes, uniform kneading may become difficult.
  • the preferred melt kneading time is preferably 0.1 to 30 minutes, more preferably 0.1 to 15 minutes, particularly preferably 0.1 to 10 minutes, and most preferably 0.1 to 5 minutes. is there.
  • the kneading apparatus is not particularly limited, and a conventionally known vertical reaction vessel, mixing tank, kneading tank, uniaxial or multiaxial horizontal kneading apparatus, or static mixer can be used. For example, a uniaxial or multiaxial ruder, kneader, Banbury mixer, pressure kneader, etc.
  • twin-screw extruder is preferable because of its good balance between the dispersibility of the cyclic carbodiimide compound and the discharge ability and self-cleaning property.
  • an addition method using a twin-screw extruder is taken up as a representative example in order to make it more clear and specific, but the present invention is not limited to this.
  • the twin screw extruder is not particularly limited as long as it has at least a first supply port for supplying a polymer and a second supply port for supplying a cyclic carbodiimide compound.
  • the length of the extruder is not particularly limited, but it needs to be long enough to melt the polymer supplied from the first supply port and knead and mix the cyclic carbodiimide compound supplied from the second supply port.
  • the second supply port only needs to be closer to the extruder outlet than the first supply port, and is not particularly limited, but it is important that the polymer is in a molten state.
  • the second supply port is preferably near the outlet.
  • the supply form of the polymer to the extruder there is no particular limitation on the supply form of the polymer to the extruder, and there are a method of directly supplying the molten polymer after polymerization and a method of supplying the polymer once in the form of chips.
  • the method for supplying the cyclic carbodiimide compound from the second supply port of the extruder is not particularly limited, and a known method can be used.
  • a method for directly feeding the cyclic carbodiimide compound metered by a weight or volume feeder, or a feeder for feeding the cyclic carbodiimide compound metered by a weight or volume feeder at the second supply port of the extruder, such as a side A method of supplying via a feeder is used.
  • the cyclic carbodiimide compound may be supplied in the form as it is, and may be supplied from the second supply port by the above-described method, or diluted in advance at a high concentration in the same type of resin or other additive to form an additive master batch pellet. After that, it may be supplied from the second supply port by the method described above.
  • a slurry (solution) prepared by dispersing (dissolving) the cyclic carbodiimide compound in a dispersion medium (solvent) in advance may be supplied from the second supply port.
  • the dispersion medium (solvent) those which are inert to the polymer and the cyclic carbodiimide compound can be used.
  • a solvent that has affinity for both and at least partially dissolves both is preferable.
  • the cyclic carbodiimide compound can be maintained in the molten state without being decomposed or thermally denatured, it may be added to the polymer in the molten state.
  • the dispersion medium (solvent) is applied in the range of 1 to 1,000 parts by weight per 100 parts by weight in total of the polymer and the cyclic carbodiimide compound. If it is less than 1 part by weight, there is no significance in applying the dispersion medium (solvent).
  • the upper limit of the amount of solvent used is not particularly limited, but is about 1,000 parts by weight from the viewpoints of operability and reaction efficiency.
  • a heat stabilizer is added to the polymer, it is possible to employ a technique in which the polymer is first heated and melted and mixed with the heat stabilizer and then heated and melted and mixed with the cyclic carbodiimide compound.
  • the kneading apparatus used for sequentially heating and melting and mixing the heat stabilizer and the cyclic carbodiimide compound with the polymer is not particularly limited, and a conventionally known vertical reaction vessel, mixing vessel, kneading vessel, or uniaxial Alternatively, a multi-axis horizontal kneader or a static mixer can be used. For example, a uniaxial or multiaxial ruder, kneader, Banbury mixer, pressure kneader, etc. are exemplified. Among these, it is preferable to melt and knead at a temperature of 200 to 300 ° C.
  • the polymer is first melt-mixed with a heat stabilizer to obtain a primary granulated composition and then melt-mixed with a cyclic carbodiimide compound, or an extruder is used.
  • a polymer having an acidic group and a heat stabilizer are supplied from the front part of the extruder, and then a cyclic carbodiimide compound is supplied from the middle part of the extruder to continue melting and kneading.
  • heat stabilizer examples include a phosphate ester having a pentaerythritol skeleton structure (or a cyclic neopentanetetrayl structure) and an alkyl (phosphite) having at least one hydroxyl group and at least one alkyl ester group. At least one compound selected from the group consisting of esters (for example, see International Publication WO 2004/087813 pamphlet) is preferably used. These heat stabilizers are blended in an amount of preferably 0.003 to 3 parts by weight, more preferably 0.005 to 1 part by weight, based on 100 parts by weight of the polymer.
  • a hopper for polymer charging is provided at the upper part, and a molding machine in which an outlet of an additive pipe for guiding a cyclic carbodiimide compound supplied from a quantitative charging machine is opened near the outlet at the lower part of the hopper, The cyclic carbodiimide compound quantitatively supplied from the additive pipe is supplied to the molding machine together with the polymer.
  • the place where the additive coming out of the additive pipe and the dried polymer are mixed is near the outlet of the hopper and immediately before the injection port of the molding machine.
  • the additive does not change in quality or discolor, and the function is not deteriorated.
  • the cyclic carbodiimide compound may be supplied in the form as it is, and supplied from the additive pipe by the above-mentioned method, or after diluting in advance at a high concentration in the same type of resin or other additive into an additive master batch pellet.
  • the above method may be used to supply from the additive pipe.
  • a slurry (solution) prepared by dispersing (dissolving) the cyclic carbodiimide compound in a dispersion medium (solvent) in advance may be supplied from the second supply port. Further, as long as the cyclic carbodiimide compound can be maintained in the molten state without being decomposed or thermally denatured, it may be added to the polymer in the molten state.
  • the polylactic acid (A) component is 95% by weight or more and 99.99% by weight or less based on the composition, and the ⁇ -hydroxycarboxylic acid (B) component other than lactic acid is 0.01%.
  • the carbodiimide compound (C) is contained in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the total amount of the components (A) and (B).
  • the polylactic acid (A) component and the ⁇ -hydroxycarboxylic acid (B) component other than lactic acid are as described above.
  • the polylactic acid composition of the present invention preferably has a lactide content of 1 to 5000 (wtppm).
  • the lactide contained in the polylactic acid composition deteriorates the polylactic acid composition and deteriorates the color tone at the time of melt processing, and may be rendered unusable as a product.
  • Poly L-lactic acid and / or poly D-lactic acid immediately after the melt ring-opening polymerization usually contains 1 to 5% by weight of lactide, but poly L-lactic acid and / or poly D-lactic acid is polymerized from the end of polymerization.
  • a conventionally known lactide weight loss method that is, a vacuum devolatilization method in a single-screw or multi-screw extruder, or a high vacuum treatment in a polymerization apparatus is used alone or in combination.
  • lactide can be reduced to a suitable range.
  • Reasonable and economical That is, it is reasonable to set it to 1 to 1000 (wtppm) at which practical melt stability is achieved. More preferably, a range of 1 to 700 (wtppm), more preferably 2 to 500 (wtppm), and particularly preferably 5 to 100 (wtppm) is selected.
  • a polylactic acid composition containing a stereocomplex phase polylactic acid is obtained by bringing a poly L-lactic acid component and a poly D-lactic acid component into contact with each other in a weight ratio of 10/90 to 90/10, preferably by melt-contacting. More preferably, it can be obtained by contact with melt kneading.
  • the contact temperature is selected in the range of 220 to 290 ° C., preferably 220 to 280 ° C., and more preferably 225 to 275 ° C. from the viewpoint of improving the stability of polylactic acid when melted and the stereocomplex crystallinity.
