JP2003041142A - Biodegradable resin composition - Google Patents
Biodegradable resin compositionInfo
- Publication number
- JP2003041142A JP2003041142A JP2001230799A JP2001230799A JP2003041142A JP 2003041142 A JP2003041142 A JP 2003041142A JP 2001230799 A JP2001230799 A JP 2001230799A JP 2001230799 A JP2001230799 A JP 2001230799A JP 2003041142 A JP2003041142 A JP 2003041142A
- Authority
- JP
- Japan
- Prior art keywords
- biodegradable resin
- resin composition
- weight
- composition according
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920006167 biodegradable resin Polymers 0.000 title claims abstract description 73
- 239000011342 resin composition Substances 0.000 title claims abstract description 63
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 33
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 32
- 239000011256 inorganic filler Substances 0.000 claims abstract description 30
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 43
- -1 polybutylene succinate Polymers 0.000 claims description 43
- 239000004310 lactic acid Substances 0.000 claims description 21
- 235000014655 lactic acid Nutrition 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 18
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 230000004580 weight loss Effects 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 8
- 239000004631 polybutylene succinate Substances 0.000 claims description 8
- 229920002961 polybutylene succinate Polymers 0.000 claims description 8
- 239000004626 polylactic acid Substances 0.000 claims description 8
- 239000013585 weight reducing agent Substances 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 229920001281 polyalkylene Polymers 0.000 claims description 6
- 239000004927 clay Substances 0.000 claims description 5
- 229910052570 clay Inorganic materials 0.000 claims description 5
- 229920009537 polybutylene succinate adipate Polymers 0.000 claims description 5
- 239000004630 polybutylene succinate adipate Substances 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 5
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000003890 succinate salts Chemical class 0.000 claims 1
- 239000000047 product Substances 0.000 description 22
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 20
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 15
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 10
- 239000004014 plasticizer Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 8
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical group C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 229940105990 diglycerin Drugs 0.000 description 4
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229930182843 D-Lactic acid Natural products 0.000 description 3
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229940022769 d- lactic acid Drugs 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 2
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 description 2
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 239000010839 body fluid Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 208000028659 discharge Diseases 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 229920005839 ecoflex® Polymers 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ODNBVEIAQAZNNM-UHFFFAOYSA-N 1-(6-chloroimidazo[1,2-b]pyridazin-3-yl)ethanone Chemical compound C1=CC(Cl)=NN2C(C(=O)C)=CN=C21 ODNBVEIAQAZNNM-UHFFFAOYSA-N 0.000 description 1
- RGMMREBHCYXQMA-UHFFFAOYSA-N 2-hydroxyheptanoic acid Chemical compound CCCCCC(O)C(O)=O RGMMREBHCYXQMA-UHFFFAOYSA-N 0.000 description 1
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 1
- SIXWIUJQBBANGK-UHFFFAOYSA-N 4-(4-fluorophenyl)-1h-pyrazol-5-amine Chemical compound N1N=CC(C=2C=CC(F)=CC=2)=C1N SIXWIUJQBBANGK-UHFFFAOYSA-N 0.000 description 1
- VVAAYFMMXYRORI-UHFFFAOYSA-N 4-butoxy-2-methylidene-4-oxobutanoic acid Chemical compound CCCCOC(=O)CC(=C)C(O)=O VVAAYFMMXYRORI-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- GUNJVIDCYZYFGV-UHFFFAOYSA-K Antimony trifluoride Inorganic materials F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 101000718497 Homo sapiens Protein AF-10 Proteins 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N Nonanedioid acid Natural products OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 102100026286 Protein AF-10 Human genes 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 101000872823 Xenopus laevis Probable histone deacetylase 1-A Proteins 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001278 adipic acid derivatives Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- UCVPKAZCQPRWAY-UHFFFAOYSA-N dibenzyl benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC=2C=CC=CC=2)C=1C(=O)OCC1=CC=CC=C1 UCVPKAZCQPRWAY-UHFFFAOYSA-N 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000002531 isophthalic acids Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N n-Decanedioic acid Natural products OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002888 oleic acid derivatives Chemical class 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
- Professional, Industrial, Or Sporting Protective Garments (AREA)
- Absorbent Articles And Supports Therefor (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、生分解性樹脂組成
物に関する。詳しくは、生理用タンポン、ナプキン、紙
おむつ、及び医療用衣類等の衛生用品の成形用材料に適
し、使用時は体液等により崩壊することがなく通常と全
く同様に使用することができ、使用後トイレ、台所流し
等に放流して水と接触した後には、崩壊及び分解する特
性を有する生分解性樹脂組成物に関する。TECHNICAL FIELD The present invention relates to a biodegradable resin composition. Specifically, it is suitable as a molding material for sanitary items such as sanitary tampons, napkins, disposable diapers, and medical clothes, and can be used in the same manner as usual without disintegrating due to body fluid during use. The present invention relates to a biodegradable resin composition having a property of disintegrating and decomposing after being discharged to a toilet, kitchen sink or the like and contacting with water.
【０００２】[0002]
【従来の技術】従来、生理用タンポン、ナプキン、使い
捨ておむつ等は、トイレ等から放流処理することを想定
して設計されていない。本来であれば、これらの物品、
特に生理用品はトイレ内で装着、脱着がされることが多
く、使用後はトイレットペーパーなどと同様に放流処理
したほうが、簡単で汚れず形跡も残らないため好まし
い。2. Description of the Related Art Conventionally, sanitary tampons, napkins, disposable diapers and the like have not been designed on the assumption that they will be discharged from a toilet or the like. Originally, these items,
In particular, sanitary products are often attached and detached in the toilet, and after use, it is preferable to discharge the sanitary product in the same manner as toilet paper because it is easy and does not leave traces.
【０００３】しかしながら、これらの物品の大部分は、
一般的にポリエチレン、ポリプロピレン等の非分解性樹
脂からなっており、放流することが出来ないため、使用
者は別途設けられた箱などへ入れるか、持ち帰って別途
処理する煩わしさがある。また、その後、ゴミとしての
処理する際に、飛散したり、埋め立て処理される場合に
分解しない等の問題もある。さらに、万が一トイレにて
放流された場合は、下水処理系に蓄積されたり閉塞を引
き起こす。また、分解されないためしばしば河川、海洋
へ放出され環境への悪影響が大きくなる。このように、
使用者にとっては処理の煩わしさ、処理時に手が汚れる
等の不衛生さ、処理の形跡が残る等の心理的圧迫からの
開放が望まれている。また、処理面からは、衛生面、環
境への負加を改善する必要性が唱えられている。However, most of these articles are
Generally, it is made of non-decomposable resin such as polyethylene and polypropylene and cannot be discharged. Therefore, it is troublesome for the user to put it in a separately provided box or take it back and treat it separately. In addition, there is also a problem that after that, when it is treated as garbage, it scatters, and when it is disposed of in landfill, it is not decomposed. Furthermore, if it is discharged to the toilet, it may accumulate in the sewage treatment system or cause blockage. In addition, since it is not decomposed, it is often released to rivers and oceans, which has a large adverse effect on the environment. in this way,
It is desired that the user is free from the burden of processing, unsanitary conditions such as soiling of hands during processing, and psychological pressure such as leaving a trace of processing. From the viewpoint of treatment, there is a need to improve hygiene and environmental impact.
【０００４】これらの問題を解決する方法として、特開
平１０−１３１０８３号公報等には、水解紙が開示され
ている。しかし、これらは、紙を原料として用いてお
り、衛生用品等のように風合いが重視される用途には不
向きであった。紙ではなくプラスチックを用いた例とし
て、特開昭６３−３０２８４５号公報、特開平５−２９
５２１１号公報、特開平６−１３４９１０号公報、特公
平７−５７２３０号公報などに、水溶性樹脂を用いた衛
生用品の例示がある。これらの開示によれば、ポリビニ
ルアルコールやポリ−３−ヒドロキシ酪酸等の水溶性樹
脂を用いる事により、上記問題の解決を図っている。As a method for solving these problems, Japanese Unexamined Patent Publication No. 10-131083 discloses a water disintegrating paper. However, these use paper as a raw material, and are not suitable for applications where texture is important, such as sanitary goods. As an example of using plastic instead of paper, Japanese Patent Laid-Open Nos. 63-302845 and 5-29 are known.
No. 5211, Japanese Patent Laid-Open No. 6-134910, Japanese Patent Publication No. 7-57230, etc., exemplify sanitary articles using a water-soluble resin. According to these disclosures, the above problem is solved by using a water-soluble resin such as polyvinyl alcohol or poly-3-hydroxybutyric acid.
【０００５】また、特開平６−２９９０７７号公報に
は、生分解性プラスチックス２０〜８０重量％と水溶性
熱可塑性樹脂８０〜２０重量％を混合して得られる生分
解性樹脂組成物の開示されている。しかしながら、これ
らの水溶性樹脂や生分解性樹脂は一般的に高価であり、
使用量、添加量を増やすと価格が高くなり、衛生用品の
ような使い捨て用途には好ましくない。逆に、安価にす
るため添加量を減らすと、水崩壊性、生分解性が不足
し、放流処理が出来ず好ましくない。さらには、本発明
者らの知見では、これらの水溶性樹脂を含む樹脂組成物
は経時的に水分を吸収しやすく、使用前に湿潤して表面
がべとべとになったり、カビが発生したりするため、実
使用上問題がある場合がある。Further, JP-A-6-299077 discloses a biodegradable resin composition obtained by mixing 20 to 80% by weight of biodegradable plastics and 80 to 20% by weight of a water-soluble thermoplastic resin. Has been done. However, these water-soluble resins and biodegradable resins are generally expensive,
If the amount used or the amount added is increased, the price becomes high, which is not preferable for disposable applications such as sanitary products. On the contrary, if the addition amount is reduced to make it cheap, the water disintegration property and the biodegradability are insufficient, and the discharge treatment cannot be performed, which is not preferable. Furthermore, according to the knowledge of the present inventors, a resin composition containing these water-soluble resins easily absorbs moisture over time, becomes moist before use and becomes sticky on the surface, or mold is generated. Therefore, there may be a problem in actual use.
