JP5662245B2 - ポリ乳酸樹脂組成物 - Google Patents
ポリ乳酸樹脂組成物 Download PDFInfo
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- JP5662245B2 JP5662245B2 JP2011116967A JP2011116967A JP5662245B2 JP 5662245 B2 JP5662245 B2 JP 5662245B2 JP 2011116967 A JP2011116967 A JP 2011116967A JP 2011116967 A JP2011116967 A JP 2011116967A JP 5662245 B2 JP5662245 B2 JP 5662245B2
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- 239000004300 potassium benzoate Substances 0.000 description 1
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- 229960000380 propiolactone Drugs 0.000 description 1
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- 229960003656 ricinoleic acid Drugs 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
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- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
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- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- JUQGWKYSEXPRGL-UHFFFAOYSA-M sodium;tetradecanoate Chemical compound [Na+].CCCCCCCCCCCCCC([O-])=O JUQGWKYSEXPRGL-UHFFFAOYSA-M 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
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- 239000001384 succinic acid Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 1
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- AOBORMOPSGHCAX-DGHZZKTQSA-N tocofersolan Chemical compound OCCOC(=O)CCC(=O)OC1=C(C)C(C)=C2O[C@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C AOBORMOPSGHCAX-DGHZZKTQSA-N 0.000 description 1
- 229960000984 tocofersolan Drugs 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- SSWCPXKXMAZRJO-UHFFFAOYSA-J tri(tetradecanoyloxy)stannyl tetradecanoate Chemical compound [Sn+4].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O SSWCPXKXMAZRJO-UHFFFAOYSA-J 0.000 description 1
- MZHULIWXRDLGRR-UHFFFAOYSA-N tridecyl 3-(3-oxo-3-tridecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCC MZHULIWXRDLGRR-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- UWSCPROMPSAQOL-UHFFFAOYSA-N trimethylazanium;sulfate Chemical compound CN(C)C.CN(C)C.OS(O)(=O)=O UWSCPROMPSAQOL-UHFFFAOYSA-N 0.000 description 1
- LZGVDNRJCGPNDS-UHFFFAOYSA-N trinitromethane Chemical compound [O-][N+](=O)C([N+]([O-])=O)[N+]([O-])=O LZGVDNRJCGPNDS-UHFFFAOYSA-N 0.000 description 1
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-UHFFFAOYSA-N 0.000 description 1
- OOZKMYBQDPXENQ-UHFFFAOYSA-N tris(2,3-diethylphenyl) phosphite Chemical compound CCC1=CC=CC(OP(OC=2C(=C(CC)C=CC=2)CC)OC=2C(=C(CC)C=CC=2)CC)=C1CC OOZKMYBQDPXENQ-UHFFFAOYSA-N 0.000 description 1