  • the melt kneading method is not particularly limited, but a conventionally known batch type or continuous type melt mixing apparatus is preferably used. For example, melt stirring tank, single-screw or twin-screw extruder, kneader, non-shaft vertical stirring tank, Sumitomo Heavy Industries, Ltd. Bivolak, Mitsubishi Heavy Industries, Ltd. N-SCR, Hitachi, Ltd.
  • polylactic acid quality especially color tone, non-axial vertical stirring tank, N-SCR A glass wing, a lattice wing, a biaxial extrusion ruder, or the like is preferably used.
  • polylactic acid composition of the present invention in order to stably and highly advance the formation of a complex phase, it is essential to apply a component having an acid value of less than 5 as a stereocomplex crystallization accelerator.
  • phosphoric acid ester metal salts can be used alone or in combination.
  • R 11 Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 12 , R 13 Each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms
  • 1 Represents an alkali metal atom, alkaline earth metal atom, zinc atom or aluminum atom
  • p represents 1 or 2
  • q represents M 1
  • alkali metal atom, alkaline earth metal atom or zinc atom, 0 is represented, and when it is an aluminum atom, 1 or 2 is represented.
  • R in the formula 14 , R 15 And R 16 Each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; 2 Represents an alkali metal atom, alkaline earth metal atom, zinc atom or aluminum atom, p represents 1 or 2, q represents M 2 When is an alkali metal atom, alkaline earth metal atom or zinc atom, 0 is represented, and when it is an aluminum atom, 1 or 2 is represented.
  • M of metal phosphate represented by the above two formulas 1 , M 2 Na, K, Al, Mg, Ca and Li are preferable, and Li and Al can be used most preferably among K, Na, Al and Li.
  • the phosphoric acid ester metal salt is 0.001 to 2 wt%, preferably 0.005 to 1 wt%, more preferably 0.01 to 0.5 wt%, and further preferably 0.02 to 0.2 wt%. It is preferable to use 3 wt%. When the amount is too small, the effect of improving the degree of crystallinity of the stereocomplex is small, and when too large, the stereocomplex phase melting point is lowered, which is not preferable.
  • a known crystallization nucleating agent described below can be used in combination in order to enhance the action of the phosphate ester metal salt within the range not departing from the gist of the present invention.
  • calcium silicate, talc, kaolinite, and montmorillonite are preferably selected.
  • the amount of the crystallization nucleating agent used is selected in the range of 0.05 to 5 wt%, more preferably 0.06 to 2 wt%, still more preferably 0.06 to 1 wt% with respect to the polylactic acid composition.
  • stereocomplex crystallization aid in order to further increase the degree of stereocomplex crystallinity of polylactic acid, [(epoxy group, oxazoline group, oxazine group, isocyanate group, ketene group and carbodiimide group) (hereinafter abbreviated as a specific functional group) as a stereocomplex crystallization aid. It is preferable to add a compound having at least one functional group selected from the group of Stereocomplex crystallizing aid is a specific functional group that reacts with the molecular terminal of polylactic acid composition to partially link poly L-lactic acid unit and poly D-lactic acid unit to promote stereocomplex phase formation. It is an agent that the present inventors speculate that it is made to be.
  • stereocomplex crystallization aid a known agent can be suitably applied as a conventional polyester carboxyl group-capping agent described below.
  • known carbodiimide compounds, oxazoline compounds and the like are suitably selected in the present invention because of the effect of promoting the formation of complex phases and the hue of the composition.
  • agents containing oxazine groups, isocyanate groups, and carbodiimide groups cause deterioration of the working environment due to malodor due to thermal decomposition of the agent during the formation of the complex phase, and deterioration of the color tone of the polylactic acid composition. Because there is a high risk of causing it, it is preferable to prepare a separate work environment for use.
  • the amount of the stereocomplex crystallization aid used is not more than 1 wt%, preferably 0 to 0.5 wt%, more preferably 0 to 0.3 wt%, still more preferably 0 to 0.1 wt% in the same standard as above. Is selected.
  • the carboxyl end group concentration of the polylactic acid composition is 0.01 to 10 (equivalent / 10 6 g), ⁇ below (equivalent / 10 6 g) may be abbreviated as (eq / ton). ⁇ Is preferred. A range of 0.02 to 5 (eq / ton) is more preferable, and a range of 0.5 to 3 (eq / ton) is more preferably selected. When the carboxyl end group concentration is within this range, the polylactic acid composition of the present invention and the molded product of the present invention comprising the composition can have good heat resistance, hue, and particularly heat and humidity resistance.
  • Examples of the epoxy compound that can be used as a stereocomplex crystallization aid having a specific functional group in the present invention include glycidyl ether compounds, glycidyl ester compounds, glycidyl amine compounds, glycidyl imide compounds, glycidyl amide compounds, and alicyclic epoxy compounds. Can be preferably used. By blending such an agent, formation of a complex phase of the polylactic acid composition can be promoted, and a polylactic acid molded product having excellent mechanical properties, heat resistance, moist heat resistance, durability, moldability, and the like can be obtained.
  • glycidyl ether compounds include, for example, stearyl glycidyl ether, phenyl glycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylene glycol diglycidyl ether Bisphenol obtained by condensation reaction of bisphenols such as polytetramethylene glycol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether and other bis (4-hydroxyphenyl) methane with epichlorohydrin A diglycidyl ether type epoxy Etc.
  • bisphenols such as polytetramethylene glycol diglycidyl ether, glycerol trigly
  • glycidyl ester compounds include, for example, glycidyl benzoate, glycidyl stearate, glycidyl stearic acid, glycidyl terephthalate, diglycidyl terephthalate, diglycidyl phthalate, cyclohexanedicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester, Examples thereof include succinic acid diglycidyl ester, dodecanedioic acid diglycidyl ester, pyromellitic acid tetraglycidyl ester and the like.
  • benzoic acid glycidyl ester and versatic acid glycidyl ester are preferable.
  • the glycidylamine compound include, for example, tetraglycidylamine diphenylmethane, triglycidyl-p-aminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidylmetaxylenediamine, triglycidyl isocyanurate, and the like.
  • Examples of glycidyl imide and glycidyl amide compounds include N-glycidyl phthalimide, N-glycidyl-4,5-dimethyl phthalimide, N-glycidyl-3,6-dimethyl phthalimide, N-glycidyl succinimide, N-glycidyl- Examples include 1,2,3,4-tetrahydrophthalimide, N-glycidyl maleimide, N-glycidyl benzamide, N-glycidyl stearyl amide, and among them, N-glycidyl phthalimide is preferable.
  • alicyclic epoxy compounds examples include 3,4-epoxycyclohexyl-3,4-cyclohexylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene diepoxide, N-methyl-4,5- Examples thereof include epoxycyclohexane-1,2-dicarboxylic imide, N-phenyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide and the like.
  • a polyepoxy compound containing the above compound as a monomer unit particularly a polyepoxy compound having an epoxy group as a pendant group in a side chain, and the like can be mentioned as suitable agents.
  • epoxy compounds that can be used include epoxy-modified fatty acid glycerides such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized whale oil, phenol novolac type epoxy resins, and cresol novolak type epoxy resins.
  • examples of oxazoline compounds that can be used as a stereocomplex crystallization aid having a specific functional group used in the present invention include 2-methoxy-2-oxazoline, 2-butoxy-2-oxazoline, and 2-stearyloxy-2-oxazoline.