【０００６】[0006]
【発明が解決しようとする課題】本発明者らは、上記問
題点を解決する手段として、特願２００１−１１４７７
２号に係わる特許出願において、生分解性樹脂２５〜８
０重量％、無機充填剤７５〜２０重量％、及び、前記生
分解性樹脂１００重量部に対して水溶性樹脂３〜１００
重量部を含むことを特徴とする生分解性樹脂組成物を提
案した。該樹脂組成物は、良好な水崩壊性、生分解性を
有し、使用時には経時的な表面状態の悪化がない成形物
を与える。しかしながら、該組成物を実際の使用形態で
あるタンポン用アプリケータなどに成形して評価した場
合、水への溶解速度が比較的速いため、使用時に体内に
成分が若干残存する可能性があり、また、成形物の保管
中、経時的に硬化が進行することがあり、用途によって
は必ずしも満足できない点があることが判った。DISCLOSURE OF THE INVENTION As a means for solving the above-mentioned problems, the inventors of the present invention have proposed a Japanese Patent Application No. 2001-11477.
No. 2 patent application, biodegradable resin 25-8
0% by weight, inorganic filler 75 to 20% by weight, and water-soluble resin 3 to 100 relative to 100 parts by weight of the biodegradable resin.
A biodegradable resin composition characterized by containing parts by weight has been proposed. The resin composition has good water-disintegrating property and biodegradability, and gives a molded product which does not deteriorate in surface condition with time during use. However, when the composition is evaluated by molding it into a tampon applicator, which is an actual use form, since the dissolution rate in water is relatively fast, some components may remain in the body during use, Further, it has been found that curing may progress over time during storage of the molded product, which is not always satisfactory depending on the application.
【０００７】本発明の目的は、上記の問題点に鑑み、優
れた水崩壊性、及び生分解性を有しながらも、実使用時
には成分が溶け出すことがほとんどなく経時的にも安定
で、使用後、トイレ、台所流し等へ放流処理するだけで
簡単に崩壊する生分解性樹脂組成物を提供することにあ
る。In view of the above problems, an object of the present invention is that it has excellent water-disintegrating property and biodegradability, but the components hardly dissolve during actual use, and it is stable over time. It is intended to provide a biodegradable resin composition which is easily disintegrated by simply discharging it to a toilet, kitchen sink or the like after use.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、上記課題
を達成するため鋭意検討した結果、特定量の生分解性樹
脂、特定量の無機充填剤、及び特定量のポリエチレング
リコールを含む生分解性樹脂組成物が、良好な水崩壊
性、生分解性を有し、使用時には成分の溶けだしがほと
んどなく、経時的にも安定な成形物を与えることを見出
し、本発明を完成するに至った。Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a biodegradable resin containing a specific amount of a biodegradable resin, a specific amount of an inorganic filler, and a specific amount of polyethylene glycol. It was found that the degradable resin composition has good water-disintegrating property and biodegradability, hardly melts components during use, and gives a stable molded product over time, and completed the present invention. It was
【０００９】すなわち、本発明は、生分解性樹脂とポリ
エチレングリコールの合計量２５〜８５重量％、及び無
機充填剤７５〜１５重量％を含む生分解性樹脂組成物で
あって、前記生分解性樹脂１００重量部に対して、数平
均分子量が５０００〜３００００であるポリエチレング
リコール１０〜１１０重量部を含むことを特徴とする生
分解性樹脂組成物である。That is, the present invention provides a biodegradable resin composition containing a total amount of biodegradable resin and polyethylene glycol of 25 to 85% by weight, and an inorganic filler of 75 to 15% by weight. A biodegradable resin composition comprising 10 to 110 parts by weight of polyethylene glycol having a number average molecular weight of 5,000 to 30,000 with respect to 100 parts by weight of the resin.
【００１０】本発明に係わる生分解性樹脂組成物の好ま
しい態様として、上記生分解性樹脂が、乳酸系ポリマ
ー、及びポリアルキレンサクシネートから選ばれた少な
くとも一種の樹脂である前記樹脂租生物が挙げられる。
それらの内、乳酸系ポリマーとしてはポリ乳酸、ポリア
ルキレンサクシネートとしては、ポリブチレンサクシネ
ート、ポリブチレンサクシネート・アジペート、ポリブ
チレンサクシネート・テレフタレート、及びポリエチレ
ンサクシネートから選ばれた少なくとも一種の樹脂が挙
げられる。また、上記無機充填剤として、炭酸カルシウ
ム、硫酸バリウム、タルク、クレー、シリカ、及び雲母
から選ばれた少なくとも一種の化合物が挙げられる。As a preferred embodiment of the biodegradable resin composition according to the present invention, there is mentioned the above-mentioned resin bacterium, wherein the biodegradable resin is at least one resin selected from a lactic acid-based polymer and polyalkylene succinate. To be
Among them, at least one resin selected from polylactic acid as a lactic acid-based polymer, polybutylene succinate, polybutylene succinate adipate, polybutylene succinate terephthalate, and polyethylene succinate as a polyalkylene succinate. Is mentioned. Further, as the inorganic filler, at least one compound selected from calcium carbonate, barium sulfate, talc, clay, silica and mica can be mentioned.
【００１１】本発明に係わる前記各種の生分解性樹脂組
成物は、これらを成形加工することにより、シート、フ
ィルム、容器、又はこれらの組み合わせ成形物となすこ
とができる。具体的成形物として、生理用タンポンのア
プリケータ、生理用ナプキン包装用フィルム、使い捨て
おむつ用バックシート、及び医療用衣類から選ばれた少
なくとも一種の成形物が挙げられる。これらは、トイレ
又は台所流しへ放流処理可能な衛生用品である。The various biodegradable resin compositions according to the present invention can be formed into a sheet, a film, a container, or a combination of these by molding and processing them. Specific examples of the molded article include at least one molded article selected from a sanitary tampon applicator, a sanitary napkin packaging film, a disposable diaper backsheet, and medical clothing. These are hygiene products that can be discharged into a toilet or kitchen sink.
【００１２】本発明の生分解性樹脂組成物の主な特性と
しては、２３℃の水に２日間浸漬したときの重量減少率
が少なくとも１０％であり、且つ２３℃の水に１０分間
浸漬したときの重量減少率が１０％未満であることが挙
げられる。The main characteristics of the biodegradable resin composition of the present invention are that the weight loss rate when immersed in water at 23 ° C. for 2 days is at least 10%, and it is immersed in water at 23 ° C. for 10 minutes. The weight reduction rate at that time is less than 10%.
【００１３】本発明の生分解性樹脂組成物は、特定量の
生分解性樹脂、ポリエチレングリコール、及び無機充填
剤を含むために、優れた水崩壊性、生分解性を有し、経
時的にも表面状態の悪化がなく、しかも廉価である。ま
た、使用時に成分が溶け出すことがなく、経時的にも安
定である。そのため、上記衛生用品などの成形物として
用いた場合、使用後の処理が非常に簡便で衛生的とな
り、処理後も環境への負加を減らすことが可能である。Since the biodegradable resin composition of the present invention contains a specific amount of biodegradable resin, polyethylene glycol, and an inorganic filler, it has excellent water-disintegrating property and biodegradability, and The surface condition does not deteriorate, and it is inexpensive. In addition, the components do not dissolve during use and are stable over time. Therefore, when it is used as a molded product such as the above-mentioned sanitary article, the treatment after use becomes very simple and hygienic, and it is possible to reduce the environmental load even after the treatment.
【００１４】[0014]
【発明の実施の形態】以下、本発明について詳しく説明
する。本発明の生分解性樹脂組成物は、特定量の生分解
性樹脂、無機充填剤、及びポリエチレングリコールを混
合することにより製造される。上記材料を混合した後、
連続溶融混練を行うことが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The biodegradable resin composition of the present invention is produced by mixing a specific amount of biodegradable resin, an inorganic filler, and polyethylene glycol. After mixing the above materials,
It is preferable to carry out continuous melt kneading.
【００１５】本発明に用いる生分解性樹脂としては、乳
酸系ポリマー、ポリブチレンサクシネート、ポリブチレ
ンサクシネート・アジペート、ポリブチレンサクシネー
ト・テレフタレート、ポリエチレンサクシネート、及び
ポリブチレンサクシーネート・カーボネート等のポリア
ルキレンサクシネート、ポリグリコール酸、ポリカプロ
ラクトン、ポリヒドロキシ酪酸、ポリヒドロキシ吉草
酸、ヒドロキシ酪酸・ヒドロキシ吉草酸共重合体等が挙
げられる。これらの内、乳酸系ポリマー、ポリブチレン
サクシネート、ポリブチレンサクシネート・アジペー
ト、ポリブチレンサクシネート・テレフタレート、及び
ポリエチレンサクシネートが好ましい。Examples of the biodegradable resin used in the present invention include lactic acid polymers, polybutylene succinate, polybutylene succinate adipate, polybutylene succinate terephthalate, polyethylene succinate, and polybutylene succinate carbonate. Examples of the polyalkylene succinate, polyglycolic acid, polycaprolactone, polyhydroxybutyric acid, polyhydroxyvaleric acid, hydroxybutyric acid / hydroxyvaleric acid copolymer, and the like. Of these, lactic acid-based polymers, polybutylene succinate, polybutylene succinate adipate, polybutylene succinate terephthalate, and polyethylene succinate are preferable.
【００１６】上記乳酸系ポリマーとしては、ポリ乳酸、
または乳酸と他のヒドロキシカルボン酸とのコポリマー
が挙げられる。コモノマーとして用いられる他のヒドロ
キシカルボン酸として、グリコール酸、ヒドロキシ酪
酸、ヒドロキシ吉草酸、ヒドロキシペンタン酸、ヒドロ
キシカプロン酸、ヒドロキシヘプタン酸等が例示され
る。Examples of the lactic acid-based polymer include polylactic acid,
Alternatively, a copolymer of lactic acid and another hydroxycarboxylic acid may be used. Examples of other hydroxycarboxylic acids used as comonomers include glycolic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxypentanoic acid, hydroxycaproic acid, and hydroxyheptanoic acid.