- AJHKJOCIGPIJFZ-UHFFFAOYSA-N tris(2,6-ditert-butylphenyl) phosphite Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1OP(OC=1C(=CC=CC=1C(C)(C)C)C(C)(C)C)OC1=C(C(C)(C)C)C=CC=C1C(C)(C)C AJHKJOCIGPIJFZ-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- QFGXDXGDZKTYFD-UHFFFAOYSA-N tris[2,3-di(propan-2-yl)phenyl] phosphite Chemical compound CC(C)C1=CC=CC(OP(OC=2C(=C(C(C)C)C=CC=2)C(C)C)OC=2C(=C(C(C)C)C=CC=2)C(C)C)=C1C(C)C QFGXDXGDZKTYFD-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
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- 235000019354 vermiculite Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 238000002424 x-ray crystallography Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Injection Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
Description
特許文献2には、有機充填剤とエステル系可塑剤を添加する組成物が示されており、耐熱性と結晶化速度に優れるポリ乳酸樹脂組成物が得られている。しかし、その結晶化速度は未だ不十分であった。
本発明のA成分として用いるポリ乳酸樹脂は、主としてL−乳酸単位からなるポリ−L乳酸、主としてD−乳酸単位からなるポリ−D乳酸の混合物である。
本発明のポリ−L乳酸樹脂(A−1成分)、ポリ−D乳酸樹脂(A−2成分)は、式(1)で表されるL‐乳酸単位またはD‐乳酸単位から実質的になる。
(1)ステレオコンプレックス結晶化度=△Hms/(△Hms+△Hmh)×100
[但し、式(1)中、△Hmhと△Hmsは、それぞれ示差走査熱量計(DSC)の昇温過程において、190℃未満に現れる結晶融点の融解エンタルピー(△Hmh)、および190℃以上250℃未満に現れる結晶融点の融解エンタルピー(△Hms)である。]
なお、上記△Hmhと△Hmsは樹脂組成物を示差走査熱量計(DSC)を用いて、窒素雰囲気下、昇温速度20℃/分で測定することにより求めた。
具体的には、ステレオコンプレックス結晶化度が80%以上であり、融点が200℃以上であり、融解エンタルピーが20J/g以上であることが好ましい。
本発明で使用する可塑剤(B成分)は、下記一般式(5)で示す可塑剤を用いる。
式1に示す様な、モノエステルタイプの構造を持った可塑剤は、ジエステルタイプの可塑剤に比べて可塑化効率が高く、成形性が良好である。
このような可塑剤としてはライオン(株)製 レオファットOC−0503Mが市販品として入手することが出来る。
C成分の末端封鎖剤とは、ポリ乳酸(A成分)のカルボキシル基末端の一部または全部と反応して封鎖する働きを示すものであり、カルボジイミド化合物、エポキシ化合物などの付加反応型の化合物である。付加反応型の化合物を用いれば、例えば、アルコールとカルボキシル基の脱水縮合反応による末端封鎖のように余分な副生成物を反応系外に排出する必要がない。従って、付加反応型の末端封鎖剤を添加・混合・反応させることにより、副生成物による樹脂の分解を抑制しつつ、十分なカルボキシル基末端封鎖効果を得ることができ、実用的に十分な耐加水分解性を備えた樹脂組成物、および該樹脂組成物からなる成形品を得ることができる。
環状構造は、下記式(6)で表される構造である。
Yは、単結合、二重結合、原子、原子団またはポリマーである。Yは結合部であり、複数の環状構造がYを介して結合し、式(8)で表される構造を形成している。かかる環状カルボジイミド化合物(3)としては、下記化合物が挙げられる。
環状カルボジイミド化合物は従来公知の方法により製造することができる。例として、アミン体からイソシアネート体を経由して製造する方法、アミン体からイソチオシアネート体を経由して製造する方法、アミン体からトリフェニルホスフィン体を経由して製造する方法、アミン体から尿素体を経由して製造する方法、アミン体からチオ尿素体を経由して製造する方法、カルボン酸体からイソシアネート体を経由して製造する方法、ラクタム体を誘導して製造する方法などが挙げられる。
Medium−and Large−Membered Rings from Bis(iminophosphoranes):An Efficient Preparation of Cyclic Carbodiimides, Pedro Molina etal.
Journal of Organic Chemistry,Vol.61,No.13,4289−4299,1996.
New Models for the Study of the Racemization Mechanism of Carbodiimides.Synthesis and Structure(X−ray Crystallography and 1H NMR) of Cyclic Carbodiimides, Pedro Molina etal.
Journal of Organic Chemistry,Vol.43,No8,1944−1946,1978.
Macrocyclic Ureas as Masked Isocyanates, Henri Ulrich etal.
Journal of Organic Chemistry,Vol.48,No.10,1694−1700,1983.
Synthesis and Reactions of Cyclic Carbodiimides,
R.Richteretal.
Journal of Organic Chemistry,Vol.59,No.24,7306−7315,1994.
A New and Efficient Preparation of Cyclic Carbodiimides from Bis(iminophosphoranea)and the System Boc2O/DMAP,Pedro Molina etal.