  • oxazoline compounds 2,2'-m-phenylenebis (2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline) and the specific oxazoline resin of the present invention are selected as preferred.
  • oxazine compounds that can be used as a stereocomplex crystallization aid having a specific functional group in the present invention include 2-methoxy-5,6-dihydro-4H-1,3-oxazine, 2-hexyloxy-5.
  • 6-dihydro-4H-1,3-oxazine 2-decyloxy-5,6-dihydro-4H-1,3-oxazine, 2-cyclohexyloxy-5,6-dihydro-4H-1,3-oxazine
  • Examples include 2-allyloxy-5,6-dihydro-4H-1,3-oxazine, 2-crotyloxy-5,6-dihydro-4H-1,3-oxazine and the like.
  • 2,2′-bis (5,6-dihydro-4H-1,3-oxazine), 2,2′-methylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′- Ethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-hexamethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-p-phenylene Bis (5,6-dihydro-4H-1,3-oxazine), 2,2′-P, P′-diphenylenebis (5,6-dihydro-4H-1,3-oxazine) and the like can be mentioned.
  • a polyoxazine compound containing the above-described compound as a monomer unit particularly a polyoxazine compound having the above functional group as a pendant group in the side chain, and the like can be mentioned as suitable agents.
  • isocyanate compounds that can be used in the present invention include aromatic isocyanates, aliphatic isocyanates, alicyclic isocyanate compounds, and mixtures thereof.
  • Examples of the monoisocyanate compound that can be used as a stereocomplex crystallization aid having a specific functional group include phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, and naphthyl isocyanate.
  • diisocyanate examples include 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, (2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate) mixture, cyclohexane-4,4′-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane 4,4 Examples include '-diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate, 2,6-diisopropylphenyl-1,4-diisocyanate, etc.
  • aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate and phenyl isocyanate are preferred.
  • ketene compounds that can be used as a stereocomplex crystallization aid having a specific functional group include aromatic ketene compounds, aliphatic ketene compounds, alicyclic ketene compounds, and mixtures thereof. Specific examples of the compound include diphenyl ketene, bis (2,6-di-tert-butylphenyl) ketene, bis (2,6-di-isopropylphenyl) ketene, dicyclohexyl ketene and the like.
  • aromatic ketenes such as diphenyl ketene, bis (2,6-di-tert-butylphenyl) ketene, and bis (2,6-di-isopropylphenyl) ketene are preferable.
  • the agent that can be used as the stereocomplex crystallization aid and the end-capping agent can be used by appropriately selecting one or more compounds.
  • One of preferred embodiments is to promote formation of a complex phase with a stereocomplex crystallization aid and to seal a carboxyl group terminal and a part of an acidic low molecular weight compound.
  • the polylactic acid composition of the present invention includes a thermoplastic resin other than polylactic acid, a stabilizer, a crystallization accelerator, a filler, a mold release agent, an antistatic agent, a carboxyl group reaction, as long as it does not contradict the gist of the present invention. At least one selected from the group consisting of a conductive end-capping agent, a plasticizer, an impact stabilizer and the like.
  • a thermoplastic resin other than the polylactic acid composition of the present invention.
  • thermoplastic resins examples include polyester resins other than polylactic acid, polyamide resins, polyacetal resins, polyolefin resins such as polyethylene resins and polypropylene resins, polystyrene resins, acrylic resins, polyurethane resins, chlorinated polyethylene resins, and chlorinated polypropylene resins.
  • Aromatic and aliphatic polyketone resins fluorine resins, polyphenylene sulfide resins, polyether ether ketone resins, polyimide resins, thermoplastic starch resins, AS resins, ABS resins, AES resins, ACS resins, polyvinyl chloride resins, poly Vinylidene chloride resin, vinyl ester resin, MS resin, polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy resin, polyphenylene oxide resin , Poly-4-methylpentene-1, polyetherimide resin, cellulose acetate resin, and thermoplastic resins such as polyvinyl alcohol resins.
  • polyacetal resins polyester resins other than polylactic acid, for example, selected from polyester resins such as PET (polyethylene terephthalate), PTT (polytrimethylene terephthalate), PBT (polybutylene terephthalate), PEN (polyethylene naphthalate), and polyamide resins. It is preferable to blend at least one kind. By blending these resins, the surface properties, moldability, mechanical properties, durability, toughness and the like of the molded article made of the composition of the present invention can be made excellent.
  • polyester resins such as PET (polyethylene terephthalate), PTT (polytrimethylene terephthalate), PBT (polybutylene terephthalate), PEN (polyethylene naphthalate), and polyamide resins. It is preferable to blend at least one kind. By blending these resins, the surface properties, moldability, mechanical properties, durability, toughness and the like of the molded article made of the composition of the present invention can be made excellent.
  • the content of the thermoplastic resin is preferably 0.5 to 200 parts by weight, more preferably 1 to 100 parts by weight, further preferably 3 to 70 parts by weight, based on 100 parts by weight of the polylactic acid composition of the present invention. More preferably, it is 5 to 50 parts by weight.
  • the polylactic acid composition of the present invention can contain a stabilizer.
  • a stabilizer what is used for the stabilizer of a normal thermoplastic resin can be used.
  • an antioxidant, a light stabilizer, etc. can be mentioned. By blending these agents, a molded product having excellent mechanical properties, moldability, heat resistance and durability can be obtained.
  • antioxidant examples include hindered phenol compounds, hindered amine compounds, phosphite compounds, thioether compounds, and the like.
  • hindered phenol compounds include n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3′-methyl-5 ′).
  • phosphite compound those in which at least one P—O bond is bonded to an aromatic group are preferable.
  • tris (2,6-di-tert-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (2,6-di-tert-butyl) -4-Methylphenyl) pentaerythritol diphosphite, tetrakis (2,6-di-tert-butylphenyl) 4,4'-biphenylene phosphite and the like can be preferably used.
  • thioether compounds include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol-tetrakis (3-lauryl thiopropionate), Pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthio) Propionate) and the like.
  • the light stabilizer examples include benzophenone compounds, benzotriazole compounds, aromatic benzoate compounds, oxalic acid anilide compounds, cyanoacrylate compounds, hindered amine compounds, and the like.
  • benzophenone compounds include benzophenone, 2,4-dihydroxybenzophenone, 2,2′-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2 ′.
  • benzotriazole compound examples include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3,5- Di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-4′-methyl-2′-hydroxyphenyl) benzotriazole, 2- (3,5- Di-tert-amyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (5-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis ( ⁇ , ⁇ -Dimethylbenzyl) phenyl] benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis ( ⁇ , ⁇ -Dimethylbenzyl) phenyl] benzotriazole, 2- [2′-hydroxy-3 ′, 5
  • aromatic benzoate compounds examples include alkylphenyl salicylates such as p-tert-butylphenyl salicylate and p-octylphenyl salicylate.
  • oxalic acid anilide compounds examples include 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxy-5-tert-butyl-2′-ethyloxalic acid bisanilide, and 2-ethoxy-3′-. Examples include dodecyl oxalic acid bisanilide.
  • Examples of the cyanoacrylate compound include ethyl-2-cyano-3,3'-diphenyl acrylate, 2-ethylhexyl-cyano-3,3'-diphenyl acrylate, and the like.
  • Examples of hindered amine compounds include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6, 6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2, 6,6-tetramethylpiperidine, 4-octadecyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2 , 6,6-tetramethylpipe
  • the E component may be used alone or in combination of two or more.
  • the stabilizer component a hindered phenol compound and / or a benzotriazole compound are preferable.
  • the content of the stabilizer is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight, per 100 parts by weight of the polylactic acid composition.