【００１７】好ましいポリ乳酸の分子構造は、Ｌ−乳酸
またはＤ−乳酸いずれかの単位８５〜１００モル％、さ
らに好ましくは該単位８５〜９８モル％、及び、それぞ
れの対掌体の乳酸単位０〜１５モル％、さらに好ましく
は、該対掌体単位２〜１５モル％を含むものである。ま
た、乳酸と他のヒドロキシカルボン酸とのコポリマー
は、Ｌ−乳酸またはＤ−乳酸いずれかの単位８５〜１０
０モル％、好ましくは該単位８５〜９８モル％、及び、
他のヒドロキシカルボン酸単位０〜１５モル％、好まし
くは該単位２〜１５モル％を含むものである。好ましい
他のヒドロキシカルボン酸として、グリコール酸、ヒド
ロキシカプロン酸が挙げられる。The preferred polylactic acid has a molecular structure of 85 to 100 mol% of either L-lactic acid or D-lactic acid unit, more preferably 85 to 98 mol% of the unit, and lactic acid unit 0 of each antipode. ˜15 mol%, and more preferably 2 to 15 mol%. Further, the copolymer of lactic acid and other hydroxycarboxylic acid has a unit of 85 to 10 of either L-lactic acid or D-lactic acid.
0 mol%, preferably 85-98 mol% of the unit, and
Other hydroxycarboxylic acid units are contained in an amount of 0 to 15 mol%, preferably 2 to 15 mol%. Preferred other hydroxycarboxylic acids include glycolic acid and hydroxycaproic acid.
【００１８】これらの乳酸系ポリマーは、Ｌ−乳酸、Ｄ
−乳酸および他のヒドロキシカルボン酸の中から必要と
する構造のものを選んで原料とし、脱水重縮合すること
により得ることができる。好ましくは、乳酸の環状二量
体であるラクチド、グリコール酸の環状二量体であるグ
リコリド、およびカプロラクトン等から必要とする構造
のものを選んで開環重合することにより得ることができ
る。These lactic acid-based polymers are L-lactic acid, D
It can be obtained by selecting a material having a required structure from lactic acid and other hydroxycarboxylic acids as a raw material and performing dehydration polycondensation. Preferably, lactide which is a cyclic dimer of lactic acid, glycolide which is a cyclic dimer of glycolic acid, caprolactone and the like can be obtained by ring-opening polymerization by selecting those having a required structure.
【００１９】ラクチドには、Ｌ−乳酸の環状二量体であ
るＬ−ラクチド、Ｄ−乳酸の環状二量体であるＤ−ラク
チド、Ｄ−乳酸とＬ−乳酸とが環状二量化したメソ−ラ
クチド、およびＤ−ラクチドとＬ−ラクチドとのラセミ
混合物であるＤＬ−ラクチドがある。本発明ではいずれ
のラクチドも用いることができる。ただし、主原料は、
Ｄ−ラクチドまたはＬ−ラクチドが好ましい。Lactide includes L-lactide, which is a cyclic dimer of L-lactic acid, D-lactide, which is a cyclic dimer of D-lactic acid, and meso-, which is a cyclic dimer of D-lactic acid and L-lactic acid. There is lactide and DL-lactide, which is a racemic mixture of D-lactide and L-lactide. Any lactide can be used in the present invention. However, the main raw material is
D-lactide or L-lactide are preferred.
【００２０】本発明に用いられる好ましい乳酸系ポリマ
ーは、上記組成のポリ乳酸、または乳酸と他のヒドロキ
シカルボン酸とのコポリマーであるが、それらは、次の
（１）〜（６）の方法により得ることができる。
（１）Ｌ−ラクチドをおよそ８５モル％以上とＤ−ラク
チドおよび、またはグリコリドをおよそ１５モル％以下
とを共重合させる、（２）Ｄ−ラクチドをおよそ８５モ
ル％以上とＬ−ラクチドおよび、またはグリコリドをお
よそ１５モル％以下とを共重合させる、（３）Ｌ−ラク
チドをおよそ７０モル％以上とＤＬ−ラクチドおよび、
またはグリコリドをおよそ３０モル％以下とを共重合さ
せる、（４）Ｌ−ラクチドをおよそ７０モル％以上とメ
ソ−ラクチドおよび、またはグリコリドをおよそ３０モ
ル％以下とを共重合させる、（５）Ｄ−ラクチドをおよ
そ７０モル％以上とＤＬ−ラクチドおよび、またはグリ
コリドをおよそ３０モル％以下とを共重合させる、
（６）Ｄ−ラクチドをおよそ７０モル％以上とメソ−ラ
クチドおよび、またはグリコリドをおよそ３０モル％以
下とを共重合させる。The preferred lactic acid-based polymer used in the present invention is polylactic acid having the above composition, or a copolymer of lactic acid and another hydroxycarboxylic acid, which can be prepared by the following methods (1) to (6). Obtainable. (1) Copolymerizing about 85 mol% or more of L-lactide and about 15 mol% or less of D-lactide, and (2) about 85 mol% or more of D-lactide and L-lactide, and Alternatively, copolymerization of glycolide with about 15 mol% or less, (3) about 70 mol% or more of L-lactide with DL-lactide, and
Or copolymerizing glycolide with about 30 mol% or less, (4) copolymerizing L-lactide with about 70 mol% or more with meso-lactide and / or glycolide with about 30 mol% or less, (5) D -Copolymerizing about 70 mol% or more of lactide with about 30 mol% or less of DL-lactide and / or glycolide,
(6) Copolymerizing about 70 mol% or more of D-lactide with about 30 mol% or less of meso-lactide and / or glycolide.
【００２１】これらの乳酸系ポリマーは高分子量である
ことが好ましく、濃度０．５ｇ／ｄｌのクロロホルム溶
液（２５℃）の固有溶液粘度が１〜１０であることが好
ましく、さらに好ましくは３〜７である。固有溶液粘度
が１未満であると、溶融粘度が低すぎて押出機のダイの
スリットから流下し、成形し難いばかりでなく、脆すぎ
て取扱が困難であり、また、１０を超えると溶融粘度が
高過ぎて押出成形性等が悪くなるので好ましくない。These lactic acid-based polymers preferably have a high molecular weight, and the inherent solution viscosity of a chloroform solution (25 ° C.) having a concentration of 0.5 g / dl is preferably 1-10, more preferably 3-7. Is. When the intrinsic solution viscosity is less than 1, the melt viscosity is too low to flow down from the slit of the die of the extruder, and it is difficult to mold, and it is too brittle to handle, and when it exceeds 10, the melt viscosity is too low. Is too high and the extrusion moldability and the like are deteriorated, which is not preferable.
【００２２】ラクチド、または、ラクチドとグリコリド
を重合させて、短時間で高分子量のポリマーを得るため
には触媒を用いるのが好ましい。このような重合触媒と
しては、この重合反応に触媒効果を示す各種のものが使
用できる。例えば、公知なものとして、オクタン酸第一
錫、四塩化錫、塩化亜鉛、四塩化チタン、塩化鉄、三フ
ッ化ホウ素エーテル錯体、塩化アルミニウム、三フッ化
アンチモン、酸化鉛等の主として多価金属を含む化合物
が挙げられ、中でも錫化合物または亜鉛化合物が好まし
く使用される。錫化合物の中ではオクタン酸第一錫が特
に好ましい。使用量はラクチド、または、ラクチドとグ
リコリドの総量に対して、およそ０．００１〜０．１重
量％程度が好ましい。A catalyst is preferably used in order to polymerize lactide or lactide and glycolide to obtain a high molecular weight polymer in a short time. As such a polymerization catalyst, various ones having a catalytic effect on the polymerization reaction can be used. For example, as well known, mainly polyvalent metals such as stannous octoate, tin tetrachloride, zinc chloride, titanium tetrachloride, iron chloride, boron trifluoride ether complex, aluminum chloride, antimony trifluoride and lead oxide. And a tin compound or a zinc compound is preferably used. Among the tin compounds, stannous octoate is particularly preferred. The amount used is preferably about 0.001 to 0.1% by weight based on the total amount of lactide or lactide and glycolide.
【００２３】また、重合の際には、公知の連鎖増大剤を
用いることができる。連鎖増大剤としては、ラウリルア
ルコール等の高級アルコール類、乳酸やグリコール酸等
のヒドロキシ酸類が好ましく用いられる。連鎖増大剤の
共存により、重合速度が大きくなるので短時間でポリマ
ーを得ることができる。また、連鎖増大剤の量を加減す
ることによりポリマーの分子量を調節することもでき
る。しかし、連鎖増大剤の量を多くしすぎると生成ポリ
マーの分子量は小さくなる傾向があるので、連鎖増大剤
を使用する場合には、その量はラクチド、または、ラク
チドとグリコリドの総量に対して０．１重量％以下であ
ることが好ましい。Further, a known chain-increasing agent can be used in the polymerization. As the chain increasing agent, higher alcohols such as lauryl alcohol and hydroxy acids such as lactic acid and glycolic acid are preferably used. The coexistence of the chain extender increases the polymerization rate, so that the polymer can be obtained in a short time. It is also possible to control the molecular weight of the polymer by adjusting the amount of chain extender. However, when the amount of the chain enhancer is too large, the molecular weight of the polymer formed tends to be small. Therefore, when the chain enhancer is used, the amount thereof is 0 relative to the total amount of lactide or lactide and glycolide. It is preferably not more than 1% by weight.
【００２４】重合または共重合するに当たって、溶媒を
用いても用いなくてもよいが、高分子量のポリマーを得
るには、ラクチドまたはグリコリドを溶融した状態で塊
状重合することが好ましい。重合温度は、溶融重合の場
合には原則的にはモノマーであるラクチド、またはラク
チドとグリコリドの融点（９０℃付近）以上の温度であ
ればよい。また、例えば、クロロホルム等の溶媒を用い
る溶液重合の場合には、ラクチド、または、ラクチドと
グリコリドの融点以下の温度で重合することが可能であ
る。いずれの場合も、２５０℃を超えると生成ポリマー
の分解が起こるので好ましくない。ポリ乳酸の代表的な
市販品として、三井化学（株）製、商品名：レイシアが
挙げられる。In the polymerization or copolymerization, a solvent may or may not be used, but in order to obtain a high molecular weight polymer, it is preferable to perform bulk polymerization in a molten state of lactide or glycolide. In the case of melt polymerization, the polymerization temperature may be a temperature above the melting point (around 90 ° C.) of lactide, which is a monomer, or lactide and glycolide in principle. Further, for example, in the case of solution polymerization using a solvent such as chloroform, it is possible to carry out the polymerization at a temperature equal to or lower than the melting point of lactide or lactide and glycolide. In any case, if the temperature exceeds 250 ° C., the produced polymer is decomposed, which is not preferable. A typical commercial product of polylactic acid is Mitsui Chemicals, Inc., trade name: LACEA.
