JP2011132328A - 5-sulfoisophthalic acid diglycol ester metal salt-copolymerized polylactic acid-based resin and method for producing the same - Google Patents
5-sulfoisophthalic acid diglycol ester metal salt-copolymerized polylactic acid-based resin and method for producing the same Download PDFInfo
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- -1 5-sulfoisophthalic acid diglycol ester Chemical class 0.000 title claims abstract description 55
- 229920005989 resin Polymers 0.000 title claims abstract description 52
- 239000011347 resin Substances 0.000 title claims abstract description 52
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 46
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 45
- 239000002184 metal Substances 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 150000003839 salts Chemical class 0.000 claims abstract description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 32
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 17
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 9
- 150000003624 transition metals Chemical class 0.000 claims abstract description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 11
- 125000004122 cyclic group Chemical group 0.000 claims description 9
- 239000004310 lactic acid Substances 0.000 claims description 8
- 235000014655 lactic acid Nutrition 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical group 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 description 15
- 239000000976 ink Substances 0.000 description 7
- 238000001953 recrystallisation Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000001023 inorganic pigment Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 1
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 description 1
- 0 *c1cc(S(O)(=O)=O)cc(*)c1 Chemical compound *c1cc(S(O)(=O)=O)cc(*)c1 0.000 description 1
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000005600 alkyl phosphonate group Chemical group 0.000 description 1
- HDTRYLNUVZCQOY-LIZSDCNHSA-N alpha,alpha-trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
Description
本発明は、５−スルホイソフタル酸ジグリコールエステル金属塩基が共重合により分子鎖に導入されている共重合ポリ乳酸系樹脂およびその製造方法に関する。 The present invention relates to a copolymerized polylactic acid resin in which a 5-sulfoisophthalic acid diglycol ester metal base is introduced into a molecular chain by copolymerization and a method for producing the same.
近年の環境問題に対する意識の高まりから、天然素材または生分解性合成素材を利用した商品の開発が盛んに行われている。ポリ乳酸系樹脂についても各種用途開発が盛んに進められている。特に、５−スルホイソフタル酸ジグリコールエステル金属塩の導入したポリ乳酸系樹脂は、無機顔料、着色顔料、フィラー等の分散性に優れ、塗料、コーティング材、インキ、接着剤、顔料マスターバッチ等への展開が進められている（たとえば特許文献１、２参照）。 Due to the recent increase in awareness of environmental issues, products using natural materials or biodegradable synthetic materials have been actively developed. Various uses of polylactic acid resins are being developed. In particular, polylactic acid resin introduced with 5-sulfoisophthalic acid diglycol ester metal salt is excellent in dispersibility of inorganic pigments, colored pigments, fillers, etc., and can be applied to paints, coating materials, inks, adhesives, pigment masterbatches, etc. (See, for example, Patent Documents 1 and 2).
しかしながら、従来市販品として入手できる５−スルホイソフタル酸ジグリコールエステル金属塩は純度が低く、二量体や環状オリゴマー等の反応副生物およびエチレングリコール等の残留溶媒が含まれている。例えば５−スルホイソフタル酸ジエチレングリコールエステルナトリウム塩は市販品が入手できるが、残留溶媒や副生成物、環状化合物等の不純物が混入しており、純度は８０〜８５％程度である。これを共重合ポリ乳酸系の合成原料として用いると、ポリ乳酸系樹脂の一部の分子には５−スルホイソフタル酸ジグリコールエステル金属塩が導入されないものが必然的に生じ、ポリ乳酸系樹脂１分子あたりの５−スルホイソフタル酸ジグリコールエステル金属塩の導入率の向上には限界があった。 However, 5-sulfoisophthalic acid diglycol ester metal salts that are conventionally available as commercially available products have low purity, and contain reaction by-products such as dimers and cyclic oligomers and residual solvents such as ethylene glycol. For example, although 5-sulfoisophthalic acid diethylene glycol ester sodium salt is commercially available, impurities such as residual solvents, by-products and cyclic compounds are mixed, and the purity is about 80 to 85%. When this is used as a synthetic raw material for copolymerized polylactic acid, some of the molecules of the polylactic acid resin inevitably have no 5-sulfoisophthalic acid diglycol ester metal salt introduced therein. There was a limit in improving the introduction rate of 5-sulfoisophthalic acid diglycol ester metal salt per molecule.
本発明は前記事情に着目してなされたものであり、分散性をさらに向上させた５−スルホイソフタル酸ジグリコールエステル金属塩共重合ポリ乳酸系樹脂を提供することである。 This invention is made | formed paying attention to the said situation, and is providing the 5-sulfoisophthalic-acid diglycol ester metal salt copolymerization polylactic acid-type resin which further improved the dispersibility.
