JP2017110122A - Polylactic resin composition, polylactic resin molding and method for producing polylactic resin molding - Google Patents
Polylactic resin composition, polylactic resin molding and method for producing polylactic resin molding Download PDFInfo
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- JP2017110122A JP2017110122A JP2015246299A JP2015246299A JP2017110122A JP 2017110122 A JP2017110122 A JP 2017110122A JP 2015246299 A JP2015246299 A JP 2015246299A JP 2015246299 A JP2015246299 A JP 2015246299A JP 2017110122 A JP2017110122 A JP 2017110122A
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- Prior art keywords
- polylactic acid
- acid resin
- resin composition
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- mass
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- 229920005989 resin Polymers 0.000 title claims abstract description 57
- 239000011342 resin composition Substances 0.000 title claims abstract description 32
- 238000000465 moulding Methods 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- -1 amide compound Chemical class 0.000 claims abstract description 85
- 239000003484 crystal nucleating agent Substances 0.000 claims abstract description 36
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 26
- 125000003118 aryl group Chemical group 0.000 claims abstract description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 11
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 8
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 75
- 239000004626 polylactic acid Substances 0.000 claims description 75
- 239000000126 substance Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical group [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000005020 hydroxyalkenyl group Chemical group 0.000 claims description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical group [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical group [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 abstract description 31
- 230000008025 crystallization Effects 0.000 abstract description 29
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000654 additive Substances 0.000 description 10
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
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- 238000004898 kneading Methods 0.000 description 7
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- 239000004645 polyester resin Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-UHFFFAOYSA-N 0.000 description 5
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- 101710148027 Ribulose bisphosphate carboxylase/oxygenase activase 1, chloroplastic Proteins 0.000 description 3
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- 238000003786 synthesis reaction Methods 0.000 description 3
- RAADBCJYJHQQBI-UHFFFAOYSA-N 2-sulfoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(S(O)(=O)=O)=C1 RAADBCJYJHQQBI-UHFFFAOYSA-N 0.000 description 2
- SDGNNLQZAPXALR-UHFFFAOYSA-N 3-sulfophthalic acid Chemical compound OC(=O)C1=CC=CC(S(O)(=O)=O)=C1C(O)=O SDGNNLQZAPXALR-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
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- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LJZKUDYOSCNJPU-UHFFFAOYSA-N dotetracontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O LJZKUDYOSCNJPU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- SWSBIGKFUOXRNJ-CVBJKYQLSA-N ethene;(z)-octadec-9-enamide Chemical compound C=C.CCCCCCCC\C=C/CCCCCCCC(N)=O.CCCCCCCC\C=C/CCCCCCCC(N)=O SWSBIGKFUOXRNJ-CVBJKYQLSA-N 0.000 description 2
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- MXJJJAKXVVAHKI-WRBBJXAJSA-N (9z,29z)-octatriaconta-9,29-dienediamide Chemical compound NC(=O)CCCCCCC\C=C/CCCCCCCCCCCCCCCCCC\C=C/CCCCCCCC(N)=O MXJJJAKXVVAHKI-WRBBJXAJSA-N 0.000 description 1
- CPUBMKFFRRFXIP-YPAXQUSRSA-N (9z,33z)-dotetraconta-9,33-dienediamide Chemical compound NC(=O)CCCCCCC\C=C/CCCCCCCCCCCCCCCCCCCCCC\C=C/CCCCCCCC(N)=O CPUBMKFFRRFXIP-YPAXQUSRSA-N 0.000 description 1
- KZVIUXKOLXVBPC-UHFFFAOYSA-N 16-methylheptadecanamide Chemical compound CC(C)CCCCCCCCCCCCCCC(N)=O KZVIUXKOLXVBPC-UHFFFAOYSA-N 0.000 description 1
- XHSVWKJCURCWFU-UHFFFAOYSA-N 19-[3-(19-amino-19-oxononadecyl)phenyl]nonadecanamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCC1=CC=CC(CCCCCCCCCCCCCCCCCCC(N)=O)=C1 XHSVWKJCURCWFU-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
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- QYDCSHQWDCFHOQ-UHFFFAOYSA-N CCCCCCCC[Mg]CCCCCCCC Chemical class CCCCCCCC[Mg]CCCCCCCC QYDCSHQWDCFHOQ-UHFFFAOYSA-N 0.000 description 1
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- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- LLHSEQCZSNZLRI-UHFFFAOYSA-M sodium;3,5-bis(methoxycarbonyl)benzenesulfonate Chemical compound [Na+].COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1 LLHSEQCZSNZLRI-UHFFFAOYSA-M 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UGKIWQRXZAAROZ-UHFFFAOYSA-N tetracontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O UGKIWQRXZAAROZ-UHFFFAOYSA-N 0.000 description 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- WPJRYESQKIBSTM-UHFFFAOYSA-N triacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O WPJRYESQKIBSTM-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、耐熱性に優れ、結晶化後も透明性を維持できるポリ乳酸樹脂組成物、ポリ乳酸樹脂成形体及びポリ乳酸樹脂成形体の製造方法に関する。 The present invention relates to a polylactic acid resin composition that is excellent in heat resistance and can maintain transparency even after crystallization, a polylactic acid resin molded body, and a method for producing a polylactic acid resin molded body.
従来、ポリエステル系樹脂と結晶核剤とを含有して成るポリエステル系樹脂組成物として、脂肪族ポリエステルと、脂肪族カルボン酸アミド、脂肪族カルボン酸塩、脂肪族アルコール及び脂肪族カルボン酸エステルから選ばれる少なくとも一種とを含有するもの（例えば、特許文献１及び２参照）、脂肪族ポリエステル樹脂と、特定の芳香族スルホン酸塩と、特定のアミド化合物とを特定割合で含有して成るもの（例えば、特許文献３参照）、脂肪族ポリエステル樹脂と、特定の芳香族スルホン酸塩とを含有して成るもの（例えば、特許文献４参照）等が提案されている。しかし、これら従来のポリエステル系樹脂組成物には、ポリエステル系樹脂としてポリ乳酸樹脂を用いた場合に特に、結晶化が依然として遅く、そのため成形に長時間を要し、したがってそれだけ生産性が悪く、得られる成形品の透明性も悪いという問題がある。 Conventionally, a polyester resin composition comprising a polyester resin and a crystal nucleating agent is selected from aliphatic polyesters, aliphatic carboxylic acid amides, aliphatic carboxylates, aliphatic alcohols and aliphatic carboxylic acid esters. (For example, see Patent Documents 1 and 2), an aliphatic polyester resin, a specific aromatic sulfonate, and a specific amide compound in a specific ratio (for example, , Patent Document 3), and those containing an aliphatic polyester resin and a specific aromatic sulfonate (for example, see Patent Document 4) have been proposed. However, in these conventional polyester resin compositions, especially when a polylactic acid resin is used as the polyester resin, the crystallization is still slow, and therefore, it takes a long time for molding, and thus the productivity is poor. There is a problem that the molded product is also poorly transparent.
本発明が解決しようとする課題は、結晶化が速く、したがってそれだけ結晶化時間が短く、結晶化後も透明性を維持できるポリ乳酸樹脂組成物、ポリ乳酸樹脂成形体の製造方法及びポリ乳酸樹脂成形体を提供する処にある。 The problem to be solved by the present invention is to provide a polylactic acid resin composition, a method for producing a polylactic acid resin molded product, and a polylactic acid resin, which can be crystallized quickly, and thus the crystallization time is so short that transparency can be maintained even after crystallization. There is a place to provide a molded body.
しかして本発明者らは、前記の課題を解決するべく研究した結果、ポリ乳酸樹脂に、結晶核剤として特定の芳香族スルホン酸塩と特定のアミド化合物とを特定割合で含有して成るものを用いたものが正しく好適であることを見出した。 Accordingly, the present inventors have studied to solve the above problems, and as a result, the polylactic acid resin contains a specific aromatic sulfonate and a specific amide compound as a crystal nucleating agent in a specific ratio. It has been found that the one using is correctly suitable.