  • the polylactic acid composition of the present invention can contain an organic or inorganic crystallization accelerator. By containing the crystallization accelerator, the action of the phosphoric acid ester metal salt can be further enhanced, and a molded product having excellent mechanical properties, heat resistance, and moldability can be obtained.
  • the crystallization accelerator by applying the crystallization accelerator, the moldability and crystallinity of the polylactic acid composition are improved, and a molded product that is sufficiently crystallized even in normal injection molding and excellent in heat resistance and moist heat resistance can be obtained. .
  • the manufacturing time for manufacturing the molded product can be greatly shortened, and the economic effect is great.
  • the crystallization nucleating agent used in the present invention those generally used as crystallization nucleating agents for crystalline resins can be used, and both inorganic crystallization nucleating agents and organic crystallization nucleating agents are used. be able to.
  • inorganic crystallization nucleating agents talc, kaolin, silica, synthetic mica, clay, zeolite, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium carbonate, calcium sulfate, barium sulfate, calcium sulfide, boron nitride , Montmorillonite, neodymium oxide, aluminum oxide, phenylphosphonate metal salt and the like.
  • These inorganic crystallization nucleating agents are treated with various dispersing aids in order to enhance the dispersibility in the composition and the effect thereof, and are in a highly dispersed state with a primary particle size of about 0.01 to 0.5 ⁇ m. are preferred.
  • Organic crystallization nucleating agents include calcium benzoate, sodium benzoate, lithium benzoate, potassium benzoate, magnesium benzoate, barium benzoate, calcium oxalate, disodium terephthalate, dilithium terephthalate, dipotassium terephthalate, Sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, barium myristate, sodium octacolate, calcium octacolate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate , Barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, salicylate Organic carboxylic acid metal salts such as zinc oxalate, aluminum dibenzoate, ⁇ -sodium naphthoate, potassium ⁇ -naphthoate, sodium cyclohexanecarboxylate,
  • organic carboxylic acid amides such as stearic acid amide, ethylenebislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, trimesic acid tris (tert-butylamide), low density polyethylene, high density polyethylene, polyiso Propylene, polybutene, poly-4-methylpentene, poly-3-methylbutene-1, polyvinylcycloalkane, polyvinyltrialkylsilane, high melting point polylactic acid, sodium salt of ethylene-acrylic acid copolymer, sodium of styrene-maleic anhydride copolymer Examples thereof include salts (so-called ionomers), benzylidene sorbitol and derivatives thereof such as dibenzylidene sorbitol.
  • the polylactic acid composition of the present invention can contain an organic or inorganic filler. By containing the filler component, a molded product having excellent mechanical properties, heat resistance, and moldability can be obtained.
  • Organic fillers such as rice husks, wood chips, okara, waste paper pulverized materials, clothing crushed materials, cotton fibers, hemp fibers, bamboo fibers, wood fibers, kenaf fibers, jute fibers, banana fibers, coconut fibers
  • Plant fibers such as pulp, cellulose fibers processed from these plant fibers and fibrous fibers such as animal fibers such as silk, wool, Angola, cashmere, camel, etc., synthetic fibers such as polyester fibers, nylon fibers and acrylic fibers , Paper powder, wood powder, cellulose powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein, starch and the like.
  • powdery materials such as paper powder, wood powder, bamboo powder, cellulose powder, kenaf powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein powder, and starch are preferred. Powder, bamboo powder, cellulose powder and kenaf powder are preferred. Paper powder and wood powder are more preferable. Paper dust is particularly preferable.
  • organic fillers may be collected directly from natural products, but may be recycled recycled waste paper such as waste paper, waste wood, and old clothes. Further, as wood, coniferous wood such as pine, cedar, firewood and fir, and hardwood such as beech, shy and eucalyptus are preferable.
  • Paper powder is an adhesive from the viewpoint of moldability, especially emulsion-based adhesives such as vinyl acetate resin-based emulsions and acrylic resin-based emulsions when processing paper, polyvinyl alcohol-based adhesives, polyamide-based adhesives, etc. Preferred examples include those containing a hot melt adhesive.
  • the amount of the organic filler is not particularly limited, but from the viewpoint of moldability and heat resistance, it is preferably 1 to 300 parts by weight, more preferably 5 to 200 parts by weight per 100 parts by weight of polylactic acid. Parts, more preferably 10 to 150 parts by weight, particularly preferably 15 to 100 parts by weight.
  • the polylactic acid composition of the present invention can contain an inorganic filler.
  • a composition excellent in mechanical properties, heat resistance and moldability can be obtained by the inorganic filler.
  • the inorganic filler used in the present invention a fibrous, plate-like, or powder-like material used for reinforcing ordinary thermoplastic resins can be used.
  • layered silicates include smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and soconite, various clay minerals such as vermiculite, halosite, kanemite, and kenyanite, Li-type fluorine teniolite, Na And swellable mica such as Li-type fluorine teniolite, Li-type tetrasilicon fluorine mica and Na-type tetrasilicon fluorine mica. These may be natural or synthetic.
  • smectite clay minerals such as montmorillonite and hectorite
  • swellable synthetic mica such as Li type fluorine teniolite and Na type tetrasilicon fluorine mica
  • fibrous or plate-like inorganic fillers are preferable, and glass fiber, wollastonite, aluminum borate whisker, potassium titanate whisker, mica, and kaolin, a cation-exchanged layered silicate. Is preferred.
  • the aspect ratio of the fibrous filler is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more.
  • Such a filler may be coated or converged with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or may be treated with a coupling agent such as aminosilane or epoxysilane. May be.
  • the amount of the inorganic filler is preferably 0.1 to 200 parts by weight, more preferably 0.5 to 100 parts by weight, still more preferably 1 to 50 parts by weight, particularly preferably 100 parts by weight of the polylactic acid composition. Is 1 to 30 parts by weight, most preferably 1 to 20 parts by weight.
  • the polylactic acid composition of the present invention can contain a release agent. As the mold release agent used in the present invention, those used for ordinary thermoplastic resins can be used.
  • release agents include fatty acids, fatty acid metal salts, oxy fatty acids, paraffins, low molecular weight polyolefins, fatty acid amides, alkylene bis fatty acid amides, aliphatic ketones, fatty acid partial saponified esters, fatty acid lower alcohol esters, fatty acid polyvalents.
  • examples include alcohol esters, fatty acid polyglycol esters, and modified silicones. By blending these, a polylactic acid molded product excellent in mechanical properties, moldability, and heat resistance can be obtained. Fatty acids having 6 to 40 carbon atoms are preferred.
  • oleic acid, stearic acid, lauric acid, hydroxystearic acid, behenic acid, arachidonic acid, linoleic acid, linolenic acid, ricinoleic acid, palmitic acid, montan examples thereof include acids and mixtures thereof.
  • the fatty acid metal salt is preferably an alkali (earth) metal salt of a fatty acid having 6 to 40 carbon atoms, and specific examples include calcium stearate, sodium montanate, and calcium montanate.
  • Examples of oxy fatty acids include 1,2-oxysteric acid. Paraffin having 18 or more carbon atoms is preferable, and examples thereof include liquid paraffin, natural paraffin, microcrystalline wax, petrolactam and the like.
  • low-molecular-weight polyolefin for example, those having a molecular weight of 5000 or less are preferable, and specific examples include polyethylene wax, maleic acid-modified polyethylene wax, oxidized polyethylene wax, chlorinated polyethylene wax, and polypropylene wax.