現状の５−スルホイソフタル酸ジグリコールエステル金属塩共重合ポリ乳酸系樹脂であっても顔料等の高い分散性およびＰＥＴフィルム等への高い密着性を示すことが既に知られているが、ポリ乳酸系樹脂１分子あたりの５−スルホイソフタル酸ジグリコールエステル金属塩の導入率をさらに向上させることにより、更なる分散性および密着性の向上がもたらされることが期待できるものと考えられる。本発明者らは、鋭意検討した結果、５−スルホイソフタル酸ジグリコールエステル金属塩を含むグリコール溶液から再結晶により特定の高純度の５−スルホイソフタル酸ジグリコールエステル金属塩を製造することができることを見い出し、更に、これを用いて共重合ポリ乳酸系樹脂を製造することによって従来品よりも高い分散性を示す共重合ポリ乳酸系樹脂を得られることを見い出し、本発明を完成するに至った。 It is already known that even the current 5-sulfoisophthalic acid diglycol ester metal salt copolymer polylactic acid resin exhibits high dispersibility of pigments and the like and high adhesion to PET films and the like. It is considered that further improvement in dispersibility and adhesion can be expected by further improving the introduction rate of 5-sulfoisophthalic acid diglycol ester metal salt per molecule of the resin. As a result of intensive studies, the inventors of the present invention can produce a specific high-purity 5-sulfoisophthalic acid diglycol ester metal salt by recrystallization from a glycol solution containing the 5-sulfoisophthalic acid diglycol ester metal salt. Furthermore, the present inventors have found that a copolymerized polylactic acid-based resin exhibiting a higher dispersibility than conventional products can be obtained by producing a copolymerized polylactic acid-based resin using the same, thereby completing the present invention. .
すなわち、本発明は以下の構成よりなる。
（１） 開環重合触媒（Ａ）、５−スルホイソフタル酸ジグリコールエステル金属塩を含有する組成物（Ｂ）、ラクチド（Ｃ）を含有する原料組成物（Ｘ）を加熱混合する工程を含み、
前記組成物（Ｂ）が下記式（１）で示される５−スルホイソフタル酸ジグリコールエステル金属塩１００重量部に対し、グリコール０．５〜６重量部を含有し、遷移金属含有量が０．０００１重量部以下である組成物である、
共重合ポリ乳酸系樹脂の製造方法。
（２） 前記原料組成物（Ｘ）がさらに共重合成分（Ｄ）を含有し、
前記共重合成分（Ｄ）が、
水酸基を有する化合物（Ｄ１）、
カルボン酸エステル基を有する環状オリゴマーである化合物（Ｄ２）、
の少なくともいずれか１種以上からなる、（１）に記載の共重合ポリ乳酸系樹脂の製造方法。
（３） 前記化合物（Ｄ２）が乳酸以外のヒドロキシカルボン酸の環状二量体および／またはカプロラクトンである請求項２に記載の共重合ポリ乳酸系樹脂の製造方法。
（４） 前記遷移金属がＭｎである請求項１〜３いずれかに記載の共重合ポリ乳酸系樹脂の製造方法。
（５） 請求項１〜４いずれかの製造方法で得られた共重合ポリ乳酸系樹脂。
That is, the present invention has the following configuration.
(1) A step of heating and mixing a ring-opening polymerization catalyst (A), a composition (B) containing a 5-sulfoisophthalic acid diglycol ester metal salt, and a raw material composition (X) containing lactide (C) ,
The composition (B) contains 0.5 to 6 parts by weight of glycol with respect to 100 parts by weight of 5-sulfoisophthalic acid diglycol ester metal salt represented by the following formula (1), and the transition metal content is 0. The composition is 0001 parts by weight or less,
A method for producing a copolymerized polylactic acid resin.
(2) The raw material composition (X) further contains a copolymer component (D),
The copolymer component (D) is
A compound having a hydroxyl group (D1),
Compound (D2), which is a cyclic oligomer having a carboxylic ester group,
The method for producing a copolymerized polylactic acid resin according to (1), comprising at least one of the following.
(3) The method for producing a copolymerized polylactic acid resin according to claim 2, wherein the compound (D2) is a cyclic dimer of hydroxycarboxylic acid other than lactic acid and / or caprolactone.
(4) The method for producing a copolymerized polylactic acid resin according to any one of claims 1 to 3, wherein the transition metal is Mn.
(5) A copolymerized polylactic acid resin obtained by the production method according to any one of claims 1 to 4.
本発明によると、従来から市販されている低純度の５−スルホイソフタル酸ジグリコールエステル金属塩を用いて製造された共重合ポリ乳酸系樹脂よりも分散性に優れた共重合ポリ乳酸系樹脂を提供することができる。 According to the present invention, a copolymerized polylactic acid-based resin having a higher dispersibility than a copolymerized polylactic acid-based resin produced by using a commercially available low-purity 5-sulfoisophthalic acid diglycol ester metal salt. Can be provided.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明は、開環重合触媒（Ａ）、５−スルホイソフタル酸ジグリコールエステル金属塩を含有する組成物（Ｂ）、ラクチド（Ｃ）を含有し、更に共重合成分（Ｄ）を含有していても良い原料組成物（Ｘ）を加熱混合する工程を含み、前記組成物（Ｂ）が式（１）で示される５−スルホイソフタル酸ジグリコールエステル金属塩１００重量部に対し、グリコール０．５〜６重量部を含有し、遷移金属含有量は０．０００１重量部以下である組成物である、共重合ポリ乳酸系樹脂の製造方法、およびこの製造方法によって得られる共重合ポリ乳酸系樹脂に関する。 The present invention contains a ring-opening polymerization catalyst (A), a composition (B) containing a 5-sulfoisophthalic acid diglycol ester metal salt, lactide (C), and further a copolymer component (D). The raw material composition (X) may be heated and mixed, wherein the composition (B) is mixed with 0.1 parts of glycol per 100 parts by weight of the 5-sulfoisophthalic acid diglycol ester metal salt represented by the formula (1). A method for producing a copolymerized polylactic acid resin, which is a composition containing 5 to 6 parts by weight and having a transition metal content of 0.0001 parts by weight or less, and a copolymerized polylactic acid resin obtained by this production method About.