【００２５】ポリアルキレンサクシネートとしては、ポ
リブチレンサクシネート、ポリブチレンサクシネート・
アジペート、ポリブチレンサクシネート・テレフタレー
ト、ポリエチレンサクシネート、及びポリブチレンサク
シーネート・カーボネートが好ましい。ポリブチレンサ
クシネートの市販品として、昭和高分子（株）製、商品
名：ビオノーレ１００１、同ビオノーレ１０２０、同ビ
オノーレ１９０３等が挙げられる。また、ポリブチレン
サクシネート・アジペートの市販品として、昭和高分子
（株）製、商品名：ビオノーレ３００１、同ビオノーレ
３０２０等が挙げられる。Examples of the polyalkylene succinate include polybutylene succinate and polybutylene succinate.
Adipate, polybutylene succinate terephthalate, polyethylene succinate, and polybutylene succinate carbonate are preferred. Commercially available products of polybutylene succinate include Showa High Polymer Co., Ltd., trade names: Bionore 1001, Bionore 1020, Bionore 1903, and the like. Commercially available products of polybutylene succinate adipate include Showa High Polymer Co., Ltd., trade names: Bionore 3001, Bionore 3020, and the like.
【００２６】ポリブチレンサクシネート・テレフタレー
トの市販品として、ＢＡＳＦ社製、商品名：エコフレッ
クス、ＤｕＰｏｎｔ社製、商品名：バイオマックス等が
挙げられる。ポリエチレンサクシネートの市販品とし
て、（株）日本触媒製、商品名：ルナーレＳＥが挙げら
れる。ポリブチレンサクシネート・カーボネートの市販
品として、三菱ガス化学（株）製、商品名：ユーペック
が挙げられる。Commercially available products of polybutylene succinate terephthalate include BASF, trade names: Ecoflex, DuPont, trade names: Biomax. As a commercial item of polyethylene succinate, the product made by Nippon Shokubai Co., Ltd. and a brand name: Lunare SE are mentioned. Commercially available products of polybutylene succinate carbonate include Mitsubishi Gas Chemical Co., Inc., trade name: UPEC.
【００２７】本発明の生分解性樹脂組成物は、上記生分
解性樹脂１００重量部に対し可塑剤を１〜５０重量部含
んでもよい。可塑剤として、例えば、ジ−ｎ−オクチル
フタレート、ジ−２−エチルヘキシルフタレート、ジベ
ンジルフタレート等のフタル酸誘導体、ジイソオクチル
フタレート等のイソフタル酸誘導体、ジ−ｎ−ブチルア
ジペート、ジオクチルアジペート等のアジピン酸誘導
体、ジ−ｎ−ブチルマレート等のマレイン酸誘導体、ト
リ−ｎ−ブチルシトレート等のクエン酸誘導体、モノブ
チルイタコネート等のイタコン酸誘導体、ブチルオレー
ト等のオレイン酸誘導体、グリセリンモノリシノレート
等のリシノール酸誘導体、トリクレジルフォスフェー
ト、トリキシレニルフォスフェート等のリン酸エステル
系可塑剤、アセチルクエン酸トリエチル、アセチルクエ
ン酸トリブチル、乳酸、直鎖状乳酸オリゴマー、環状乳
酸オリゴマーまたはラクチド等が例示できる。特に分子
内に２個以上のカルボン酸エステル基を有する、クエン
酸エステル、グリセリンエステル、フタル酸エステル、
アジピン酸エステル、セバシン酸エステル、アゼライン
酸エステルおよびトリエチレングリコールエステルから
選ばれた少なくとも１種のエステル化合物であることが
好ましい。これらの可塑剤は単独でも良いし、また２種
以上を混合して用いてもよい。The biodegradable resin composition of the present invention may contain 1 to 50 parts by weight of a plasticizer with respect to 100 parts by weight of the above biodegradable resin. Examples of the plasticizer include phthalic acid derivatives such as di-n-octyl phthalate, di-2-ethylhexyl phthalate and dibenzyl phthalate, isophthalic acid derivatives such as diisooctyl phthalate, di-n-butyl adipate and dioctyl adipate. Adipic acid derivative, maleic acid derivative such as di-n-butyl maleate, citric acid derivative such as tri-n-butyl citrate, itaconic acid derivative such as monobutyl itaconate, oleic acid derivative such as butyl oleate, glycerin monoricinoleate Ricinoleic acid derivatives such as, tricresyl phosphate, phosphoryl ester plasticizers such as trixylenyl phosphate, triethyl acetyl citrate, tributyl acetyl citrate, lactic acid, linear lactic acid oligomers, cyclic lactic acid oligomers or lactide Is an example It can be. Particularly, citric acid ester, glycerin ester, phthalic acid ester having two or more carboxylic acid ester groups in the molecule,
At least one ester compound selected from adipic acid ester, sebacic acid ester, azelaic acid ester, and triethylene glycol ester is preferable. These plasticizers may be used alone or in combination of two or more.
【００２８】かかる可塑剤を乳酸系ポリマーに添加する
ことにより、乳酸系ポリマーは効果的に可塑化され、得
られる樹脂組成物は柔軟性を帯びる。樹脂組成物中の可
塑剤の量が１重量％以上になると柔軟性がはっきり現れ
るようになり、５０重量％を超えると、該組成物を溶融
押出する時の成形性が悪くなり、また、得られた成形物
の強度が弱くなったり、経時的に可塑剤が浮き出してく
るため好ましくない。By adding such a plasticizer to the lactic acid-based polymer, the lactic acid-based polymer is effectively plasticized and the resulting resin composition becomes flexible. When the amount of the plasticizer in the resin composition is 1% by weight or more, the flexibility becomes apparent, and when it exceeds 50% by weight, the moldability at the time of melt extrusion of the composition is deteriorated, and It is not preferable because the strength of the obtained molded product becomes weak and the plasticizer comes out over time.
【００２９】本発明の生分解性樹脂組成物には、上記生
分解樹脂と、特定量の無機充填剤、及び生分解性樹脂に
対し特定量のポリエチレングリコールが添加される。ポ
リエチレングリコールとしては、ポリエチレングリコー
ル、またはその変性物が挙げられる。ポリエチレングリ
コールの数平均分子量は、本発明の樹脂組成物を成形し
た際の、水への溶解速度、及び経時的な安定性に影響を
及ぼす。数平均分子量が低すぎると、水への溶解速度が
速すぎ、例えばタンポンアプリケータとして用いた場
合、使用時に体内に成分が残存したり、極端な場合、体
内で崩壊が進行する可能性が大きくなる。また、成形後
に保管する際、経時的に樹脂が硬化するなどの問題が生
じる。To the biodegradable resin composition of the present invention, the above biodegradable resin, a specific amount of inorganic filler, and a specific amount of polyethylene glycol are added to the biodegradable resin. Examples of polyethylene glycol include polyethylene glycol and modified products thereof. The number average molecular weight of polyethylene glycol affects the dissolution rate in water and the stability over time when the resin composition of the present invention is molded. If the number average molecular weight is too low, the dissolution rate in water will be too fast.For example, when used as a tampon applicator, there is a high possibility that components will remain in the body during use, or in extreme cases, disintegration will progress in the body. Become. Further, when stored after molding, there arises a problem that the resin is cured with time.
【００３０】かかる点を考慮すると、ポリエチレングリ
コールの数平均分子量は５０００以上であることが好ま
しい。更に好ましくは７０００以上、特に好ましくは９
０００以上である。数平均分子量の上限については、高
ければ高いほど好ましい。原料の入手の容易なことを考
慮すると、通常、数平均分子量の上限は３００００程度
である。好ましくは２００００程度である。上記ポリエ
チレングリコールは数平均分子量の異なるものを混合し
ても良い。混合前の個別の数平均分子量が５０００以下
であっても、混合後の全体としての数平均分子量（以
下、Ｍｎという）が５０００以上であれば問題はない。Considering this point, the number average molecular weight of polyethylene glycol is preferably 5,000 or more. More preferably 7,000 or more, particularly preferably 9
It is more than 000. The higher the upper limit of the number average molecular weight, the more preferable. Considering the easy availability of raw materials, the upper limit of the number average molecular weight is usually about 30,000. It is preferably about 20,000. As the polyethylene glycol, those having different number average molecular weights may be mixed. Even if the individual number average molecular weight before mixing is 5000 or less, there is no problem as long as the number average molecular weight (hereinafter referred to as Mn) as a whole after mixing is 5000 or more.
【００３１】ポリエチレングリコールの市販品として、
三洋化成工業（株）製、商品名：ＰＥＧ−１０００（Ｍ
ｎ：１０００）、同−４０００Ｓ（Ｍｎ：３３００）、
同−６０００Ｓ（Ｍｎ：８３００）、同−１００００
（Ｍｎ：１１０００）、同−１３０００（Ｍｎ：１３０
００）、同−２００００（Ｍｎ：２００００）等が挙げ
られる。ポリエチレングリコールのＭｎの算出方法とし
ては、まず無水酢酸・ピリジン法により水酸基価を求
め、その水酸基価からＭｎを算出する。詳細については
後述の実施例に記載する。As a commercial product of polyethylene glycol,
Sanyo Chemical Industry Co., Ltd., trade name: PEG-1000 (M
n: 1000), the same-4000S (Mn: 3300),
Same-6000S (Mn: 8300), Same-10000
(Mn: 11000), the same-13000 (Mn: 130
00), the same -20,000 (Mn: 20,000) and the like. As a method of calculating Mn of polyethylene glycol, first, a hydroxyl value is obtained by the acetic anhydride / pyridine method, and Mn is calculated from the hydroxyl value. Details will be described in Examples below.