  • Fatty acid amides having 6 or more carbon atoms are preferred, and specific examples include oleic acid amide, erucic acid amide, and behenic acid amide.
  • Alkylene bis fatty acid amides preferably have 6 or more carbon atoms, and specific examples include methylene bis stearic acid amide, ethylene bis stearic acid amide, N, N-bis (2-hydroxyethyl) stearic acid amide and the like.
  • aliphatic ketone those having 6 or more carbon atoms are preferable, and examples thereof include higher aliphatic ketones.
  • fatty acid partial saponified esters include montanic acid partial saponified esters.
  • fatty acid lower alcohol ester include stearic acid ester, oleic acid ester, linoleic acid ester, linolenic acid ester, adipic acid ester, behenic acid ester, arachidonic acid ester, montanic acid ester, isostearic acid ester and the like.
  • fatty acid polyhydric alcohol esters examples include glycerol tristearate, glycerol distearate, glycerol monostearate, pentaerythritol tetrastearate, pentaerythritol tristearate, pentaerythritol dimyristate, pentaerythritol Examples include tall stearate, pentaerythritol adipate stearate, sorbitan monobehenate, and the like.
  • fatty acid polyglycol esters examples include polyethylene glycol fatty acid esters and polypropylene glycol fatty acid esters.
  • modified silicone examples include polyether-modified silicone, higher fatty acid alkoxy-modified silicone, higher fatty acid-containing silicone, higher fatty acid ester-modified silicone, methacryl-modified silicone, and fluorine-modified silicone.
  • fatty acid, fatty acid metal salt, oxy fatty acid, fatty acid ester, fatty acid partial saponified ester, paraffin, low molecular weight polyolefin, fatty acid amide, and alkylene bis fatty acid amide are preferred, and fatty acid partial saponified ester and alkylene bis fatty acid amide are more preferred.
  • montanic acid ester, montanic acid partial saponified ester, polyethylene wax, acid value polyethylene wax, sorbitan fatty acid ester, erucic acid amide, and ethylene bisstearic acid amide are preferred, and particularly, montanic acid partial saponified ester and ethylene bisstearic acid amide are preferred.
  • the release agent may be used alone or in combination of two or more.
  • the content of the release agent is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight, with respect to 100 parts by weight of polylactic acid.
  • the polylactic acid composition of the present invention may contain an antistatic agent, specifically, a quaternary ammonium salt compound such as ( ⁇ -lauramidopropionyl) trimethylammonium sulfate, sodium dodecylbenzenesulfonate, Examples thereof include sulfonate compounds and alkyl phosphate compounds.
  • an antistatic agent specifically, a quaternary ammonium salt compound such as ( ⁇ -lauramidopropionyl) trimethylammonium sulfate, sodium dodecylbenzenesulfonate, Examples thereof include sulfonate compounds and alkyl phosphate compounds.
  • the above-mentioned antistatic agents may be used alone or in combination of two or more.
  • the amount is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polylactic acid composition.
  • the polylactic acid composition of the present invention can contain a plasticizer, and generally known plasticizers can be used as the plasticizer to be used.
  • a plasticizer for example, a polyester plasticizer, a glycerin plasticizer, a polyvalent carboxylic ester plasticizer, a phosphoric ester plasticizer, a polyalkylene glycol plasticizer, and an epoxy plasticizer.
  • polyester plasticizer As a polyester plasticizer, acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, Examples thereof include polyesters composed of diol components such as 1,6-hexanediol and diethylene glycol, and polyesters composed of hydroxycarboxylic acids such as polycaprolactone. These polyesters may be end-capped with a monofunctional carboxylic acid or a monofunctional alcohol.
  • glycerol plasticizer examples include glycerol monostearate, glycerol distearate, glycerol monoacetomonolaurate, glycerol monoacetomonostearate, glycerol diacetomonooleate, and glycerol monoacetomonomontanate.
  • Polyvalent carboxylic acid plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, trimellitic acid tributyl, trimellitic acid trioctyl, Trimellitic acid esters such as trihexyl meritate, isodecyl adipate, adipic acid esters such as adipate-n-decyl-n-octyl, citrate esters such as tributyl acetylcitrate, and bis (2-ethylhexyl) azelate Examples include sebacic acid esters such as azelaic acid ester, dibutyl sebacate, and bis (2-ethylhexyl) sebacate.
  • phosphate ester plasticizer examples include tributyl phosphate, tris phosphate (2-ethylhexyl), trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl-2-ethylhexyl phosphate, and the like.
  • Polyalkylene glycol plasticizers such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (ethylene oxide.propylene oxide) block and / or random copolymers, ethylene oxide addition polymers of bisphenols, tetrahydrofuran addition polymers of bisphenols, etc.
  • end-capping compounds such as a terminal epoxy-modified compound, a terminal ester-modified compound, and a terminal ether-modified compound.
  • the epoxy plasticizer include an epoxy triglyceride composed of an epoxy alkyl stearate and soybean oil, and an epoxy resin using bisphenol A and epichlorohydrin as raw materials.
  • specific examples of other plasticizers include benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol-bis (2-ethylbutyrate), and fatty acids such as stearamide.
  • plasticizer examples thereof include fatty acid esters such as amide and butyl oleate, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, various sorbitols, polyacrylic acid esters, silicone oils, and paraffins.
  • the plasticizer at least one selected from polyester-type plasticizers and polyalkylene-type plasticizers can be preferably used, and only one type may be used or two or more types may be used in combination.
  • the amount when the plasticizer is contained is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight, still more preferably 0.1 to 10 parts by weight per 100 parts by weight of the polylactic acid composition.
  • the crystallization nucleating agent and the plasticizer may be used singly or in combination.
  • the impact resistance improver that may be added to the polylactic acid composition of the present invention can be used to improve the impact resistance of thermoplastic resins, and is not particularly limited. For example, at least one selected from the following impact resistance improvers can be used.
  • impact modifiers include ethylene-propylene copolymers, ethylene-propylene-nonconjugated diene copolymers, ethylene-butene-1 copolymers, various acrylic rubbers, ethylene-acrylic acid copolymers and their Alkali metal salt (so-called ionomer) ethylene-glycidyl (meth) acrylate copolymer, ethylene-acrylate copolymer (for example, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer), modified ethylene- Propylene copolymer, diene rubber (eg, polybutadiene, polyisoprene, polychloroprene), diene and vinyl copolymer (eg, styrene-butadiene random copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer,
  • various micro structures such as those having a cis structure, a trans structure, etc., a core layer and one or more shell layers covering the core layer, and adjacent layers are composed of heterogeneous polymers.
  • a so-called core-shell type multi-layered polymer can also be used.
  • any of the various (co) polymers mentioned in the above specific examples can be used as the impact resistance improver of the present invention, such as a randomum copolymer, a block copolymer, and a block copolymer.
  • the impact resistance improver is preferably 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, and further preferably 10 to 20 parts by weight with respect to 100 parts by weight of polylactic acid.
  • thermosetting resin such as a phenol resin, a melamine resin, a thermosetting polyester resin, a silicone resin, or an epoxy resin
  • flame retardants such as bromine, phosphorus, silicone, and antimony compounds may be included within the scope not departing from the spirit of the present invention.
  • Colorants containing organic and inorganic dyes and pigments for example, oxides such as titanium dioxide, hydroxides such as alumina white, sulfides such as zinc sulfide, ferrocyanides such as bitumen, and chromium such as zinc chromate Contains acid salts, sulfates such as barium sulfate, carbonates such as calcium carbonate, silicates such as ultramarine, phosphates such as manganese violet, carbon such as carbon black, metal colorants such as bronze powder and aluminum powder, etc. You may let them.