本発明の開環重合触媒（Ａ）は、ラクチドの開環重合に対して触媒作用をもつ従来公知の触媒のいずれか１種あるいは２種以上の混合物であり、好ましい例として、オクチル酸スズ、アルミニウムアセチルアセトナートを挙げることができる。 The ring-opening polymerization catalyst (A) of the present invention is any one or a mixture of two or more conventionally known catalysts having a catalytic action on the ring-opening polymerization of lactide. Preferred examples include tin octylate, Mention may be made of aluminum acetylacetonate.
本発明の組成物（Ｂ）は、下記式（１）で示される５−スルホイソフタル酸ジグリコールエステル金属塩を含有する。 The composition (B) of the present invention contains a 5-sulfoisophthalic acid diglycol ester metal salt represented by the following formula (1).
式（１）において、Ｒは炭素数２〜４のヒドロキシアルキル基を示し、Ｍn+はＬｉ、Ｎａ、Ｋ、Ｍｇ等の１価または２価の金属イオンを示す。また、Ｍn+はＬｉ、Ｎａ、Ｋの１価の金属イオンであることが顔料分散性の面から好ましい。さらに、エステル交換性の点で、ヒドロキシアルキル基がヒドロキシエチル基、金属がアルカリ金属であるものが好ましく、５−スルホイソフタル酸ジエチレングリコールエステルナトリウム塩がより好ましい。 In formula (1), R represents a hydroxyalkyl group having 2 to 4 carbon atoms, and M n + represents a monovalent or divalent metal ion such as Li, Na, K, or Mg. M n + is preferably a monovalent metal ion of Li, Na, or K from the viewpoint of pigment dispersibility. Further, from the viewpoint of transesterification, a hydroxyalkyl group is preferably a hydroxyethyl group and a metal is an alkali metal, and 5-sulfoisophthalic acid diethylene glycol ester sodium salt is more preferable.
本発明の組成物（Ｂ）は、５−スルホイソフタル酸ジグリコールエステル金属塩１００重量部に対し、グリコール０．５〜６重量部を含有し、遷移金属含有率が０．０００１重量部以下である組成物である。 The composition (B) of the present invention contains 0.5 to 6 parts by weight of glycol with respect to 100 parts by weight of 5-sulfoisophthalic acid diglycol ester metal salt, and the transition metal content is 0.0001 parts by weight or less. It is a composition.
本発明の組成物（Ｂ）は、例えば、５−スルホイソフタル酸ジグリコールエステル金属塩を３０〜６０重量％含むグリコール溶液から、５−スルホイソフタル酸ジグリコールエステル金属塩を再結晶することにより得ることができる。好ましくは３０〜５０重量％、より好ましくは３０〜４０重量％の５−スルホイソフタル酸ジグリコールエステル金属塩を含む溶液からの再結晶を行うことにより、高純度の組成物（Ｂ）を得ることができる。 The composition (B) of the present invention is obtained, for example, by recrystallizing 5-sulfoisophthalic acid diglycol ester metal salt from a glycol solution containing 30 to 60% by weight of 5-sulfoisophthalic acid diglycol ester metal salt. be able to. A highly pure composition (B) is obtained by performing recrystallization from a solution containing preferably 30 to 50% by weight, more preferably 30 to 40% by weight of 5-sulfoisophthalic acid diglycol ester metal salt. Can do.
本発明の組成物（Ｂ）の遷移金属含有量は、５−スルホイソフタル酸ジグリコールエステル金属塩１００重量部に対して０．０００１重量部以下である。遷移金属、例えばＭｎが検出可能な濃度で含まれていると結晶が生成しないため、再結晶法により高純度の５−スルホイソフタル酸ジグリコールエステル金属塩を得ることができない。 The transition metal content of the composition (B) of the present invention is 0.0001 parts by weight or less with respect to 100 parts by weight of the 5-sulfoisophthalic acid diglycol ester metal salt. If a transition metal such as Mn is contained at a detectable concentration, crystals are not formed, and therefore, a high purity 5-sulfoisophthalic acid diglycol ester metal salt cannot be obtained by recrystallization.
但し、本発明の組成物（Ｂ）は、再結晶法により精製されたものには限定されず、その他の公知の精製方法や重合方法によって得られらものであっても差し支えないことは言うまでもない。 However, it is needless to say that the composition (B) of the present invention is not limited to those purified by the recrystallization method, and may be obtained by other known purification methods or polymerization methods. .