【００３２】本発明の生分解性樹脂組成物は、上記生分
解性樹脂に対し、特定量の上記ポリエチレングリコール
を含む。ポリエチレングリコールの含有量は、樹脂組成
物の水崩壊性、生分解性に影響を及ぼす。水溶性樹脂の
含有量が少な過ぎると、水崩壊性が不足し、その結果、
生分解性も抑制されることとなり好ましくない。逆に、
水溶性樹脂の含有量が多過ぎると、水崩壊性は良好であ
るが、樹脂組成物の水親和性が過剰となり、水と隔離さ
れた状態であっても、空気中の湿気により経時的に成形
物の表面がべとべとしたり、カビが発生したりすること
がある。また、樹脂組成物が高価となるため、廉価性が
必要とされる衛生用品のような使い捨て用途には好まし
くない。さらに、結果として相対的に生分解性樹脂の量
が低下するため、強度が低下する問題がある。かかる点
を考慮すると、生分解性樹脂１００重量部に対して、ポ
リエチレングリコール１０〜１１０重量部を含むことが
好ましい。より好ましい添加量としては１５〜１０５重
量部である。The biodegradable resin composition of the present invention contains the polyethylene glycol in a specific amount with respect to the biodegradable resin. The content of polyethylene glycol affects the water disintegration property and biodegradability of the resin composition. If the content of the water-soluble resin is too low, the water disintegration is insufficient, and as a result,
Biodegradability is also suppressed, which is not preferable. vice versa,
If the content of the water-soluble resin is too large, the water-disintegrating property is good, but the water affinity of the resin composition becomes excessive, and even if the resin composition is isolated from water, the moisture content in the air causes aging over time. The surface of the molded product may be sticky or mold may occur. Further, since the resin composition becomes expensive, it is not preferable for disposable use such as sanitary goods which requires low cost. Further, as a result, the amount of the biodegradable resin is relatively reduced, which causes a problem that the strength is reduced. Considering this point, it is preferable to include 10 to 110 parts by weight of polyethylene glycol with respect to 100 parts by weight of the biodegradable resin. A more preferable addition amount is 15 to 105 parts by weight.
【００３３】本発明に用いられる無機充填剤としては、
炭酸カルシウム、炭酸マグネシウム、炭酸バリウム、硫
酸マグネシウム、硫酸バリウム、硫酸カルシウム、酸化
亜鉛、酸化マグネシウム、酸化カルシウム、酸化チタ
ン、酸化マグネシウム、アルミナ、水酸化アルミニウ
ム、ヒドロキシアパタイト、シリカ、マイカ、タルク、
カオリン、クレー、ガラス粉、アスベスト粉、ゼオライ
ト、珪酸白土、雲母等が挙げられる。これらの内、炭酸
カルシウム、酸化マグネシウム、硫酸バリウム、シリ
カ、珪酸白土等が好ましく用いられる。より好ましく
は、炭酸カルシウム、硫酸バリウムである。これらの無
機充填剤は単独で用いても良いし、２種以上混合して用
いても良い。The inorganic filler used in the present invention includes:
Calcium carbonate, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, calcium sulfate, zinc oxide, magnesium oxide, calcium oxide, titanium oxide, magnesium oxide, alumina, aluminum hydroxide, hydroxyapatite, silica, mica, talc,
Examples thereof include kaolin, clay, glass powder, asbestos powder, zeolite, clay silicate, and mica. Of these, calcium carbonate, magnesium oxide, barium sulfate, silica, silicate clay and the like are preferably used. More preferred are calcium carbonate and barium sulfate. These inorganic fillers may be used alone or in combination of two or more.
【００３４】上記無機充填剤と生分解性樹脂との配合比
は、得られる樹脂組成物の分解性、表面状態、廉価性に
影響を及ぼす。無機充填剤の含有量が多過ぎると、樹脂
成分が極端に低下し強度が不足するため好ましくない。
また、樹脂への混練も困難となり生産性が低下する。逆
に少な過ぎると、強度や混練の難易性には問題がない
が、水崩壊性が低下する上に、樹脂組成物の廉価性が損
なわれるために好ましくない。また、無機充填剤は多少
なりとも吸着性があり、樹脂組成物が空気中の湿気によ
り経時的に表面がべとべとしたり、カビが発生したりす
るのを防ぐ効果があるが、その効果が低下するために好
ましくない。かかる観点から、本発明の生分解性樹脂組
成物は、生分解性樹脂とポリエチレングリコールの合計
量２５〜８５重量％、及び無機充填剤７５〜１５重量％
を含むことが好ましい。より好ましくは、生分解性樹脂
とポリエチレングリコールの合計量３０〜９０重量％、
無機充填剤７０〜１０重量％である。The compounding ratio of the above-mentioned inorganic filler and biodegradable resin affects the degradability, surface condition and low cost of the obtained resin composition. If the content of the inorganic filler is too large, the resin component is extremely reduced and the strength becomes insufficient, which is not preferable.
In addition, the kneading with the resin becomes difficult and the productivity decreases. On the other hand, if the amount is too small, there is no problem in the strength and the difficulty of kneading, but it is not preferable because the water disintegration property is lowered and the inexpensiveness of the resin composition is impaired. Further, the inorganic filler has some adsorbability, and the resin composition has the effect of preventing the surface from becoming sticky or moldy due to moisture in the air, but the effect is reduced. It is not preferable to do. From this viewpoint, the biodegradable resin composition of the present invention has a total amount of the biodegradable resin and polyethylene glycol of 25 to 85% by weight, and an inorganic filler of 75 to 15% by weight.
It is preferable to include. More preferably, the total amount of biodegradable resin and polyethylene glycol is 30 to 90% by weight,
The amount of the inorganic filler is 70 to 10% by weight.
【００３５】これらの無機充填剤の平均粒径としては、
０．３〜１０μｍのものが好ましい。さらに好ましくは
０．５〜５μｍである。平均粒径が１０μｍを超えると
樹脂組成物の表面状態が荒くなる上に、美観も損ねるた
め好ましくない。また、フィルムやシートなどへの成形
の際、穴があくなどの不良が発生しやすく生産性、作業
性等の点でも好ましくない。平均粒径が０．３μｍ未満
の場合、無機充填剤の凝集が発生しやすく、均一な練り
込みが出来ないため好ましくない。また、無機充填剤の
嵩密度が低くなり、混練時の作業性が低下し生産性が低
下するため好ましくない。The average particle size of these inorganic fillers is
It is preferably 0.3 to 10 μm. More preferably, it is 0.5 to 5 μm. If the average particle size exceeds 10 μm, the surface state of the resin composition becomes rough and the aesthetic appearance is impaired, which is not preferable. In addition, when molding into a film or sheet, defects such as holes are likely to occur, which is not preferable in terms of productivity, workability, and the like. If the average particle size is less than 0.3 μm, aggregation of the inorganic filler easily occurs and uniform kneading cannot be performed, which is not preferable. In addition, the bulk density of the inorganic filler becomes low, the workability at the time of kneading decreases, and the productivity decreases, which is not preferable.
【００３６】無機充填剤は、樹脂との分散性を向上させ
るために表面処理を行っても良い。但し、表面処理によ
り無機充填剤の吸湿性が損なわれ、樹脂組成物の経時的
な表面状態の悪化を抑制できない場合はこの限りではな
い。表面処理剤としては、例えば、ステアリン酸、ラウ
リン酸等の高級脂肪酸またはそれらの金属塩等を挙げる
ことができる。本発明の生分解性樹脂組成物には、その
他に本発明の目的を妨げない範囲で分散剤、顔料、安定
剤、酸化防止剤、着色剤、紫外線吸収剤等の他の添加剤
を添加してもよい。The inorganic filler may be surface-treated in order to improve the dispersibility with the resin. However, this is not the case when the hygroscopicity of the inorganic filler is impaired by the surface treatment and deterioration of the surface state of the resin composition over time cannot be suppressed. Examples of the surface treatment agent include higher fatty acids such as stearic acid and lauric acid, or metal salts thereof. In the biodegradable resin composition of the present invention, other additives such as a dispersant, a pigment, a stabilizer, an antioxidant, a colorant, and an ultraviolet absorber are added to the biodegradable resin composition within a range not hindering the purpose of the present invention. May be.
【００３７】上記の通り、本発明の生分解性樹脂組成物
は、特定量の生分解性樹脂、ポリエチレングリコール、
及び無機充填剤を含み、優れた水崩壊性、生分解性樹脂
を有し、経時的にも表面状態の悪化がなく、しかも廉価
である。優れた水崩壊性及び生分解性を有する理由は定
かではないが、一応、次ぎのような機構を推定する。As described above, the biodegradable resin composition of the present invention contains a specific amount of biodegradable resin, polyethylene glycol,
It also contains an inorganic filler, has an excellent water-disintegrating and biodegradable resin, does not deteriorate the surface condition even with time, and is inexpensive. The reason why it has excellent water-disintegrating property and biodegradability is not clear, but for the time being, the following mechanism is presumed.
【００３８】本発明の生分解性樹脂組成物が水中あるい
は土壌中に廃棄された場合、先ず、樹脂組成物中のポリ
エチレングリコールが水に溶解する。その結果、樹脂組
成物中には空隙が多くでき、ポリエチレングリコールの
溶解が進むにつれて破断され、場合によっては粒状にま
で崩壊する。本発明の生分解性樹脂組成物には無機充填
剤が多く含まれているため、この崩壊の際に同時に無機
充填剤が脱落することにより、ますます崩壊が促進され
る。その結果、樹脂組成物中には空隙が多く形成され、
樹脂の表面積が増えることとなり、残った生分解性樹脂
は比較的速やかに分解するものと推定される。When the biodegradable resin composition of the present invention is discarded in water or soil, first, polyethylene glycol in the resin composition is dissolved in water. As a result, many voids are formed in the resin composition, and the resin composition is broken as the dissolution of polyethylene glycol proceeds, and in some cases, it is disintegrated into particles. Since the biodegradable resin composition of the present invention contains a large amount of inorganic filler, the disintegration of the inorganic filler at the same time as this disintegration promotes further disintegration. As a result, many voids are formed in the resin composition,
It is estimated that the surface area of the resin increases and the remaining biodegradable resin decomposes relatively quickly.