  • nitroso type such as naphthol green B, nitro type such as naphthol yellow S, azo type such as naphthol red, chromophthal yellow, phthalocyanine type such as phthalocyanine blue and fast sky blue, condensed polycyclic colorants such as indanthrone blue
  • additives such as slidability improvers such as graphite and fluorine resin may be added. These additives can be used alone or in combination of two or more. A polylactic acid composition containing these additives can be prepared by mixing each component.
  • a tumbler for the mixing, a tumbler, a V-type blender, a super mixer, a nauter mixer, a Banbury mixer, a kneading roll, a monoaxial or biaxial extruder can be used.
  • the resulting composition can be molded as it is or after being once pelletized with a melt extruder.
  • the shape of the pellet may be any shape such as a spherical shape, a die shape, a linear shape, a curved shape, and a cross-sectional shape such as a circle, an ellipse, a flat shape, a triangle, a polygon having a square shape or more, and a star shape.
  • the pellet length is preferably 1 to 7 mm, the major axis 3 to 5 mm, and the minor axis 1 to 4 mm. Further, it is preferable that the shape does not vary.
  • Molded products made of the polylactic acid composition of the present invention are injection molded products, extruded molded products, vacuum molded products, compressed air molded products, blow molded products, and the like, specifically, pellets, fibers and cloth, and other materials. And the like, including a fiber structure, a film, a sheet, a sheet nonwoven fabric, and a compression molded product.
  • the melt molding method is not limited at all, and those produced by a known pellet production method can be suitably used. That is, after the polylactic acid composition applied in the form of a strand or plate is completely solidified or not completely solidified and still in a molten state, a method such as cutting in air or water Are conventionally known, but any of them can be suitably applied to the polylactic acid composition of the present invention.
  • Conventionally known molding methods can be applied to the injection molded product of the present invention without any limitation. From the viewpoint of increasing the crystallization of the molded product and the molding cycle at the time of injection molding, the mold temperature is preferably 30 ° C. or more, more preferably Is 60 ° C.
  • the mold temperature is preferably 140 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 110 ° C. or lower.
  • These molded products may include various housings, electrical / electronic parts such as gears and gears, building members, civil engineering members, agricultural materials, automobile parts (interior and exterior parts, etc.) and daily parts.
  • the polylactic acid composition is melted by an extruder type or pressure melter type melt extruder, it is weighed by a gear pump, filtered in a pack, and then monofilament and multifilament from a nozzle provided on the base.
  • Etc. The shape of the base and the number of bases are not particularly limited, and any of circular, irregular, solid, hollow, etc. can be adopted.
  • the discharged yarn is immediately cooled and solidified, then converged, added with oil, and wound.
  • the winding speed is not particularly limited, but a range of 300 m / min to 5000 m / min is preferable because a stereo complex crystal is easily formed.
  • a winding speed at which the stereocomplex crystallization ratio of the undrawn yarn is 0% is preferable.
  • the wound undrawn yarn is then subjected to a drawing process, but the spinning process and the drawing process are not necessarily separated from each other. Even if a direct spinning drawing method is used in which the drawing is continued without being wound once after spinning. I do not care.
  • the stretching may be one-stage stretching or multi-stage stretching of two or more stages. From the viewpoint of producing a high-strength fiber, the stretching ratio is preferably 3 times or more, and more preferably 4 times or more. Preferably 3 to 10 times is selected.
  • the preheating method for stretching in addition to raising the temperature of the roll, a flat or pin-like contact heater, non-contact hot plate, heating medium bath, etc. may be mentioned, but a commonly used method may be used. Following the stretching, it is preferable that heat treatment is performed at a temperature of 170 ° C. or higher and lower than the melting point of the polylactic acid composition before winding. In addition to the hot roller, any method such as a contact heater or a non-contact hot plate can be adopted for the heat treatment.
  • the stretching temperature is selected from the glass transition point of polylactic acid to 170 ° C., preferably 70 ° C. to 140 ° C., particularly preferably 80 ° C. to 130 ° C.
  • the high-strength, heat-resistant, heat-and-moisture-resistant stability of the present invention can take the form of various fiber structures such as woven fabrics, knitted fabrics, nonwoven fabrics, and molded articles such as cups.
  • thread form products such as sewing thread, embroidery thread, string, fabric such as woven fabric, knitted fabric, nonwoven fabric, felt, outer clothing such as shirt, blouson, pants, coat, sweater, uniform, underwear, pantyhose, socks, Lining, interlining, sports clothing, high value-added clothing products such as women's clothing and formal wear, clothing products such as cups and pads, curtains, carpets, chair upholstery, mats, furniture, baskets, furniture upholstery, wall materials, etc.
  • Products for daily use such as belts and slings, as well as various textile products such as canvas, belts, nets, ropes, heavy cloth, bags, industrial materials such as felts and filters, vehicle interior products, and artificial leather products.
  • the fiber and fiber structure of the present invention may be composed of a single fiber molded from a polylactic acid composition, or may be mixed with other types of fibers.
  • mixed modes include mixed yarns with other fibers, composite false twisted yarns, mixed spun yarns, long and short composite yarns, fluid processed yarns, covering yarns, and twisted yarns. Examples thereof include union, union, pile, pile, mixed cotton, mixed non-woven fabric of long fibers and short fibers, and felt.
  • the mixed ratio is selected in the range of 1 wt% or more, more preferably 10 wt% or more, and further preferably 30 wt% or more.
  • cellulose fibers such as cotton, hemp, rayon and tencel, wool, silk, acetate, polyester, nylon, acrylic, vinylon, polyolefin, polyurethane and the like can be raised.
  • cellulose fibers such as cotton, hemp, rayon and tencel, wool, silk, acetate, polyester, nylon, acrylic, vinylon, polyolefin, polyurethane and the like can be raised.
  • ⁇ Film, sheet> The film and sheet made of the polylactic acid composition of the present invention are formed by a conventionally known method.
  • molding techniques such as extrusion molding and cast molding can be used. That is, an unstretched film can be extruded using an extruder or the like equipped with a T die, a circular die, or the like, and further stretched and heat treated to be molded. At this time, the unstretched film can be used as it is as a sheet.
  • an unstretched film with few surface defects can be obtained by blending an electrostatic adhesive such as a sulfonic acid quaternary phosphonium salt into the molten resin.
  • an unstretched film can be cast-molded by dissolving, casting, and drying and solidifying the polylactic acid composition and the additive component using a common solvent such as chloroform and methylene dichloride.
  • Unstretched film can be uniaxially stretched longitudinally in the direction of mechanical flow and transversely uniaxially stretched in the direction perpendicular to the direction of mechanical flow. Simultaneous biaxial stretching by roll and tenter stretching, and simultaneous biaxial stretching by tenter stretching A biaxially stretched film can be produced by stretching by a biaxial stretching method using a method such as tubular stretching. Further, the film is usually subjected to a heat setting treatment after stretching in order to suppress heat shrinkability and the like. The stretched film thus obtained can be subjected to a surface activation treatment, for example, a plasma treatment, an amine treatment, or a corona treatment by a conventionally known method if desired.
  • a surface activation treatment for example, a plasma treatment, an amine treatment, or a corona treatment by a conventionally known method if desired.
  • the film and sheet of the present invention can be used in combination with other types of films and sheets in addition to a single form.
  • Examples of the mixed use include various combinations with films and sheets made of other kinds of materials, such as lamination and lamination, as well as combinations with other kinds of forms, such as injection molded articles and fiber structures.
