WO2011096299A1 - ポリ乳酸樹脂組成物の製造方法 - Google Patents
ポリ乳酸樹脂組成物の製造方法 Download PDFInfo
- Publication number
- WO2011096299A1 WO2011096299A1 PCT/JP2011/051307 JP2011051307W WO2011096299A1 WO 2011096299 A1 WO2011096299 A1 WO 2011096299A1 JP 2011051307 W JP2011051307 W JP 2011051307W WO 2011096299 A1 WO2011096299 A1 WO 2011096299A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polylactic acid
- nucleating agent
- crystal nucleating
- acid resin
- resin composition
- Prior art date
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 229
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 229
- 239000011342 resin composition Substances 0.000 title claims abstract description 131
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- 238000000034 method Methods 0.000 title claims abstract description 32
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- 239000002994 raw material Substances 0.000 claims abstract description 19
- 238000004898 kneading Methods 0.000 claims abstract description 16
- 239000002667 nucleating agent Substances 0.000 claims abstract description 8
- 239000003484 crystal nucleating agent Substances 0.000 claims description 179
- -1 phosphate ester Chemical class 0.000 claims description 117
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- 229910019142 PO4 Inorganic materials 0.000 claims description 44
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- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims description 18
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
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- 238000002844 melting Methods 0.000 claims description 12
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- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
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- 230000000694 effects Effects 0.000 description 13
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- YETJDUSSMZWBME-UHFFFAOYSA-N tris[2-(2-butoxyethoxy)ethyl] phosphate Chemical compound CCCCOCCOCCOP(=O)(OCCOCCOCCCC)OCCOCCOCCCC YETJDUSSMZWBME-UHFFFAOYSA-N 0.000 description 1
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- GDQGUZQTTHPXGN-UHFFFAOYSA-N tris[2-(2-propoxyethoxy)ethyl] phosphate Chemical compound CCCOCCOCCOP(=O)(OCCOCCOCCC)OCCOCCOCCC GDQGUZQTTHPXGN-UHFFFAOYSA-N 0.000 description 1
- JNUDHPJKPDJVCM-UHFFFAOYSA-N tris[2-[2-(2-ethoxyethoxy)ethoxy]ethyl] phosphate Chemical compound CCOCCOCCOCCOP(=O)(OCCOCCOCCOCC)OCCOCCOCCOCC JNUDHPJKPDJVCM-UHFFFAOYSA-N 0.000 description 1
- CFFLFIVJXKFMDC-UHFFFAOYSA-N tris[2-[2-(2-methoxyethoxy)ethoxy]ethyl] phosphate Chemical compound COCCOCCOCCOP(=O)(OCCOCCOCCOC)OCCOCCOCCOC CFFLFIVJXKFMDC-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
- C08L93/04—Rosin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/007—Methods for continuous mixing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/72—Measuring, controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/201—Pre-melted polymers
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
Definitions
- the present invention relates to a method for producing a polylactic acid resin composition. More specifically, for example, the present invention relates to a method for producing a polylactic acid resin composition that can be suitably used as household goods, home appliance parts, automobile parts, and the like, and a polylactic acid resin composition obtained by the production method.
- Polylactic acid resin is inexpensive because L-lactic acid as a raw material is produced by fermentation using sugars extracted from corn, straw, etc., and the carbon dioxide emission is extremely low because the raw material is derived from plants. In addition, since the resin has high rigidity and high transparency, its use is expected now.
- the polylactic acid resin has a slow crystallization speed, and therefore, when crystallization is performed, it takes a long time and productivity is poor. Therefore, a technique for improving the crystallization rate by blending a crystal nucleating agent or the like with polylactic acid resin is known.
- Patent Document 1 a polylactic acid resin composition having an excellent crystallization speed is obtained by blending a polyphosphoric acid derivative with a phenylphosphone derivative having a specific structure.
- the biodegradable resin is excellent in crystallization speed and heat resistance by blending a mixture of at least one compound selected from compounds having a hydroxyl group and an amide group in the molecule with a metal salt of phenylphosphonic acid.
- a polylactic acid resin composition has been obtained.
- Patent Document 3 a polylactic acid resin composition excellent in crystallization speed and heat resistance is obtained by blending a specific polyester polyol and a crystal nucleating agent with a polylactic acid resin.
- the polyester polyol and the crystal nucleating agent are mixed in advance and the crystal nucleating agent is refined to obtain a polylactic acid resin composition having higher heat resistance.
- Patent Document 4 discloses a method in which an aliphatic phosphate compound having a fatty chain having 12 to 28 carbon atoms or the like is used as a lubricant for molding a polylactic acid resin composition.
- Patent Document 5 discloses that by adding several aliphatic phosphate triesters as a plasticizer together with a crystal nucleating agent, secondary processability such as stretch processability in the production of a porous sheet can be improved. .
- polylactic acid resin compositions are expected to be used in a wide range of applications such as automobile applications, and polylactic acid resin compositions having higher crystallization speed and excellent heat resistance are desired.
- polylactic acid resin compositions since it is required to have the same level of moldability as polypropylene resin or the like in order to be used as a substitute for a conventional petroleum resin, molding processability at a lower temperature is required.
- the effect is not sufficient in the prior art, and further improvement is required.
- An object of the present invention is to provide a method for producing a polylactic acid resin composition having a high crystallization rate, excellent moldability at low temperatures and excellent heat resistance, and a polylactic acid resin composition obtained by the production method There is to do.
- an organic crystal nucleating agent is a carboxylic acid ester having a weight average molecular weight of 150 to 600 and a viscosity at 23 ° C.
- the resulting polylactic acid resin composition has an excellent crystallization rate.
- the present inventors have found that it has molding processability at low temperatures and heat resistance, and has completed the present invention.
- the present invention [1] A method for producing a polylactic acid resin composition
- the organic crystal nucleating agent is a carboxylic acid ester having a weight average molecular weight of 150 to 600 and a viscosity at 23 ° C. of 1 to 500 mPa ⁇ s and / or a weight average molecular weight of 150 to 600 and a viscosity at 23 ° C.
- the present invention relates to a step of melt-kneading a raw material for a polylactic acid resin composition containing a nucleating agent composition and a polylactic acid resin, and [2] a polylactic acid resin composition obtained by the production method described in [1] above.
- the polylactic acid resin composition obtained by the production method of the present invention has the effect of being excellent in crystallization speed, molding processability at low temperature, and heat resistance.
- an organic crystal nucleating agent is used as the crystal nucleating agent.
- a carboxylic acid ester having an average molecular weight of 150 to 600 and a viscosity of 1 to 500 mPa ⁇ s at 23 ° C. and / or a phosphate ester having a weight average molecular weight of 150 to 600 and a viscosity of 1 to 500 mPa ⁇ s at 23 ° C. It has a great feature in using an organic crystal nucleating agent composition obtained by wet pulverization in
- a polyester polyol and a crystal nucleating agent are mixed in advance at the time of melt-kneading in order to increase the crystallization speed, molding processability at low temperature, and heat resistance.
- the agent is made finer.
- This polyester polyol has a high molecular weight and high viscosity in order to improve compatibility with polylactic acid resin, which is a kind of polyester, and wettability with fine particles of inorganic natural products such as talc, which is a crystal nucleating agent. Is used.
- the organic crystal nuclei obtained by wet pulverizing the organic crystal nucleating agent using a carboxylic acid ester and / or a phosphoric acid ester having a low molecular weight and low viscosity are obtained.
- the agent composition increases the crystallization speed of the polylactic acid resin composition, that is, the polylactic acid resin composition can be crystallized in a shorter time, and has a good moldability at a lower temperature and excellent heat resistance. It has been found that a lactic acid resin composition can be obtained.
- the carboxylic acid ester and the phosphoric acid ester used in the present invention have a low molecular weight and a low viscosity, they are considered to serve as both a dispersion medium and a solvent for suppressing reaggregation of the organic crystal nucleating agent during the wet grinding process. It is done. For this reason, miniaturization of the organic crystal nucleating agent is achieved, and the resulting organic crystal nucleating agent composition is such that the ester adheres to the surface of the organic crystal nucleating agent. It is considered that the nucleating agent composition is finely dispersed without reaggregating in the polylactic acid resin.
- stimulates crystallization in a polylactic acid resin composition increases, and the crystallization rate of a polylactic acid resin improves. Furthermore, since the ester present on the surface of the organic crystal nucleating agent composition also functions as a plasticizer, the refined organic crystal nucleating agent composition is effective as a result of promoting plasticization of the polylactic acid resin. It is considered that a polylactic acid resin composition excellent in molding processability and heat resistance at a low temperature can be obtained while further improving the crystallization speed.
- the production method of the present invention comprises: Step (1):
- the organic crystal nucleating agent is a carboxylic acid ester having a weight average molecular weight of 150 to 600 and a viscosity at 23 ° C. of 1 to 500 mPa ⁇ s and / or a weight average molecular weight of 150 to 600 and a viscosity at 23 ° C.
- the organic crystal nucleating agent is a carboxylic acid ester having a weight average molecular weight of 150 to 600 and a viscosity at 23 ° C. of 1 to 500 mPa ⁇ s and / or a weight average molecular weight of 150 to 600 and a viscosity at 23 ° C.
- This is a step of obtaining a refined organic crystal nucleating agent composition (hereinafter also referred to as a refined organic crystal nucleating agent) by wet pulverization in the presence of a phosphate ester of 1 to 500 mPa ⁇ s.
- the carboxylic acid ester and phosphate ester used for wet pulverization of the organic crystal nucleating agent are collectively referred to as a pulverization aid ester.
- Organic crystal nucleating agent used in the present invention is preferably a solid at all times within the range of 20 to 200 ° C. from the viewpoint of improving the crystallization speed of the polylactic acid resin. From the following (a) to (c) More preferred is at least one selected from the group consisting of (A) From the group consisting of a compound having an isoindolinone skeleton, a compound having a diketopyrrolopyrrole skeleton, a compound having a benzimidazolone skeleton, a compound having an indigo skeleton, a compound having a phthalocyanine skeleton, and a compound having a porphyrin skeleton At least one organic compound selected [referred to as organic crystal nucleating agent (a)] (B) at least one organic compound selected from the group consisting of carbohydrazides, melamine compounds, uracils, and N-substituted ureas (referred to as organic crystal nucleating agent (a)] (B)
- Organic crystal nucleating agent (a) includes a compound having an isoindolinone skeleton, a compound having a diketopyrrolopyrrole skeleton, a compound having a benzimidazolone skeleton, a compound having an indigo skeleton, a compound having a phthalocyanine skeleton, and a porphyrin skeleton
- the at least 1 sort (s) of organic compound chosen from the group which consists of a compound which has these is mentioned.
- Examples of the compound having an isoindolinone skeleton include compounds having an isoindolinone skeleton and substituted compounds thereof, and specific examples include yellow pigments PY109, PY110, PY173, and orange pigment PO61.
- Compounds having a diketopyrrolopyrrole skeleton include compounds having a diketopyrrolopyrrole skeleton and substituted compounds thereof. Specifically, red pigments PR254, PR255, PR264, PR270, PR272, orange pigments PO71 and PO73 are included. Illustrated.
- the compound having a benzimidazolone skeleton includes a compound having a benzimidazolone skeleton and a substituted compound thereof.
- a purple pigment PV32, a red pigment PR171, PR175, PR176, PR185, PR208, a yellow pigment PY120, PY151, PY154, PY156, PY175, PY180, PY181, PY194, orange pigments PO36, PO60, PO62, and PO72 are exemplified.
- Compounds having an indigo skeleton include compounds having an indigo skeleton and substituted compounds thereof. Specifically, the blue dye Vat Blue 1, blue pigment PB66, PB63, red pigment PR88, PR181, brown pigment PBr27, indigo carmine Is exemplified.
- Compounds having a phthalocyanine skeleton include compounds having a phthalocyanine skeleton and substituted compounds thereof. Specifically, phthalocyanine, blue pigments PB15, PB15: 2, PB15: 3, PB15: 4, PB15: 5, PB15: 6, PB16, green pigment PG7, PG36, copper phthalocyanine, zinc phthalocyanine, titanyl phthalocyanine, aluminum phthalocyanine, vanadium phthalocyanine, cadmium phthalocyanine, antimony phthalocyanine, chromium phthalocyanine, germanium phthalocyanine, iron phthalocyanine, chloroaluminum phthalocyanine, chloroindium phthalocyanine, chlorogallium Phthalocyanine, magnesium phthalocyanine, dialkyl phthalocyanine, tetramethylphthalocyanine , Tetraphenyl phthalocyanine, uranium complex having five isoindole rings
- substituents such as a halide and an alkylated substance
- substituents include halogen atoms such as chlorine, bromine, fluorine and iodine, alkyl groups such as methyl, ethyl and propyl, alkoxy groups such as methoxy and ethoxy, hydroxyl groups and amino groups.
- Examples of the compound having a porphyrin skeleton include compounds having a porphyrin skeleton and substituted compounds thereof, and specific examples include chlorophyll compounds, hemin compounds, and esters thereof.
- the substituted form includes those substituted by the following substituents, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isoamyl, tert-amyl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, alkyl groups
- Aryl groups such as monocyclic groups or condensed polycyclic groups of the above; those substituted with a bridged cyclic hydrocarbon group such as 1-adamantyl, 2-adamantyl, 2-norbornanyl, 5-norbornen-2-yl, etc. Can be mentioned. Further, it may be a halide or a sulfonate.
- Organic crystal nucleating agent (b) examples include at least one organic compound selected from the group consisting of carbohydrazides, melamine compounds, uracils, and N-substituted ureas.
- Carbohydrazides include ethylenedicarbonyldibenzoylhydrazide, tetramethylenedicarbonyldibenzoylhydrazide, hexamethylenedicarbonyldibenzoylhydrazide, octamethylenedicarbonyldibenzoylhydrazide, decamethylenedicarbonyldibenzoylhydrazide, dodecamethylenedicarbonyldi Benzoyl hydrazide, cyclohexylene dicarbonyldibenzoyl hydrazide, octamethylene dicarbonyldi (4-methylbenzoyl) hydrazide, octamethylene dicarbonyldi (4-t-butylbenzoyl) hydrazide, octamethylene dicarbonyldi (2-methylbenzoyl) ) Hydrazide, octamethylenedicarbonyldi (3-methylbenz
- melamine compounds include melamine, substituted melamine compounds, melamine deammonium condensates, and salts of melamines and acids.
- Examples of the substituted melamine compound include compounds in which hydrogen of the amino group of melamine is substituted.
- substituent include an alkyl group, an alkenyl group, a phenyl group, a hydroxyalkyl group, a hydroxyalkyl (oxaalkyl) group, and an aminoalkyl group.
- Melamine deammonium condensate includes melam, melem, melon, methone and the like.
- Examples of the salt of melamine and acid include a salt of at least one melamine and acid selected from melamine, a substituted melamine compound, and a deammonia condensate of melamine.