本発明のラクチド（Ｃ）としては、メソラクチド、Ｄ−ラクチド、Ｌ−ラクチドおよびＤＬ−ラクチドのいずれか１種、あるいはこれらの２種以上の混合物、を使用することができる。 As the lactide (C) of the present invention, any one of meso lactide, D-lactide, L-lactide and DL-lactide, or a mixture of two or more thereof can be used.
本発明の共重合成分（Ｄ）は、本発明の共重合ポリ乳酸系樹脂における、５−スルホイソフタル酸ジグリコールエステル金属塩以外の共重合成分であり、水酸基を有する化合物（Ｄ１）、カルボン酸エステルエステル機を有する環状オリゴマーである化合物（Ｄ２）から選ばれる少なくとも１種以上からなる。 The copolymer component (D) of the present invention is a copolymer component other than the 5-sulfoisophthalic acid diglycol ester metal salt in the copolymer polylactic acid resin of the present invention, a compound having a hydroxyl group (D1), a carboxylic acid It consists of at least 1 or more types chosen from the compound (D2) which is a cyclic oligomer which has an ester ester machine.
本発明の化合物（Ｄ１）は水酸基を有する化合物であり、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等のポリエーテルポリオール、エチレングリコール、プロピレングリコール、ブタンジオール等のジオール化合物、ラクトース、トレハロース等の糖類、グリセリン、トリメチロールプロパン、ペンタエリスリトール等の多価アルコール化合物、ポリビニルアルコール、ポリグリセリン、ポリエステル樹脂、ポリウレタン樹脂等の分子の末端および／または側鎖に水酸基を有するポリマーおよびオリゴマーを例示することができる。本発明の化合物（Ｄ１）は、ラクチド（Ｃ）の開環重合の開始剤として作用し、共重合ポリ乳酸系樹脂の共重合成分となる。 The compound (D1) of the present invention is a compound having a hydroxyl group, a polyether polyol such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol, a diol compound such as ethylene glycol, propylene glycol or butanediol, or a saccharide such as lactose or trehalose. Examples thereof include polymers and oligomers having a hydroxyl group at the terminal and / or side chain of a molecule such as polyhydric alcohol compounds such as glycerin, trimethylolpropane and pentaerythritol, polyvinyl alcohol, polyglycerin, polyester resin and polyurethane resin. . The compound (D1) of the present invention acts as an initiator for ring-opening polymerization of lactide (C) and becomes a copolymerization component of a copolymerized polylactic acid resin.
本発明の化合物（Ｄ２）は、カルボン酸エステル基を有する環状オリゴマーであり、数平均分子量５００以下のものであって、ラクチド以外のものである。好ましい例としては、グリコリド等の脂肪族ヒドロキシカルボン酸の環状二量体、ε−カプロラクトン等の脂肪族ヒドロキシカルボン酸の環状自己縮合体が挙げられる。 The compound (D2) of the present invention is a cyclic oligomer having a carboxylic acid ester group, which has a number average molecular weight of 500 or less and is other than lactide. Preferred examples include cyclic dimers of aliphatic hydroxycarboxylic acids such as glycolide, and cyclic self-condensates of aliphatic hydroxycarboxylic acids such as ε-caprolactone.
本発明の原料組成物（Ｘ）は、開環重合触媒（Ａ）、組成物（Ｂ）、ラクチド（Ｃ）を必須成分とし、さらに共重合成分（Ｄ）およびその他の成分を含有していても良い。 The raw material composition (X) of the present invention comprises a ring-opening polymerization catalyst (A), a composition (B), and lactide (C) as essential components, and further contains a copolymerization component (D) and other components. Also good.
本発明の原料組成物（Ｘ）を加熱混合することによって、共重合ポリ乳酸系樹脂を製造することができる。加熱温度は１４０℃〜２００℃であることが好ましく、加熱時間は１時間〜５時間であることが好ましい。 A copolymerized polylactic acid-based resin can be produced by heating and mixing the raw material composition (X) of the present invention. The heating temperature is preferably 140 ° C. to 200 ° C., and the heating time is preferably 1 hour to 5 hours.
本発明の原料組成物（Ｘ）を加熱混合する工程の開始前および／または工程の途中で一般式（２）および／または一般式（３）で表される有機リン化合物を添加することができ、得られる共重合ポリ乳酸系樹脂の耐加水分解性を向上させる等の効果が発揮される場合がある。 The organophosphorus compound represented by the general formula (2) and / or the general formula (3) can be added before the start of the step of heating and mixing the raw material composition (X) of the present invention and / or during the step. The effect of improving the hydrolysis resistance of the resulting copolymerized polylactic acid resin may be exhibited.