  • GPC measuring instrument is a detector; differential refractometer (manufactured by Shimadzu Corporation) RID-6A column; Tosoh Corporation TSKgelG3000HXL, TSKgelG4000HXL, TSKgelG5000HXL and TSKguardcolumnHXL-L, or Tosoh Corporation GX , TSKgelG3000HXL and TSKguardcolumnHXL-L connected in series were used.
  • intermediate product A (0.1 mol), hydroxylamine hydrochloride (0.11 mol), sodium bicarbonate (0.15 mol), and 100 ml of methanol were placed in a reactor equipped with a stirrer and a heating device under N 2 atmosphere. The reaction was refluxed under N 2 atmosphere. After 6 hours of reaction, the reaction mixture was filtered, and intermediate product B was obtained by recrystallization from the filtrate.
  • intermediate product D (nitro form).
  • intermediate product D (0.1 mol), 5% palladium carbon (Pd / C) (1 g), and 200 ml of ethanol / dichloromethane (70/30) were charged into a reactor equipped with a stirrer, and 5 hydrogen substitution was performed.
  • the reaction was performed in a state where hydrogen was constantly supplied at 25 ° C., and the reaction was terminated when there was no decrease in hydrogen.
  • Pd / C was recovered and the mixed solvent was removed, an intermediate product E (amine body) was obtained.
  • triphenylphosphine dibromide (0.11 mol) and 150 ml of 1,2-dichloroethane are charged and stirred in an N 2 atmosphere.
  • a solution prepared by dissolving intermediate product E (0.05 mol) and triethylamine (0.25 mol) in 50 ml of 1,2-dichloroethane is gradually added dropwise thereto at 25 ° C.
  • the reaction is carried out at 70 ° C. for 5 hours. Thereafter, the reaction solution was filtered, and the filtrate was separated 5 times with 100 ml of water.
  • CC2 of the following structure was obtained by refine
  • the structure of CC2 was confirmed by NMR and IR.
  • intermediate product D (nitro form).
  • intermediate product D (0.1 mol), 5% palladium carbon (Pd / C) (2 g), and 400 ml of ethanol / dichloromethane (70/30) were charged into a reactor equipped with a stirrer, and 5 hydrogen substitution was performed. The reaction was performed in a state where hydrogen was constantly supplied at 25 ° C., and the reaction was terminated when there was no decrease in hydrogen.
  • CC3 of the following structure was obtained by refine
  • the structure of CC3 was confirmed by NMR and IR.
  • Production Example 4 As a raw material for the ⁇ -hydroxycarboxylic acid (B) component other than lactic acid, a cyclic dimer composed of 2-hydroxybutyric acid, a cyclic dimer composed of lactic acid and 2-hydroxybutyric acid, and a raw material for the lactic acid (A) component L-lactide was mixed in a molten state, adjusted to 0.1 parts by weight of 2-hydroxybutyric acid with respect to 100 parts by weight of lactic acid (the optical purity of lactic acid was 99.9%), and the molecular weight modifier was adjusted to 0.0.
  • the resulting polylactic acid composition had a carboxyl end group concentration of 14 equivalents / ton, a weight average molecular weight of 160,000, and a melting point of 175 ° C.
  • Production Example 6 50 parts by weight of the polylactic acid composition obtained by the operation of Production Example 4 and the polylactic acid composition obtained by the operation of Production Example 5 were each mixed with a phosphate metal salt (“ADEKA STAB” NA-11 manufactured by ADEKA Corporation).
  • the resulting polylactic acid composition had a carboxyl end group concentration of 14 equivalents / ton, a weight average molecular weight of 200,000, a melting point of 159 ° C., and a glass transition point of 63 ° C.
  • Production Example 8 50 parts by weight of each of the polylactic acid composition obtained by the operation of Production Example 7 and the polylactic acid composition obtained by the operation of Production Example 5, phosphate metal salt (“ADEKA STAB” NA-produced by ADEKA Corporation) 11) After mixing 0.3 parts by weight with a blender, vacuum drying at 110 ° C. for 5 hours, from the first supply port of the extruder, melt kneading while evacuating at a cylinder temperature of 270 ° C.
  • ADEKA STAB phosphate metal salt
  • stereocomplex polylactic acid having a stereocomplex crystallinity (S) of 100% and a crystal melting temperature of 216 ° C.
  • the resulting stereocomplex polylactic acid had a carboxyl end group concentration of 11 equivalents / ton and a weight average molecular weight of 130,000.
  • the polylactic acid composition produced in Production Example 4 is quantitatively supplied from the first supply port, and the polylactic acid composition is produced from the second supply port provided with cyclic carbodiimide (CC2) at the barrel 14 position by the side feeder.
  • CC2 cyclic carbodiimide
  • the product was 100 parts by weight, 1 part by weight of cyclic carbodiimide (CC2) was supplied, kneaded and pelletized to obtain a polylactic acid composition of the present invention containing a cyclic carbodiimide compound.
  • the carboxyl end group concentration of the obtained polylactic acid composition was reduced to 0.4 equivalent / ton or less.
  • the resulting polylactic acid composition had a weight average molecular weight of 175,000 and a melting point of 176 ° C.
  • Example 2 In Example 1, when the reaction was carried out in the same manner except that the cyclic carbodiimide (CC2) was changed to the cyclic carbodiimide (CC1), the carboxyl end group concentration was reduced to 0.7 equivalent / ton or less. The resulting polylactic acid had a weight average molecular weight of 180,000 and a melting point of 174 ° C. Further, there was no isocyanate odor at the exit of the ruder after kneading.
  • Example 3 In Example 1, when the polylactic acid composition obtained by the operation of Production Example 4 was changed to the polylactic acid composition obtained by the operation of Production Example 5, the same operation was carried out to obtain a reaction. The carboxyl end group concentration of the obtained polylactic acid composition was reduced to 0.5 equivalent / ton or less. The resulting polylactic acid composition had a weight average molecular weight of 173,000 and a melting point of 174 ° C. Further, there was no isocyanate odor at the exit of the ruder after kneading.
  • Example 4 In Example 1, the cyclic carbodiimide (CC2) was converted to the cyclic carbodiimide (CC3), the polylactic acid composition obtained by the operation of Production Example 4 was converted to the stereocomplex polylactic acid composition obtained by the operation of Production Example 6, and biaxial extrusion When the reaction was carried out in the same manner except that the temperature of the machine was changed to 180 to 260 ° C., the carboxyl end group concentration of the obtained polylactic acid composition was reduced to 0.3 equivalent / ton or less.
  • the resulting polylactic acid had a weight average molecular weight of 152,000 and a melting point of 220 ° C. Further, there was no isocyanate odor at the exit of the ruder after kneading. When the resin filter at the outlet of the extruder was confirmed, no foreign matter due to thermal modification of the cyclic carbodiimide (CC3) was found.
  • Example 5 the stereocomplex polylactic acid composition obtained by the operation of Production Example 6 was obtained as the polylactic acid composition obtained by the operation of Production Example 4, and the polylactic acid composition obtained by the operation of Production Example 5 was 1: 1.
  • Example 6 In Example 4, it produced by the same method except having made the polylactic acid composition obtained by operation of manufacture example 6 into the stereocomplex polylactic acid composition obtained by operation of manufacture example 8.
  • FIG. The carboxyl end group concentration of the obtained polylactic acid composition was reduced to 0.3 equivalent / ton or less.
  • the resulting polylactic acid composition had a weight average molecular weight of 160,000 and a melting point of 210 ° C. Further, there was no isocyanate odor at the exit of the ruder after kneading. When the resin filter at the outlet of the extruder was confirmed, no foreign matter due to thermal modification of the cyclic carbodiimide (CC3) was found.