- Acids include organic acids such as isocyanuric acid, formic acid, acetic acid, oxalic acid, malonic acid, lactic acid, citric acid, benzoic acid, isophthalic acid, terephthalic acid; hydrochloric acid, nitric acid, sulfuric acid, pyrosulfuric acid, methanesulfonic acid, ethanesulfone Acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, sulfamate, phosphate, pyrophosphate, polyphosphate, phosphonate, phenylphosphonate, alkylphosphonate, phosphite, borate And inorganic acids such as tungstate.
- uracils include uracil, 6-methyluracil, 5-methyluracil (thymine), 6-azathymine, 6-azauracil, 5-crouracil, 6-benzyl-2-thiouracil, 5-cyanouracil, ethyl 2-thiouracil- 5-carboxylate, 5-ethyluracil, 5,6-dihydro-6-methyluracil, 5- (hydroxymethyl) uracil, 5-iodouracil, 5-methyl-2-thiouracil, 5-nitrouracil, 5- ( Trifluoromethyl) uracil, 2-thiouracil, 5-fluorouracil and the like.
- N-substituted ureas examples include xylene bislauryl urea, xylene bismyristyl urea, xylene bispalmityl urea, xylene bisstearyl urea, and the like.
- Organic crystal nucleating agent (c) examples include metal salts of aromatic dialkyl sulfonates, metal salts of phosphate esters, metal salts of phenylphosphonic acid, metal salts of rosin acids, aromatic carboxylic acid amides, and rosin acid amides. And at least one organic compound selected from the group consisting of:
- Examples of the metal salt of dialkyl aromatic sulfonate include dimethyl dibarium 5-sulfoisophthalate, dimethyl dicalcium 5-sulfoisophthalate, and dimethyl potassium 5-sulfoisophthalate.
- Metal salts of phosphate esters include sodium-2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate, aluminum bis (2,2'-methylenebis-4,6-di-t-butyl) Phenyl phosphate) and the like.
- the metal salt of phenylphosphonic acid is a metal salt of phenylphosphonic acid having a phenyl group which may have a substituent and a phosphone group (—PO (OH) 2 ), and the substituent of the phenyl group includes carbon Examples thereof include an alkyl group having 1 to 10 carbon atoms and an alkoxycarbonyl group having 1 to 10 carbon atoms in an alkoxy group.
- phenylphosphonic acid examples include unsubstituted phenylphosphonic acid, methylphenylphosphonic acid, ethylphenylphosphonic acid, propylphenylphosphonic acid, butylphenylphosphonic acid, dimethoxycarbonylphenylphosphonic acid, and diethoxycarbonylphenylphosphonic acid. And unsubstituted phenylphosphonic acid is preferred.
- metal salt of phenylphosphonic acid examples include salts of lithium, sodium, magnesium, aluminum, potassium, calcium, barium, copper, zinc, iron, cobalt, nickel, and the like, and zinc salts are preferable.
- metal salts of rosin acids include pimaric acid, sandaracopimalic acid, parastrinic acid, isopimaric acid, abietic acid, dehydroabietic acid, methyldehydroabietic acid, neoabietic acid, dihydropimaric acid, dihydroabietic acid, tetrahydroabietic acid, etc. Metal salts are mentioned.
- aromatic carboxylic acid amides include 1,3,5-benzenetricarboxylic acid tris (t-butylamide) (trimesic acid tris (t-butylamide)), m-xylylene bis 12-hydroxystearic acid amide, 1,3,5- Examples include benzenetricarboxylic acid tricyclohexylamide (trimesic acid tricyclohexylamide), trimesic acid tri (2-methylcyclohexylamide), 2,6-naphthalenedicarboxylic acid dicyclohexylamide, and the like.
- rosin acid amides examples include p-xylylene bis rosin acid amide and p-phenylenediamine mono rosin acid amide.
- organic crystal nucleating agent (b) and the organic crystal nucleating agent (c) can be used in combination.
- metal salts of phenylphosphonic acid, PY109, PB15: 3, PB15, and PB15: 6 are preferable. Metal salts are more preferred.
- the shape and average particle size of the organic crystal nucleating agent to be subjected to wet pulverization are not particularly limited as long as wet pulverization can be performed, but the efficiency of wet pulverization is improved and the resulting organic crystal nucleating agent composition
- the volume median particle size (D 50 ) is preferably 500 nm to 5 ⁇ m, more preferably 600 nm to 2 ⁇ m, and even more preferably 700 nm to 1.5 ⁇ m.
- the average particle diameter of the organic crystal nucleus agent is meant a volume-median particle size (D 50), it can be determined according to the method described in Examples set forth below.
- the wet pulverization of the organic crystal nucleating agent is carried out by using a carboxylic acid ester having a weight average molecular weight of 150 to 600 and a viscosity of 1 to 500 mPa ⁇ s at 23 ° C. and / or a weight average molecular weight of 150 to 600 and 23 ° C.
- a phosphate having a viscosity of 1 to 500 mPa ⁇ s is used.
- the phosphate used for wet pulverization has a viscosity of 1 to 500 mPa ⁇ s at 23 ° C., whereas the phosphate of the organic crystal nucleating agent used for pulverization is in the range of 20 to 200 ° C. It is clear that it is different from being solid.
- the carboxylic acid ester and / or phosphoric acid ester used for wet pulverization of the organic crystal nucleating agent in the present invention has a weight average molecular weight of 150 to 600 and a viscosity of 1 to 500 mPa ⁇ s, and a weight average molecular weight of 150 to 600. 600, a phosphate ester having a viscosity of 1 to 500 mPa ⁇ s, and serves as both a solvent and a dispersant when the organic crystal nucleating agent is refined.
- the micronized organic crystal nucleating agent composition in the present invention has a small particle size and a carboxylic acid ester and / or a phosphoric acid ester having a specific molecular weight and viscosity on its surface.
- the finely divided organic crystal nucleating agent composition being finely dispersed without being re-agglomerated in the polylactic acid resin composition, a large number of crystal nuclei increase in the polylactic acid resin composition, and the ester is plasticized.
- the refined organic crystal nucleating agent composition works effectively, further improves the crystallization speed, and excels in molding processability and heat resistance at low temperature. It is considered that a polylactic acid resin composition can be obtained.
- Carboxylic acid ester having a weight average molecular weight of 150 to 600 and a viscosity at 23 ° C. of 1 to 500 mPa ⁇ s The weight average molecular weight of the carboxylic acid ester is 150 to 600. If the weight average molecular weight is 600 or less, the organic crystal nucleating agent will not be sufficiently refined due to its bulk, and if the molecular weight is 150 or more, a plasticizing effect on the polylactic acid resin will act. Thus, a polylactic acid resin composition having a sufficient crystallization rate can be obtained.
- the weight average molecular weight of the carboxylic acid ester is preferably 250 to 600, more preferably 300 to 600, and still more preferably 350, from the viewpoint of refining the organic crystal nucleating agent and the plasticizing effect on the polylactic acid resin. ⁇ 550, more preferably 400 ⁇ 500.
- pulverization of an organic crystal nucleating agent can be measured according to the method as described in the below-mentioned Example.
- the viscosity (23 ° C.) of the carboxylic acid ester is 1 to 500 mPa ⁇ s. If the viscosity is 500 mPa ⁇ s or less, the viscosity is too high and it is difficult to make the organic crystal nucleating agent finer. On the other hand, if the viscosity is 1 mPa ⁇ s or more, the plasticizing effect on the polylactic acid resin is good. And a polylactic acid resin composition having a sufficient crystallization rate can be obtained.
- the viscosity (23 ° C.) of the carboxylic acid ester is preferably 1 to 400 mPa ⁇ s, more preferably 2 to 200 mPa ⁇ s, from the viewpoint of refining the organic crystal nucleating agent and the plasticizing effect on the polylactic acid resin. s, more preferably 3 to 100 mPa ⁇ s, still more preferably 3 to 50 mPa ⁇ s.
- the viscosity of the ester used for wet pulverization of the organic crystal nucleating agent can be measured according to the method described in the examples described later.
- a carboxylic acid ester having a weight average molecular weight of 150 to 600 and a viscosity (23 ° C.) of 1 to 500 mPa ⁇ s can be obtained by condensation polymerization of an alcohol component and a carboxylic acid component shown below.
- the alcohol component may contain monoalcohol, polyhydric alcohol, etc., but it is possible to refine organic crystal nucleating agent and compatibility with polylactic acid resin, plasticity of polylactic acid resin, and volatilization resistance of the carboxylic acid ester. From the viewpoint of properties, it is preferable to contain a monoalcohol having preferably 3 to 18, more preferably 3 to 16, and still more preferably 3 to 14 carbon atoms. From the same viewpoint, an alkyleneoxy group having 2 or 3 carbon atoms per hydroxyl group of the alcohol is preferably 0.5 to 5 mol, more preferably 1.0 to 4 mol, and still more preferably as an average added mole number.
- the alkyleneoxy group having 2 or 3 carbon atoms is preferably an ethyleneoxy group from the viewpoint of plasticizing efficiency with respect to the polylactic acid resin.
- the number of carbon atoms is preferably 1-8, more preferably 1-6,
- the hydrocarbon group is preferably 1 to 4, more preferably 1 to 2.
- the hydrocarbon group has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
- the alcohol constituting the ester group may be one type or two or more types, and the alcohol component preferably contains an alkylene oxide adduct of the alcohol, and all the alcohols are alkylene oxide adducts of the alcohol. More preferably, all alcohols are more preferably alkylene oxide adducts of the same alcohol.
- the alcohol component may contain an aromatic alcohol. Since the aromatic alcohol is more compatible with the polylactic acid resin than the aliphatic alcohol having the same carbon number, the weight average molecular weight can be increased while maintaining the bleed resistance.
- the aromatic alcohol include benzyl alcohol.
- the two or more ester groups contained in the ester compound preferably more than 0 and 1.5 or less, more preferably more than 0 and 1.2 or less, still more preferably It is desirable that an ester group of more than 0 and 1.0 or less is constituted by an aromatic alcohol.
- Examples of the carboxylic acid compound contained in the carboxylic acid component include known carboxylic acids, anhydrides thereof, and alkyl (1 to 3 carbon atoms) esters of acids. From the viewpoints of compatibility with the resin, plasticity, and volatile resistance of the carboxylic acid ester, a carboxylic acid having 1 to 6 carbon atoms is preferable, and a carboxylic acid having 2 to 5 carbon atoms is more preferable.
- examples of the monocarboxylic acid having 1 to 6 carbon atoms include acetic acid, propanoic acid, butanoic acid, pentanoic acid, and hexanoic acid.
- dicarboxylic acid having 2 to 6 carbon atoms examples include oxalic acid, malonic acid, Mention may be made of succinic acid, glutaric acid and adipic acid. Of these, dicarboxylic acids having 2 to 6 carbon atoms are preferred from the viewpoints of compatibility between the resulting ester, the organic crystal nucleating agent and the polylactic acid resin, plasticity, and volatile resistance of the carboxylic acid ester, and oxalic acid and malonic acid. Succinic acid, glutaric acid and adipic acid are more preferable, and succinic acid, glutaric acid and adipic acid are more preferable.
- the carboxylic acid, its anhydride, and the alkyl ester of the acid are collectively referred to as a carboxylic acid compound in this specification.
- the condensation polymerization of the alcohol component and the carboxylic acid component can be performed according to a known method.
- the carboxylic acid ester used in the present invention is a polyvalent carboxylic acid ether ester
- the number of carbon atoms in the presence of an acid catalyst such as paratoluenesulfonic acid monohydrate, sulfuric acid, or a metal catalyst such as dibutyltin oxide.
- an acid catalyst such as paratoluenesulfonic acid monohydrate, sulfuric acid, or a metal catalyst such as dibutyltin oxide.
- 3-5 saturated dibasic acid or anhydride thereof and polyalkylene glycol monoalkyl ether are directly reacted, or lower alkyl ester of saturated dibasic acid having 3-5 carbon atoms and polyalkylene glycol monoalkyl ether. Obtained by transesterification.
- polyethylene glycol monoalkyl ether, saturated dibasic acid, and paratoluenesulfonic acid monohydrate as a catalyst
- the carboxylic acid ester used in the present invention is a polyhydric alcohol ester
- an alkylene oxide having a carbon number of 2 to 3 at a temperature of 120 to 160 ° C. is used in glycerol with an autoclave in the presence of an alkali metal catalyst.
- 3 mol of acetic anhydride is added dropwise at 110 ° C. to 1 mol of the glycerin alkylene oxide adduct obtained, and aging is carried out at 110 ° C. for 2 hours after the completion of the addition.
- the product can be obtained by performing steam distillation under reduced pressure to distill off the acetic acid and unreacted acetic anhydride.
- the carboxylic acid ester used in the present invention is a hydroxycarboxylic acid ether ester
- an alkylene having 2 to 3 carbon atoms at a temperature of 120 to 160 ° C. is used in a hydroxycarboxylic acid such as lactic acid in the presence of an alkali metal catalyst in an autoclave. 2 to 5 moles of oxide are added per mole of hydroxycarboxylic acid. Then, 1 mol of acetic anhydride is added dropwise at 110 ° C. to 1 mol of the obtained lactate alkylene oxide adduct, and after completion of the addition, aging is performed at 110 ° C. for 2 hours to perform acetylation.
- the product is subjected to steam distillation under reduced pressure to distill off the acetic acid and unreacted acetic anhydride.
- the carboxylic acid ester used in the step (1) can be obtained.
- the organic crystal nucleating agent is made finer and the strength and flexibility of the polylactic acid resin composition are compatible, moldability, plasticity, and From the viewpoint of bleeding resistance of the carboxylic acid ester, selected from the group consisting of carboxylic acid ester of succinic acid or adipic acid and polyethylene glycol monomethyl ether, and carboxylic acid ester of acetic acid and glycerin or ethylene glycol ethylene oxide adduct At least one selected from the group consisting of succinic acid or adipic acid and polyethylene glycol monomethyl ether is more preferable.
- ethylene of acetic acid and glycerin is used.
- a carboxylic acid ester of adipic acid and a diethylene glycol monomethyl ether / benzyl alcohol mixture (weight ratio: 1/1) is preferable.
- the phosphate ester has a weight average molecular weight of 150 to 600. If the weight average molecular weight is 600 or less, the organic crystal nucleating agent will not be sufficiently refined due to its bulk, and if the molecular weight is 150 or more, a plasticizing effect on the polylactic acid resin will act. Thus, a polylactic acid resin composition having a sufficient crystallization rate can be obtained.
- the weight average molecular weight of the phosphoric acid ester is preferably 250 to 600, more preferably 300 to 600, and still more preferably 350, from the viewpoint of refining the organic crystal nucleating agent and the plasticizing effect on the polylactic acid resin. ⁇ 550, more preferably 400 ⁇ 500.