すなわち本発明は、ポリ乳酸樹脂と結晶核剤とを含有して成るポリ乳酸樹脂組成物であって、該結晶核剤が下記の化１で示される芳香族スルホン酸塩を１〜４９質量％及び下記の化２で示されるアミド化合物を５１〜９９質量％（合計１００質量％）の割合で含有して成ることを特徴とするポリ乳酸樹脂組成物に係る。また本発明はかかるポリ乳酸樹脂組成物から成形されているポリ乳酸樹脂成形体及びかかるポリ乳酸樹脂成形体の製造方法に係る。
That is, the present invention is a polylactic acid resin composition comprising a polylactic acid resin and a crystal nucleating agent, wherein the crystal nucleating agent is an aromatic sulfonate represented by the following chemical formula 1 to 49% by mass. And an amide compound represented by the following chemical formula 2 in a proportion of 51 to 99% by mass (total 100% by mass). The present invention also relates to a polylactic acid resin molded article molded from such a polylactic acid resin composition and a method for producing such a polylactic acid resin molded article.
化１において、
Ｘ：ベンゼンから３個の水素原子を除いた残基
Ｒ１，Ｒ２：炭素数１〜６の炭化水素基
Ｍ：アルカリ金属原子又はアルカリ土類金属原子
ｎ：１又は２であって、Ｍがアルカリ金属原子の場合はｎ＝１、Ｍがアルカリ土類金属原子の場合はｎ＝２
In chemical formula 1,
X: residue obtained by removing three hydrogen atoms from benzene R 1 , R 2 : hydrocarbon group having 1 to 6 carbon atoms M: alkali metal atom or alkaline earth metal atom n: 1 or 2, N = 1 when is an alkali metal atom, n = 2 when M is an alkaline earth metal atom
化２において、
Ｒ ３ ，Ｒ ７ ：炭素数１〜２２の炭化水素基、炭素数１〜２２のヒドロキシアルキル
基又は炭素数１〜２２のヒドロキシアルケニル基
Ｒ ４ ，Ｒ ６ ：水素原子
Ｒ ５ ：炭素数１〜６のアルキレン基
In chemical formula 2,
R 3 , R 7 : a hydrocarbon group having 1 to 22 carbon atoms, a hydroxyalkyl group having 1 to 22 carbon atoms, or a hydroxyalkenyl group having 1 to 22 carbon atoms
R 4 and R 6 : hydrogen atoms
R 5 : an alkylene group having 1 to 6 carbon atoms
先ず、本発明に係るポリ乳酸樹脂組成物（以下、本発明の組成物という）について説明する。本発明の組成物は、ポリ乳酸樹脂と結晶核剤とを含有して成るポリ乳酸樹脂組成物であって、該結晶核剤が前記の化１で示される芳香族スルホン酸塩を１〜４９質量％及び前記の化２で示されるアミド化合物を５１〜９９質量％（合計１００質量％）の割合で含有して成ることを特徴とするものである。 First, the polylactic acid resin composition according to the present invention (hereinafter referred to as the composition of the present invention) will be described. The composition of the present invention is a polylactic acid resin composition comprising a polylactic acid resin and a crystal nucleating agent, wherein the crystal nucleating agent is an aromatic sulfonate represented by the above chemical formula 1 to 49. The amide compound represented by the above formula 2 is contained in a proportion of 51 to 99% by mass (total 100% by mass).
化１で示される芳香族スルホン酸塩において、化１中のＸは、ベンゼンから３個の水素原子を除いた残基である。化１中のＲ１及びＲ２は、メチル基、エチル基、プロピル基、イソプロピル基、イソブチル基、ペンチル基、ヘキシル基、シクロペンチル基、シクロヘキシル基、アリル基、シクロヘキセニル基等の炭素数１〜６の炭化水素基である。化１中のＭは、リチウム原子、ナトリウム原子、カリウム原子、ルビジウム原子、セシウム原子等のアルカリ金属原子又はベリリウム原子、マグネシウム原子、カルシウム原子、ストロンチウム原子、バリウム原子等のアルカリ土類金属原子であるが、なかでもカリウム原子、バリウム原子、ルビジウム原子、ストロンチウム原子又はカルシウム原子が好ましく、化１中のＭがカリウム原子又はバリウム原子であり、且つＲ１及びＲ２がメチル基がより好ましい。化１中のｎは、１又は２であるが、Ｍがアルカリ金属原子の場合はｎ＝１、Ｍがアルカリ土類金属原子の場合はｎ＝２である。 In the aromatic sulfonate represented by Chemical Formula 1, X in Chemical Formula 1 is a residue obtained by removing three hydrogen atoms from benzene. R 1 and R 2 in Chemical Formula 1 are each a C 1 -C 1 such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, a pentyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, an allyl group, and a cyclohexenyl group. 6 hydrocarbon groups. M in Chemical Formula 1 is an alkali metal atom such as a lithium atom, sodium atom, potassium atom, rubidium atom or cesium atom, or an alkaline earth metal atom such as beryllium atom, magnesium atom, calcium atom, strontium atom or barium atom. However, among them, a potassium atom, a barium atom, a rubidium atom, a strontium atom or a calcium atom is preferable, M in Chemical Formula 1 is a potassium atom or a barium atom, and R 1 and R 2 are more preferably a methyl group. N in Chemical Formula 1 is 1 or 2, but when M is an alkali metal atom, n = 1, and when M is an alkaline earth metal atom, n = 2.
以上説明した化１で示される芳香族スルホン酸塩の具体例としては、１）スルホフタル酸ジアルキルのアルカリ金属塩、２）スルホイソフタル酸ジアルキルのアルカリ金属塩、３）スルホテレフタル酸ジアルキルのアルカリ金属塩、４）スルホフタル酸ジアルキルのアルカリ土類金属塩、５）スルホイソフタル酸ジアルキルのアルカリ土類金属塩、６）スルホテレフタル酸ジアルキルのアルカリ土類金属塩、７）以上の１）〜６）の任意の混合物が挙げられるが、なかでもスルホイソフタル酸ジアルキルのアルカリ金属塩、スルホイソフタル酸ジアルキルのアルカリ土類金属塩が好ましい。 Specific examples of the aromatic sulfonate represented by Chemical Formula 1 described above are as follows: 1) alkali metal salt of dialkyl sulfophthalate, 2) alkali metal salt of dialkyl sulfoisophthalate, and 3) alkali metal salt of dialkyl sulfoterephthalate. 4) Alkaline earth metal salt of dialkyl sulfophthalate, 5) Alkaline earth metal salt of dialkyl sulfoisophthalate, 6) Alkaline earth metal salt of dialkyl sulfoterephthalate, 7) Any of 1) to 6) above Among them, preferred are alkali metal salts of dialkyl sulfoisophthalates and alkaline earth metal salts of dialkyl sulfoisophthalates.
化１で示される芳香族スルホン酸塩それ自体は、公知の方法で合成できる。これには例えば、特公昭３４−１０４９７号公報、特開２０１０−１５０３６５号公報記載の方法が挙げられる。これらの方法で合成された芳香族スルホン酸塩には、硫酸塩、塩化物塩、酢酸塩、炭酸塩等の金属塩等の副生成物、スルホイソフタル酸ジアルキル及びその金属塩等の原料及び中和に使用した水酸化物等の不純物が含有されている。かかる不純物の含有量に特に制限はないが、５％以下であることが好ましい。 The aromatic sulfonate salt represented by Chemical Formula 1 can be synthesized by a known method. Examples thereof include the methods described in JP-B No. 34-10497 and JP-A No. 2010-150365. Aromatic sulfonates synthesized by these methods include by-products such as sulfates, chlorides, acetates, carbonates and other metal salts, dialkyl sulfoisophthalates and metal salts thereof, and Impurities such as hydroxide used in the sum are contained. Although there is no restriction | limiting in particular in content of this impurity, It is preferable that it is 5% or less.