  • CC3 cyclic carbodiimide
  • Example 7 In Example 1, when the reaction was carried out in the same manner except that the polylactic acid composition obtained by the operation of Production Example 7 was used instead of the polylactic acid composition of Production Example 4, the carboxyl end group concentration was 0.00. It decreased to 7 equivalents / ton or less.
  • the resulting polylactic acid composition had a weight average molecular weight of 220,000 and a melting point of 154 ° C. Further, there was no isocyanate odor at the exit of the ruder after kneading. When the resin filter at the outlet of the extruder was confirmed, no foreign matter due to thermal denaturation of the cyclic carbodiimide compound (CC1) was found.
  • Example 4 the same operation was carried out except that the addition amount of the cyclic carbodiimide compound (CC3) was changed from 0.5 to 6 parts by weight.
  • the results are shown in Table 1. Comparative Example 1 In Example 1, the cyclic carbodiimide compound (CC2) was replaced with linear carbodiimide manufactured by Rhein Chemie Japan Co., Ltd., “STABAXOL” I, and reacted under the same conditions except that the carboxyl end group concentration was 0. The equivalent malodor of isocyanate was strongly generated at the exit of the ruder.
  • Example 4 Comparative Example 2
  • the cyclic carbodiimide compound (CC3) was replaced with a linear polycarbodiimide compound [manufactured by Nisshinbo Chemical Co., Ltd .; “Carbodilite” HMV-8CA], and other conditions were reacted in the same manner.
  • the concentration was 0.6 equivalent / ton, a strong malodor of isocyanate was generated at the outlet of the ruder.
  • Example 12 The pellets obtained in Example 4 were dried for 12 hours in a vacuum dryer set at 110 ° C.
  • the dried chip was melt-extruded into a 210 ⁇ m film at a die temperature of 220 ° C., and adhered and solidified to the surface of the mirror-cooled drum by electrostatic casting using a platinum-coated linear electrode.
  • the unstretched film is further stretched at 100 ° C., 1.1 to 1.5 times in the longitudinal direction, 1.1 to 2.0 times in the transverse direction, and further heat-fixed at 140 to 160 ° C.
  • a biaxially stretched film was obtained.
  • An irritating odor derived from isocyanate gas was not felt in the process of film formation, stretching and heat setting.
  • Example 13 The pellets obtained in Example 4 were dried with a dehumidifying dryer at 50 ° C., melted at a temperature of 220 ° C.
  • the undrawn yarn was wound up at a speed of 500 m / min.
  • the wound undrawn yarn was drawn 4.9 times with a drawing machine at 80 ° C. by preheating to wind the drawn yarn, and then heat treated at 130 ° C.
  • the processability in the spinning process and the drawing process was good, and the wound drawn yarn was a multifilament having a fineness of 167 dTex / 36 fil, a strength of 3.7 cN / dTex, an elongation of 35%, and a melting point of 213 ° C. .
  • the melting peak temperature was 224 ° C.
  • the stereocomplex crystallinity was 100%.
  • the obtained stereocomplex polylactic acid filament was twisted at 80 T / m (twisting coefficient 6.2), and then placed on warps and wefts to weave a twill-woven fabric.
  • Example 14 The pellets obtained in Example 4 were dried with a dehumidifying dryer at 50 ° C., mixed and spun at 220 ° C. with a discharge rate of 8.35 g / min with an extruder-type spinning machine, and then at a speed of 500 m / min. Undrawn yarn was wound up.
  • the wound undrawn yarn was drawn 4.9 times with a drawing machine at 80 ° C. by preheating to wind the drawn yarn, and then heat treated at 180 ° C.
  • the process passability in the spinning process and the drawing process was good, and the wound drawn yarn was a multifilament having a fineness of 167 dTex / 36 fil, a strength of 3.6 cN / dTex, an elongation of 36%, and a melting point of 219 ° C. .
  • it had a single melting peak in DSC measurement, the melting peak temperature (melting point) was 222 ° C., and the stereocomplex crystallization rate was 100%.
  • the knitted fabric was set at 150 ° C. for 2 minutes by dry heat, and then 20 ° C. at 120 ° C. using a liquid dyeing machine. Minute staining was performed. At that time, a black disperse dye was used. Furthermore, a dry heat set at a temperature of 160 ° C. for 2 minutes was performed. Generation of isocyanate odor was not felt during melt-kneading, yarn production and knitting. Moreover, when the obtained knitted fabric was melted at 300 ° C. for 5 minutes, the isocyanate odor evaluation was acceptable.
  • Example 15 The pellets obtained in Example 4 were dried with a dehumidifying dryer at 50 ° C., melted at 220 ° C. with an extruder type spinning machine, spun from the pores, and then spun at a spinning speed of 4300 m / min with an ejector. Then, the web collected on the moving net conveyor was heated with an embossing roll and a flat roll having a convex area of 16% at a temperature of 160 ° C. and a linear pressure of 245 cN / cm (25 kg / cm).
  • a spunbonded nonwoven fabric having a single fiber fineness of 1.6 dtex and a basis weight of 30 g / m 2 was produced by pressure bonding. Generation of isocyanate odor was not felt during melt-kneading, yarn production and spunbond production. Moreover, when the obtained textile fabric was melted at 300 ° C. for 5 minutes, the isocyanate odor evaluation was acceptable. Further, the carboxyl end group concentration of the polylactic acid filament immediately after spinning was 1 equivalent / ton, and the carboxyl end group concentration of the polylactic acid structure was 2 equivalent / ton.
  • Example 16 The pellets obtained in Example 4 were dried with a dehumidifying dryer at 50 ° C., and a test piece was prepared with an injection molding machine at a nozzle of 220 ° C. and a mold temperature of 110 ° C. Generation of isocyanate odor was not felt during melt-kneading and injection molding. Moreover, when the obtained test piece was melted at 300 ° C. for 5 minutes, the isocyanate odor evaluation was acceptable. Further, the carboxyl end group concentration of the molded product was 1 equivalent / ton.

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Abstract

La présente invention concerne une composition d'acide polylactique se composant principalement d'un composant acide polylactique (A) dans lequel, par rapport à une composition de résine, la composition d'acide polylactique contient de 95 à 99,99% en poids du composant acide polylactique (A), de 0,01 à 5% en poids d'un composant acide a-hydroxycarboxylique (B) autre que l'acide lactique, et 0,01 à 10 parties en poids d'un composé carbodiimide (C) représenté par une formule structurelle particulière pour 100 parties en poids du composant (A) et du composant (B).
PCT/JP2011/063750 2010-06-14 2011-06-09 Composition d'acide polylactique, et article moulé formé à partir de cette composition WO2011158884A1 (fr)

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JP2010-135096 2010-06-14
JP2010135096A JP6059417B2 (ja) 2010-06-14 2010-06-14 ポリエステル樹脂組成物の製造方法
JP2010136130A JP6087487B2 (ja) 2010-06-15 2010-06-15 樹脂組成物の製造方法
JP2010-136129 2010-06-15
JP2010-136130 2010-06-15
JP2010-136128 2010-06-15
JP2010136128A JP6087486B2 (ja) 2010-06-15 2010-06-15 樹脂組成物の製造方法
JP2010136129A JP2012001594A (ja) 2010-06-15 2010-06-15 樹脂組成物の製造方法
JP2010137328A JP2012001620A (ja) 2010-06-16 2010-06-16 ポリ乳酸組成物およびそれからなる成形品
JP2010-137328 2010-06-16

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