- the viscosity (23 ° C.) of the phosphate ester is 1 to 500 mPa ⁇ s. If the viscosity is 500 mPa ⁇ s or less, the viscosity is too high and it is difficult to make the organic crystal nucleating agent finer. On the other hand, if the viscosity is 1 mPa ⁇ s or more, the plasticizing effect on the polylactic acid resin is good. And a polylactic acid resin composition having a sufficient crystallization rate can be obtained.
- the viscosity (23 ° C.) of the phosphoric acid ester is preferably 1 to 400 mPa ⁇ s, more preferably 2 to 200 mPa ⁇ s, from the viewpoint of refining the organic crystal nucleating agent and the plasticizing effect on the polylactic acid resin. s, more preferably 3 to 100 mPa ⁇ s, still more preferably 3 to 50 mPa ⁇ s.
- a phosphate ester having a weight average molecular weight of 150 to 600 and a viscosity (23 ° C.) of 1 to 500 mPa ⁇ s can be obtained by condensation polymerization of an alcohol component and a phosphate component shown below.
- Examples of the alcohol component include alcohol components used in preparing the carboxylic acid ester.
- Examples of the phosphoric acid compound contained in the phosphoric acid component include known phosphoric acid, its anhydride, phosphorus oxyhalide, and alkyl (1 to 3 carbon atoms) esters of acids. From the viewpoints of compatibility with plasticizing and polylactic acid resins, plasticity, and volatile resistance of phosphate esters, phosphorus oxyhalides are preferred. Specific examples include phosphorus oxychloride, phosphorus oxybromide, and phosphorus oxyfluoride. Among these, phosphorus oxychloride is preferable from the viewpoint of compatibility between the obtained ester, the organic crystal nucleating agent, and the polylactic acid resin, plasticity, and volatility resistance of the phosphate ester. In addition, phosphoric acid, its anhydride, phosphorus oxyhalide, and an alkyl ester of an acid are collectively referred to herein as a phosphoric acid compound.
- the condensation polymerization of the alcohol component and the phosphoric acid component can be performed according to a known method.
- the phosphate ester used in the step (1) can be obtained.
- a phosphate triester is preferable from the viewpoint of increasing chemical stability during kneading with the polylactic acid resin.
- R 1 , R 2 and R 3 each independently represents an alkyl group having 1 to 4 carbon atoms, and A 1 , A 2 and A 3 each independently represents an alkylene group having 2 or 3 carbon atoms
- M, n, and p are each independently a positive number indicating the average number of moles added of the oxyalkylene group, and m + n + p is a number exceeding 3 and satisfying 12 or less
- the compound represented by these is preferable.
- the compound represented by the formula (I) is a polyether-type phosphate triester, which may be a symmetric structure or an asymmetric structure. However, from the viewpoint of ease of production, a symmetric structure phosphate triester is preferable.
- R 1 , R 2 , and R 3 each independently represents an alkyl group having 1 to 4 carbon atoms, and may be linear or branched. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group, and an ethyl group, a propyl group, and a butyl group are preferable.
- a 1 , A 2 , and A 3 each independently represent an alkylene group having 2 or 3 carbon atoms, and may be linear or branched. Specific examples include an ethylene group, an n-propylene group, and an isopropylene group.
- a 1 , A 2 , and A 3 form adjacent oxygen atoms and an oxyalkylene group (alkylene oxide) to form a repeating structure in the compound represented by formula (I).
- M, n, and p are each independently a positive number indicating the average added mole number of the oxyalkylene group, and m + n + p is a number exceeding 3 and satisfying 12 or less.
- m, n, and p are positive numbers, and m + n + p is a number that exceeds 3 and less than 12 Is preferable, and a number satisfying less than 12 and more than 4 is more preferable.
- the compound represented by the formula (I) may be a commercially available product or a compound synthesized according to a known production method, for example, the method described in JP-A-10-17581.
- the carboxylic acid ester and the phosphoric acid ester are all esterified from the viewpoint of miniaturizing the organic crystal nucleating agent and sufficiently exhibiting the function as a plasticizer.
- the carboxylic acid ester and the phosphoric acid ester can be used alone or in combination of two or more.
- the weighted average molecular weight and viscosity (23 ° C.) each have a weighted average value within the above range.
- the weight of the grinding aid ester here means the total weight of the carboxylic acid ester and the phosphoric acid ester used in the wet grinding in the step (1), and the organic crystal nucleating agent, the carboxylic acid ester and The weight ratio with the phosphate ester represents the ratio between the weight of the organic crystal nucleating agent and the total weight of the carboxylic acid ester and the phosphate ester.
- esters and the like in addition to the carboxylic acid ester and / or phosphoric acid ester, other esters and the like can be used in combination with the fine pulverization of the organic crystal nucleating agent as long as the effects of the present invention are not impaired.
- a known pulverizer such as a medium pulverizer or a non-media pulverizer can be used, but a medium pulverizer is preferable from the viewpoint of pulverization efficiency.
- the non-medium pulverizer include a high-pressure pulverizer such as a jet mill.
- the medium type pulverizer includes a container drive type pulverizer and a medium stirring type pulverizer.
- the container-driven crusher include a rolling mill, a vibration mill, a planetary mill, and a centrifugal fluid mill. Among these, a vibration mill is preferable from the viewpoint of high grinding efficiency and productivity.
- a medium agitation pulverizer such as a tower mill; an agitator-type pulverizer such as an attritor, an aquamizer, and a sand grinder;
- a continuous dynamic type pulverizer For example, a stirring tank type pulverizer is preferable from the viewpoint of high pulverization efficiency and productivity.
- the peripheral speed at the tip of the stirring blade is preferably 0.5 to 20 m / s, more preferably 1.0 to 15 m / s.
- the kind of grinder can refer to "Progress of chemical engineering, the 30th collection, fine particle control” (Chemical Engineering Society Tokai branch edition, published on October 10, 1996, Tsuji Shoten).
- a processing method either a batch type or a continuous type may be sufficient.
- the material of the medium of the medium pulverizer is not particularly limited, and examples thereof include iron, stainless steel, alumina, zirconia, silicon carbide, silicon nitride, and glass. Zirconia is preferable from the viewpoint of pulverization efficiency.
- bowl, a rod, a tube, etc. are mentioned.
- the rod is a rod-shaped medium, and a rod having a cross section of a quadrangle, a polygon such as a hexagon, a circle, an ellipse or the like can be used, but a ball is preferable from the viewpoint of grinding efficiency.
- the outer diameter of the rod is preferably 0.5 to 200 mm, more preferably 1.0 to 100 mm, and still more preferably. 5 to 50 mm. If the size of the rod is within the above range, the desired pulverization force can be obtained, and the organic crystal nucleating agent can be efficiently refined without contaminating the organic crystal nucleating agent due to contamination of the rod fragments. Can be made.
- the rod filling rate varies depending on the model of the container-driven crusher, but is preferably in the range of 10 to 70%, more preferably 15 to 60%. If the filling rate is within this range, the contact frequency between the organic crystal nucleating agent and the grinding aid ester and the rod can be improved, and the grinding efficiency can be improved.
- the filling rate refers to the apparent volume of the rod with respect to the volume of the stirring unit of the container-driven crusher. From the viewpoint of increasing the contact frequency between the organic crystal nucleating agent and the grinding aid ester and the rod and improving the grinding efficiency, it is preferable to use a plurality of rods.
- the outer diameter of the ball is preferably 0.01 to 5 mm, more preferably 0.02 to The range is 5 mm, more preferably 0.02 to 1 mm. If the size of the ball is within the above range, the desired pulverizing force can be obtained, and the organic crystal nucleating agent can be efficiently refined without contaminating the organic crystal nucleating agent due to contamination of the ball fragments. Can be made.
- the filling rate of balls varies depending on the type of the stirring tank type pulverizer, but is preferably in the range of 10 to 97%, more preferably 15 to 95%. When the filling rate is within this range, the contact frequency between the organic crystal nucleating agent and the grinding aid ester and the ball is improved, and the grinding efficiency can be improved without hindering the movement of the medium.
- the filling rate means the apparent volume of the ball with respect to the volume of the stirring unit of the stirring tank type pulverizer.
- the treatment time cannot be determined unconditionally depending on the type of pulverizer, the type of medium, the size, the filling rate, etc., but from the viewpoint of miniaturizing the organic crystal nucleating agent, it is preferably 0.01 to 50 hr, more preferably 0. .05 to 30 hours, more preferably 0.10 to 20 hours, still more preferably 0.10 to 10 hours.
- the treatment temperature is not particularly limited, but is preferably 5 to 250 ° C., more preferably 10 to 200 ° C. from the viewpoint of preventing deterioration due to heat.
- wet pulverization is performed by adding the organic crystal nucleating agent and the carboxylic acid ester and / or phosphate ester independently or simultaneously to a medium pulverizer.
- the mode to do is mentioned.
- a refined organic crystal nucleating agent composition (a refined organic crystal nucleating agent is used.
- a volume-median particle size (D 50) of preferably is 50 ⁇ 700 nm, more preferably 75 ⁇ 680 nm, more preferably 100 ⁇ 650 nm, more preferably 100 ⁇ 600 nm, more preferably 200 ⁇ 600 nm.
- the volume median particle size (D 50 ) of the organic crystal nucleating agent composition is 20 to 70% with respect to the volume median particle size (D 50 ) of the organic crystal nucleating agent before wet pulverization. It is preferably 25 to 65%, more preferably 30 to 60%.
- the cumulative volume particle size (D 90 ) is preferably 50 to 1400 nm, more preferably 75 to 1200 nm, further preferably 100 to 1000 nm, and further preferably 200 to 900 nm.
- the cumulative volume particle size (D 10 ) is preferably 10 to 600 nm, more preferably 20 to 500 nm, and further preferably 100 to 400 nm.
- the ratio of D 10 to D 50 (D 10 / D 50 ) is preferably 0.5 to 1.0, more preferably 0.6 to 1.0
- the ratio of D 90 to D 50 (D 90 / D 50 ) is preferably 1.0 to 2.0, more preferably 1.0 to 1.8.
- the volume median particle size (D 50 ) is 100 to 600 nm
- the cumulative volume particle size (D 90 ) is 100 to 1000 nm
- the cumulative volume particle size ( D 10 ) is preferably 10 to 600 nm
- the volume median particle size (D 50 ) is 200 to 600 nm
- the cumulative volume particle size (D 90 ) is 200 to 900 nm
- the cumulative volume particle size (D 10 ) is 100. More preferably, it is ⁇ 400 nm.
- the average particle diameter of the organic crystal nucleating agent composition refers to a volume-median particle size (D 50), it can be determined according to the method described in Examples set forth below.
- the cumulative volume particle size (D x ) means a particle size at which the cumulative volume frequency calculated by the volume fraction becomes x% when calculated from the smaller particle size, and is a method described in Examples described later. Can be measured according to.
- Step (2) is a step of melt-kneading the finely divided organic crystal nucleating agent composition obtained in step (1) and the raw material for polylactic acid resin composition containing polylactic acid resin.
- the raw material for polylactic acid resin composition contains the refined organic crystal nucleating agent composition and polylactic acid resin obtained in step (1).
- the content of the refined organic crystal nucleating agent composition obtained in the step (1) in the raw material for the polylactic acid resin composition is such that the polylactic acid resin composition is obtained with respect to 100 parts by weight of the polylactic acid resin. From the viewpoint of the crystallization speed of the product and the heat resistance of the molded article comprising the polylactic acid resin composition, it is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, still more preferably 7 to 30 parts by weight. More preferred is 25 parts by weight.
- “content” means “content or blending amount”.
- the polylactic acid resin in the present invention is polylactic acid or a copolymer of lactic acid and hydroxycarboxylic acid.
- the hydroxycarboxylic acid include glycolic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxypentanoic acid, hydroxycaproic acid, hydroxyheptanoic acid and the like, and glycolic acid and hydroxycaproic acid are preferable.
- the molecular structure of polylactic acid is preferably composed of 80 to 100 mol% of either L-lactic acid (L-form) or D-lactic acid (D-form) and 0 to 20 mol% of the enantiomer of the enantiomer.
- the copolymer of lactic acid and hydroxycarboxylic acid comprises 85 to 100 mol% of either L-lactic acid or D-lactic acid and 0 to 15 mol% of hydroxycarboxylic acid units.
- polylactic acid resins can be obtained by dehydrating polycondensation using L-lactic acid, D-lactic acid and hydroxycarboxylic acid as raw materials by selecting them from the required structure.
- lactide which is a cyclic dimer of lactic acid, glycolide, which is a cyclic dimer of glycolic acid, and caprolactone.
- Lactide includes L-lactide, which is a cyclic dimer of L-lactic acid, D-lactide, which is a cyclic dimer of D-lactic acid, meso-lactide obtained by cyclic dimerization of D-lactic acid and L-lactic acid, and D-lactide.
- DL-lactide which is a racemic mixture of lactide and L-lactide. Any lactide can be used in the present invention.
- the main raw material is preferably D-lactide or L-lactide.
- a polylactic acid resin having a high optical purity of the lactic acid component from the viewpoint of moldability of the polylactic acid resin composition. That is, it is preferable that 80% or more of the L-form or D-form is included in the total lactic acid component of the polylactic acid resin, more preferably 90% or more of the L-form or D-form, and 95% for the L-form or D-form. % Or more, more preferably 98% or more of L-form or D-form, and still more preferably 99% or more of L-form or D-form.
- polylactic acid is a different isomer from the viewpoints of moldability and transparency of the polylactic acid resin composition, compatibility between the strength and impact resistance of the molded product made of the polylactic acid resin composition, and heat resistance.
- One polylactic acid constituting the stereocomplex polylactic acid (hereinafter referred to as polylactic acid (A)) contains 90 to 100 mol% of L isomer and 0 to 10 mol% of other components including D isomer.
- the other polylactic acid (hereinafter referred to as polylactic acid (B)) contains 90 to 100 mol% of D isomer and 0 to 10 mol% of other components including L isomer.
- the other components other than the L-form and D-form include dicarboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones and the like having a functional group capable of forming two or more ester bonds. Polyester, polyether, polycarbonate or the like having two or more functional groups in the reaction may be used.
- the weight ratio of polylactic acid (A) to polylactic acid (B) [polylactic acid (A) / polylactic acid (B)] is preferably 10/90 to 90/10, and 20/80 to 80 / 20 is more preferable, and 40/60 to 60/40 is more preferable.
- the weight average molecular weight of the polylactic acid resin is preferably 100,000 or more from the viewpoint of the mechanical properties of the molded article made of the polylactic acid resin composition, and 400 from the viewpoint of fluidity at the time of molding the polylactic acid resin composition. 1,000 or less.