化２で示されるアミド化合物において、化２中のＲ３及びＲ７は、１）メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ヘキシル基、ペンチル基、オクチル基、デシル基、ドデシル基、トリデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、エイコシル基、ドコシル基、ｎ−プロペニル基、イソプロペニル基、ｎ−ブテニル基、イソブテニル基、ｓｅｃ−ブテニル基、ｔｅｒｔ−ブテニル基、ｎ−ペンテニル基、ｎ−ヘキセニル基、ｎ−ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基、トリデセニル基、テトラデセニル基、ペンタデセニル基、ヘキサデセニル基、ヘプタデセニル基、オクタデセニル基、エイコセニル基、ドコセニル基等の炭素数１〜２２の炭化水素基、２）ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基、ヒドロキシヘキシル基、ヒドロキシペンチル基、ヒドロキシオクチル基、ヒドロキシデシル基、ヒドロキシドデシル基、ヒドロキシトリデシル基、ヒドロキシテトラデシル基、ヒドロキシヘキサデシル基、ヒドロキシオクタデシル基、ヒドロキシエイコシル基、ヒドロキシドコシル基等の炭素数１〜２２のヒドロキシアルキル基、又は３）ヒドロキシｎ−プロペニル基、ヒドロキシイソプロペニル基、ヒドロキシｎ−ブテニル基、ヒドロキシイソブテニル基、ヒドロキシｓｅｃ−ブテニル基、ヒドロキシｔｅｒｔ−ブテニル基、ヒドロキシｎ−ペンテニル基、ヒドロキシｎ−ヘキセニル基、ヒドロキシｎ−ヘプテニル基、ヒドロキシオクテニル基、ヒドロキシノネニル基、ヒドロキシデセニル基、ヒドロキシウンデセニル基、ヒドロキシドデセニル基、トリデセニル基、ヒドロキシテトラデセニル基、ヒドロキシペンタデセニル基、ヒドロキシヘキサデセニル基、ヒドロキシヘプタデセニル基、ヒドロキシオクタデセニル基、ヒドロキシエイコセニル基、ヒドロキシドコセニル基等の炭素数１〜２２のヒドロキシアルケニル基であるが、なかでも、炭素数１〜１８の炭化水素基、炭素数１〜１８のヒドロキシアルキル基又は炭素数１〜１８のヒドロキシアルケニル基が好ましい。化２中のＲ４及びＲ６は、水素原子である。化２中のＲ５は、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキサレン基等の炭素数１〜６のアルキレン基である。 In the amide compound represented by Chemical Formula 2, R 3 and R 7 in Chemical Formula 2 are: 1) methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, pentyl group, octyl group, decyl Group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, docosyl group, n-propenyl group, isopropenyl group, n-butenyl group, isobutenyl group, sec-butenyl group, tert-butenyl group, n-pentenyl, n-hexenyl, n-heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, eicosenyl , C 1-2 such as dococenyl group 2) Hydroxymethyl group, hydroxyethyl group, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxyhexyl group, hydroxypentyl group, hydroxyoctyl group, hydroxydecyl group, hydroxydodecyl group , A hydroxytridecyl group, a hydroxytetradecyl group, a hydroxyhexadecyl group, a hydroxyoctadecyl group, a hydroxyeicosyl group, a hydroxydocosyl group, or the like, or 3) a hydroxy n-propenyl group, Hydroxyisopropenyl group, hydroxy n-butenyl group, hydroxyisobutenyl group, hydroxy sec-butenyl group, hydroxy tert-butenyl group, hydroxy n-pentenyl group, hydroxy n-hexenyl Group, hydroxy n-heptenyl group, hydroxyoctenyl group, hydroxynonenyl group, hydroxydecenyl group, hydroxyundecenyl group, hydroxydodecenyl group, tridecenyl group, hydroxytetradecenyl group, hydroxypentadecenyl group Although it is a C1-C22 hydroxyalkenyl group, such as a senyl group, a hydroxyhexadecenyl group, a hydroxyheptadecenyl group, a hydroxyoctadecenyl group, a hydroxyeicocenyl group, a hydroxydocosenyl group, etc. Of these, a hydrocarbon group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 18 carbon atoms, or a hydroxyalkenyl group having 1 to 18 carbon atoms is preferable. R 4 and R 6 in Chemical formula 2 are hydrogen atoms. R 5 in Chemical Formula 2 is an alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, or a hexalene group.
以上説明した化２で示されるアミド化合物の具体例としては、メチレンビスステアリン酸アミド、エチレンビスカプリン酸アミド、エチレンビスラウリン酸アミド、エチレンビスオレイン酸アミド、エチレンビスステアリン酸アミド、エチレンビスエルカ酸アミド、エチレンビスベヘニン酸アミド、エチレンビスイソステアリン酸アミド、ブチレンビスステアリン酸アミド、ヘキサメチレンビスラウリン酸アミド、ヘキサメチレンビスオレイン酸アミド、へキサメチレンビスステアリン酸アミド、へキサメチレンビスベヘニン酸アミド、エチレンビス−１２−ヒドロキシステアリン酸アミド、ヘキサメチレンビス−１２−ヒドロキシステアリン酸アミド、エチレンビス−リシノール酸アミド等が挙げられるが、なかでもエチレンビスカプリン酸アミド、エチレンビスラウリン酸アミド、エチレンビスオレイン酸アミド、エチレンビスステアリン酸アミド、エチレンビス−１２−ヒドロキシステアリン酸アミド、エチレンビス−リシノール酸アミド等が好ましい。これらのアミド化合物は、単独で使用してもよいし、複数を組み合わせて使用してもよい。 Specific examples of the amide compound represented by Chemical Formula 2 described above include methylene bis stearic acid amide, ethylene bis capric acid amide, ethylene bis lauric acid amide, ethylene bis oleic acid amide, ethylene bis stearic acid amide, ethylene bis erucic acid. Amide, Ethylene bis behenic acid amide, Ethylene bis isostearic acid amide, Butylene bis stearic acid amide, Hexamethylene bis lauric acid amide, Hexamethylene bis oleic acid amide, Hexamethylene bis stearic acid amide, Hexamethylene bis behen Examples thereof include ninamide, ethylenebis-12-hydroxystearic acid amide, hexamethylene bis-12-hydroxystearic acid amide, and ethylene bis-ricinoleic acid amide. Amide, ethylenebis lauric acid amide, ethylenebis oleic acid amide, ethylenebis stearic acid amide, ethylenebis-12-hydroxystearic acid amide, ethylene bis - ricinoleic acid amide, and the like are preferable. These amide compounds may be used alone or in combination of two or more.
結晶核剤は前記したような化１で示される芳香族スルホン酸塩を１〜４９質量％及び化２で示されるアミド化合物を５１〜９９質量％（合計１００質量％）の割合で含有して成るものであるが、なかでも芳香族スルホン酸塩を５〜３０質量％及びアミド化合物を７０〜９５質量％（合計１００質量％）の割合で含有して成るものが好ましい。 The crystal nucleating agent contains 1 to 49% by mass of the aromatic sulfonate represented by Chemical Formula 1 and 51 to 99% by mass (total 100% by mass) of the amide compound represented by Chemical Formula 2 as described above. Among them, those containing 5 to 30% by mass of aromatic sulfonate and 70 to 95% by mass (total 100% by mass) of amide compounds are preferable.
本発明の組成物に供する結晶核剤は、その平均粒子径を特に制限されないが、０．０１〜４０μｍの範囲内に調整したものが好ましい。ここで平均粒子径とは、レーザー回折・散乱法により測定して得られえた５０％体積径（メジアン径）を意味する。結晶核剤の平均粒子径が４０μｍより大きいと、結晶化に影響を及ぼすようになり、逆に結晶核剤の平均粒子径が０．０１μｍより小さいと、取り扱い時の粉立ちによって作業環境が悪くなりやすい。 The crystal nucleating agent to be used for the composition of the present invention is not particularly limited in its average particle diameter, but is preferably adjusted to a range of 0.01 to 40 μm. Here, the average particle diameter means a 50% volume diameter (median diameter) obtained by measurement by a laser diffraction / scattering method. If the average particle size of the crystal nucleating agent is larger than 40 μm, crystallization will be affected. Conversely, if the average particle size of the crystal nucleating agent is smaller than 0.01 μm, the working environment will be poor due to dusting during handling. Prone.