【００３９】次いで、本発明の生分解性樹脂組成物の製
造方法を例示する。例えば、生分解性樹脂、無機充填
剤、ポリエチレングリコール、必要に応じて可塑剤、分
散剤、安定剤などその他の添加物をヘンシェルミキサ
ー、スーパーミキサー、タンブラー型ミキサー等を用い
て混合した後、一軸または二軸スクリュー型押出機を用
いて連続混練する。ここで、生分解性樹脂中への無機充
填剤、ポリエチレングリコールの分散性をより向上させ
るためには、二軸押出機の方が好ましい。Next, a method for producing the biodegradable resin composition of the present invention will be illustrated. For example, a biodegradable resin, an inorganic filler, polyethylene glycol, and if necessary, other additives such as a plasticizer, a dispersant, and a stabilizer are mixed using a Henschel mixer, a super mixer, a tumbler type mixer, or the like, and then uniaxially mixed. Alternatively, continuous kneading is performed using a twin screw type extruder. Here, in order to further improve the dispersibility of the inorganic filler and polyethylene glycol in the biodegradable resin, a twin-screw extruder is preferable.
【００４０】押出温度は、好ましくは１００〜２７０℃
の範囲、更に好ましくは１３０〜２５０℃の範囲であ
る。１００℃未満では、押出安定性が得難く、また過負
荷に陥りやすく、２７０℃を超えると、生分解性樹脂や
ポリエチレングリコールの分解が激しくなるので好まし
くない。The extrusion temperature is preferably 100 to 270 ° C.
The range is more preferably 130 to 250 ° C. If it is less than 100 ° C., extrusion stability is difficult to obtain, and if it is easily overloaded, if it exceeds 270 ° C., the biodegradable resin or polyethylene glycol is severely decomposed, which is not preferable.
【００４１】本発明の生分解性樹脂組成物から成形し得
る成形体としては、例えば、生理用タンポン用アプリケ
ータ、生理用ナプキン包装用フィルム、生理用ナプキン
用バックシート、使い捨てオムツ用バックシート、使い
捨てオムツ包装用フィルム等の衛生用品の容器、フィル
ム、シートが挙げられる。例えば、生理用タンポンアプ
リケータは、直径が２〜３０ｍｍ、長さが１０〜２００
ｍｍ、厚みが０．０５〜５ｍｍの筒状容器であって、射
出成形で成形したり、シート状物を得た後、筒状に丸め
る等により成形できる。Examples of molded articles that can be molded from the biodegradable resin composition of the present invention include applicators for sanitary tampon, films for sanitary napkin packaging, back sheets for sanitary napkins, back sheets for disposable diapers, Examples include containers, films and sheets for hygiene products such as films for disposable diaper packaging. For example, a sanitary tampon applicator has a diameter of 2 to 30 mm and a length of 10 to 200.
A cylindrical container having a thickness of 0.05 mm and a thickness of 0.05 to 5 mm, which can be molded by injection molding or after obtaining a sheet-like material and then rolling into a cylindrical shape.
【００４２】また、フィルム、シートを得る場合には、
Ｔダイなどが装着された押出機により溶融押出成形する
ことにより、厚み０．０１〜５ｍｍに成形可能である。
これらの成形物は、その分解速度を高めるために薄く成
形することが好ましいが、強度等を満足させるように自
由に調整可能である。好ましい厚みは、タンポン用アプ
リケータとしては０．１〜５ｍｍ厚、より好ましくは
０．２〜２ｍｍ厚である。また、フィルムとしては、
０．０１〜０．１ｍｍ厚、より好ましくは０．０２〜
０．０７ｍｍ厚である。When obtaining a film or sheet,
Melt extrusion molding with an extruder equipped with a T-die or the like enables molding to a thickness of 0.01 to 5 mm.
These molded products are preferably thinly molded in order to increase the decomposition rate, but can be freely adjusted so as to satisfy the strength and the like. A preferable thickness for an tampon applicator is 0.1 to 5 mm, more preferably 0.2 to 2 mm. Also, as a film,
0.01-0.1 mm thickness, more preferably 0.02-
It is 0.07 mm thick.
【００４３】上記製造方法により得られる本発明の生分
解性樹脂組成物、及びその成形物は、２３℃の水に２日
間浸漬したときの重量減少率が少なくとも１０％であ
り、且つ２３℃の水に１０分間浸漬したときの重量減少
率が１０％未満である。該２日間浸漬したときの重量減
少率の上限は特に制限されるものではないが、本発明の
範囲では主に生分解性樹脂や無機充填剤の配合比に影響
され、約９０％程度である。該２日間浸漬したときの重
量減少率が１０％未満であるような従来の樹脂組成物
は、水崩壊性が不十分であり、上記条件を経過した後の
崩壊、分解が極めて長期間に及ぶため好ましくない。よ
り好ましくは、２日間浸漬したときの重量減少率が少な
くとも１２％である。The biodegradable resin composition of the present invention obtained by the above production method and the molded product thereof have a weight loss rate of at least 10% when immersed in water at 23 ° C. for 2 days, and at 23 ° C. The weight reduction rate when immersed in water for 10 minutes is less than 10%. The upper limit of the weight reduction rate after soaking for 2 days is not particularly limited, but is about 90% mainly affected by the compounding ratio of the biodegradable resin and the inorganic filler within the scope of the present invention. . A conventional resin composition having a weight loss rate of less than 10% when soaked for 2 days has insufficient water disintegration property, and the disintegration and decomposition after the above conditions have passed are extremely long. Therefore, it is not preferable. More preferably, the weight loss rate after soaking for 2 days is at least 12%.
【００４４】さらに、該２３℃の水に１０分間浸漬した
ときの重量減少率は１０％未満である。１０分間浸漬し
たときの重量減少率が１０％以上の場合、水への溶解速
度は速すぎるため、例えばタンポンアプリケータなどに
用いた場合、体内に成分が残存したり、極端な場合体内
で崩壊が進む可能性が高くなり好ましくない。より好ま
しくは、１０分間浸漬したときの重量減少率は８％未満
である。Further, the weight reduction rate when immersed in the water at 23 ° C. for 10 minutes is less than 10%. If the weight loss rate after immersion for 10 minutes is 10% or more, the rate of dissolution in water is too fast. Therefore, when used in a tampon applicator, for example, components remain in the body or, in extreme cases, disintegrate in the body. Is likely to progress, which is not preferable. More preferably, the weight loss rate after immersion for 10 minutes is less than 8%.
【００４５】該２日間浸漬したときの重量減少率、及び
１０分間浸漬したときの重量減少率は、ポリエチレング
リコールの数平均分子量、及びその含有率やその他の添
加剤も含んだ含有率と大きな相関がある。これらの３種
の材料を本発明で規定する範囲で含むことにより、優れ
た水崩壊性、及び生分解性樹脂が発現するのである。そ
の上、経時的にも表面状態の悪化及び樹脂の硬化などの
現象がなく、実使用時には成分が溶け出すことがほとん
どないため、使い捨ての衛生材料として極めて有用であ
る。The weight loss rate after soaking for 2 days and the weight loss rate after soaking for 10 minutes have a large correlation with the number average molecular weight of polyethylene glycol and its content rate and content rate including other additives. There is. By including these three kinds of materials within the range specified in the present invention, an excellent water-disintegrating and biodegradable resin is developed. In addition, there are no phenomena such as deterioration of the surface condition and hardening of the resin over time, and the components hardly dissolve out during actual use, and therefore it is extremely useful as a disposable sanitary material.
【００４６】[0046]
【実施例】以下、実施例を示して本発明についてさらに
詳細に説明する。なお、この実施例で用いた評価方法
は、以下の通りである。EXAMPLES The present invention will be described in more detail below with reference to examples. The evaluation method used in this example is as follows.
【００４７】（１）表面状態
実施例で得られた樹脂シートから、縦横それぞれ１０ｃ
ｍ、厚み０．５ｍｍの試料を調製する。試料を４０℃、
相対湿度６０％の恒温恒湿槽に２４時間放置した後の表
面状態を観察する。評価基準は以下の通りである。○：
表面状態の変化はほとんど認められない。ヌメリ感な
し。△：表面状態の変化が若干認められる。ヌメリ感が
ある。×：表面がべとついている。(1) Surface condition From the resin sheet obtained in the example, 10c in length and width
A sample with m and a thickness of 0.5 mm is prepared. Sample at 40 ℃,
The surface condition after observing for 24 hours in a thermo-hygrostat having a relative humidity of 60% is observed. The evaluation criteria are as follows. ○:
Almost no change in surface condition is observed. There is no slimy feeling. Δ: Some change in surface condition is observed. There is a slimy feeling. X: The surface is sticky.
【００４８】（２）２日間重量減少率（％）
前項（１）と同様の試料を室温において、２３℃の純水
５リットル中に２日間浸漬した後に取り出す。取り出し
た後、水道流水にて表面のヌメリ等がなくなるまで洗
う。洗浄後、室温で２時間傾斜放置し水切りを行う。そ
の後、シリカゲルを入れたデシケータ中で１２時間乾燥
させる。下記数式（１）により重量減少率を算出する。
１０枚の試料について測定し、その平均値を算出する。
ＷR＝［（Ｗ1−Ｗ2）／Ｗ1］×１００・・（１）
ここで、ＷR：重量減少率（％）、Ｗ1：浸漬前の重量、
Ｗ2：浸漬後の重量。(2) Weight loss rate for 2 days (%) A sample similar to the above item (1) was immersed in 5 liters of pure water at 23 ° C. for 2 days at room temperature and then taken out. After taking out, wash with running tap water until there is no slimy surface. After washing, the product is drained by leaving it standing at room temperature for 2 hours. Then, it is dried for 12 hours in a desiccator containing silica gel. The weight reduction rate is calculated by the following mathematical formula (1).
The measurement is performed on 10 samples and the average value is calculated. W R = [(W 1 −W 2 ) / W 1 ] × 100 ... (1) where, W R : weight reduction rate (%), W 1 : weight before immersion,
W 2 : Weight after immersion.