- the weight average molecular weight of the polylactic acid resin was determined by using gel permeation chromatography (GPC), chloroform as the solvent, Tosoh Corporation column, high temperature SEC column (GMHHR-H series), flow rate 1.0 mL / min, column
- GPC gel permeation chromatography
- chloroform as the solvent
- Tosoh Corporation column high temperature SEC column (GMHHR-H series)
- flow rate 1.0 mL / min column
- the temperature can be calculated by using a differential refractive index detector (RI) as a detector at a temperature of 40 ° C., and styrene having a known molecular weight as a reference.
- RI differential refractive index detector
- Polylactic acid can be synthesized according to a known method, but a commercially available product can be used.
- a commercially available product can be used.
- Mitsui Chemicals Co., Ltd. trade name Lacia; Toyota Motor Co., Ltd., trade name Eco Plastic U'z; Nature Works Co., Ltd., trade name Nature works; Zhejiang Haisho Biomaterials Co., Ltd., trade name REVODE, etc.
- the content of the polylactic acid resin in the polylactic acid resin composition of the present invention is preferably 50% by weight or more, more preferably 70% by weight or more from the viewpoint of achieving the object of the present invention.
- the polylactic acid resin composition of the present invention contains a crystal nucleating agent, a plasticizer, a hydrolysis inhibitor and the like as appropriate in addition to the finely divided organic crystal nucleating agent composition and the polylactic acid resin. Also good.
- Crystal nucleating agent In the present invention, from the viewpoint of further improving the crystallization speed of the polylactic acid resin composition of the present invention and the heat resistance and moldability of the molded body made of the polylactic acid resin composition, A crystal nucleating agent may be contained.
- the other crystal nucleating agent a compound having a hydroxyl group and an amide group in the molecule is preferable from the viewpoint of the crystallization speed of the polylactic acid resin and the heat resistance of the molded article made of the polylactic acid resin composition.
- the crystal nucleating agent dissolves at the time of melt kneading of the polylactic acid resin to generate a large number of crystal nuclei, and by interaction with the fine organic crystal nucleating agent, the crystallization speed of the obtained polylactic acid resin composition and Heat resistance can be further improved.
- the compound having a hydroxyl group and an amide group in the molecule includes a hydroxyl group from the viewpoint of crystallization speed of the polylactic acid resin composition, compatibility with the polylactic acid resin, and impact resistance and moldability of the polylactic acid resin composition.
- An aliphatic amide having 2 or more hydroxyl groups and 2 or more amide groups in the molecule is more preferable.
- the melting point of the compound having a hydroxyl group and an amide group in the molecule is preferably 65 ° C. or higher, more preferably 70 to 220 ° C. from the viewpoint of improving the dispersibility of the crystal nucleating agent during kneading and improving the crystallization rate. 80 to 190 ° C. is more preferable.
- fusing point of a crystal nucleating agent is measured by the method as described in the below-mentioned Example.
- hydroxy fatty acid monoamides such as 12-hydroxystearic acid monoethanolamide, methylene bis 12-hydroxystearic amide, ethylene bis 12-hydroxystearic amide, hexamethylene bis
- hydroxy fatty acid bisamides such as 12-hydroxystearic acid amide
- hydroxy fatty acid triamides such as 12-hydroxystearic acid triglyceride.
- ethylene bis 12-hydroxystearic acid amide ethylene bis 12-hydroxystearic acid amide, hexamethylene bis 12 -Hydroxy fatty acid bisamides such as -hydroxystearic acid amide, 12-hydroxystearic acid triglyceride are preferred, and ethylene bis 12-hydroxystearic acid amide is more preferred.
- the weight ratio of the compound having a hydroxyl group and an amide group in the molecule to the refined organic crystal nucleating agent increases the crystallization speed of the polylactic acid resin.
- 0.5 / 99.5 to 20/80 is preferable, and 0.5 / 99.5 is preferable.
- 17/83 is more preferable, 1.0 / 99.0 to 10/90 is more preferable, and 3/97 to 8/92 is even more preferable.
- the content of the crystal nucleating agent other than the miniaturized organic crystal nucleating agent in the polylactic acid resin composition is 100% by weight of the polylactic acid resin from the viewpoint of heat resistance, impact resistance and moldability of the molded body made of the polylactic acid resin composition. 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, and more preferably 0.5 to 2 parts by weight with respect to parts.
- a plasticizer in the present invention, can be contained from the viewpoint of further improving the transparency and moldability of the polylactic acid resin composition.
- the organic crystal nucleating agent in the step (1), is wet pulverized in the presence of the pulverization aid ester, and the obtained fine organic crystal nucleating agent is combined with the polylactic acid resin in the step (2). Since the pulverization aid ester present on the surface of the refined organic crystal nucleating agent functions as a plasticizer for melt kneading, good crystallization speed and heat resistance can be obtained without adding a separate plasticizer in the melt kneading process. A polylactic acid resin composition having properties can be obtained.
- the plasticizer those similar to the grinding aid ester used in the step (1) can be used, and the total content of the plasticizer and the grinding aid ester is the heat resistance of the molded article made of the polylactic acid resin composition. From the viewpoints of transparency and moldability, it is preferably contained in an amount of 0.05 to 3 parts by weight, more preferably 0.10 to 2 parts by weight with respect to 100 parts by weight of the polylactic acid resin.
- the polylactic acid resin composition of the present invention can further contain a hydrolysis inhibitor from the viewpoint of improving durability and hydrolysis resistance.
- the hydrolysis inhibitor include carbodiimide compounds such as polycarbodiimide compounds and monocarbodiimide compounds.
- carbodiimide compounds such as polycarbodiimide compounds and monocarbodiimide compounds.
- polycarbodiimide compounds are preferable, and durability of the polylactic acid resin composition is preferred.
- a monocarbodiimide compound is preferable.
- it is preferable to use together monocarbodiimide and polycarbodiimide from the viewpoint of further improving the durability, impact resistance, and moldability of the molded article made of the polylactic acid resin composition.
- polycarbodiimide compound examples include poly (4,4′-diphenylmethanecarbodiimide), poly (4,4′-dicyclohexylmethanecarbodiimide), poly (1,3,5-triisopropylbenzene) polycarbodiimide, poly (1,3,3). 5-triisopropylbenzene and 1,5-diisopropylbenzene) polycarbodiimide and the like, and examples of the monocarbodiimide compound include N, N′-di-2,6-diisopropylphenylcarbodiimide and the like.
- the carbodiimide compound may be used singly or in combination of two or more in order to satisfy the durability, impact resistance and moldability of the molded article made of the polylactic acid resin composition.
- Poly (4,4′-dicyclohexylmethane carbodiimide) is obtained by converting carbodilite LA-1 (manufactured by Nisshinbo Co., Ltd.), poly (1,3,5-triisopropylbenzene) polycarbodiimide and poly (1,3,5-trimethyl).
- the content of the hydrolysis inhibitor is preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of the polylactic acid resin, from the viewpoint of the transparency and moldability of the molded body made of the polylactic acid resin composition. 10 to 2 parts by weight is more preferable.
- the polylactic acid tree composition of the present invention preferably further contains an inorganic filler from the viewpoint of improving physical properties such as rigidity.
- inorganic filler fibers, plates, granules, and powders that are usually used for reinforcing thermoplastic resins can be used. Specifically, glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, sepiolite, asbestos, slag fiber, zonolite, Elastadite, gypsum fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber and other fibrous inorganic fillers, glass flakes, non-swellable mica, swellable mica, graphite, metal foil , Ceramic beads, talc, clay, mica, sericite, zeolite, bentonite, organic modified bentonite, organic modified montmorillonite, dolomite, kaolin, fine powder silicic acid, feld
- the aspect ratio of the fibrous filler is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more.
- the inorganic filler may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer, or a thermosetting resin such as an epoxy resin, and may be a coupling agent such as aminosilane or epoxysilane. It may be processed.
- a thermoplastic resin such as an ethylene / vinyl acetate copolymer, or a thermosetting resin such as an epoxy resin, and may be a coupling agent such as aminosilane or epoxysilane. It may be processed.
- the content of the inorganic filler is preferably 1 to 100 parts by weight and more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the polylactic acid resin.
- the polylactic acid resin composition of the present invention preferably further contains an organic filler from the viewpoint of improving physical properties such as rigidity.
- the organic filler there can be used a chip-like, fiber-like, plate-like or powder-like one usually used for reinforcing thermoplastic resins.
- specific examples include rice husks, wood chips, okara, waste paper pulverized materials, chip-shaped materials such as clothing pulverized materials, cotton fibers, hemp fibers, bamboo fibers, wood fibers, kenaf fibers, jute fibers, banana fibers, coconut fibers.
- Plant fibers such as, or pulp and cellulose fibers processed from these plant fibers and fibrous materials such as animal fibers such as silk, wool, Angola, cashmere, camel, pulp powder, paper powder, wood powder, bamboo powder, Cellulose powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein, starch, etc. are mentioned, and from the viewpoint of moldability, paper powder, wood powder, bamboo powder, cellulose powder, kenaf powder, Powdered powder such as rice husk powder, fruit shell powder, chitin powder, chitosan powder, protein powder, starch, etc., paper powder, wood powder, bamboo powder, cellulose powder, kenaf powder More preferable. From the viewpoint of improving toughness, it is preferable to use a powdered organic filler obtained by amorphizing cellulose using a vibrating rod mill, a bead mill or the like.
- the content of the organic filler is preferably 1 to 100 parts by weight and more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the polylactic acid resin.
- the polylactic acid resin composition of the present invention can contain high-strength organic synthetic fibers from the viewpoint of improving physical properties such as strength, heat resistance, impact resistance, etc. of the molded body made of the polylactic acid resin composition.
- high-strength organic synthetic fibers include aramid fibers, polyarylate fibers, PBO fibers, and the like, and aramid fibers are preferable from the viewpoint of heat resistance.
- the content of the high-strength organic synthetic fiber is preferably 3 to 20 parts by weight and more preferably 5 to 10 parts by weight with respect to 100 parts by weight of the polylactic acid resin.
- the polylactic acid resin composition of the present invention may contain other resins from the viewpoint of improving physical properties such as rigidity, flexibility, heat resistance, and durability of the molded body made of the polylactic acid resin composition.
- resins include polyethylene, polypropylene, polystyrene, ABS resin, AS resin, acrylic resin, polyamide, polyphenylene sulfide, polyether ether ketone, polyester, polyacetal, polysulfone, polyphenylene oxide, polyimide, polyetherimide, Alternatively, thermoplastic resins such as ethylene / glycidyl methacrylate copolymer, polyester elastomer, polyamide elastomer, soft thermoplastic resin such as ethylene / propylene terpolymer, ethylene / butene-1 copolymer, phenol resin, melamine resin, unsaturated Thermosetting resins such as polyester resins, silicone resins, and epoxy resins can be mentioned.
- amide bonds and S are preferred from the viewpoint of compatibility with polylactic acid resins.
- the resin having a bond containing a carbonyl group of a carbonate bond or the like are preferred because structurally polylactic acid resin and affinity tends to be high.
- the polylactic acid resin composition of the present invention can further contain a flame retardant from the viewpoint of improving physical properties such as rigidity, flexibility, heat resistance and durability of the molded body made of the polylactic acid resin composition.
- a flame retardant include halogenated compounds containing bromine or chlorine, such as tetrabromobisphenol-A-epoxy oligomer, tetrabromobisphenol-A-carbonate oligomer, brominated epoxy resin, antimony trioxide, boric acid, etc.
- Inorganic flame retardants such as zinc, silicone flame retardants such as silicone resin and silicone oil, inorganic hydrates such as aluminum hydroxide and magnesium hydroxide (surface treatment with silane coupling agent, especially isocyanate silane from the viewpoint of physical properties
- phosphorous compounds such as triaryl isopropylates, condensed phosphates, melamine polyphosphates, piperazine polyphosphates and phosphazene compounds, and nitrogen-containing compounds such as melamine cyanurate.
- inorganic hydrates or phosphorus compounds are preferable, and from the viewpoint of physical properties, the combined use of inorganic hydrates and phosphorus compounds is preferable.
- the content of the flame retardant is preferably 10 to 60 parts by weight and more preferably 15 to 50 parts by weight with respect to 100 parts by weight of the polylactic acid resin.
- the polylactic acid resin composition of the present invention may contain a core-shell type rubber from the viewpoint of improving physical properties such as impact resistance and toughness of a molded article made of the polylactic acid resin composition.
- a core-shell type rubber from the viewpoint of improving physical properties such as impact resistance and toughness of a molded article made of the polylactic acid resin composition.
- Specific examples include (core; silicone / acrylic polymer, shell; methyl methacrylate polymer), (core; silicone / acrylic polymer, shell; methyl methacrylate / glycidyl methacrylate polymer), (core; butanediene / Styrene polymer, shell; methyl methacrylate polymer), (core; acrylic polymer, shell; methyl methacrylate polymer) and the like.
- the content of the core-shell type rubber is preferably 2 to 30 parts by weight and more preferably 3 to 20 parts by weight with respect to 100 parts by weight of the polylactic acid resin.
- the polylactic acid resin composition of the present invention is further a hindered phenol or phosphite antioxidant, or an aliphatic amide, a fatty acid metal salt, a hydrocarbon wax, or an anionic surfactant.
- a lubricant and the like can be contained.
- the content of each of the antioxidant and the lubricant is preferably 0.05 to 3 parts by weight and more preferably 0.10 to 2 parts by weight with respect to 100 parts by weight of the polylactic acid resin.
- the polylactic acid resin composition of the present invention contains, as components other than those described above, conventional additives such as ultraviolet absorbers (benzophenone compounds, benzotriazole compounds, aromatic benzoates) within the range not impairing the object of the present invention.
- ultraviolet absorbers benzophenone compounds, benzotriazole compounds, aromatic benzoates
- One type or two or more types such as a foaming agent, a release agent, a coloring agent including a dye and a pigment, a fungicide, and an antibacterial agent can be further contained.
- Step (2) is a step of melt-kneading the micronized organic crystal nucleating agent composition, the polylactic acid resin, and further, if necessary, the raw material for the polylactic acid resin composition containing various additives.
- Examples include a step of melt kneading at 160 to 250 ° C. using a twin screw extruder or the like.
- the melt kneading temperature is preferably from 160 to 250 ° C., more preferably from 165 to 230 ° C., further preferably from 170 to 210 ° C., and from 170 to 200 ° C. from the viewpoint of moldability and prevention of deterioration of the polylactic acid resin composition. Even more preferred.
- a polylactic acid resin composition is obtained by the production method of the present invention. Therefore, this invention also provides the polylactic acid resin composition obtained by the manufacturing method of this invention. Since the polylactic acid resin composition of the present invention has good processability and can be processed at a low temperature of, for example, 200 ° C. or less, there is also an advantage that the pulverization aid ester and the plasticizer are not easily decomposed. And can be used for various purposes. Further, due to the high crystallization speed, it is possible to perform molding at a low mold temperature and in a short time in injection molding.