本発明の共重合ポリ乳酸系樹脂の製造方法において、前記加熱混合工程よりも後に、減圧工程を行うことが好ましい。減圧工程では未反応のラクチドやその他揮発性成分が留去され、得られる共重合ポリ乳酸系樹脂の耐加水分解性を向上させる等の効果が発揮される場合がある。 In the method for producing a copolymerized polylactic acid-based resin of the present invention, it is preferable to perform a decompression step after the heating and mixing step. In the decompression step, unreacted lactide and other volatile components may be distilled off, and the effect of improving the hydrolysis resistance of the resulting copolymerized polylactic acid resin may be exhibited.
本発明の共重合ポリ乳酸系樹脂の製造方法において、前記加熱混合工程よりも後に、リン酸、ピロリン酸等のリン酸類、亜りん酸等の亜リン酸類、アルキルホスフェート、アルキルホスホネート等のリン化合物に代表される、開環重合触媒（Ａ）を失活させることのできる化合物を添加することができる。この操作により、得られる共重合ポリ乳酸系樹脂の耐加水分解性を向上させる等の効果が発揮される場合がある。 In the method for producing a copolymerized polylactic acid resin of the present invention, after the heating and mixing step, phosphoric acids such as phosphoric acid and pyrophosphoric acid, phosphorous acids such as phosphorous acid, phosphorus compounds such as alkyl phosphate and alkylphosphonate A compound capable of deactivating the ring-opening polymerization catalyst (A) represented by (2) can be added. By this operation, effects such as improving the hydrolysis resistance of the resulting copolymerized polylactic acid resin may be exhibited.
本発明の共重合ポリ乳酸系樹脂において、スルホン酸金属塩濃度は５〜１５０ｅｑ／１０6ｇの濃度範囲であることが好ましい。５ｅｑ／１０6ｇ以下であると、良好な無機顔料、有機顔料等の分散性およびインキの安定性が得られない傾向にある。また、１５０ｅｑ／１０6ｇを超えると、樹脂溶液粘度が高くなりすぎて、塗料、インキ、接着剤などにおける良好なコーティング適性や良好な生分解性が得られない傾向にある。 In the copolymerized polylactic acid-based resin of the present invention, the sulfonic acid metal salt concentration is preferably in the concentration range of 5 to 150 eq / 10 6 g. If it is 5 eq / 10 6 g or less, good dispersibility of inorganic pigments, organic pigments, etc. and ink stability tend not to be obtained. On the other hand, if it exceeds 150 eq / 10 6 g, the viscosity of the resin solution becomes too high and good coating suitability and good biodegradability in paints, inks, adhesives and the like tend not to be obtained.
本発明の共重合ポリ乳酸系樹脂の還元粘度は、０．１〜１．１ｄｌ／ｇの範囲であることが好ましい。還元粘度が０．１ｄｌ／ｇよりも低いと、塗料、インキ、接着剤等で使用する場合には塗膜物性が低下してしまい、問題が生じることがある。また、還元粘度が高すぎると、塗料、インキ、接着剤等で使用する場合には溶液粘度が増大し、良好なコーティング適性が得られないことがある。 The reduced viscosity of the copolymerized polylactic acid resin of the present invention is preferably in the range of 0.1 to 1.1 dl / g. When the reduced viscosity is lower than 0.1 dl / g, when used in paints, inks, adhesives, etc., the physical properties of the coating film are lowered, which may cause problems. On the other hand, if the reduced viscosity is too high, the solution viscosity increases when used in paints, inks, adhesives, etc., and good coating suitability may not be obtained.
本発明の共重合ポリ乳酸系樹脂を用いて顔料分散体を製造する場合、用いることのできる顔料は通常用いられるものであれば特に限定されず、たとえば、酸化チタン、炭酸カルシウム、硫酸バリウム、黄色酸化鉄、ベンガラ、カーボンブラック、アルミニウム粉、雲母、チタン粉等の無機顔料、アゾ系顔料、フタロシアニン系顔料各種の有機顔料等が挙げられる。これらは、１種類でも２種類以上でも用いることができる。 In the case of producing a pigment dispersion using the copolymerized polylactic acid resin of the present invention, the pigment that can be used is not particularly limited as long as it is usually used. For example, titanium oxide, calcium carbonate, barium sulfate, yellow Examples thereof include inorganic pigments such as iron oxide, bengara, carbon black, aluminum powder, mica and titanium powder, azo pigments, and various organic pigments of phthalocyanine pigments. These may be used alone or in combination of two or more.
本発明の共重合ポリ乳酸系樹脂を用いて顔料分散体を製造する場合、溶剤を併用してもよい。この場合の溶剤としては、本発明の共重合ポリ乳酸系樹脂の溶解性、作業性、乾燥速度等の点から、好ましくはメチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、酢酸エチル、酢酸ブチル、トルエン、キシレン、イソプロピルアルコール等が用いられる。これらは、１種類でも２種類以上でも用いることができる。 When a pigment dispersion is produced using the copolymerized polylactic acid resin of the present invention, a solvent may be used in combination. The solvent in this case is preferably methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, from the viewpoint of solubility, workability, drying speed, etc. of the copolymer polylactic acid resin of the present invention. Isopropyl alcohol or the like is used. These may be used alone or in combination of two or more.