【００４９】（３）１０分間重量減少率（％）
前項（１）と同様の試料を室温において、２３℃の純水
５リットル中に１０分間浸漬した後に取り出す。取り出
した後、室温で２時間傾斜放置し水切りを行う。その
後、シリカゲルを入れたデシケータ中で１２時間乾燥さ
せる。重量減少率を前項（２）と同様の方法で算出す
る。(3) 10-minute weight loss rate (%) A sample similar to the above item (1) was immersed in 5 liters of pure water at 23 ° C. for 10 minutes at room temperature and then taken out. After taking it out, it is drained by leaving it for 2 hours at room temperature. Then, it is dried for 12 hours in a desiccator containing silica gel. The weight reduction rate is calculated by the same method as in the above item (2).
【００５０】（４）無機充填剤の平均粒径（μｍ）
レーザー回折散乱法粒度分布測定器（日機装（株）製、
形式：マイクロトラックＸ−１００）を用いて計測し、
平均粒径（μｍ）を測定する。(4) Average particle size (μm) of inorganic filler Laser diffraction / scattering particle size distribution analyzer (manufactured by Nikkiso Co., Ltd.,
Format: Measured using Microtrack X-100),
The average particle size (μm) is measured.
【００５１】（５）経時強度
実施例で得られた試料（厚み０．５ｍｍのシート）を５
０℃のオーブンに４日間放置したのち、１８０°に折り
曲げ、下記の基準に従って評価を行う。
○：折り曲げ箇所が破壊せず、亀裂が生じない。△：折
り曲げ箇所に亀裂が生じる。×：２つ以上の断片に破壊
する。(5) Temporal strength Five samples (sheets having a thickness of 0.5 mm) obtained in the examples were used.
After leaving it in an oven at 0 ° C. for 4 days, it is bent at 180 ° and evaluated according to the following criteria. ◯: The bent portion does not break and cracks do not occur. Δ: A crack is generated at the bent portion. X: Break into two or more pieces.
【００５２】（６）ポリエチレングリコールの数平均分
子量
水酸基価を測定し、得られた水酸基価から数平均分子量
を算出する。
＜水酸基価（ＫＯＨｍｇ／ｇ）の測定＞［表１］に基づ
き、試料を三角フラスコに精秤し、無水酢酸・ピリジン
混合試薬（無水酢酸１容にピリジン４容の割合で混合し
たもの）５ｍｌをホールピペットにて加える。９５〜１
００℃の油浴に上記三角フラスコを浸け、冷却器を付け
１時間反応する。イオン交換水１ｍｌを加え、よく攪拌
し、さらに１０分間油浴上で放置する。油浴から取り出
し、さらに１０分間放置する。０．５％フェノールフタ
レインを指示薬として、０．５ｍｏｌ／Ｌ水酸化カリウ
ム標準溶液で滴定する。以上の操作を２回行うと同時
に、併行して空試験も行う。以下の式に従い水酸基価を
求め、２回の平均をとる。
ＯＨ＝［｛（Ｂ−Ａ）×２８．０５×ｆ｝／Ｓ］
ここで、ＯＨ：水酸基価（ＫＯＨｍｇ／ｇ）、Ｂ：空試
験に要した０．５ｍｏｌ／Ｌ水酸化カリウム標準溶液の
ｍｌ数、Ａ：本試験に要した０．５ｍｏｌ／Ｌ水酸化カ
リウム標準溶液のｍｌ数、ｆ：０．５ｍｏｌ／Ｌ水酸化
カリウム標準溶液の力価、Ｓ：試料採取量（ｇ）。(6) Number average molecular weight of polyethylene glycol The hydroxyl value is measured, and the number average molecular weight is calculated from the obtained hydroxyl value. <Measurement of Hydroxyl Value (KOHmg / g)> Based on [Table 1], a sample was precisely weighed in an Erlenmeyer flask and 5 ml of acetic anhydride / pyridine mixed reagent (mixture of 1 volume of acetic anhydride and 4 volumes of pyridine). Add with a whole pipette. 95-1
Immerse the Erlenmeyer flask in an oil bath at 00 ° C., attach a condenser and react for 1 hour. Add 1 ml of ion-exchanged water, stir well, and leave on oil bath for 10 minutes. Remove from oil bath and leave for another 10 minutes. Titrate with 0.5 mol / L potassium hydroxide standard solution using 0.5% phenolphthalein as an indicator. Perform the above operation twice, and simultaneously perform a blank test. The hydroxyl value is calculated according to the following formula, and the average is taken twice. OH = [{(B−A) × 28.05 × f} / S] where OH: hydroxyl value (KOHmg / g), B: 0.5 mol / L potassium hydroxide standard solution required for blank test Number of ml, A: number of ml of 0.5 mol / L potassium hydroxide standard solution required for this test, f: titer of 0.5 mol / L potassium hydroxide standard solution, S: sampled amount (g).
【００５３】尚、試料が遊離酸を含むときは、ＪＩＳ
Ｋ−１５５７−１９７０に規定される方法により酸価
（ＫＯＨｍｇ／ｇ）を測定して、次の式により修正す
る。
修正ＯＨ＝ＯＨ＋酸価
ここで、修正ＯＨ：修正水酸基価（ＫＯＨｍｇ／ｇ）、
ＯＨ：滴定で得られた水酸基価（ＫＯＨｍｇ／ｇ）。When the sample contains free acid, JIS
The acid value (KOHmg / g) is measured by the method defined in K-1557-1970 and corrected by the following formula. Modified OH = OH + Acid Value Here, modified OH: modified hydroxyl value (KOHmg / g),
OH: hydroxyl value (KOHmg / g) obtained by titration.
【００５４】[0054]
【表１】 [Table 1]
【００５５】＜数平均分子量の算出＞下記数式により算
出する。
Ｍｎ＝（５６１００×２）／０Ｈ
ここで、Ｍｎ：数平均分子量、ＯＨ：滴定で得られた水
酸基価又は上記修正水酸基価（ＫＯＨｍｇ／ｇ）。
調製例１
＜ジグリセリンテトラアセテートの調製＞ジグリセリン
８４ｇ、及び無水酢酸４１５ｇを反応フラスコに入れ、
強酸性イオン交換樹脂（ダウケミカル社製、商品名：ダ
ウエックスＭＳＣ−１）２．５ｇを追加し、撹拌しなが
ら８０〜９０℃で１時間反応を行った。冷却後、イオン
交換樹脂を濾別し、生成した酢酸および未反応の無水酢
酸を減圧留去し、ジグリセリンテトラアセテート１６
１．５ｇを得た。これは、一般式（１）におけるＲ1〜
Ｒ4が全て炭素数２のアシル基、ｎは１である、酸価が
０．２、水酸基価が３．１である。<Calculation of number average molecular weight> The number average molecular weight is calculated by the following mathematical formula. Mn = (56100 × 2) / 0H Here, Mn: number average molecular weight, OH: hydroxyl value obtained by titration or the above-mentioned modified hydroxyl value (KOHmg / g). Preparation Example 1 <Preparation of diglycerin tetraacetate> 84 g of diglycerin and 415 g of acetic anhydride were placed in a reaction flask,
2.5 g of a strongly acidic ion exchange resin (Dow Chemical Co., trade name: Dowex MSC-1) was added, and the reaction was carried out at 80 to 90 ° C. for 1 hour while stirring. After cooling, the ion exchange resin was filtered off and the acetic acid produced and unreacted acetic anhydride were distilled off under reduced pressure to give diglycerin tetraacetate 16
1.5 g was obtained. This is R 1 ~ in the general formula (1).
R 4 is an acyl group having 2 carbon atoms, n is 1, the acid value is 0.2, and the hydroxyl value is 3.1.
【００５６】実施例１〜１６、比較例１〜８
生分解性樹脂、可塑剤、ポリエチレングリコール、無機
充填剤を〔表２〕〜［表４］に示す銘柄、割合にて混合
し、分散剤としてステアリン酸カルシウム（日東化成
（株）製、商品名：Ｃａ−Ｓｔ）を上記樹脂組成物１０
０重量部に対して１重量部加え、ヘンシェルミキサーを
用いて室温で混合して生分解性樹脂組成物を製造した。
得られた樹脂組成物を１９０℃において、２軸スクリュ
ー押出機にて混練した。さらに、混練物を１８０℃、１
０ＭＰａにおいてプレス後、３０℃にてクエンチして、
厚さ０．５ｍｍのシート状に加工した。得られたシート
について上記方法に従って物性を評価し、その結果を
〔表２〕〜［表４］に示す。Examples 1 to 16 and Comparative Examples 1 to 8 Biodegradable resin, plasticizer, polyethylene glycol, and inorganic filler were mixed in the brands and proportions shown in [Table 2] to [Table 4] to prepare a dispersant. Calcium stearate (manufactured by Nitto Kasei Co., Ltd., trade name: Ca-St) is used as the resin composition 10
1 part by weight was added to 0 parts by weight and mixed at room temperature using a Henschel mixer to produce a biodegradable resin composition.
The obtained resin composition was kneaded at 190 ° C. with a twin-screw extruder. Furthermore, the kneaded product is heated to 180 ° C.
After pressing at 0 MPa, quench at 30 ° C,
It was processed into a sheet having a thickness of 0.5 mm. The physical properties of the obtained sheet were evaluated according to the methods described above, and the results are shown in [Table 2] to [Table 4].