具体的なカルボキシル基末端封鎖の程度としてはポリ乳酸樹脂のカルボキシル基末端の濃度が10当量/103 kg以下であることが耐加水分解性向上の点から好ましく、6当量/103 kg以下であることがさらに好ましい。
本発明の樹脂組成物には、酸化防止剤(D成分)として、ヒンダードフェノール系化合物、ホスファイト系化合物、ホスホナイト系化合物およびチオエーテル系化合物からなる群より選ばれる少なくとも1種の酸化防止剤を使用する。酸化防止剤(D成分)を配合する事により、成形加工時の色相や流動性が安定するだけでなく、耐加水分解性の向上にも効果がある。
本発明の組成物は衝撃改質剤(E成分)を含有することができる。衝撃改質剤(E成分)を配合することで、耐衝撃性だけでなく、耐加水分解性の向上にも効果が有る。衝撃改質剤(E成分)としては、(E−α)その内部に少なくとも1種以上のゴム層を有し、その成分がアクリル系成分、シリコン系成分、スチレン系成分、ニトリル系成分、共役ジエン系成分、ウレタン系成分、およびエチレンプロピレン系成分からなる群より選ばれる1種以上であり、ゴム層以外の成分がビニル単量体である衝撃改質剤(E−α成分)および/または(E−β)実質的にゴム成分を含まない衝撃改質剤(E−β成分)が好ましく使用される。これら2種は、単独でも使用してもよく、併用しても良く、各々の種類の中で単数以上の化合物を使用しても構わないことは言うまでもない。その使用は目的に応じて使い分けることが好ましい。
内部に少なくとも1種以上のゴム層を有し、その成分がアクリル系成分、シリコン系成分、スチレン系成分、ニトリル系成分、共役ジエン系成分、ウレタン系成分、およびエチレンプロピレン系成分からなる群より選ばれる1種以上であり、ゴム層以外の成分がビニル単量体である衝撃改質剤(E−α成分)としては、ゴム成分を含有し、その含有量が40重量%未満のビニル単位含有樹脂(E−α−1成分)、ゴム成分含有量40重量%以上のビニル単位含有樹脂(E−α−2成分)からなる群より選ばれる少なくとも一種の樹脂が好ましい。
ゴム成分を含有し、その含有量が40重量%未満のビニル単位含有樹脂(E−α−1成分)とは、少なくとも1種類以上のビニル単量体および40重量%未満のゴム成分を重合して得られる樹脂である。
ゴム成分含有量40重量%以上のビニル単位含有樹脂とは、少なくとも1種類以上のビニル単量体および40重量%以上のゴム成分を重合して得られる樹脂である。
またかかるゴム成分と上記モノマーのブロック共重合体も挙げられる。かかるブロック共重合体としては具体的にはスチレン・エチレンプロピレン・スチレンエラストマー(水添スチレン・イソプレン・スチレンエラストマー)、および水添スチレン・ブタジエン・スチレンエラストマーなどの熱可塑性エラストマーを挙げることができる。
ここでいうゴム成分としては、ブタジエンゴム、ブタジエン−アクリル複合ゴム、アクリルゴム、アクリル−シリコン複合ゴム、イソブチレン−シリコン複合ゴム、イソプレンゴム、スチレン−ブタジエンゴム、クロロプレンゴム、エチレン−プロピレンゴム、ニトリルゴム、エチレン−アクリルゴム、シリコンゴム、エピクロロヒドリンゴム、フッ素ゴムおよびこれらの不飽和結合部分に水素が添加されたものを挙げることができる。
本発明の実質的にゴム成分を含まない衝撃改質剤(E−β成分)として、共重合ポリエステル、および共重合ポリエチレンからなる群より選ばれる少なくとも一種の樹脂が好ましい。
本発明の組成物は、無機充填剤(F成分)を含有してもよい。無機充填剤を含有することにより、機械特性、耐熱性、成形性の優れた組成物を得ることができる。本発明で使用する無機充填剤としては、通常の熱可塑性樹脂の強化に用いられる繊維状、板状、粉末状のものを用いることができる。
かかる充填剤はエチレン/酢酸ビニル共重合体等の熱可塑性樹脂やエポキシ樹脂等の熱硬化性樹脂で被覆または収束処理されていてもよく、またアミノシランやエポキシシラン等のカップリング剤で処理されていても良い。
本発明ではハイドロタルサイト(G成分)を含むことができる。本発明で使用するハイドロタルサイト(G成分)は、下記一般式(10)で表される合成ハイドロタルサイトが好ましい。