- the polylactic acid resin molded product of the present invention can be obtained by molding the polylactic acid resin composition of the present invention. Specifically, for example, a plasticizer and a hydrolysis inhibitor are blended as necessary while mixing and melting the finely divided organic crystal nucleating agent composition and the polylactic acid resin using an extruder or the like. Then, the obtained melt is filled into a mold by an injection molding machine or the like and molded.
- a preferred method for producing the polylactic acid resin molded article of the present invention is a step of wet-grinding an organic crystal nucleating agent in the presence of the grinding aid ester to obtain a refined organic crystal nucleating agent composition [step (1) And a step of melt-kneading the raw material for a polylactic acid resin composition containing the refined organic crystal nucleating agent obtained in step (1) and a polydairy resin [step (2)] and obtained in step (2).
- This is a method including a step of filling the obtained melt into a mold of 110 ° C. or lower and molding (hereinafter referred to as step (3)).
- the step (3) is performed after the step (2), after cooling to an amorphous state (that is, a condition that the degree of crystallinity measured by the wide angle X-ray diffraction method is 1% or less).
- the method of performing and the method of performing the step (3) immediately after passing through the step (2) are preferable. From the viewpoint of the effect of improving the crystallization speed of the polylactic acid resin, the method is cooled after the step (2). More preferably, the step (3) is performed immediately.
- the step (3) include, for example, a step of filling and molding the polylactic acid resin composition of the present invention in a mold of 110 ° C. or less with an injection molding machine or the like.
- the mold temperature in the step (3) is preferably 110 ° C. or less, more preferably 90 ° C. or less, and still more preferably 80 ° C. or less, from the viewpoint of improving the crystallization speed and workability of the polylactic acid resin composition.
- 30 degreeC or more is preferable, 40 degreeC or more is more preferable, and 60 degreeC or more is further more preferable.
- the mold temperature is preferably 30 to 110 ° C, more preferably 40 to 90 ° C, and further preferably 60 to 80 ° C. Since the polylactic acid resin composition of the present invention has an excellent crystallization rate and can be molded at a low temperature, a molded product having sufficient heat resistance can be obtained even at the mold temperature.
- the holding time in the mold in the step (3) is preferably 20 to 90 seconds, more preferably 20 to 80 seconds, more preferably 20 to 80 seconds, from the viewpoint of heat resistance and productivity of the molded body made of the polylactic acid resin composition. More preferred is 60 seconds. That is, since the polylactic acid resin composition obtained by the production method of the present invention has a high crystallization rate, a molded body comprising the polylactic acid resin composition having sufficient heat resistance even with the short holding time described above is obtained. It is done.
- the heat resistance of the molded body made of the polylactic acid resin composition is proportional to the relative crystallinity.
- the relative crystallinity refers to the crystallinity represented by the following formula.
- Relative crystallinity (%) ⁇ ( ⁇ Hm ⁇ Hcc) / ⁇ Hm ⁇ 100 ⁇ Specifically, the relative crystallinity was raised from 20 ° C. to 200 ° C. at a rate of temperature increase of 20 ° C./min using a DSC apparatus (Diamond DSC manufactured by PerkinElmer Co., Ltd.) at a rate of temperature increase of 20 ° C./min. After holding, the temperature is lowered from 200 ° C. to 20 ° C.
- Weight average molecular weight of polylactic acid resin (Mw) The weight average molecular weight (Mw) is measured by GPC (gel permeation chromatography) under the following measurement conditions. ⁇ Measurement conditions> Column: GMHHR-H + GMHHR-H Column temperature: 40 ° C Detector: RI Eluent: Chloroform Flow rate: 1.0 mL / min Sample concentration: 1 mg / mL Injection volume: 0.1 mL Conversion standard: Polystyrene
- optical purity of polylactic acid The optical purity was determined according to the D-body content measurement method described in “Voluntary Standard for Food Containers and Packaging Made of Synthetic Resins such as Polyolefins, Third Edition, Revised June 2004, Part 3 Sanitation Test Method P12-13”. Perform under measurement conditions. Specifically, 10 mL of 0.7 mol / L sodium hydroxide / methanol was added to precisely weighed polylactic acid (500 mg) and set in a water bath shaker set at 65 ° C. until the resin content became a homogeneous solution. Hydrolyze.
- Diluted hydrochloric acid (2 mol / L hydrochloric acid) is added to the resulting alkaline solution to neutralize it, and after further dissolving with pure water, a certain volume is separated into a volumetric flask and diluted with a high-performance liquid chromatography (HPLC) mobile phase solution. Then, adjust the pH to be in the range of 3-7, quantify the volumetric flask, filter the resulting solution through a membrane filter (0.45 ⁇ m), and then quantify D-lactic acid and L-lactic acid by HPLC. To obtain the optical purity of polylactic acid.
- HPLC high-performance liquid chromatography
- the melting point is measured by increasing the temperature from 20 ° C. to 500 ° C. at a temperature increase rate of 10 ° C./min using a DSC apparatus (Perkin Elmer, Diamond DSC).
- the particle size (nm) of the crystal nucleating agent was diluted with ethanol (Deer Grade 1, manufactured by Kanto Chemical Co., Inc.) so that the concentration of the crystal nucleating agent was 0.5% by weight, and an ultrasonic device (device name: 1510J- MT, manufactured by Yamato Kagaku Co., Ltd.) for 5 minutes, and the resulting solution was placed in a glass cell (optical path length 10 mm ⁇ width 10 mm ⁇ height 45 mm, glass double-sided transparent cell: manufactured by Sansho Co., Ltd.) The thickness is 10 mm and measured at 25 ° C. using a Zetasizer Nano-S (manufactured by Sysmex Corporation, dynamic light scattering measuring instrument).
- Viscosity of carboxylate ester and phosphate ester Viscosity is measured at 23 ° C. using a BII viscometer BLII (manufactured by Toki Sangyo Co., Ltd.) based on the method of measuring viscosity according to the S method (rotation speed: 12 r / min) defined in JIS K7117. To do.
- Weight average molecular weight (Mw) of carboxylate ester and phosphate ester The weight average molecular weight (Mw) is measured by GPC (gel permeation chromatography) under the following conditions. ⁇ Measurement conditions> Column: TSKPWXL + G4000PWXL + G2500PWXL (both manufactured by Tosoh Corporation) Column temperature: 40 ° C Detector: RI (210 nm) Eluent: 0.2 mol / L phosphate buffer / acetonitrile (9/1) Flow rate: 10 mL / min Sample concentration: 1 mg / mL Injection volume: 0.1 mL Standard: Polyethylene glycol
- the obtained diester had a weight average molecular weight of 410, a viscosity (23 ° C.) of 27 mPa ⁇ s, an acid value of 0.2 KOH mg / g, a saponification value of 274 KOH mg / g, a hydroxyl value of 1 KOH mg / g or less, and a hue APHA200.
- ⁇ Carboxylic ester production example 2> (Triester compound with an ethylene oxide adduct obtained by adding 6 mol of ethylene oxide to acetic acid and glycerin) An autoclave is charged with a specified amount of 6 moles of ethylene oxide to 1 mole of concentrated glycerin for cosmetics manufactured by Kao Co., Ltd., and a constant pressure of 0.3 MPa is added using 1 mole% of KOH as a catalyst until the pressure becomes constant. After reacting at 0 ° C., the mixture was cooled to 80 ° C. to obtain a catalyst-unneutralized product.
- Kyoward 600S manufactured by Kyowa Chemical Industry Co., Ltd.
- an adsorption treatment was performed at 80 ° C. for 1 hour in the presence of nitrogen. Further, the liquid after the treatment was No.
- the adsorbent was filtered with a Nutse pre-coated with Radiolite # 900 on the filter paper No. 2 to obtain an adduct with 6 mol of glycerin ethylene oxide (hereinafter referred to as POE (6) glycerin). This was charged into a four-necked flask, heated to 105 ° C.
- POE (6) glycerin 6 mol of glycerin ethylene oxide
- the resulting esterified product had an acid value of 0.9 mgKOH / g, a hydroxyl value of 51 mgKOH / g, a water content of 0.04 g, a weight average molecular weight of 2200, and a viscosity (23 ° C.) of 21000 mPa ⁇ s.
- phase-separated lower phase was drained, and the remaining upper phase was dehydrated under reduced pressure at 75 ° C., and the solid content was further removed by filtration to obtain 266 g of the desired tris (ethoxyethoxyethyl) phosphate ( Yield 80%).
- This tris (ethoxyethoxyethyl) phosphate is a colorless and transparent uniform liquid.
- the chloro ion content was 10 mg / kg or less.
- Tables 1 to 9 show the average particle diameters of the crystal nucleating agent compositions obtained in the following production examples.
- Production Example 1 of Crystal Nucleating Agent Composition 720 g of the carboxylic acid ester [(MeEO 3 ) 2 SA] obtained in Production Example 1 of carboxylic acid ester and 36 g of an unsubstituted phenylphosphonic acid zinc salt (manufactured by Nissan Chemical Co., Ltd .: “Eco Promote”) It was put into a pulverizer (“Sand Grinder TSG-6H” manufactured by Igarashi Machinery Manufacturing Co., Ltd .: container volume 800 mL, filled with 720 g of 1 mm ⁇ zirconia beads, filling rate 30%, stirring blade diameter 70 mm).
- Crystal nucleating agent-2 miniaturized zinc salt of phenylphosphonic acid
- Crystal nucleating agent-3 (refined to refinement) was prepared in the same manner as in Production Example 2, except that the amount of carboxylic acid ester [(MeEO 3 ) 2 SA] was changed to 360 g, and 360 g of “DAIFATTY-101” was further added. A zinc salt of phenylphosphonic acid).
- Crystal nucleating agent-4 (refined phenylphosphonic acid zinc salt) was obtained in the same manner as in Production Example 1 except that the amount of unsubstituted phenylphosphonic acid zinc salt was changed to 72 g.
- Crystal nucleating agent-5 (refined phenylphosphonic acid zinc salt) was obtained in the same manner as in Production Example 1, except that the amount of unsubstituted phenylphosphonic acid zinc salt was changed to 144 g.
- Crystal nucleating agent-6 (refined phenylphosphonic acid zinc salt) was obtained in the same manner as in Production Example 1, except that the amount of unsubstituted phenylphosphonic acid zinc salt was changed to 216 g.
- Crystal nucleating agent-7 (refined phenylphosphonic acid zinc salt) was obtained in the same manner as in Production Example 1, except that the amount of unsubstituted phenylphosphonic acid zinc salt was changed to 18 g.
- the type of carboxylic acid ester is a triester compound [(AcEO 6 ) of acetic acid obtained from (MeEO 3 ) 2 SA in the preparation of carboxylic acid ester 2 and an ethylene oxide adduct obtained by adding 6 mol of ethylene oxide to glycerol.
- the crystal nucleating agent-8 (refined zinc salt of phenylphosphonic acid) was obtained in the same manner as in Production Example 1, except for changing to [ 3 Gly].
- Crystal nucleating agent-9 was obtained in the same manner as in Production Example 1 except that the type of carboxylic acid ester was changed from (MeEO 3 ) 2 SA to the polyester polyol obtained in Production Example 3 of carboxylic acid ester.
- Production Example 10 of Crystal Nucleating Agent Composition The kind of carboxylic acid ester was changed from (MeEO 3 ) 2 SA to the polyester polyol obtained in Production Example 3 of carboxylic acid ester, and 36 g of unsubstituted phenylphosphonic acid zinc salt was changed to talc (manufactured by Nippon Talc, “ MICRO ACE P-6 ”) Crystal nucleating agent-10 was obtained in the same manner as in Production Example 1, except that the amount was changed to 720 g.
- Production Example 11 of Crystal Nucleating Agent Composition The type of carboxylic acid ester is a triester compound of 1,3,6-hexanetricarboxylic acid and triethylene glycol monomethyl ether obtained in Production Example 4 of carboxylic acid ester from (MeEO 3 ) 2 SA [(MeEO 3 ) 3 A crystal nucleating agent-11 was obtained in the same manner as in Production Example 1 except that it was changed to HTC].
- Crystal Nucleating Agent Composition 50 g of unsubstituted phenylphosphonic acid zinc salt (Nissan Chemical Co., Ltd .: “Eco Promote”) was put into a vibration mill (Chuo Kakoki Co., Ltd. “MB-1”: container volume 3.5 L) and a rod (cross-sectional shape). : Circular, diameter: 30 mm, length: 218 mm, material: stainless steel) 11 pieces were filled into a vibration mill (filling rate 48%), and the treatment was performed for 60 minutes under the conditions of amplitude 8 mm and rotation speed 1200 r / min. Crystal nucleating agent-12 was obtained.
- Production Examples 13-47 of Crystal Nucleating Agent Composition Referring to Production Example 1, the crystal nucleating agent and grinding aid ester used in step (1) were crystallized in the apparatus and conditions shown in Tables 3 to 10 using the types and amounts shown in Tables 3 to 10. Nucleating agents-13 to 47 were obtained.
- the zinc salt of phenylphosphonic acid is refined by grinding the zinc salt of phenylphosphonic acid in the presence of a carboxylic acid ester or phosphate ester having a specific weight average molecular weight and a specific viscosity.
- the crystal nucleating agent composition (crystal nucleating agent-9, 10) obtained by pulverizing with polyester polyol cannot be dispersed in ethanol because the viscosity is too high, and the particle size is measured. I could't.
- the organic crystal nucleating agent is refined by grinding various organic crystal nucleating agents in the presence of a carboxylic acid ester or phosphate ester having a specific weight average molecular weight and a specific viscosity.
- the crystal nucleating agent composition obtained by pulverizing with polyester polyol cannot be dispersed in ethanol because the viscosity is too high, and the particle size can be measured. could not.
- Examples 1 to 49 and Comparative Examples 1 to 36 The raw materials for the polylactic acid resin composition shown in Tables 11 to 18 were melt-kneaded at a rotation speed of 100 r / min and a kneading temperature of 190 ° C. with a twin-screw extruder (PCM-45 manufactured by Ikekai Tekko Co., Ltd.), and strand cutting was performed. A pellet of a polylactic acid resin composition was obtained. The obtained pellets were dried at 70 ° C. under reduced pressure for 1 day, and the water content was adjusted to 500 ppm or less.
- PCM-45 twin-screw extruder
- the raw materials in Tables 11 to 18 are as follows. ⁇ Polylactic acid resin> NW3001D; polylactic acid resin (manufactured by Nature Works LLC, NatureWorks 3001D, optical purity 98.5%, weight average molecular weight 120,000) ⁇ Crystal nucleating agent> Crystal nucleating agent-1 to 47; Crystal nucleating agent composition PPA-Zn produced in Production Examples 1 to 47 of the above-mentioned crystal nucleating agent composition; unsubstituted phenylphosphonic acid zinc salt (manufactured by Nissan Chemical Industries, Eco Promote, No melting point) OHC18EB; ethylene bis 12-hydroxystearic acid amide (Nippon Kasei Co., Ltd., SLIPAX H, melting point 145 ° C.) PY109: Compound having an isoindolinone skeleton (Ciba Fine Chemicals, IRGAZIN Yellow 2GLTE) ⁇ Plasticizer> (MeEO 3 ) 2 SA: the same as used in the production of the
- Examples 1 to 49 and Comparative Examples 1 to 36 Polylactic Acid Resin Composition Molded Body
- the pellets of the examples and comparative examples were injection molded using an injection molding machine (manufactured by Nippon Steel Works, J75E-D) with a cylinder temperature of 200 ° C., and gold at 80 ° C., 70 ° C., or 60 ° C.