また、本発明の共重合ポリ乳酸系樹脂を用いて顔料分散体を製造する場合、分散方法は従来公知の方法であれば特に限定されず、通常用いられる方法によって調製される。たとえば、上記乳酸系樹脂を上記溶剤に溶解させ、これに上記顔料を配合し、ボールミルやガラスビーズ等を用いて分散させる等の方法で製造することができる。 Moreover, when manufacturing a pigment dispersion using the copolymerization polylactic acid-type resin of this invention, if a dispersion method is a conventionally well-known method, it will not specifically limit, It will prepare by the method used normally. For example, it can be produced by a method in which the lactic acid resin is dissolved in the solvent, the pigment is blended in the solvent, and dispersed using a ball mill or glass beads.
ここで、上記各成分の配合量は、共重合ポリ乳酸系樹脂１００質量部に対して、顔料を１〜１０００質量部、溶剤を１００〜２０００質量部配合するのが好ましい。より好ましくは、乳酸系樹脂１００質量部に対して、インキ顔料２〜５００質量部であり、溶剤２００〜１５００質量部である。 Here, as for the compounding quantity of each said component, it is preferable to mix | blend 1-1000 mass parts of pigments, and 100-2000 mass parts of solvents with respect to 100 mass parts of copolymer polylactic acid-type resin. More preferably, the ink pigment is 2 to 500 parts by mass and the solvent is 200 to 1500 parts by mass with respect to 100 parts by mass of the lactic acid resin.
以下に実例を用いて本発明を具体的に説明するが、本発明はもとより下記の実施例によって制限を受けるものではなく、前後記の主旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術範囲に含まれる。なお、実施例中の純度、金属含有量、分散性は以下のように測定したものである。 Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited by the following examples, but may be implemented with appropriate modifications within a range that can meet the gist of the preceding and following descriptions. Of course, it is also possible and they are all included in the technical scope of the present invention. The purity, metal content, and dispersibility in the examples were measured as follows.
純度：生成物１５ｍｇをＤＭＳＯ−ｄ６ ０．５ｍｌに溶解し、４００ＭＨｚの核磁気共鳴（ＮＭＲ）スペクトル装置（Ｖａｒｉａｎ製）を用いて1Ｈ−ＮＭＲ分析を行った。測定条件は、室温、ｄ１＝２６ｓである。例えば、５−スルホイソフタル酸ジエチレングリコールエステル金属塩の場合、エチレングリコール残基のメチレン基に由来するプロトンの積分値とメチルエステルのメチル基に由来するプロトンの積分値から純度を算出した。 Purity: 15 mg of the product was dissolved in 0.5 ml of DMSO-d6, and 1 H-NMR analysis was performed using a 400 MHz nuclear magnetic resonance (NMR) spectrometer (manufactured by Varian). The measurement conditions are room temperature and d1 = 26 s. For example, in the case of 5-sulfoisophthalic acid diethylene glycol ester metal salt, the purity was calculated from the integral value of protons derived from the methylene group of the ethylene glycol residue and the integral value of protons derived from the methyl group of the methyl ester.
金属含有量：白金るつぼに５−スルホイソフタル酸ジグリコールエステル金属塩１．０ｇを精秤した後、電気マッフル炉により５５０℃／８時間の条件で加熱した。加熱後、１．２Ｍ塩酸溶液２０ｍｌを加え、ＩＣＰ測定用の試料溶液とした。ＩＣＰ発光分析装置（島津製作所製、ＩＣＰＳ−２０００）を用いて発光強度を測定し、金属含有量を定量化した。なお、今回用いた測定法による検出下限濃度は、１ｍｇ／ｋｇである。 Metal content: After accurately weighing 1.0 g of 5-sulfoisophthalic acid diglycol ester metal salt in a platinum crucible, it was heated in an electric muffle furnace at 550 ° C. for 8 hours. After heating, 20 ml of 1.2 M hydrochloric acid solution was added to obtain a sample solution for ICP measurement. The emission intensity was measured using an ICP emission analyzer (manufactured by Shimadzu Corporation, ICPS-2000), and the metal content was quantified. In addition, the detection lower limit concentration by the measurement method used this time is 1 mg / kg.
還元粘度：共重合ポリ乳酸系樹脂をクロロホルムに濃度０．１２５ｇ／２５ｍｌで溶解し、測定温度２５℃で、ウベローデ粘度管を用いて測定した。 Reduced viscosity: The copolymerized polylactic acid resin was dissolved in chloroform at a concentration of 0.125 g / 25 ml, and measured at a measurement temperature of 25 ° C. using an Ubbelohde viscosity tube.
分散性：共重合ポリ乳酸系樹脂１０部を酢酸エチル１０部に溶解させ、カーボンブラック１部を加えガラスビーズを１０部加えてペイントシェーカーにて６時間混合分散させた。ポリエステルフィルムに塗布し乾燥して得られた塗膜について、ハンディ光沢計グロスチェッカ（HORIBA製）で光沢度を測定した。 Dispersibility: 10 parts of a copolymerized polylactic acid resin was dissolved in 10 parts of ethyl acetate, 1 part of carbon black was added, 10 parts of glass beads were added, and the mixture was mixed and dispersed in a paint shaker for 6 hours. About the coating film obtained by applying and drying on a polyester film, the glossiness was measured with a handy gloss meter gloss checker (manufactured by HORIBA).