〈光安定剤〉
本発明の組成物は光安定剤を含有していてもよい。光安定剤としては、具体的には例えば、ベンゾフェノン系化合物、ベンゾトリアゾール系化合物、芳香族ベンゾエート系化合物、蓚酸アニリド系化合物、シアノアクリレート系化合物およびヒンダードアミン系化合物等を挙げることができる。
光安定剤の含有量は、ポリ乳酸(A成分)100重量部当たり、好ましくは0.01〜3重量部、より好ましくは0.03〜2重量部である。
本発明の組成物は結晶化促進剤を含有していてもよい。結晶化促進剤を含有することで、機械的特性、耐熱性、および成形性に優れた成形品を得ることができる。
即ち結晶化促進剤の適用により、ポリ乳酸(A成分)の成形性、結晶性が向上し、通常の射出成形においても十分に結晶化し耐熱性、耐湿熱安定性に優れた成形品を得ることができる。加えて、成形品を製造する製造時間を大幅に短縮でき、その経済的効果は大きい。
無機系の結晶化核剤として、タルク、カオリン、シリカ、合成マイカ、クレイ、ゼオライト、グラファイト、カーボンブラック、酸化亜鉛、酸化マグネシウム、酸化チタン、炭酸カルシウム、硫酸カルシウム、硫酸バリウム、硫化カルシウム、窒化ホウ素、モンモリロナイト、酸化ネオジム、酸化アルミニウム、フェニルフォスフォネート金属塩等が挙げられる。これらの無機系の結晶化核剤は組成物中での分散性およびその効果を高めるために、各種分散助剤で処理され、一次粒子径が0.01〜0.5μm程度の高度に分散状態にあるものが好ましい。
結晶化促進剤の含有量は、ポリ乳酸(A成分)100重量部当たり、好ましくは0.01〜30重量部、より好ましくは0.05〜20重量部である。
本発明の組成物は、有機充填剤を含有することができる。有機充填剤を含有することで、機械的特性、耐熱性および成形性に優れた組成物を得ることができる。
有機充填剤として、籾殻、木材チップ、おから、古紙粉砕材、衣料粉砕材等のチップ状のもの、綿繊維、麻繊維、竹繊維、木材繊維、ケナフ繊維、ジュート繊維、バナナ繊維、ココナツ繊維等の植物繊維もしくはこれらの植物繊維から加工されたパルプやセルロース繊維および絹、羊毛、アンゴラ、カシミヤ、ラクダ等の動物繊維等の繊維状のもの、ポリエステル繊維、ナイロン繊維、アクリル繊維等の合成繊維、紙粉、木粉、セルロース粉末、籾殻粉末、果実殻粉末、キチン粉末、キトサン粉末、タンパク質、澱粉等の粉末状のものが挙げられる。成形性の観点から紙粉、木粉、竹粉、セルロース粉末、ケナフ粉末、籾殻粉末、果実殻粉末、キチン粉末、キトサン粉末、タンパク質粉末、澱粉等の粉末状のものが好ましく、紙粉、木粉、竹粉、セルロース粉末、ケナフ粉末が好ましい。紙粉、木粉がより好ましい。特に紙粉が好ましい。
紙粉は成形性の観点から接着剤、取り分け紙を加工する際に通常使用される酢酸ビニル樹脂系エマルジョンやアクリル樹脂系エマルジョン等のエマルジョン系接着剤、ポリビニルアルコール系接着剤、ポリアミド系接着剤等のホットメルト接着剤等を含むものが好ましく例示される。
本発明の組成物は離型剤を含有していてもよい。離型剤として具体的には、脂肪酸、脂肪酸金属塩、オキシ脂肪酸、パラフィン、低分子量のポリオレフィン、脂肪酸アミド、アルキレンビス脂肪酸アミド、脂肪族ケトン、脂肪酸部分鹸化エステル、脂肪酸低級アルコールエステル、脂肪酸多価アルコールエステル、脂肪酸ポリグリコールエステル、変性シリコーン等を挙げることができる。これらを配合することで機械特性、成形性、耐熱性に優れたポリ乳酸成形品を得ることができる。
本発明の組成物は帯電防止剤を含有していてもよい。帯電防止剤として、(β−ラウラミドプロピオニル)トリメチルアンモニウムスルフェート、ドデシルベンゼンスルホン酸ナトリウムなどの第4級アンモニウム塩系、スルホン酸塩系化合物、アルキルホスフェート系化合物等が挙げられる。