- Molding of polylactic acid resin composition by molding test pieces [flat plate (70 mm ⁇ 40 mm ⁇ 2 mm), prismatic test piece (125 mm ⁇ 12 mm ⁇ 6 mm) and prismatic test piece (63 mm ⁇ 12 mm ⁇ 5 mm)] at mold temperature Got the body.
- the polylactic acid resin compositions (Examples 1 to 13, 14, and 15) obtained by the production method of the present invention have a short mold holding time even at a mold temperature of 60 ° C. It can be seen that molding is possible and the crystallization speed is excellent.
- the polylactic acid resin composition of the comparative example obtained by the production method other than the present invention was molded within the same mold holding time as the examples at any mold temperature of 60 ° C., 70 and 80 ° C. Was impossible.
- the polylactic acid resin compositions (Examples 16 to 49) obtained by the production method of the present invention can be molded at a mold temperature of 60 to 80 ° C. with a short mold holding time. It can be seen that the crystallization speed is excellent.
- the polylactic acid resin compositions of Comparative Examples (Comparative Examples 13 to 36) obtained by the production methods other than the present invention were the same as the Examples at any mold temperature of 60 ° C., 70 and 80 ° C. Molding within the mold holding time was impossible.
- the crystallization speed can be remarkably improved even in the polylactic acid resin composition containing the same crystal nucleating agent. I understand.
- Example 11 to 13 and Comparative Examples 10 to 12, and Examples 27 and 37 were used with an injection molding machine (J75E-D, manufactured by Nippon Steel) with a cylinder temperature of 200 ° C. It was obtained by injection molding and molding a test piece [flat plate (70 mm ⁇ 40 mm ⁇ 2 mm) and prismatic test piece (125 mm ⁇ 12 mm ⁇ 6 mm)] at a mold temperature of 30 ° C. with a mold holding time of 30 seconds. The physical properties of the molded bodies were examined according to the methods of Test Examples 1 and 2 below. The results are shown in Tables 19 and 20. Comparative Example 37 was prepared in the same manner as Example 27 by blending 1.0 part by weight of PY109 and 20.0 parts by weight of (MeEO 3 ) 2 SA with respect to 100 parts by weight of the polylactic acid resin.
- the molded body of the polylactic acid resin composition of the example molded at a mold temperature of 30 ° C. and a mold holding time of 30 seconds has a relative crystallinity of 90% or more, and is 80 ° C. It had the above heat resistance. From this, it is considered that the polylactic acid resin compositions of Examples 1 to 49 also have a relative crystallinity of 90% or higher and heat resistance of 80 ° C. or higher in the same test.
- the molded article of the comparative polylactic acid resin composition obtained by the production method other than the present invention can be removed from the mold, but the relative crystallinity is a low value of 60% or less. It had only heat resistance of less than 50 ° C.
- the polylactic acid resin composition obtained by the production method of the present invention can be suitably used for various industrial uses such as household goods, household appliance parts, packaging materials for household appliance parts, and automobile parts.
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Abstract
Description
〔1〕 下記工程(1)及び(2)を含むポリ乳酸樹脂組成物の製造方法、
工程(1):有機結晶核剤を、重量平均分子量が150~600かつ23℃における粘度が1~500mPa・sであるカルボン酸エステル及び/又は重量平均分子量が150~600かつ23℃における粘度が1~500mPa・sであるリン酸エステル存在下で湿式粉砕して、微細化された有機結晶核剤組成物を得る工程
工程(2):工程(1)で得られた微細化された有機結晶核剤組成物とポリ乳酸樹脂を含有するポリ乳酸樹脂組成物用原料を溶融混練する工程
ならびに
〔2〕 前記〔1〕記載の製造方法により得られるポリ乳酸樹脂組成物
に関する。
本発明の製造方法は、
工程(1):有機結晶核剤を、重量平均分子量が150~600かつ23℃における粘度が1~500mPa・sであるカルボン酸エステル及び/又は重量平均分子量が150~600かつ23℃における粘度が1~500mPa・sであるリン酸エステル存在下で湿式粉砕して、微細化された有機結晶核剤組成物を得る工程
工程(2):工程(1)で得られた微細化された有機結晶核剤組成物とポリ乳酸樹脂を含有するポリ乳酸樹脂組成物用原料を溶融混練する工程
を含む。
工程(1)は、有機結晶核剤を、重量平均分子量が150~600かつ23℃における粘度が1~500mPa・sのカルボン酸エステル及び/又は重量平均分子量が150~600かつ23℃における粘度が1~500mPa・sであるリン酸エステル存在下、湿式粉砕して微細化された有機結晶核剤組成物(以降、微細化有機結晶核剤ともいう)を得る工程である。なお、本明細書では、有機結晶核剤の湿式粉砕に用いられる前記カルボン酸エステル、リン酸エステルをまとめて粉砕助剤エステルとも言う。
本発明において用いられる有機結晶核剤は、ポリ乳酸樹脂の結晶化速度を向上させる観点から、20~200℃の範囲内で常に固体であるものが好ましく、以下の(a)~(c)からなる群より選ばれる少なくとも1種がより好ましい。
(a)イソインドリノン骨格を有する化合物、ジケトピロロピロール骨格を有する化合物、ベンズイミダゾロン骨格を有する化合物、インジゴ骨格を有する化合物、フタロシアニン骨格を有する化合物、及びポルフィリン骨格を有する化合物からなる群より選ばれる少なくとも1種の有機化合物〔有機結晶核剤(a)という〕
(b)カルボヒドラジド類、メラミン化合物、ウラシル類、及びN-置換尿素類からなる群より選ばれる少なくとも1種の有機化合物〔有機結晶核剤(b)という〕
(c)芳香族スルホン酸ジアルキルの金属塩、リン酸エステルの金属塩、フェニルホスホン酸の金属塩、ロジン酸類の金属塩、芳香族カルボン酸アミド、及びロジン酸アミドからなる群より選ばれる少なくとも1種の有機化合物〔有機結晶核剤(c)という〕
有機結晶核剤(a)としては、イソインドリノン骨格を有する化合物、ジケトピロロピロール骨格を有する化合物、ベンズイミダゾロン骨格を有する化合物、インジゴ骨格を有する化合物、フタロシアニン骨格を有する化合物、及びポルフィリン骨格を有する化合物からなる群より選ばれる少なくとも1種の有機化合物が挙げられる。
有機結晶核剤(b)としては、カルボヒドラジド類、メラミン化合物、ウラシル類、及びN-置換尿素類からなる群より選ばれる少なくとも1種の有機化合物が挙げられる。
有機結晶核剤(c)としては、芳香族スルホン酸ジアルキルの金属塩、リン酸エステルの金属塩、フェニルホスホン酸の金属塩、ロジン酸類の金属塩、芳香族カルボン酸アミド、及びロジン酸アミドからなる群より選ばれる少なくとも1種の有機化合物が挙げられる。
本発明において、前記有機結晶核剤の湿式粉砕には、重量平均分子量が150~600、23℃における粘度が1~500mPa・sのカルボン酸エステル及び/又は重量平均分子量が150~600かつ23℃における粘度が1~500mPa・sであるリン酸エステルを用いる。なお、本発明において、湿式粉砕に用いられるリン酸エステルは23℃における粘度が1~500mPa・sであり、一方、粉砕に供される有機結晶核剤のリン酸エステルは20~200℃の範囲で固体であることから相違するものであることは明らかである。
前記カルボン酸エステルの重量平均分子量は、150~600である。重量平均分子量が600以下であると、嵩が大きいために有機結晶核剤の微細化が不十分となることがなく、一方、分子量が150以上であればポリ乳酸樹脂への可塑化効果が作用して、十分な結晶化速度を有するポリ乳酸樹脂組成物を得ることができる。前記カルボン酸エステルの重量平均分子量は、有機結晶核剤を微細化させる観点、及びポリ乳酸樹脂への可塑化効果の観点から、好ましくは250~600、より好ましくは300~600、さらに好ましくは350~550、さらに好ましくは400~500である。なお、本明細書において、有機結晶核剤の湿式粉砕に用いられるエステルの重量平均分子量は、後述の実施例に記載の方法に従って測定することができる。
前記リン酸エステルの重量平均分子量は、150~600である。重量平均分子量が600以下であると、嵩が大きいために有機結晶核剤の微細化が不十分となることがなく、一方、分子量が150以上であればポリ乳酸樹脂への可塑化効果が作用して、十分な結晶化速度を有するポリ乳酸樹脂組成物を得ることができる。前記リン酸エステルの重量平均分子量は、有機結晶核剤を微細化させる観点、及びポリ乳酸樹脂への可塑化効果の観点から、好ましくは250~600、より好ましくは300~600、さらに好ましくは350~550、さらに好ましくは400~500である。
で表される化合物が好ましい。
工程(2)は、工程(1)で得られた微細化された有機結晶核剤組成物とポリ乳酸樹脂を含有するポリ乳酸樹脂組成物用原料を溶融混練する工程である。
ポリ乳酸樹脂組成物用原料は、工程(1)で得られた微細化された有機結晶核剤組成物及びポリ乳酸樹脂を含有する。ポリ乳酸樹脂組成物用原料中の、前記工程(1)で得られた微細化された有機結晶核剤組成物の含有量は、ポリ乳酸樹脂100重量部に対して、得られるポリ乳酸樹脂組成物の結晶化速度及びポリ乳酸樹脂組成物からなる成形体の耐熱性の観点から、1~50重量部が好ましく、5~40量部がより好ましく、7~30重量部がさらに好ましく、10~25重量部がさらに好ましい。なお、本明細書において「含有量」とは、「含有量もしくは配合量」のことを意味する。
本発明におけるポリ乳酸樹脂とは、ポリ乳酸、又は乳酸とヒドロキシカルボン酸とのコポリマーである。ヒドロキシカルボン酸として、グリコール酸、ヒドロキシ酪酸、ヒドロキシ吉草酸、ヒドロキシペンタン酸、ヒドロキシカプロン酸、ヒドロキシヘプタン酸等が挙げられ、グリコール酸、ヒドロキシカプロン酸が好ましい。
本発明においては、本発明のポリ乳酸樹脂組成物の結晶化速度、ポリ乳酸樹脂組成物からなる成形体の耐熱性及び成形性をさらに向上する観点から、前記微細化有機結晶核剤と共に他の結晶核剤を含有してもよい。他の結晶核剤としては、ポリ乳酸樹脂の結晶化速度及びポリ乳酸樹脂組成物からなる成形体の耐熱性の観点から、分子中に水酸基とアミド基を有する化合物が好ましい。前記結晶核剤は、ポリ乳酸樹脂の溶融混練時に溶解して多数の結晶核を生成するとともに、前記微細化有機結晶核剤との相互作用により、得られるポリ乳酸樹脂組成物の結晶化速度及び耐熱性をより向上することができる。
本発明においては、ポリ乳酸樹脂組成物の透明性及び成形性をさらに向上する観点から、可塑剤を含有することができる。本発明においては、工程(1)において、有機結晶核剤を、前記粉砕助剤エステル存在下で湿式粉砕し、得られた微細化有機結晶核剤を、工程(2)において、ポリ乳酸樹脂と溶融混練するため、微細化された有機結晶核剤の表面に存在する粉砕助剤エステルが可塑剤として働くために、溶融混練工程において別途可塑剤を添加しなくても良好な結晶化速度及び耐熱性を有するポリ乳酸樹脂組成物を得ることができる。
本発明のポリ乳酸樹脂組成物は、耐久性、耐加水分解性を向上させる観点から、さらに加水分解抑制剤を含有することができる。加水分解抑制剤としては、ポリカルボジイミド化合物やモノカルボジイミド化合物等のカルボジイミド化合物が挙げられ、ポリ乳酸樹脂組成物の耐久性、耐衝撃性の観点からポリカルボジイミド化合物が好ましく、ポリ乳酸樹脂組成物の耐久性、成形性(流動性)の観点から、モノカルボジイミド化合物が好ましい。また、ポリ乳酸樹脂組成物からなる成形体の耐久性、耐衝撃性、成形性をより向上させる観点から、モノカルボジイミドとポリカルボジイミドを併用することが好ましい。