（実施例１）
５−スルホイソフタル酸ジエチレングリコールエステルナトリウム塩を３３重量％含むエチレングリコール溶液から再結晶により得た５−スルホイソフタル酸ジエチレングリコールエステルナトリウム塩を用いた。純度および金属含有量の結果をそれぞれ、表１、２に示す。
ＤＬ−ラクチド５００部、５−スルホイソフタル酸ジエチレングリコールエステルナトリウム塩３．５６部、開環重合触媒としてオクチル酸錫０．１部を４つ口フラスコに仕込み、窒素雰囲気下、１９０℃で１時間加熱し、開環重合を進め、その後、残留ラクチドを減圧下留去することによりポリ乳酸の主鎖中にスルホン酸金属塩を有する乳酸系樹脂を得た。還元粘度と分散性を評価した。結果を表１に示す。
Example 1
5-sulfoisophthalic acid diethylene glycol ester sodium salt obtained by recrystallization from an ethylene glycol solution containing 33% by weight of 5-sulfoisophthalic acid diethylene glycol ester sodium salt was used. The results of purity and metal content are shown in Tables 1 and 2, respectively.
DL-Lactide 500 parts, 5-sulfoisophthalic acid diethylene glycol ester sodium salt 3.56 parts, and ring-opening polymerization catalyst 0.1 part tin octylate as a four-necked flask were charged in a nitrogen atmosphere and heated at 190 ° C. for 1 hour. Then, ring-opening polymerization was carried out, and then the residual lactide was distilled off under reduced pressure to obtain a lactic acid-based resin having a sulfonic acid metal salt in the main chain of polylactic acid. The reduced viscosity and dispersibility were evaluated. The results are shown in Table 1.
（実施例２）
５−スルホイソフタル酸ジエチレングリコールエステルナトリウム塩を３３重量％含むエチレングリコール溶液から再結晶により得た５−スルホイソフタル酸ジエチレングリコールエステルナトリウム塩を用いた。純度および金属含有量の結果をそれぞれ、表１、２に示す。
Ｌ−ラクチド２５０部、ＤＬ−ラクチド２５０部、５−スルホイソフタル酸ジエチレングリコールエステルナトリウム塩３．５６部、開環重合触媒としてオクチル酸錫０．１部を４つ口フラスコに仕込み、窒素雰囲気下、１９０℃で１時間加熱し、開環重合を進め、その後、残留ラクチドを減圧下留去することによりポリ乳酸の主鎖中にスルホン酸金属塩を有する乳酸系樹脂を得た。還元粘度と分散性を評価した。結果を表１に示す。
(Example 2)
5-sulfoisophthalic acid diethylene glycol ester sodium salt obtained by recrystallization from an ethylene glycol solution containing 33% by weight of 5-sulfoisophthalic acid diethylene glycol ester sodium salt was used. The results of purity and metal content are shown in Tables 1 and 2, respectively.
L-lactide 250 parts, DL-lactide 250 parts, 5-sulfoisophthalic acid diethylene glycol ester sodium salt 3.56 parts, tin octylate 0.1 part as a ring-opening polymerization catalyst was charged into a four-necked flask, under a nitrogen atmosphere, The mixture was heated at 190 ° C. for 1 hour to proceed with ring-opening polymerization, and then the residual lactide was distilled off under reduced pressure to obtain a lactic acid resin having a sulfonic acid metal salt in the main chain of polylactic acid. The reduced viscosity and dispersibility were evaluated. The results are shown in Table 1.
（実施例３）
５−スルホイソフタル酸ジエチレングリコールエステルナトリウム塩を３３重量％含むエチレングリコール溶液から再結晶により得た５−スルホイソフタル酸ジエチレングリコールエステルナトリウム塩を用いた。純度および金属含有量の結果をそれぞれ、表１、２に示す。
Ｌ−ラクチド４００部、Ｄ−ラクチド１００部、５−スルホイソフタル酸ジエチレングリコールエステルナトリウム塩３．５６部、開環重合触媒としてオクチル酸錫０．１部を４つ口フラスコに仕込み、窒素雰囲気下、１９０℃で１時間加熱し、開環重合を進め、その後、残留ラクチドを減圧下留去することによりポリ乳酸の主鎖中にスルホン酸金属塩を有する乳酸系樹脂を得た。還元粘度と分散性を評価した。結果を表１に示す。
(Example 3)
5-sulfoisophthalic acid diethylene glycol ester sodium salt obtained by recrystallization from an ethylene glycol solution containing 33% by weight of 5-sulfoisophthalic acid diethylene glycol ester sodium salt was used. The results of purity and metal content are shown in Tables 1 and 2, respectively.