また本発明においては、本発明の趣旨に反しない範囲において、フェノール樹脂、メラミン樹脂、熱硬化性ポリエステル樹脂、シリコーン樹脂、エポキシ樹脂等の熱硬化性樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリアリレート樹脂、液晶性ポリエステル樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリエーテルイミド樹脂、ポリフェニレンエーテル樹脂、ポリフェニレンスルフィド樹脂、ポリスルホン樹脂、ポリスチレン樹脂、アクリロニトリル/スチレン共重合体(AS樹脂)、ポリスチレン樹脂、高衝撃ポリスチレン樹脂、シンジオタクチックポリスチレン樹脂などの熱可塑性樹脂を含んでいてもよい。また有機、無機系の染料、顔料を含む着色剤、例えば、二酸化チタン等の酸化物、アルミナホワイト等の水酸化物、硫化亜鉛等の硫化物、紺青等のフェロシアン化物、ジンククロメート等のクロム酸塩、硫酸バリウム等の硫酸塩、炭酸カルシウム等の炭酸塩、群青等の珪酸塩、マンガンバイオレット等のリン酸塩、カーボンブラック等の炭素、ブロンズ粉やアルミニウム粉等の金属着色剤等を含有させても良い。また、ナフトールグリーンB等のニトロソ系、ナフトールイエローS等のニトロ系、ナフトールレッド、クロモフタルイエローどのアゾ系、フタロシアニンブルーやファストスカイブルー等のフタロシアニン系、インダントロンブルー等の縮合多環系着色剤等、グラファイト、フッソ樹脂等の摺動性改良剤等の添加剤を含有させても良い。これらの添加剤は単独であるいは2種以上を併用することもできる。
i)共存組成物の調製
本発明において、ポリ乳酸樹脂(A成分)としてポリ−L乳酸樹脂(A−1成分)、ポリ−D乳酸樹脂(A−2成分)とを混合するとき、他の添加剤成分と溶融混合する前に、式(3)および/または式(4)で表される燐酸エステル金属塩、ポリ−L乳酸樹脂(A−1成分)並びにポリ−D乳酸樹脂(A−2成分)を予め共存させておくのが好ましい。共存させる方法としては、ポリ−L乳酸樹脂(A−1成分)と、ポリ−D乳酸樹脂(A−2成分)とをできるだけ均一に混合させる方法が、それらを熱処理したときにステレオコンプレックス結晶を効率的に生成させることが可能となるため好ましい。かかる共存組成物の調製は、それらが熱処理されたときに均一に混合される方法であれば、いかなる方法をもとることができ、溶媒の存在下で行う方法、溶媒の非存在下で行う方法などが例示される。
本発明において、ポリ乳酸樹脂(A成分)としてポリ−L乳酸樹脂(A−1成分)、ポリ−D乳酸樹脂(A−2成分)とを混合物するとき、他の添加剤成分と溶融混合する前に、ポリ乳酸(A−1成分、A−2成分)と式(3)または式(4)で表される燐酸エステル金属塩の共存組成物を熱処理するのが好ましい。かかる熱処理とは、その組成物を240〜300℃の温度領域で一定時間保持することをいう。熱処理の温度は好ましくは250〜300℃、より好ましくは260〜290℃である。300℃を超えると、分解反応を抑制するのが難しくなるので好ましくなく、240℃未満の温度では熱処理による均一混合が進まず、ステレオコンプレックス結晶が効率的に生成しにくくなるので好ましくない。熱処理の時間は特に限定されるものではないが、0.2〜60分、好ましくは1〜20分である。熱処理時の雰囲気は、常圧の不活性雰囲気下、または減圧のいずれも適用可能である。熱処理に用いる装置、方法としては、雰囲気調整を行いながら加熱できる装置、方法であればいかなる方法をも用いることができるが、たとえば、バッチ式の反応器、連続式の反応器、二軸あるいは一軸のエクストルーダーなど、またはプレス機、流管式の押出機を用いて、成形しながら処理する方法をとることも出来る。ここで、ポリ乳酸(A−1成分、A−2成分)並びに、式(3)または式(4)で表される燐酸エステル金属塩の共存組成物の調製を、溶媒の非存在下にて溶融混合する方法により行う場合には、かかる共存組成物の調製と同時に、該共存組成物の熱処理をも達成できる。
本発明の樹脂組成物は、ポリ乳酸樹脂(A成分)(前記熱処理された共存組成物を含む)、可塑剤(B成分)、末端封鎖剤(C成分)、酸化防止剤(D成分)、衝撃改質剤(E成分)、無機充填剤(F成分)、ハイドロタルサイト(G成分)並びにその他添加剤成分を混合することによって製造される。(ただし、共存組成物中に含有されている成分は除く。)