結晶核剤の平均粒子径を０．０１〜４０μｍに調整する方法としては、特に制限されないが、結晶核剤を、１）ジェットミル、ボールミル、ビーズミル、サイクロンミル等の乾式粉砕機に供してその平均粒子径を調整する方法、２）水、有機溶剤及び水と有機溶剤の混合溶液と共に用い、サンドグラインダー、ボールミル、ビーズミル等の湿式粉砕機に供してその平均粒子径を調整する方法が挙げられる。 The method for adjusting the average particle size of the crystal nucleating agent to 0.01 to 40 μm is not particularly limited, but the crystal nucleating agent is subjected to 1) a dry pulverizer such as a jet mill, a ball mill, a bead mill, or a cyclone mill. A method for adjusting the average particle size, 2) A method for adjusting the average particle size by using it with a wet grinder such as a sand grinder, a ball mill, a bead mill, etc., together with water, an organic solvent and a mixed solution of water and an organic solvent. .
本発明の組成物において、組成物中のポリ乳酸樹脂及び結晶核剤の含有割合に特に制限はないが、ポリ乳酸樹脂１００質量部に対し結晶核剤を０．０５〜５質量部の割合で含有して成るものが好ましく、ポリ乳酸樹脂１００質量部に対し結晶核剤を０．１０〜２．５質量部の割合で含有して成るものがより好ましい。 In the composition of the present invention, the content ratio of the polylactic acid resin and the crystal nucleating agent in the composition is not particularly limited, but the crystal nucleating agent is in a ratio of 0.05 to 5 parts by mass with respect to 100 parts by mass of the polylactic acid resin. What contains is preferable, and what contains a crystal nucleating agent in the ratio of 0.10-2.5 mass parts with respect to 100 mass parts of polylactic acid resin is more preferable.
本発明の組成物において、ポリ乳酸樹脂の光学純度に特に制限はないが、９５〜１００％のものが好ましく、９６〜１００％のものがより好ましい。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よって求めることができる。 In the composition of the present invention, the optical purity of the polylactic acid resin is not particularly limited, but is preferably 95 to 100%, more preferably 96 to 100%. The optical purity can be determined by the D-body content measurement method described in “Voluntary Standards for Food Containers and Packaging Made of Synthetic Resins such as Polyolefins, Third Edition, Revised June 2004, Part 3 Sanitation Test Method P12-13”. it can.
本発明の組成物に用いるポリ乳酸樹脂は、公知の方法で合成できる。これには例えば、特開平５−４８２５８号公報、特開平７−３３８６１号公報、特開昭５９−９６１２３号公報、高分子討論会予稿集第４４巻の３１９８−３１９９頁に記載されているような、１）乳酸を直接脱水縮合反応する方法、２）乳酸のラクチドを開環重合する方法等が挙げられる。前記１）の方法では、Ｌ−乳酸、Ｄ−乳酸、ＤＬ−乳酸又はこれらの混合物のいずれの乳酸を用いてもよい。前記２）の方法では、Ｌ−ラクチド、Ｄ−ラクチド、ＤＬ−ラクチド、メソ−ラクチド又はこれら混合物のいずれのラクチドを用いてもよい。原料のラクチドの合成、精製及び重合方法にも、公知の方法を適用できる。これには例えば、米国特許第４０５７５３７号明細書、公開欧州特許出願第２６１５７２号明細書、Ｐｏｌｙｍｅｒ Ｂｕｌｌｅｔｉｎ，１４，４９１−４９５（１９８５）、Ｍａｃｒｏｍｏｌ．Ｃｈｅｍ．，１８７，１６１１−１６２８（１９８６）等に記載されている方法が挙げられる。 The polylactic acid resin used in the composition of the present invention can be synthesized by a known method. This is described in, for example, JP-A-5-48258, JP-A-7-33861, JP-A-59-96123, and Polymer Sciences Conference Proceedings Vol. 44, pages 3198-3199. 1) a method of directly dehydrating condensation reaction of lactic acid, and 2) a method of ring-opening polymerization of lactide of lactic acid. In the method 1), any lactic acid of L-lactic acid, D-lactic acid, DL-lactic acid, or a mixture thereof may be used. In the method 2), any one of L-lactide, D-lactide, DL-lactide, meso-lactide, or a mixture thereof may be used. Known methods can also be applied to the synthesis, purification, and polymerization methods of the starting lactide. For example, U.S. Pat. No. 4,057,537, published European Patent Application No. 261572, Polymer Bulletin, 14, 491-495 (1985), Macromol. Chem. 187, 1611-1628 (1986) and the like.
本発明の組成物に用いるポリ乳酸樹脂の質量平均分子量は特に制限されないが、３００００以上としたものが好ましく、５００００以上としたものがより好ましく、５００００〜４０００００としたものが特に好ましい。得られる成形体の強度や弾性率等の機械特性、更には成形時の流動性をより良く確保するためである。尚、質量平均分子量はゲルパーミエーションクロマトグラフ（ＧＰＣ）法によるポリスチレン換算値である。 The mass average molecular weight of the polylactic acid resin used in the composition of the present invention is not particularly limited, but is preferably 30000 or more, more preferably 50000 or more, and particularly preferably 50000-400000. This is to ensure better mechanical properties such as strength and elastic modulus of the obtained molded body and further fluidity during molding. In addition, a mass average molecular weight is a polystyrene conversion value by a gel permeation chromatograph (GPC) method.
本発明の組成物に用いるポリ乳酸樹脂は、これに含まれる残存モノマーを５０００ｐｐｍ以下としたものが好ましく、４０００ｐｐｍ以下としたものがより好ましく、３０００ｐｐｍ以下としたものが特に好ましい。得られる成形体の耐湿熱老化性や耐熱性等をより良く確保するためである。 The polylactic acid resin used in the composition of the present invention preferably has a residual monomer content of 5000 ppm or less, more preferably 4000 ppm or less, and particularly preferably 3000 ppm or less. This is for better securing the heat and moisture aging resistance and heat resistance of the obtained molded body.
本発明の組成物は、得られる成形体の剛性、柔軟性、耐熱性、耐久性等を向上する観点から、その他の樹脂を含有することもできる。かかるその他の樹脂としては、ポリカーボネート、ポリエステル、ポリフェニレンエーテル、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリオキシメチレン、ポリフェニレンスルフィド、ＡＢＳ樹脂、ポリスチレン、ポリメチルメタクリレート、ポリアミド等が挙げられる。これらは単独もしくは２種以上組み合わせて用いることができる。 The composition of the present invention can also contain other resins from the viewpoint of improving the rigidity, flexibility, heat resistance, durability and the like of the resulting molded article. Examples of such other resins include polycarbonate, polyester, polyphenylene ether, polyethylene, polypropylene, polyvinyl chloride, polyoxymethylene, polyphenylene sulfide, ABS resin, polystyrene, polymethyl methacrylate, polyamide and the like. These can be used alone or in combination of two or more.
本発明の組成物には、合目的的に他の添加剤を含有することもできる。かかる他の添加剤としては、可塑剤、酸化防止剤、熱安定剤、光安定剤、紫外線吸収剤、顔料、着色剤、各種フィラー、アンチブロッキング剤、帯電防止剤、防曇剤、流滴剤、赤外吸収剤、離型剤、香料、滑剤、難燃剤、発泡剤、充填剤、抗菌・抗カビ剤等が挙げられる。 The composition of the present invention may contain other additives for the purpose. Examples of such other additives include plasticizers, antioxidants, heat stabilizers, light stabilizers, UV absorbers, pigments, colorants, various fillers, antiblocking agents, antistatic agents, antifogging agents, and drop-dropping agents. , Infrared absorbers, release agents, fragrances, lubricants, flame retardants, foaming agents, fillers, antibacterial / antifungal agents, and the like.