無機充填剤としては、通常熱可塑性樹脂の強化に用いられる繊維状、板状、粒状、粉末状のものを用いることができる。具体的には、ガラス繊維、アスベスト繊維、炭素繊維、グラファイト繊維、金属繊維、チタン酸カリウムウイスカー、ホウ酸アルミニウムウイスカー、マグネシウム系ウイスカー、珪素系ウイスカー、ワラステナイト、セピオライト、アスベスト、スラグ繊維、ゾノライト、エレスタダイト、石膏繊維、シリカ繊維、シリカ・アルミナ繊維、ジルコニア繊維、窒化硼素繊維、窒化硅素繊維及び硼素繊維などの繊維状無機充填剤、ガラスフレーク、非膨潤性雲母、膨潤性雲母、グラファイト、金属箔、セラミックビーズ、タルク、クレー、マイカ、セリサイト、ゼオライト、ベントナイト、有機変性ベントナイト、有機変性モンモリロナイト、ドロマイト、カオリン、微粉ケイ酸、長石粉、チタン酸カリウム、シラスバルーン、炭酸カルシウム、炭酸マグネシウム、硫酸バリウム、酸化カルシウム、酸化アルミニウム、酸化チタン、ケイ酸アルミニウム、酸化ケイ素、石膏、ノバキュライト、ドーソナイト及び白土などの板状や粒状の無機充填剤が挙げられる。これらの無機充填剤の中では、炭素繊維、ガラス繊維、ワラステナイト、マイカ、タルク及びカオリンが好ましい。また、繊維状充填剤のアスペクト比は5以上であることが好ましく、10以上であることがより好ましく、20以上であることがさらに好ましい。
また、本発明のポリ乳酸樹脂組成物には、前記以外に、更に剛性等の物性向上の観点から、有機充填剤を含有することが好ましい。
本発明のポリ乳酸樹脂組成物は、ポリ乳酸樹脂組成物からなる成形体の強度、耐熱性、耐衝撃性等の物性向上の観点から、高強度有機合成繊維を含有することができる。高強度有機合成繊維の具体例としては、アラミド繊維、ポリアリレート繊維、PBO繊維等が挙げられ、耐熱性の観点からアラミド繊維が好ましい。高強度有機合成繊維の含有量は、ポリ乳酸樹脂100重量部に対して、3~20重量部が好ましく、5~10重量部がより好ましい。
本発明のポリ乳酸樹脂成形体は、本発明のポリ乳酸樹脂組成物を成形することにより得られる。具体的には、例えば、押出し機等を用いて前記微細化された有機結晶核剤組成物とポリ乳酸樹脂とを混合して溶融させながら、必要により可塑剤や加水分解抑制剤等を配合し、次に得られた溶融物を射出成形機等により金型に充填して成形する。
相対結晶化度(%)={(ΔHm-ΔHcc)/ΔHm×100}
具体的には、相対結晶化度は、DSC装置(パーキンエルマー社製ダイアモンドDSC)を用い、1stRUNとして、昇温速度20℃/分で20℃から200℃まで昇温し、200℃で5分間保持した後、降温速度-20℃/分で200℃から20℃まで降温し、20℃で1分間保持した後、さらに2ndRUNとして、昇温速度20℃/分で20℃から200℃まで昇温し、1stRUNに観測されるポリ乳酸樹脂の冷結晶化エンタルピーの絶対値ΔHcc、2ndRUNに観測される結晶融解エンタルピーΔHmを用いて求めることができる。
重量平均分子量(Mw)は、GPC(ゲルパーミエーションクロマトグラフィー)により、下記の測定条件で行う。
<測定条件>
カラム:GMHHR-H+GMHHR-H
カラム温度:40℃
検出器:RI
溶離液:クロロホルム
流速:1.0mL/min
サンプル濃度:1mg/mL
注入量:0.1mL
換算標準:ポリスチレン
光学純度は、「ポリオレフィン等合成樹脂製食品容器包装等に関する自主基準 第3版改訂版 2004年6月追補 第3部 衛生試験法 P12-13」記載のD体含有量の測定方法に従って、下記の測定条件で行う。具体的には、精秤したポリ乳酸(500mg)に0.7mol/L水酸化ナトリウム/メタノールを10mL加え、65℃に設定した水浴振とう器にセットして、樹脂分が均一溶液になるまで加水分解を行う。得られるアルカリ溶液に希塩酸(2mol/L塩酸)を加え中和し、さらに純水にて定溶した後、一定容量をメスフラスコに分液して高速液体クロマトグラフィー(HPLC)移動相溶液により希釈し、pHが3~7の範囲になるように調整してメスフラスコを定量し、得られた溶液をメンブレンフィルター(0.45μm)によりろ過後、HPLCにてD-乳酸、L-乳酸を定量することによってポリ乳酸の光学純度を求める。
<HPLC測定条件>
カラム :光学分割カラム
スミキラルOA6100(46mmφ×150mm、5μm)、住化分析センター社製
プレカラム:光学分割カラム
スミキラルQA6100(4mmφ×10mm、5μm)、住化分析センター社製
カラム温度:25℃
移動相 :2.5%メタノール含有1.5mM硫酸銅水溶液
移動相流量:1.0mL/分
検出器 :紫外線検出器(UV254nm)
注入量 :20μL
融点は、DSC装置(パーキンエルマー社製、ダイアモンドDSC)を用い、昇温速度10℃/分で20℃から500℃まで昇温して測定を行う。
結晶核剤の粒径(nm)は、結晶核剤の濃度が0.5重量%となるようにエタノール(鹿1級、関東化学社製)で希釈し、超音波装置(装置名:1510J-MT、ヤマト科学社製)で5分間分散させた後、得られた溶液をガラスセル(光路長10mm×幅10mm×高さ45mm、ガラス2面透明セル:三商社製)に下底からの高さ10mmまで入れ、ゼータサイザーNano-S(シスメックス社製、動的光散乱測定器)を用いて25℃で測定する。
粘度は、BII型粘度計BLII(東機産業社製)を使用して、JIS K7117で規定されたS法(回転数:12r/min)による粘度の測定方法に基づき、23℃における粘度を測定する。
重量平均分子量(Mw)はGPC(ゲルパーミエーションクロマトグラフィー)により、下記条件で測定する。
<測定条件>
カラム:TSKPWXL+G4000PWXL+G2500PWXL(いずれも東ソー社製)
カラム温度:40℃
検出器:RI(210nm)
溶離液:0.2mol/L リン酸緩衝液/アセトニトリル(9/1)
流速:10mL/min
サンプル濃度:1mg/mL
注入量:0.1mL
標準:ポリエチレングリコール
5-スルホイソフタル酸ジメチルエステルナトリウム塩296gとイオン交換水2000gを、攪拌機を装着した反応器に採り、攪拌しながら80℃まで加温して内容物を溶解した。ここに塩化バリウム104gをイオン交換水900gに溶解した溶液を攪拌下に徐々に滴下した。30℃まで冷却後、生成した白色粒子を濾過し、得られた白色粒子をイオン交換水3000gに分散し、80℃まで加温して1時間保持した後、30℃まで冷却して白色粉末を濾別して洗浄した。同様な洗浄操作をさらに1回行った後、120℃で5時間乾燥して、5-スルホイソフタル酸ジメチル二バリウム塩の白色粉体297gを得た。
冷却管および攪拌装置をつけた反応容器に、p-キシリレンジアミン21.8g(0.16モル)およびテトラヒドロフラン256.6gを加え溶解し、これにデヒドロアビエチン酸クロライド26.1g(0.08モル)をテトラヒドロフラン130.5gに混合した溶液を攪拌しながら室温で1時間半かけて滴下した。一晩攪拌した後、反応液をろ過し副生成物を取り除いた。ろ液からテトラヒドロフランを留去し得られた粗結晶約40gをメチルイソブチルケトン1200gに溶解し10%塩酸で洗浄後、イオン交換水で洗浄した。硫酸マグネシウムで乾燥後、反応液を濃縮し、全量430gにして再結晶を行った。得られた粗結晶27gをメチルイソブチルケトン400gに溶解し全量300gにまで濃縮し再結晶した。減圧下100℃にて乾燥し、13.6gのp-キシリレンビスロジン酸アミドを得た。
攪拌機、温度計、脱水管を備えた3Lフラスコに、無水コハク酸500g、トリエチレングリコールモノメチルエーテル2463g、パラトルエンスルホン酸一水和物9.5gを仕込み、空間部に窒素(500mL/分)を吹き込みながら、減圧下(4~10.7kPa)、110℃で15時間反応させた。反応液の酸価は1.6(KOHmg/g)であった。反応液に吸着剤キョーワード500SH(協和化学工業社製)27gを添加して80℃、2.7kPaで45分間攪拌してろ過した後、液温115~200℃、圧力0.03kPaでトリエチレングリコールモノメチルエーテルを留去し、80℃に冷却後、残液を減圧ろ過して、ろ液として、コハク酸とトリエチレングリコールモノメチルエーテルとのジエステル〔(MeEO3)2SA〕を得た。得られたジエステルは、重量平均分子量410、粘度(23℃)27mPa・s、酸価0.2KOHmg/g、鹸化価274KOHmg/g、水酸基価1KOHmg/g以下、色相APHA200であった。
オートクレーブに花王社製化粧品用濃グリセリン1モルに対しエチレンオキサイド6モルのモル比で規定量仕込み、1モル%のKOHを触媒として反応圧力0.3MPaの定圧付加し、圧力が一定になるまで150℃で反応した後、80℃まで冷却し、触媒未中和の生成物を得た。この生成物に触媒の吸着剤としてキョーワード600S(協和化学工業社製)を触媒重量の8倍添加し、窒素存在下で80℃、1時間吸着処理をおこなった。さらに処理後の液をNo.2のろ紙にラヂオライト#900をプレコートしたヌッツェで吸着剤を濾過し、グリセリンエチレンオキサイド6モル付加物(以下POE(6)グリセリンという)を得た。これを四つ口フラスコに仕込み、105℃に昇温して300r/minで攪拌し、無水酢酸をPOE(6)グリセリン1モルに対し7.2モルの比率で規定量を約1時間で滴下し反応させた。滴下後110℃で2時間熟成し、さらに120℃で1時間熟成した。熟成後、減圧下で未反応の無水酢酸及び副生の酢酸をトッピングし、さらにスチーミングして、POE(6)グリセリントリアセテートを得た。得られたPOE(6)グリセリントリアセテートは重量平均分子量490、粘度(23℃)79mPa・sであった。
還流冷却機、加熱装置、温度計、圧力計などを装備した容積が1リットルのガラス製反応器に、コハク酸478g、トリエチレングリコール668gを仕込み、反応器の空間部を窒素ガスで置換した後、反応器内容物を加熱し、反応を開始した。その後、2時間かけて内温を200~210℃に昇温し、反応終了までこの温度に保持した。一方、反応器内の圧力は、内温が180℃の時点から200℃に達するまでは、常圧に対する減圧度で87kPaに維持した。その後、触媒としてテトライソプロピルチタネート0.05重量%(対仕込み総量)を仕込み、4時間かけて、原料アルコールを留去しない範囲内で徐々に4kPaまで減圧し反応が終了するまでこの圧力を保持した。組成物を一部抜き出し、酸価を測定して2.0mgKOH/g未満になったことを確認して反応を終了し、1kgのエステル化反応物が得られた。得られたエステル化物の酸価は0.9mgKOH/g、水酸基価は51mgKOH/g、水分量は0.04g、重量平均分子量は2200、粘度(23℃)は21000mPa・sであった。
攪拌機、温度計、脱水管を備えた1Lフラスコに1,3,6-ヘキサントリカルボン酸139g、トリエチレングリコールモノメチルエーテル376g、ジブチル酸化スズ1.59gを仕込み、185℃で12時間反応させた。反応終了後、85%リン酸1.2gを加えて70℃で30分間加熱攪拌した後、キョーワード600S(協和化学工業社製)を添加して吸着処理を行い、加圧ろ過した。さらに、減圧で過剰のトリエチレングリコールを留去した後、加圧ろ過を行い、1,3,6-ヘキサントリカルボン酸とトリエチレングリコールモノメチルエーテルのトリエステルを得た。得られたトリエステルは重量平均分子量656、粘度(23℃)40mPa・sであった。
4ツ口フラスコ(攪拌機、温度計、滴下漏斗、蒸留管、窒素吹き込み管付き)にジエチレングリコール999g(9.41モル)及び触媒として28重量%ナトリウムメトキシド含有メタノール溶液23.6g(ナトリウムメトキシド0.122モル)を入れ、常圧(101.3kPa)、120℃で0.5時間攪拌しながらメタノールを留去した。その後、コハク酸ジメチル(和光純薬工業社製)4125g(28.2モル)を3時間かけて滴下し、常圧120℃で、反応により生じるメタノールを留去した。次に、75℃に冷却し、圧力を2時間かけて常圧から6.7kPaまで徐々に下げてメタノールを留去した後、常圧にもどし、さらに、触媒として28重量%ナトリウムメトキシド含有メタノール溶液4.4g(ナトリウムメトキシド0.023モル)を添加して、100℃で、圧力を2時間かけて常圧から2.9kPaまで徐々に下げてメタノールを留出させた。その後、80℃に冷却してキョーワード600S(協和化学工業社製)41gを添加し、圧力4.0kPa、80℃で1時間攪拌した後、減圧ろ過を行った。ろ液を圧力0.3kPaで、温度を4時間かけて70℃から190℃に上げ、未反応のコハク酸ジメチルを留去し、黄色の液体(エステル化合物A)を得た。なお、触媒の使用量は、ジカルボン酸エステル100モルに対して0.51モルであった。得られたエステル化合物は重量平均分子量450、粘度(23℃)260mPa・sであった。
1リットル四つ口フラスコに、ジエチレングリコールモノエチルエーテル600g(4.47モル)を加え、乾燥窒素ガスを毎分50mLの流量で吹き込みながら、減圧下(20kPa)で攪拌した。次いで反応系内を室温(15℃)に保ちながらオキシ塩化リン114g(0.745モル)をゆっくりと滴下し、その後、40~60℃で5時間熟成した。その後、16重量%の水酸化ナトリウム水溶液149gを添加して中和し、過剰の未反応ジエチレングリコールモノエチルエーテルを70~120℃の温度条件で減圧留去し、さらに水蒸気と接触させて粗リン酸トリエステル367gを得た。さらに、この粗リン酸トリエステルに16重量%の塩化ナトリウム水溶液300gを加えて洗浄した。その後、分相した下相を廃水し、残りの上相を75℃の減圧下で脱水した後、さらにろ過で固形分を除去し、目的とするトリス(エトキシエトキシエチル)ホスフェート266gを得た(収率80%)。このトリス(エトキシエトキシエチル)ホスフェートは無色透明の均一液体であり、クロルイオン分析を行った結果、クロルイオン含量は10mg/kg以下であった。
カルボン酸エステルの製造例1で得られたカルボン酸エステル〔(MeEO3)2SA〕720gと、無置換のフェニルホスホン酸の亜鉛塩(日産化学社製:「エコプロモート」)36gを、媒体式粉砕機(五十嵐機械製造社製「サンドグラインダー TSG-6H」:容器容積800mL、1mmΦジルコニアビーズを720g充填、充填率30%、攪拌翼径70mm)に投入した。容器ジャケットに冷却水を通しながら、回転数2000r/min(攪拌周速7m/s)で9時間粉砕処理を行い、結晶核剤-1(微細化されたフェニルホスホン酸の亜鉛塩)を得た。操作の際の温度は、10~90℃の範囲であった。
カルボン酸エステルの種類を「DAIFATTY-101」(大八化学工業社製、アジピン酸と、ジエチレングリコールモノメチルエーテル/ベンジルアルコール=1/1混合物とのジエステル)に変更した以外は製造例1と同様にして結晶核剤-2(微細化されたフェニルホスホン酸の亜鉛塩)を得た。
カルボン酸エステル〔(MeEO3)2SA〕の投入量を360gに変更すると共に、さらに「DAIFATTY-101」を360g投入した以外は製造例2と同様にして結晶核剤-3(微細化されたフェニルホスホン酸の亜鉛塩)を得た。
無置換のフェニルホスホン酸の亜鉛塩の投入量を72gに変更した以外は製造例1と同様にして結晶核剤-4(微細化されたフェニルホスホン酸の亜鉛塩)を得た。
無置換のフェニルホスホン酸の亜鉛塩の投入量を144gに変更した以外は製造例1と同様にして結晶核剤-5(微細化されたフェニルホスホン酸の亜鉛塩)を得た。
無置換のフェニルホスホン酸の亜鉛塩の投入量を216gに変更した以外は製造例1と同様にして結晶核剤-6(微細化されたフェニルホスホン酸の亜鉛塩)を得た。
無置換のフェニルホスホン酸の亜鉛塩の投入量を18gに変更した以外は製造例1と同様にして結晶核剤-7(微細化されたフェニルホスホン酸の亜鉛塩)を得た。
カルボン酸エステルの種類を、(MeEO3)2SAからカルボン酸エステルの製造2で得られた酢酸とグリセリンにエチレンオキサイドを6モル付加させたエチレンオキサイド付加物とのトリエステル化合物〔(AcEO6)3Gly〕に変更した以外は製造例1と同様にして結晶核剤-8(微細化されたフェニルホスホン酸の亜鉛塩)を得た。