L-lactide 400 parts, D-lactide 100 parts, 5-sulfoisophthalic acid diethylene glycol ester sodium salt 3.56 parts, tin octylate 0.1 part as a ring-opening polymerization catalyst was charged into a four-necked flask under a nitrogen atmosphere. The mixture was heated at 190 ° C. for 1 hour to proceed with ring-opening polymerization, and then the residual lactide was distilled off under reduced pressure to obtain a lactic acid resin having a sulfonic acid metal salt in the main chain of polylactic acid. The reduced viscosity and dispersibility were evaluated. The results are shown in Table 1.
（比較例１）
市販品の５−スルホイソフタル酸ジエチレングリコールエステルナトリウム塩の純度および金属含有量の測定を行った。それぞれの結果を表１、２に示す。
ＤＬ−ラクチド５００部、５−スルホイソフタル酸ジエチレングリコールエステルナトリウム塩３．５６部、開環重合触媒としてオクチル酸錫０．１部を４つ口フラスコに仕込み、窒素雰囲気下、１９０℃で１時間加熱し、開環重合を進め、その後、残留ラクチドを減圧下留去することによりポリ乳酸の主鎖中にスルホン酸金属塩を有する乳酸系樹脂を得た。還元粘度と分散性を評価した。結果を表１に示す。
(Comparative Example 1)
The purity and metal content of commercially available sodium 5-sulfoisophthalic acid diethylene glycol ester sodium salt were measured. The results are shown in Tables 1 and 2.
DL-Lactide 500 parts, 5-sulfoisophthalic acid diethylene glycol ester sodium salt 3.56 parts, and ring-opening polymerization catalyst 0.1 part tin octylate as a four-necked flask were charged in a nitrogen atmosphere and heated at 190 ° C. for 1 hour. Then, ring-opening polymerization was carried out, and then the residual lactide was distilled off under reduced pressure to obtain a lactic acid-based resin having a sulfonic acid metal salt in the main chain of polylactic acid. The reduced viscosity and dispersibility were evaluated. The results are shown in Table 1.
表１に示す結果の通り、本発明の共重合ポリ乳酸系樹脂は、分散性に優れることが明らかとなった。 As shown in Table 1, it was revealed that the copolymerized polylactic acid resin of the present invention is excellent in dispersibility.
本発明によると、高純度の５−スルホイソフタル酸ジグリコールエステル金属塩を共重合することで高分散性の共重合ポリ乳酸系樹脂が得られるため、短時間で分散でき、工程時間を短くできる。また、分散性に優れているため、長期間顔料が沈降せず、保存安定性に優れ、さらに、インキ、塗料として用いると、光沢に優れる塗膜を得ることができる。 According to the present invention, a highly dispersible copolymerized polylactic acid resin can be obtained by copolymerizing a high-purity 5-sulfoisophthalic acid diglycol ester metal salt, so that it can be dispersed in a short time and the process time can be shortened. . Moreover, since the pigment is excellent in dispersibility, the pigment does not settle for a long period of time, it is excellent in storage stability, and further, when used as an ink or paint, a coating film having excellent gloss can be obtained.
Claims (5)
前記組成物（Ｂ）が下記式（１）で示される５−スルホイソフタル酸ジグリコールエステル金属塩１００重量部に対し、グリコール０．５〜６重量部を含有し、遷移金属含有量が０．０００１重量部以下である組成物である、
共重合ポリ乳酸系樹脂の製造方法。
The composition (B) contains 0.5 to 6 parts by weight of glycol with respect to 100 parts by weight of 5-sulfoisophthalic acid diglycol ester metal salt represented by the following formula (1), and the transition metal content is 0. The composition is 0001 parts by weight or less,
A method for producing a copolymerized polylactic acid resin.
前記共重合成分（Ｄ）が、
水酸基を有する化合物（Ｄ１）、
カルボン酸エステル基を有する環状オリゴマーである化合物（Ｄ２）、
の少なくともいずれか１種以上からなる、請求項１に記載の共重合ポリ乳酸系樹脂の製造方法。 The raw material composition (X) further contains a copolymer component (D),
The copolymer component (D) is
A compound having a hydroxyl group (D1),
Compound (D2), which is a cyclic oligomer having a carboxylic ester group,
The method for producing a copolymerized polylactic acid resin according to claim 1, comprising at least one of the following.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015021088A (en) * | 2013-07-22 | 2015-02-02 | 株式会社クレハ | Method of producing aliphatic polyester |
| JP2015165007A (en) * | 2014-02-06 | 2015-09-17 | 株式会社リコー | Polylactic acid resin fine particles |
| WO2025069893A1 (en) * | 2023-09-26 | 2025-04-03 | 日清紡ホールディングス株式会社 | Crosslinked marine biodegradable polymer compound comprising different anionic polymer compounds, and method for producing same |
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2009
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015021088A (en) * | 2013-07-22 | 2015-02-02 | 株式会社クレハ | Method of producing aliphatic polyester |
| JP2015165007A (en) * | 2014-02-06 | 2015-09-17 | 株式会社リコー | Polylactic acid resin fine particles |
| WO2025069893A1 (en) * | 2023-09-26 | 2025-04-03 | 日清紡ホールディングス株式会社 | Crosslinked marine biodegradable polymer compound comprising different anionic polymer compounds, and method for producing same |
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