本発明の組成物は公知の方法で調製できる。これには例えば、１）粉末又はペレット状のポリ乳酸樹脂、結晶核剤と、要すれば他の添加剤とを、同時にドライブレンドした後、混練する方法、２）粉末又はペレット状のポリ乳酸樹脂と、結晶核剤とを溶融混練した後、更に要すれば他の添加剤をドライブレンドした後、混練する方法、３）粉末又はペレット状のポリ乳酸樹脂を混練溶融した後、サイドフィードにて結晶核剤と、要すれば他の添加剤を添加する方法、４）粉末又はペレット状のポリ乳酸樹脂と、要すれば他の添加剤をドライブレンドし、混練溶融した後、サイドフィードにて結晶核剤を添加する方法、５）粉末又はペレット状のポリ乳酸樹脂と、結晶核剤と、要すれば他の添加剤をドライブレンドした後、混練溶融し、更に要すれば液体の添加物を液体供給装置等により添加する方法、６）粉末又はペレット状のポリ乳酸樹脂と、要すれば他の添加剤をドライブレンドし、混練溶融した後、サイドフィードにて結晶核剤を添加し、要すれば液体の添加物を液体供給装置等により添加する方法等が挙げられる。かかるドライブレンドの装置としては、ミルロール、バンバリーミキサー、スーパーミキサー等が挙げられる。また混練機としては、単軸又は二軸押出機等が挙げられる。混練機の混練温度は、通常１２０〜２８０℃程度とする。ポリ乳酸樹脂の重合段階で、結晶核剤や要すれば他の添加剤を加えることもでき、また結晶核剤や要すれば他の添加剤を高濃度で含有するマスターバッチを作製しておき、これをポリ乳酸樹脂に加えることもできる。 The composition of the present invention can be prepared by a known method. This includes, for example, 1) a method in which powder or pellet-shaped polylactic acid resin, crystal nucleating agent and, if necessary, other additives are simultaneously dry blended and then kneaded, and 2) powder or pellet-shaped polylactic acid After melt-kneading the resin and the crystal nucleating agent, and if necessary, dry blending with other additives and then kneading, and 3) kneading and melting the powdered or pelleted polylactic acid resin, and then feeding it to the side feed 4) A method of adding a crystal nucleating agent and, if necessary, other additives, 4) dry blending, kneading and melting the powder or pellet-like polylactic acid resin and, if necessary, other additives, to the side feed 5) A method of adding a crystal nucleating agent 5) Dry blending a powdered or pelleted polylactic acid resin, a crystal nucleating agent, and other additives as required, kneading and melting, and if necessary, adding a liquid Using a liquid supply device 6) Powder or pellet-like polylactic acid resin and other additives, if necessary, dry blend, knead and melt, then add crystal nucleating agent by side feed, and if necessary add liquid The method of adding a thing with a liquid supply apparatus etc. is mentioned. Examples of the dry blending apparatus include a mill roll, a Banbury mixer, and a super mixer. Examples of the kneader include a single screw or twin screw extruder. The kneading temperature of the kneader is usually about 120 to 280 ° C. In the polymerization stage of polylactic acid resin, a crystal nucleating agent and other additives can be added if necessary, and a master batch containing a high concentration of the crystal nucleating agent and other additives if necessary is prepared. This can also be added to the polylactic acid resin.
次に、本発明に係るポリ乳酸樹脂成形体（以下、本発明の成形体という）について説明する。本発明の成形体は、本発明の組成物から成形されているポリ乳酸樹脂成形体であって、ＪＩＳ Ｋ ７１３６により求められる１００μｍ厚のヘイズ値が２０以下であるポリ乳酸樹脂成形体である。 Next, the polylactic acid resin molded product according to the present invention (hereinafter referred to as the molded product of the present invention) will be described. The molded body of the present invention is a polylactic acid resin molded body molded from the composition of the present invention, and is a polylactic acid resin molded body having a 100 μm-thick haze value determined by JIS K 7136 of 20 or less.
成形方法は特に制限されず、これには例えば、射出成形、押出成形、ブロー成形、インフレーション成形、異形押出成形、射出ブロー成形、真空圧空成形、紡糸等が挙げられる。 The molding method is not particularly limited, and examples thereof include injection molding, extrusion molding, blow molding, inflation molding, profile extrusion molding, injection blow molding, vacuum pressure molding, and spinning.
本発明の成形体は、フィルム、袋、チューブ、シート、カップ、ボトル、トレー、糸等を包含し、その形状、大きさ、厚み、意匠等に関して何ら制限はない。具体的には、本発明の成形体は、包装用袋、食器、フォーク、スプーン、トレイ、ボトル、ラップフィルム、化粧品容器、ゴミ袋、かさ、テント、防水シート、テープ、エアーマット、つり糸、魚網、カプセル、肥料用の容器や包装材及びカプセル、種苗用の容器や包装材及びカプセル、農園芸用フィルム、製品包装用フィルム、オーバーヘッドプロジェクター用フィルム、熱線反射フィルム、液晶ディスプレー用フィルム等に用いることができる。この他、本発明の成形体は、多層構造の積層体の層材とすることもできる。 The molded body of the present invention includes a film, a bag, a tube, a sheet, a cup, a bottle, a tray, a thread, and the like, and there is no limitation on the shape, size, thickness, design, and the like. Specifically, the molded article of the present invention is a packaging bag, tableware, fork, spoon, tray, bottle, wrap film, cosmetic container, garbage bag, umbrella, tent, tarpaulin, tape, air mat, hanging thread, Used for fish nets, capsules, fertilizer containers and packaging materials and capsules, seedling containers and packaging materials and capsules, agricultural and horticultural films, product packaging films, overhead projector films, heat ray reflective films, liquid crystal display films, etc. be able to. In addition, the molded body of the present invention can be used as a layer material of a multilayered structure.
最後に、本発明に係るポリ乳酸樹脂成形体の製造方法（以下、本発明の製造方法という）について説明する。本発明の製造方法は、本発明の組成物を熱処理し、成形するポリ乳酸樹脂成形体の製造方法である。熱処理温度に特に制限はないが、５０〜１５０℃で行うことが好ましく、７０〜１４０℃で行うことがより好ましい。 Finally, a method for producing a polylactic acid resin molded product according to the present invention (hereinafter referred to as the production method of the present invention) will be described. The manufacturing method of this invention is a manufacturing method of the polylactic acid resin molded object which heat-processes and shape | molds the composition of this invention. Although there is no restriction | limiting in particular in heat processing temperature, It is preferable to carry out at 50-150 degreeC, and it is more preferable to carry out at 70-140 degreeC.
本発明の組成物の熱処理方法としては、該組成物の溶融物を金型内に充填し、金型内でそのまま加熱する方法（以下、金型内加熱法という）と、該組成物の非晶性の成形体を熱処理する方法（以下、後加熱法という）を挙げることができる。熱処理方法について特に制限はないが、後加熱法の方が好ましい。 As a heat treatment method for the composition of the present invention, a melt of the composition is filled in a mold and heated in the mold as it is (hereinafter referred to as an in-mold heating method); Examples thereof include a method of heat-treating the crystalline molded body (hereinafter referred to as a post-heating method). Although there is no restriction | limiting in particular about the heat processing method, The post-heating method is more preferable.
後加熱法による熱処理方法としては、ヒーターの輻射熱で加熱する方法、加温した金属板等に接触させて加熱する方法、送風定温乾燥機を用いて加熱する方法、オーブン（加熱炉）中や温水中に連続的に通過させて加熱する方法、高温空気に接触させて加熱する方法、及びこれらを組み合わせた方法等が挙げられる。本発明の組成物はいずれの熱処理方法にも適応できる。 As a heat treatment method by the post-heating method, a method of heating by radiant heat of a heater, a method of heating by contacting a heated metal plate, a method of heating using a blast constant temperature dryer, an oven (heating furnace) or hot water Examples thereof include a method of heating by passing continuously through, a method of heating by contacting with high-temperature air, and a method combining these. The composition of the present invention can be applied to any heat treatment method.