【００５７】[0057]
【表２】 [Table 2]
【００５８】[0058]
【表３】 [Table 3]
【００５９】[0059]
【表４】 [Table 4]
【００６０】＜表２〜表４の記載の説明＞ＰＬＡ：ポリ
乳酸（三井化学（株）製、商品名：レイシア）、ＰＢ
Ｓ：ポリブチレンサクシネート（昭和高分子（株）製、
商品名：ビオノーレ１００１）、ｍ−ＰＢＴ：ポリブチ
レンサクシネート・テレフタレート（ＢＡＳＦ社製、商
品名：エコフレックス）、Ａ：可塑剤（調製例１で得ら
れたジグリセリンテトラアセテート）、ＰＥＧ：ポリエ
チレングリコール［三洋化成工業（株）製、商品名：Ｐ
ＥＧ−１０００（Ｍｎ；１０００）、同−４０００Ｓ
（Ｍｎ；４０００）、同−６０００Ｓ（Ｍｎ；６００
０）、同−１００００（Ｍｎ；１００００）、同−１３
０００（Ｍｎ；１３０００）、同−２００００（Ｍｎ；
２００００）］、ＣａＣＯ3：重質炭酸カルシウム（同
和カルフィン（株）製、商品名：ＳＳＴ−４０、平均粒
径２μｍ）、ＢａＳＯ4：沈降性硫酸バリウム（バライ
ト工業（株）製、商品名：ＳＴ、平均粒径０．９μ
ｍ）。<Description of Tables 2 to 4> PLA: polylactic acid (manufactured by Mitsui Chemicals, Inc., trade name: LACEA), PB
S: Polybutylene succinate (manufactured by Showa Highpolymer Co., Ltd.,
Trade name: Bionole 1001), m-PBT: polybutylene succinate terephthalate (manufactured by BASF, trade name: Ecoflex), A: plasticizer (diglycerin tetraacetate obtained in Preparation Example 1), PEG: polyethylene Glycol [Sanyo Chemical Industry Co., Ltd., trade name: P
EG-1000 (Mn; 1000), the same-4000S
(Mn; 4000), the same -6000S (Mn; 600)
0), ibid-10000 (Mn; 10000), ibid-13
000 (Mn; 13000), the same -20,000 (Mn;
20000)], CaCO 3 : heavy calcium carbonate (manufactured by Dowa Calfin Co., Ltd., trade name: SST-40, average particle size 2 μm), BaSO 4 : precipitated barium sulfate (manufactured by Barite Industry Co., Ltd., trade name: ST, average particle size 0.9μ
m).
【００６１】実施例１７
実施例１〜１６で得られた、厚み０．５ｍｍの各シート
を筒状に丸めて、直径１０ｍｍ、長さ５０ｍｍの筒状の
生理用タンポンアプリケータを製造した。Example 17 Each sheet having a thickness of 0.5 mm obtained in Examples 1 to 16 was rolled into a tubular shape to produce a tubular sanitary tampon applicator having a diameter of 10 mm and a length of 50 mm.
【００６２】[0062]
【発明の効果】本発明により提供される生分解性樹脂組
成物は、優れた水崩壊性及び生分解性を有し、経時的に
も表面状態の悪化がなく、しかも廉価である。そのた
め、本発明の生分解性樹脂組成物からの成形物は、使用
時は体液等により崩壊することがなく通常と全く同様に
使用でき、使用した後トイレ、台所流し等に放流した場
合、水崩壊及び生分解する効果を奏する。その結果、環
境への負加を減らすことが可能である。従って、生理用
タンポンのアプリケータ、生理用ナプキン包装用フィル
ム、使い捨て紙おむつのバックシート、及び医療用衣類
等の衛生用品や、キッチンタオル、掃除用タオル、ワイ
ピングクロス等の生活用品の分野において好適に使用さ
れる。The biodegradable resin composition provided by the present invention has excellent water disintegration property and biodegradability, does not deteriorate in surface condition with time, and is inexpensive. Therefore, the molded product from the biodegradable resin composition of the present invention, can be used in exactly the same manner as usual without disintegrating due to body fluids, etc., when used and discharged to the toilet, kitchen sink, etc. It has the effect of disintegrating and biodegrading. As a result, it is possible to reduce the burden on the environment. Therefore, it is suitable in the field of sanitary tampon applicators, sanitary napkin packaging films, back sheets of disposable paper diapers, and sanitary items such as medical clothing, and household items such as kitchen towels, cleaning towels, and wiping cloths. used.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｋ 3/00 Ｃ０８Ｌ 71/02 Ｃ０８Ｌ 67/02 Ａ６１Ｆ 13/20 ３５０ 67/04 13/18 ３７０ 71/02 (72)発明者 曽 逸文 愛知県名古屋市南区丹後通２−１ 三井化 学株式会社内 Ｆターム(参考） 4C003 CA05 GA08 4F071 AA01 AA43 AA44 AA51 AA81 AB00 AB21 AB24 AB26 AB30 AE17 AF10 AF52 AF57 AH04 AH05 AH19 BC01 BC04 4J002 CF03W CF18W CF19W CH02X DE076 DE086 DE106 DE136 DE146 DE236 DG046 DG056 DH046 DJ006 DJ016 DJ026 DJ036 DJ046 DJ056 DL006 FD016 FD020 GB01 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C08K 3/00 C08L 71/02 C08L 67/02 A61F 13/20 350 67/04 13/18 370 71/02 (72) Inventor Sou Ibun, 2-1 Tango-dori, Minami-ku, Aichi Prefecture Mitsui Chemicals Co., Ltd. F-term (reference) 4C003 CA05 GA08 4F071 AA01 AA43 AA44 AA51 AA81 AB00 AB21 AB24 AB26 AB30 AE17 AF10 AF52 AF57 AH04 AH05 AH19 BC01 BC04 4J002 CF03W CF18W CF19W CH02X DE076 DE086 DE106 DE136 DE146 DE236 DG046 DG056 DH046 DJ006 DJ016 DJ026 DJ036 DJ046 DJ056 DL006 FD016 FD020 GB01
Claims (8)
の合計量２５〜８５重量％、及び無機充填剤７５〜１５
重量％を含む生分解性樹脂組成物であって、前記生分解
性樹脂１００重量部に対して、数平均分子量が５０００
〜３００００であるポリエチレングリコール１０〜１１
０重量部を含むことを特徴とする生分解性樹脂組成物。1. A total amount of biodegradable resin and polyethylene glycol of 25 to 85% by weight, and an inorganic filler of 75 to 15
A biodegradable resin composition containing 100% by weight, wherein the number average molecular weight is 5,000 relative to 100 parts by weight of the biodegradable resin.
~ 30000 polyethylene glycol 10-11
A biodegradable resin composition comprising 0 parts by weight.
ポリアルキレンサクシネートから選ばれた少なくとも一
種の樹脂であることを特徴とする請求項１記載の生分解
性樹脂組成物。2. The biodegradable resin composition according to claim 1, wherein the biodegradable resin is at least one resin selected from lactic acid-based polymers and polyalkylene succinates.
特徴とする請求項２記載の生分解性樹脂組成物。3. The biodegradable resin composition according to claim 2, wherein the lactic acid-based polymer is polylactic acid.
チレンサクシネート、ポリブチレンサクシネート・アジ
ペート、ポリブチレンサクシネート・テレフタレート、
及びポリエチレンサクシネートから選ばれた少なくとも
一種の樹脂であることを特徴とする請求項２記載の生分
解性樹脂組成物。4. The polyalkylene succinate is polybutylene succinate, polybutylene succinate adipate, polybutylene succinate terephthalate,
The biodegradable resin composition according to claim 2, which is at least one resin selected from the group consisting of polyethylene succinate and polyethylene succinate.
リウム、タルク、クレー、シリカ、及び雲母から選ばれ
た少なくとも一種の化合物であることを特徴とする請求
項１記載の生分解性樹脂組成物。5. The biodegradable resin composition according to claim 1, wherein the inorganic filler is at least one compound selected from calcium carbonate, barium sulfate, talc, clay, silica, and mica. .
生分解性樹脂組成物を成形加工したシート、フィルム、
及び容器から選ばれた少なくとも一種の成形物であるこ
とを特徴とする生分解性樹脂組成物。6. A sheet, a film obtained by molding and processing the biodegradable resin composition according to claim 1, which is a biodegradable resin composition.
And a biodegradable resin composition, which is at least one type of molded product selected from containers.
タ、生理用ナプキン包装用フィルム、使い捨ておむつ用
バックシート、及び医療用衣類から選ばれた少なくとも
一種の衛生用品であることを特徴とする請求項６記載の
樹脂組成物。7. The molded product is at least one sanitary article selected from an applicator for a sanitary tampon, a film for a sanitary napkin packaging, a backsheet for a disposable diaper, and a medical garment. Item 7. The resin composition according to item 6.
減少率が少なくとも１０％であり、且つ２３℃の水に１
０分間浸漬したときの重量減少率が１０％未満であるこ
とを特徴とする請求項１〜７のいずれか１項に記載の生
分解性樹脂組成物。8. The weight loss rate when immersed in water at 23 ° C. for 2 days is at least 10%, and 1% in water at 23 ° C.
The biodegradable resin composition according to any one of claims 1 to 7, wherein a weight reduction rate when immersed for 0 minutes is less than 10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001230799A JP5041639B2 (en) | 2001-07-31 | 2001-07-31 | Biodegradable resin composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001230799A JP5041639B2 (en) | 2001-07-31 | 2001-07-31 | Biodegradable resin composition |
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| Publication Number | Publication Date |
|---|---|
| JP2003041142A true JP2003041142A (en) | 2003-02-13 |
| JP5041639B2 JP5041639B2 (en) | 2012-10-03 |
Family
ID=19062946
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001230799A Expired - Lifetime JP5041639B2 (en) | 2001-07-31 | 2001-07-31 | Biodegradable resin composition |
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| Country | Link |
|---|---|
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| WO2008044471A1 (en) * | 2006-10-10 | 2008-04-17 | Nec Corporation | Thermoplastic resin composition |
| DE102007026719A1 (en) * | 2007-06-06 | 2008-12-18 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Polymer composition, useful e.g. to manufacture molded body and as an adhesive foil, comprises natural polymer e.g. polysaccharide or synthetic polymer e.g. polyester amide, polyethylene oxide and further auxiliary materials and additives |
| JP2010535920A (en) * | 2007-08-14 | 2010-11-25 | フータマキ フォルヒハイム ツヴァイクニーダーラッスング デア フータマキ ドイチュラント ゲゼルシャフト ミット ベシュレンクテル ハフツング ウント コンパニー コマンディートゲゼルシャフト | Film arrangement |
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| JP2015535027A (en) * | 2012-11-15 | 2015-12-07 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Biodegradable polyester blend |
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| WO2017104415A1 (en) * | 2015-12-18 | 2017-06-22 | 株式会社リコー | Water-disintegrable composite material, and method for producing three-dimensional model |
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| EP3792314B1 (en) | 2018-10-26 | 2023-01-11 | TBM Co., Ltd. | Biodegradable resin molded product, method for producing the same, and pellets used therefor |
| US20220325039A1 (en) * | 2021-03-25 | 2022-10-13 | Tbm Co., Ltd. | Resin composition and molded article |
| US11680136B2 (en) * | 2021-03-25 | 2023-06-20 | Tbm Co., Ltd. | Resin composition and molded article |
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