カルボン酸エステルの種類を、(MeEO3)2SAからカルボン酸エステルの製造例3で得られたポリエステルポリオールに変更した以外は製造例1と同様にして結晶核剤-9を得た。
カルボン酸エステルの種類を、(MeEO3)2SAからカルボン酸エステルの製造例3で得られたポリエステルポリオールに変更し、無置換のフェニルホスホン酸の亜鉛塩36gをタルク(日本タルク社製、「MICRO ACE P-6」)720gに変更した以外は製造例1と同様にして結晶核剤-10を得た。
カルボン酸エステルの種類を、(MeEO3)2SAからカルボン酸エステルの製造例4で得られた1,3,6-ヘキサントリカルボン酸とトリエチレングリコールモノメチルエーテルのトリエステル化合物〔(MeEO3)3HTC〕に変更した以外は製造例1と同様にして結晶核剤-11を得た。
無置換のフェニルホスホン酸の亜鉛塩(日産化学社製:「エコプロモート」)50gを振動ミル(中央化工機社製「MB-1」:容器容積3.5L)に投入し、ロッド(断面形状:円形、直径:30mm、長さ:218mm、材質:ステンレス)11本を振動ミルに充填(充填率48%)して、振幅8mm、回転数1200r/minの条件で、60分間処理を行い、結晶核剤-12を得た。
製造例1を参照して、工程(1)に供される結晶核剤と粉砕助剤エステルを表3~10に示す種類と量を用いて、表3~10に示す装置と条件にて結晶核剤-13~47を得た。
<結晶核剤>
(有機結晶核剤(a))
PY109;イソインドリノン骨格を有する化合物(チバファインケミカル社製、IRGAZIN Yellow 2GLTE)
PY110;イソインドリノン骨格を有する化合物(チバファインケミカル社製、CROMOPHTAL Yellow 2RLP)
PR272;ジケトピロロピロール骨格を有する化合物(チバファインケミカル社製、CROMOPHTAL DPP Flame Red FP)
PR254(1);ジケトピロロピロール骨格を有する化合物(チバファインケミカル社製、CROMOPHTAL DPP Red RP)
PR254(2);ジケトピロロピロール骨格を有する化合物(チバファインケミカル社製、IRGAZIN DPP Red BTR)
PV32;ベンズイミダゾロン骨格を有する化合物(クラリアントジャパン社製、Graphtol Bordeaux HF3R)
PR185;ベンズイミダゾロン骨格を有する化合物(クラリアントジャパン社製、Graphtol Cermine HF4C)
PR208;ベンズイミダゾロン骨格を有する化合物(クラリアントジャパン社製、Graphtol Red HF2B)
PB15:3;フタロシアニン骨格を有する化合物(チバファインケミカル社製、IRGALITE Blue GBP)
PB15;フタロシアニン骨格を有する化合物(チバファインケミカル社製、IRGALITE Blue BLPO)
PB15:6;フタロシアニン骨格を有する化合物(大日本インキ社製、FASTROGEN Blue EP-7)
Vat Blue 1;インジゴ骨格を有する化合物(関東化学社製)
(有機結晶核剤(b))
T-1287;デカメチレンジカルボニルジベンゾイルヒドラジド(アデカ社製)
XyStUre;キシレンビスステアリル尿素(日本化成社製、ハクリーンSX)
6-MeUra;6-メチルウラシル(和工純薬工業社製)
MC-6000;メラミンシアヌレート(日産化学工業社製)
(有機結晶核剤(c))
PPA-Zn;無置換のフェニルホスホン酸亜鉛塩(日産化学工業社製、エコプロモート、融点無し)
SIP2MeBa;前記有機結晶核剤の製造例1で製造した5-スルホイソフタル酸ジメチル二バリウム
NA-21;リン酸エステルのナトリウム塩(アデカ社製、アデカスタブNA-21)
KM-1500;ロジン酸類のマグネシウム塩(荒川化学社製、パインクリスタルKM-1500)
BTTCHA;1,3,5-ベンゼントリカルボン酸トリシクロヘキシルアミド(新日本理化社製 エヌジェスターTF-1)
XBRA;前記有機結晶核剤の製造例2で製造したp-キシリレンビスロジン酸アミド
(その他の結晶核剤)
タルク;MICRO ACE P-6(日本タルク社製、融点無し)
<粉砕助剤エステル>
(MeEO3)2SA:前記カルボン酸エステルの製造例1で製造したコハク酸とトリエチレングリコールモノメチルエーテルとのジエステル化合物(重量平均分子量410、粘度27mPa・s)
DAIFATTY-101:アジピン酸と、ジエチレングリコールモノメチルエーテル/ベンジルアルコール=1/1混合物とのジエステル(大八化学工業社製、重量平均分子量338、粘度19mPa・s)
(AcEO6)3Gly:前記カルボン酸エステルの製造例2で製造した酢酸とグリセリンにエチレンオキサイドを6モル付加させたエチレンオキサイド付加物とのトリエステル化合物(重量平均分子量490、粘度79mPa・s)
ポリエステルポリオール:前記カルボン酸エステルの製造例3で製造したポリエステルポリオール(重量平均分子量は2200、粘度は21000mPa・s)
(MeEO3)3HTC:前記カルボン酸エステルの製造例4で製造した1,3,6-ヘキサントリカルボン酸とトリエチレングリコールモノメチルエーテルのトリエステル(重量平均分子量656、粘度40mPa・s)
TEP-2:前記リン酸エステルの製造例1で製造したトリス(エトキシエトキシエチル)ホスフェート(重量平均分子量446、粘度13mPa・s)
MeSA-DEG:前記カルボン酸エステルの製造例5で製造したコハク酸ジメチルとジエチレングリコールとのジエステル(重量平均分子量450、粘度260mPa・s)
表11~18に示すポリ乳酸樹脂組成物用原料を2軸押出機(池貝鉄工社製PCM-45)にて、回転数100r/min、混練温度190℃で溶融混練し、ストランドカットを行い、ポリ乳酸樹脂組成物のペレットを得た。得られたペレットは、70℃減圧下で1日乾燥し、水分量を500ppm以下とした。
<ポリ乳酸樹脂>
NW3001D;ポリ乳酸樹脂(ネイチャーワークスLLC社製、NatureWorks 3001D、光学純度98.5%、重量平均分子量120000)
<結晶核剤>
結晶核剤-1~47;前記結晶核剤組成物の製造例1~47で製造した結晶核剤組成物
PPA-Zn;無置換のフェニルホスホン酸亜鉛塩(日産化学工業社製、エコプロモート、融点無し)
OHC18EB;エチレンビス12-ヒドロキシステアリン酸アミド(日本化成社製、スリパックスH、融点145℃)
PY109;イソインドリノン骨格を有する化合物(チバファインケミカル社製、IRGAZIN Yellow 2GLTE)
<可塑剤>
(MeEO3)2SA:前記結晶核剤組成物の製造において使用したものと同じ
DAIFATTY-101:前記結晶核剤組成物の製造において使用したものと同じ
(AcEO6)3Gly:前記結晶核剤組成物の製造において使用したものと同じ
ポリエステルポリオール:前記結晶核剤組成物の製造において使用したものと同じ
(MeEO3)3HTC:前記結晶核剤組成物の製造において使用したものと同じ
次に、実施例及び比較例のペレットを、シリンダー温度を200℃とした射出成形機(日本製鋼所製、J75E-D)を用いて射出成形し、80℃、70℃、又は60℃の金型温度におけるテストピース〔平板(70mm×40mm×2mm)、角柱状試験片(125mm×12mm×6mm)及び角柱状試験片(63mm×12mm×5mm)〕を成形してポリ乳酸樹脂組成物の成形体を得た。
表11~18に示す金型温度において、テストピース3種類すべてについて変形がなく、取り出しが容易と判断されるまでに有する時間を、離型に必要な金型保持時間とした。金型保持時間が短いほど、金型内部及びランナー部分でテストピースの結晶化速度が速く、成形性に優れることを示す。なお、取り出しができないか、取出しができても変形が生じている場合は不可と判断する。
角柱状試験片(125mm×12mm×6mm)について、JIS-K7191に基づいて、熱変形温度測定機(東洋精機製作所製、B-32)を使用して、荷重0.45MPaにおいて0.25mmたわむときの熱変形温度(℃)を測定した。この温度が高い方が耐熱性に優れていることを示す。
平板(70mm×40mm×2mm)について、中央部から7.5mgサンプリングを行い、DSC装置(パーキンエルマー社製、ダイアモンドDSC)を用い、1stRUNとして、昇温速度20℃/分で20℃から200℃まで昇温し、200℃で5分間保持した後、降温速度-20℃/分で200℃から20℃まで降温し、20℃で1分間保持した後、さらに2ndRUNとして、昇温速度20℃/分で20℃から200℃まで昇温し、1stRUNに観測されるポリ乳酸樹脂の冷結晶化エンタルピーの絶対値ΔHcc、2ndRUNに観測される結晶融解エンタルピーΔHmを用いて次式で求めた。この数値が高い方が結晶性に優れることを示す。
相対結晶化度(%)={(ΔHm-ΔHcc)/ΔHm×100}
Claims (9)
- 下記工程(1)及び(2)を含むポリ乳酸樹脂組成物の製造方法。
工程(1):有機結晶核剤を、重量平均分子量が150~600かつ23℃における粘度が1~500mPa・sであるカルボン酸エステル及び/又は重量平均分子量が150~600かつ23℃における粘度が1~500mPa・sであるリン酸エステル存在下で湿式粉砕して、微細化された有機結晶核剤組成物を得る工程
工程(2):工程(1)で得られた微細化された有機結晶核剤組成物とポリ乳酸樹脂を含有するポリ乳酸樹脂組成物用原料を溶融混練する工程 - 有機結晶核剤が、芳香族スルホン酸ジアルキルの金属塩、リン酸エステルの金属塩、フェニルホスホン酸の金属塩、ロジン酸類の金属塩、芳香族カルボン酸アミド、及びロジン酸アミドからなる群より選ばれる少なくとも1種の有機化合物を含む、請求項1記載のポリ乳酸樹脂組成物の製造方法。
- 有機結晶核剤がフェニルホスホン酸の金属塩を含む、請求項1又は2記載のポリ乳酸樹脂組成物の製造方法。
- 工程(1)が、有機結晶核剤を、重量平均分子量が150~600かつ23℃における粘度が1~500mPa・sであるカルボン酸エステル存在下で湿式粉砕して、微細化された有機結晶核剤組成物を得る工程を有する、請求項1記載のポリ乳酸樹脂組成物の製造方法。
- 微細化された有機結晶核剤組成物の体積中位粒径(D50)が50~700nmである、請求項1~4いずれか記載のポリ乳酸樹脂組成物の製造方法。
- 工程(1)が、前記有機結晶核剤の重量と前記カルボン酸エステル及びリン酸エステルの合計重量との比(有機結晶核剤/カルボン酸エステル及びリン酸エステル)が1/99~50/50となる範囲内で、有機結晶核剤をカルボン酸エステル及び/又はリン酸エステル存在下で湿式粉砕する工程を有する、請求項1~5いずれか記載のポリ乳酸樹脂組成物の製造方法。
- カルボン酸エステルが、分子中に2個以上のエステル基を有するカルボン酸エステルであって、該カルボン酸エステルを構成するアルコール成分が、水酸基1個当たり炭素数2~3のアルキレンオキサイドを平均0.5~5モル付加したアルコールを含有してなる、請求項1~6いずれか記載のポリ乳酸樹脂組成物の製造方法。
- 請求項1~8いずれか記載の製造方法で得られるポリ乳酸樹脂組成物。
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US (2) | US8785520B2 (ja) |
EP (1) | EP2532711A4 (ja) |
JP (1) | JP5654501B2 (ja) |
KR (1) | KR20120120387A (ja) |
CN (1) | CN102753621A (ja) |
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WO (1) | WO2011096299A1 (ja) |
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Cited By (14)
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JP2012062467A (ja) * | 2010-08-19 | 2012-03-29 | Kao Corp | 樹脂組成物 |
EP2607428A4 (en) * | 2010-08-19 | 2015-08-19 | Kao Corp | Resin composition |
US20130261214A1 (en) * | 2010-12-14 | 2013-10-03 | Kao Corporation | Polylactic acid resin composition |
JP2014051646A (ja) * | 2012-05-18 | 2014-03-20 | Kao Corp | 熱成形用ポリ乳酸樹脂シート |
US9938406B2 (en) | 2012-05-18 | 2018-04-10 | Kao Corporation | Polylactic acid resin sheet for thermal molding use |
JP2014047234A (ja) * | 2012-08-29 | 2014-03-17 | Kao Corp | ポリ乳酸樹脂組成物 |
US9505913B2 (en) | 2013-03-13 | 2016-11-29 | Kao Corporation | Polylactic acid resin composition |
WO2014141952A1 (ja) * | 2013-03-13 | 2014-09-18 | 花王株式会社 | ポリ乳酸樹脂組成物 |
JP2014198820A (ja) * | 2013-03-13 | 2014-10-23 | 花王株式会社 | ポリ乳酸樹脂組成物 |
WO2015020120A1 (ja) * | 2013-08-07 | 2015-02-12 | ユニチカ株式会社 | ポリ乳酸樹脂組成物 |
JPWO2015020120A1 (ja) * | 2013-08-07 | 2017-03-02 | ユニチカ株式会社 | ポリ乳酸樹脂組成物 |
WO2015079755A1 (ja) * | 2013-11-29 | 2015-06-04 | 花王株式会社 | ポリ乳酸樹脂組成物 |
JP2016020441A (ja) * | 2014-07-15 | 2016-02-04 | 富士ゼロックス株式会社 | 樹脂組成物および樹脂成形体 |
TWI644928B (zh) * | 2016-03-24 | 2018-12-21 | 三菱化學股份有限公司 | (Meth)acrylic resin composition, resin molded body, resin Method for producing laminated body and (meth)acrylic resin composition |
Also Published As
Publication number | Publication date |
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JP5654501B2 (ja) | 2015-01-14 |
US20140296399A1 (en) | 2014-10-02 |
JPWO2011096299A1 (ja) | 2013-06-10 |
EP2532711A4 (en) | 2014-03-26 |
EP2532711A1 (en) | 2012-12-12 |
US20120296017A1 (en) | 2012-11-22 |
US8785520B2 (en) | 2014-07-22 |
BR112012018996A2 (pt) | 2016-09-13 |
CN102753621A (zh) | 2012-10-24 |
KR20120120387A (ko) | 2012-11-01 |
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