以上説明した本発明によると、結晶化が速く、したがってそれだけ結晶化時間が短く、結晶化後も透明性を維持できるポリ乳酸樹脂組成物、かかるポリ乳酸樹脂組成物を用いたポリ乳酸樹脂成形体及びかかるポリ乳酸樹脂成形体の製造方法を提供できるという効果がある。 According to the present invention described above, a polylactic acid resin composition that can be crystallized quickly, and therefore, has a short crystallization time and can maintain transparency after crystallization, and a polylactic acid resin molded article using such a polylactic acid resin composition. And there exists an effect that the manufacturing method of this polylactic acid resin molding can be provided.
以下、本発明の構成及び効果をより具体的にするため、実施例等を挙げるが、本発明がこれらの実施例に限定されるというものではない。尚、以下の実施例及び比較例において、部は質量部を、また％は質量％を意味する。 Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to these examples. In the following Examples and Comparative Examples, “part” means “part by mass” and “%” means “% by mass”.
・芳香族スルホン酸塩（Ａ−１）の合成と調整
還流管を取り付けた１Ｌのセパラブルフラスコに、イソフタル酸７１．９４ｇ（０．４３モル）と発煙硫酸１９０．４ｇを仕込み、撹拌しながら内温２００〜２５０℃加温してスルホン化物を得た。別に、冷却管を取り付けた１Ｌのセパラブルフラスコにイオン交換水８９．０ｇを加え６０〜９０℃に加温し、前記のスルホン化物を滴下して、滴下後に５０℃以下まで冷却した後、水溶液を除去して５−スルホイソフタル酸を得た。還流管を取り付けた１Ｌのセパラブルフラスコに、得られた５−スルホイソフタル酸とメタノール６２．０ｇを仕込み、撹拌しながらメタノール還流下で反応させた。反応後、内温を５０℃以下まで冷却し、２０％水酸化カリウム水溶液１１２．２ｇを加え、ｐＨを６．５に中和した。冷却管を取り付けた３Ｌのセパラブルフラスコに、得られた中和物を仕込み、イオン交換水１９３０．０ｇを加えた後、撹拌しながら加温してメタノールを留去した。メタノール留去後、内温を３０℃まで徐冷して析出させたところ、５−スルホイソフタル酸ジメチルカリウム塩を含む固形分のスラリーを得た。このスラリーから固形分を濾別し、１００ｇのイオン交換水を加えて水洗処理した。水洗処理した固形分を１０５〜１２０℃の熱風乾燥機で乾燥して白色粉末１２１．６ｇを得た。最後に、得られた白色粉末をジェットミル（セイシン企業社製の商品名シングルトラックジェットミルＳＴＪ−２００型）を用いて粉砕圧力０．７Ｍｐａの条件で粉砕処理して、芳香族スルホン酸塩（Ａ−１）を得た。この芳香族スルホン酸塩（Ａ−１）には、液体クロマトグラフィーを用いて分析した結果、不純物として水酸化カリウムを２８０ｐｐｍ含有していた。
Synthesis and adjustment of aromatic sulfonate (A-1) A 1 L separable flask equipped with a reflux tube was charged with 71.94 g (0.43 mol) of isophthalic acid and 190.4 g of fuming sulfuric acid while stirring. An internal temperature of 200 to 250 ° C. was heated to obtain a sulfonated product. Separately, 89.0 g of ion-exchanged water was added to a 1 L separable flask equipped with a cooling tube and heated to 60 to 90 ° C., and the sulfonated product was added dropwise. Was removed to give 5-sulfoisophthalic acid. A 1 L separable flask equipped with a reflux tube was charged with the obtained 5-sulfoisophthalic acid and 62.0 g of methanol, and reacted under reflux of methanol with stirring. After the reaction, the internal temperature was cooled to 50 ° C. or lower, and 112.2 g of a 20% aqueous potassium hydroxide solution was added to neutralize the pH to 6.5. The obtained neutralized product was charged into a 3 L separable flask equipped with a condenser, and 1930.0 g of ion-exchanged water was added, followed by heating with stirring to distill off methanol. After the methanol was distilled off, the internal temperature was gradually cooled to 30 ° C. to cause precipitation. As a result, a solid slurry containing 5-sulfoisophthalic acid dimethyl potassium salt was obtained. Solid content was separated by filtration from this slurry, and 100 g of ion-exchanged water was added and washed with water. The solid content washed with water was dried with a hot air dryer at 105 to 120 ° C. to obtain 121.6 g of a white powder. Finally, the obtained white powder was pulverized using a jet mill (trade name: Single Track Jet Mill STJ-200, manufactured by Seishin Enterprise Co., Ltd.) under a pulverization pressure of 0.7 MPa, and an aromatic sulfonate ( A-1) was obtained. As a result of analyzing this aromatic sulfonate (A-1) using liquid chromatography, it contained 280 ppm of potassium hydroxide as an impurity.
・芳香族スルホン酸塩（Ａ−２）の合成と調整
還流管を取り付けた２Ｌのセパラブルフラスコに、５−スルホイソフタル酸ジメチルナトリウム塩１００．０ｇ（０．３４モル）とイオン交換水９００．０ｇを仕込み、撹拌しながら７０〜９０℃に加温し、５−スルホイソフタル酸ジメチルナトリウム塩が溶解したことを確認後、塩化バリウム・２水和物４１．７ｇ（０．１７モル）を加え、３時間撹拌した後、５−スルホイソフタル酸ジメチルバリウム塩を含む固形分のスラリーを得た。内温３０℃以下まで急冷した後、このスラリーから固形分を濾別し、１００ｇのイオン交換水を加えて水洗処理した。水洗処理した固形分を１０５〜１２０℃の熱風乾燥機で４時間乾燥して白色粉末１０１．８ｇを得た。最後に、得られた白色粉末をジェットミル（セイシン企業社製の商品名シングルトラックジェットミルＳＴＪ−２００型）を用いて粉砕圧力０．７Ｍｐａの条件下で粉砕処理して、芳香族スルホン酸塩（Ａ−２）を得た。この芳香族スルホン酸塩（Ａ−２）には、原子吸光分析及び液体クロマトグラフィー分析をした結果、不純物として５−スルホイソフタル酸ジメチルナトリウム塩を０．８％及び塩化ナトリウムを４００ｐｐｍ含有していた。
Synthesis and adjustment of aromatic sulfonate (A-2) In a 2 L separable flask equipped with a reflux tube, 100.0 g (0.34 mol) of 5-sulfoisophthalic acid dimethyl sodium salt and ion-exchanged water 900. Charge 0 g and warm to 70-90 ° C. with stirring. After confirming that dimethylsodium 5-sulfoisophthalate is dissolved, add 41.7 g (0.17 mol) of barium chloride dihydrate. After stirring for 3 hours, a solid slurry containing dimethylbarium 5-sulfoisophthalate was obtained. After rapidly cooling to an internal temperature of 30 ° C. or lower, the solid content was separated from the slurry, and washed with 100 g of ion-exchanged water. The solid content washed with water was dried with a hot air dryer at 105 to 120 ° C. for 4 hours to obtain 101.8 g of a white powder. Finally, the obtained white powder was pulverized using a jet mill (trade name: single track jet mill STJ-200, manufactured by Seishin Enterprise Co., Ltd.) under a pulverization pressure of 0.7 Mpa to obtain an aromatic sulfonate. (A-2) was obtained. As a result of atomic absorption analysis and liquid chromatography analysis, this aromatic sulfonate (A-2) contained 0.8% dimethyl sodium 5-sulfoisophthalic acid sodium salt and 400 ppm sodium chloride as impurities. .
芳香族スルホン酸塩（Ａ−１）、（Ａ−２）と同様にして、芳香族スルホン酸塩（Ａ−３）〜（Ａ−５）及び（ＲＡ−１）〜（ＲＡ−２）を得た。 In the same manner as the aromatic sulfonates (A-1) and (A-2), the aromatic sulfonates (A-3) to (A-5) and (RA-1) to (RA-2) Obtained.
試験区分１ （結晶核剤の調製）
・結晶核剤（Ｃ−１）の調製
予め所定の粒径に調整した表１に示す芳香族スルホン酸塩（Ａ−１）１０部及び表２に示すアミド化合物（Ｂ−１）１０部をブレンダーを用いてドライブレンドし、表３に示す結晶核剤（Ｃ−１）を得た。
Test category 1 (Preparation of crystal nucleating agent)
-Preparation of crystal nucleating agent (C-1) 10 parts of the aromatic sulfonate (A-1) shown in Table 1 and 10 parts of the amide compound (B-1) shown in Table 2 were adjusted to a predetermined particle size in advance. Dry blending was performed using a blender to obtain crystal nucleating agents (C-1) shown in Table 3.
・結晶核剤（Ｃ−２）〜（Ｃ−１３）及び（ＲＣ−１）〜（ＲＣ−７）の調製
結晶核剤（Ｃ−１）の調製と同様にして、結晶核剤（Ｃ−２）〜（Ｃ−１３）及び（ＲＣ−１）〜（ＲＣ−７）を調製し、その内容を表１〜３にまとめて示した。
Preparation of crystal nucleating agent (C-2) to (C-13) and (RC-1) to (RC-7) In the same manner as the preparation of crystal nucleating agent (C-1), 2) to (C-13) and (RC-1) to (RC-7) were prepared, and their contents are summarized in Tables 1 to 3.
表１において、
Ａ−１：５−スルホイソフタル酸ジメチルカリウム塩（合成品）
Ａ−２：５−スルホイソフタル酸ジメチルバリウム塩（合成品）
Ａ−３：５−スルホイソフタル酸ジメチルカルシウム塩（合成品）
Ａ−４：５−スルホイソフタル酸ジエチルストロンチウム塩（合成品）
Ａ−５：５−スルホイソフタル酸ジイソプロピルルビジウム塩（合成品）
ＲＡ−１：５−スルホイソフタル酸ジオクチルマグネシウム塩（合成品）
ＲＡ−２：５−スルホイソフタル酸ジヘキシルマンガン塩（合成品）
In Table 1,
A-1: 5-sulfoisophthalic acid dimethyl potassium salt (synthetic product)
A-2: Dimethyl barium salt of 5-sulfoisophthalic acid (synthetic product)
A-3: Dimethyl calcium salt of 5-sulfoisophthalic acid (synthetic product)
A-4: Diethylstrontium salt of 5-sulfoisophthalic acid (synthetic product)
A-5: Diisopropyl rubidium salt of 5-sulfoisophthalic acid (synthetic product)
RA-1: Dioctylmagnesium salt of 5-sulfoisophthalate (synthetic product)
RA-2: 5-sulfoisophthalic acid dihexyl manganese salt (synthetic product)
表２において、
Ｂ−１：エチレンビスオレイン酸アミド（日本化成社製の商品名スリパックスＯ）
Ｂ−２：エチレンビス−１２−ヒドロキシステアリン酸アミド（日本化成社製の商品名スリパックスＨ）
Ｂ−３：エチレンビスステアリン酸アミド（日本化成社製の商品名スリパックスＥ）
Ｂ−４：ヘキサメチレンビスステアリン酸アミド（日本化成社製の商品名スリパックスＺＨＳ）
ＲＢ−１：ｍ−キシリレンビスステアリン酸アミド（日本化成社製の商品名スリパックスＰＸＳ）
ＲＢ−２：Ｎ，Ｎ’−メチル−ｍ−キシリレンビスステアリン酸アミド（合成品）
In Table 2,
B-1: Ethylene bis-oleic acid amide (trade name Sripax O manufactured by Nippon Kasei Co., Ltd.)
B-2: Ethylenebis-12-hydroxystearic acid amide (Nippon Kasei Co., Ltd. trade name Sripac H)
B-3: Ethylene bis-stearic acid amide (Nippon Kasei Co., Ltd. trade name Sripax E)
B-4: Hexamethylenebisstearic acid amide (trade name Sripac ZHS, manufactured by Nippon Kasei Co., Ltd.)
RB-1: m-xylylene bis-stearic acid amide (Nippon Kasei Co., Ltd. trade name Sripacs PXS)
RB-2: N, N′-methyl-m-xylylenebisstearic acid amide (synthetic product)
表３において、
Ａ−１〜Ａ−５及びＲＡ−１〜ＲＡ−２：表１に記載のもの
Ｂ−１〜Ｂ−４及びＲＢ−１〜ＲＢ−２：表２に記載のもの
In Table 3,
A-1 to A-5 and RA-1 to RA-2: those described in Table 1 B-1 to B-4 and RB-1 to RB-2: those described in Table 2
試験区分２（ポリ乳酸樹脂組成物の調製及びポリ乳酸樹脂成形体の製造）
・実施例１
・ポリ乳酸樹脂組成物の調製
ポリ乳酸樹脂（Ｎａｔｕｒｅ Ｗｏｒｋｓ社製の商品名Ｉｎｇｅｏ ２５００ＨＰ）１００部及び結晶核剤（Ｃ−１）１部をブレンダーを用いてドライブレンドして混合材料を得た。この混合材料をホッパーに投入し、２００℃に設定された二軸混練押出機にて溶融混練し、口金よりストランド状に押出し、水で急冷してストランドを得た。このストランドをストランドカッターで切断して、ペレット状のポリ乳酸樹脂組成物を得た。
Test Category 2 (Preparation of polylactic acid resin composition and production of polylactic acid resin molding)
Example 1
-Preparation of polylactic acid resin composition 100 parts of polylactic acid resin (trade name Ingeo 2500HP manufactured by Nature Works) and 1 part of crystal nucleating agent (C-1) were dry blended using a blender to obtain a mixed material. This mixed material was put into a hopper, melt-kneaded by a twin-screw kneading extruder set at 200 ° C., extruded into a strand shape from a die, and rapidly cooled with water to obtain a strand. This strand was cut with a strand cutter to obtain a pellet-shaped polylactic acid resin composition.
次いで、得られたペレット状のポリ乳酸樹脂組成物を、樹脂温度が２００℃に設定されたＴ−ダイ押出成形機にて溶融し、溶融物を温度を３０℃に調整したキャストロール上に押出し、厚み１００μｍのフィルム状のポリ乳酸樹脂成形体を製造した。 Next, the obtained pellet-shaped polylactic acid resin composition was melted with a T-die extruder with a resin temperature set to 200 ° C., and the melt was extruded onto a cast roll whose temperature was adjusted to 30 ° C. A film-like polylactic acid resin molded body having a thickness of 100 μm was produced.
・実施例２〜１５及び比較例１〜７
実施例１の場合と同様にして、実施例２〜１５及び比較例１〜７のポリ乳酸樹脂組成物を調整し、ポリ乳酸樹脂成形体を製造した。これらの内容を表４にまとめて示した。
-Examples 2-15 and Comparative Examples 1-7
In the same manner as in Example 1, the polylactic acid resin compositions of Examples 2 to 15 and Comparative Examples 1 to 7 were prepared to produce polylactic acid resin molded bodies. These contents are summarized in Table 4.
試験区分３（成形体の評価）
・アニーリング時間
試験区分２で調製した各例のフィルム状のポリ乳酸樹脂成形体について、９０℃又は１３０℃に調整した送風定温乾燥機（ＥＹＥＬＡ社製のＷＦＯ−６００Ｄ）を用い、熱処理時間を１０秒〜３００秒まで５秒刻みで変更する熱処理を行なった後、８０℃のお湯につけ、フィルムが変形しなくなるまでに必要な熱処理時間を求め、次の基準で評価した。結果を表４にまとめて示した。この熱処理時間は短いほど、フィルム状のポリ乳酸樹脂成形体が短時間で結晶化していることを示す。
Test category 3 (evaluation of molded product)
-Annealing time About the film-like polylactic acid resin molded body of each example prepared in Test Category 2, using a constant-temperature air dryer (WFO-600D manufactured by EYELA) adjusted to 90 ° C or 130 ° C, the heat treatment time was 10 After performing the heat treatment which is changed every 5 seconds from second to 300 seconds, it was put in hot water at 80 ° C., and the heat treatment time required until the film was not deformed was determined and evaluated according to the following criteria. The results are summarized in Table 4. A shorter heat treatment time indicates that the film-like polylactic acid resin molded body is crystallized in a shorter time.
・アニーリング時間の評価基準
熱処理温度９０℃
ＡＡ：熱処理時間が９０秒未満であった。
Ａ：熱処理時間が９０〜１２０秒であった。
Ｂ：熱処理時間が１２０秒超であった。
熱処理温度１３０℃
ＡＡ：熱処理時間が４５秒未満であった。
Ａ：熱処理時間が４５〜７０秒であった。
Ｂ：熱処理時間が７０秒超であった。
・ Evaluation criteria for annealing time Heat treatment temperature 90 ℃
AA: The heat treatment time was less than 90 seconds.
A: The heat treatment time was 90 to 120 seconds.
B: The heat treatment time was more than 120 seconds.
Heat treatment temperature 130 ° C
AA: The heat treatment time was less than 45 seconds.
A: The heat treatment time was 45 to 70 seconds.
B: The heat treatment time was more than 70 seconds.
・結晶化温度（昇温時）
試験区分１で調製した各例のペレット状のポリ乳酸樹脂組成物３ｍｇをアルミニウムセルに充填し、示差走査熱量計（セイコーインスツル社製のＤＳＣ−６２００）を用いて、室温から２００℃まで３０℃／分の昇温速度で昇温し、結晶化ピーク温度を測定し、次の基準で評価した。結果を表４にまとめて示した。かかる結晶化ピーク温度は昇温時の発熱ピークのピークトップ温度を示し、昇温時の結晶化ピーク温度が低い程、昇温時の結晶化が速く、したがってそれだけ昇温時の結晶化時間が短くなることを示す。
-Crystallization temperature (at elevated temperature)
3 mg of the pellet-shaped polylactic acid resin composition prepared in Test Category 1 was filled in an aluminum cell, and 30 ° C. from room temperature to 200 ° C. using a differential scanning calorimeter (DSC-6200 manufactured by Seiko Instruments Inc.). The temperature was raised at a rate of temperature rise of ° C./min, the crystallization peak temperature was measured, and evaluated according to the following criteria. The results are summarized in Table 4. The crystallization peak temperature indicates the peak top temperature of the exothermic peak at the time of temperature rise. The lower the crystallization peak temperature at the time of temperature rise, the faster the crystallization at the time of temperature rise. Indicates shortening.
・昇温時の結晶化温度の評価基準
ＡＡ：結晶化ピーク温度が１００℃未満であった。
Ａ：結晶化ピーク温度が１００〜１１０℃であった。
Ｂ：結晶化ピーク温度が１１０℃超であった。
-Evaluation criteria of crystallization temperature at the time of temperature increase AA: The crystallization peak temperature was less than 100 ° C.
A: The crystallization peak temperature was 100 to 110 ° C.
B: The crystallization peak temperature was higher than 110 ° C.
・結晶化温度（降温時）
試験区分１で調製した各例のペレット状のポリ乳酸樹脂組成物３ｍｇをアルミニウムセルに充填し、示差走査熱量計（セイコーインスツル社製のＤＳＣ−６２００）を用いて、３０℃／分で室温から２００℃まで昇温して、５分間保持した後、３５℃／分で２００℃から降温して、結晶化ピーク温度を測定し、次の基準で評価した。結果を表４にまとめて示した。かかる結晶化ピーク温度は降温時の発熱ピークのピークトップ温度を示し、降温時の結晶化ピーク温度が高い程、降温時の結晶化が速く、したがってそれだけ降温時の結晶化時間が短くなることを示す。
-Crystallization temperature (when the temperature falls)
3 mg of the pelletized polylactic acid resin composition prepared in Test Category 1 was filled in an aluminum cell, and room temperature was measured at 30 ° C./min using a differential scanning calorimeter (DSC-6200 manufactured by Seiko Instruments Inc.). The temperature was raised from 200 ° C. to 200 ° C. and held for 5 minutes, then the temperature was lowered from 200 ° C. at 35 ° C./minute, the crystallization peak temperature was measured, and evaluated according to the following criteria. The results are summarized in Table 4. The crystallization peak temperature indicates the peak top temperature of the exothermic peak at the time of temperature decrease, and the higher the crystallization peak temperature at the time of temperature decrease, the faster the crystallization at the time of temperature decrease, and accordingly the crystallization time at the time of temperature decrease accordingly. Show.
・降温時の結晶化温度の評価基準
ＡＡ：結晶化ピーク温度が１００℃超であった。
Ａ：結晶化ピーク温度が９５〜１００℃であった。
Ｂ：結晶化ピーク温度が９５℃未満であった。
-Evaluation criteria of crystallization temperature at the time of temperature fall AA: The crystallization peak temperature was over 100 degreeC.
A: The crystallization peak temperature was 95-100 ° C.
B: The crystallization peak temperature was less than 95 ° C.
・透明性
試験区分１で製造した各例の厚み１００μｍのフィルム状のポリ乳酸樹脂成形体について、ヘーズメーター（日本電色工業製のＮＤＨ５０００）を用いてヘイズ値を測定し、次の基準で評価した。結果を表４にまとめて示した。
-Transparency About the 100-micrometer-thick film-shaped polylactic acid resin molded object of each example manufactured by the test category 1, a haze value is measured using a haze meter (NDH5000 made by Nippon Denshoku Industries Co., Ltd.), and evaluated according to the following criteria. did. The results are summarized in Table 4.
透明性の評価基準
ＡＡ：ヘイズ値が１０未満であった。
Ａ：ヘイズ値が１０〜２０であった。
Ｂ：ヘイズ値が２０超であった。
Evaluation criteria for transparency AA: Haze value was less than 10.
A: The haze value was 10-20.
B: The haze value was more than 20.
表１〜３に対応する表４の結果からも明らかなように、本発明のポリ乳酸樹脂組成物を用いると、結晶化が速く、したがってそれだけ結晶化時間が短く、結晶化後も透明性を維持できることが解る。 As is clear from the results of Table 4 corresponding to Tables 1 to 3, when the polylactic acid resin composition of the present invention is used, crystallization is fast, and thus the crystallization time is shortened accordingly, and transparency is also maintained after crystallization. I understand that it can be maintained.
Claims (12)
Ｘ：ベンゼンから３個の水素原子を除いた残基
Ｒ１，Ｒ２：炭素数１〜６の炭化水素基
Ｍ：アルカリ金属原子又はアルカリ土類金属原子
ｎ：１又は２であって、Ｍがアルカリ金属原子の場合はｎ＝１、Ｍがアルカリ土類金属原子の場合はｎ＝２）
Ｒ３，Ｒ７：炭素数１〜２２の炭化水素基、炭素数１〜２２のヒドロキシアルキル基又は炭素数１〜２２のヒドロキシアルケニル基
Ｒ４，Ｒ６：水素原子
Ｒ５：炭素数１〜６のアルキレン基） A polylactic acid resin composition comprising a polylactic acid resin and a crystal nucleating agent, wherein the crystal nucleating agent comprises 1 to 49% by mass of an aromatic sulfonate represented by the following chemical formula 1 and the chemical formula 2 shown below. A polylactic acid resin composition comprising an amide compound represented by formula (51) to 99% by mass (total 100% by mass).
X: residue obtained by removing three hydrogen atoms from benzene R 1 , R 2 : hydrocarbon group having 1 to 6 carbon atoms M: alkali metal atom or alkaline earth metal atom n: 1 or 2, When n is an alkali metal atom, n = 1 when M is an alkaline earth metal atom)
R 3 , R 7 : hydrocarbon group having 1 to 22 carbon atoms, hydroxyalkyl group having 1 to 22 carbon atoms, or hydroxyalkenyl group having 1 to 22 carbon atoms R 4 , R 6 : hydrogen atom R 5 : 1 to 1 carbon atom 6 alkylene group)
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