その他添加剤成分としては、無機充填材折れ抑制剤、滑剤、紫外線吸収剤、光安定剤、離型剤、流動改質剤、着色剤、光拡散剤、蛍光増白剤、蓄光顔料、蛍光染料、帯電防止剤、抗菌剤、結晶核剤等、任意の添加剤成分が挙げられる。
本発明の樹脂組成物は、通常前記方法で製造されたペレットとして得られ、これを原料として射出成形、押出成形など、各種成形方法による製品を製造することができる。
射出成形においては、通常のコールドランナー方式の成形法だけでなく、ホットランナー方式の成形法も可能である。かかる射出成形においては、通常の成形方法だけでなく、適宜目的に応じて、射出圧縮成形、射出プレス成形、ガスアシスト射出成形、発泡成形(超臨界流体の注入によるものを含む)、インサート成形、インモールドコーティング成形、断熱金型成形、急速加熱冷却金型成形、二色成形、サンドイッチ成形、および超高速射出成形などの射出成形法を用いて成形品を得ることができる。これら各種成形法の利点は既に広く知られるところである。
本発明の樹脂組成物を成形してなる成形品は、例えば電気・電子部品、OA機器や家電製品の外装材に好適であり、例えばパソコン、ノートパソコン、ゲーム機(家庭用ゲーム機、業務用ゲーム機、パチンコ、およびスロットマシーンなど)、ディスプレー装置(CRT、液晶、プラズマ、プロジェクタ、および有機ELなど)、マウス、並びにプリンター、コピー機、スキャナーおよびファックス(これらの複合機を含む)などの外装材や電気・電子部品、キーボードのキーや各種スイッチなどのスイッチ成形品が例示される。さらに本発明の成形品は、その他幅広い用途に有用であり、例えば、携帯情報端末(いわゆるPDA)、携帯電話、携帯書籍(辞書類等)、携帯テレビ、記録媒体(CD、MD、DVD、次世代高密度ディスク、ハードディスクなど)のドライブ、記録媒体(ICカード、スマートメディア、メモリースティックなど)の読取装置、光学カメラ、デジタルカメラ、パラボラアンテナ、電動工具、VTR、アイロン、ヘアードライヤー、炊飯器、電子レンジ、音響機器、照明機器、冷蔵庫、エアコン、空気清浄機、マイナスイオン発生器、およびタイプライターなど電気・電子機器を挙げることができ、これらの外装材などの各種部品に本発明の成形品を適用することができる。また各種容器、カバー、筆記具本体、装飾品などの各種雑貨においても好適である。さらにはランプソケット、ランプリフレクター、ランプハウジング、インストルメンタルパネル、センターコンソールパネル、ディフレクター部品、カーナビケーション部品、カーオーディオビジュアル部品、オートモバイルコンピュータ部品などの車両用部品を挙げることができる。
下記の製造例に示す方法により、ポリ乳酸樹脂の製造を行った。また製造例中における各値は下記の方法で求めた。
(1)ポリマーの重量平均分子量(Mw)および数平均分子量(Mn)
ゲルパーミエーションクロマトグラフィー(GPC)により測定、標準ポリスチレンに換算した。GPC測定機器は、検出器として、示差屈折計島津RID−6Aを用い、カラムとして東ソ−TSKgelG3000HXLを使用した。測定は、クロロホルムを溶離液とし温度40℃、流速1.0ml/minにて、濃度1mg/ml(1%ヘキサフルオロイソプロパノールを含むクロロホルム)の試料を10μl注入することにより行った。
(2)カルボキシル基濃度
試料を精製o−クレゾールに窒素気流下で溶解した後、ブロモクレゾールブルーを指示薬とし、0.05規定水酸化カリウムのエタノール溶液で滴定した。
(3)ステレオコンプレックス結晶化度
DSC(TAインスルメント社製 TA−2920)測定の昇温過程におけるポリ乳酸樹脂(A成分)結晶由来の融解エンタルピーを用いて、下記式(1)より、ステレオコンプレックス結晶化度のパラメーターを評価した。
ステレオコンプレックス結晶化度=△Hms/(△Hms+△Hmh)×100 (1)
[但し、式(1)中、△Hmhと△Hmsは、それぞれ示差走査熱量計(DSC)の昇温過程において、190℃未満に現れる結晶融点の融解エンタルピー(△Hmh)、および190℃以上250℃未満に現れる結晶融点の融解エンタルピー(△Hms)である。]
なお、上記△Hmhと△Hmsは樹脂組成物を示差走査熱量計(DSC)を用いて、窒素雰囲気下、昇温速度20℃/分で測定することにより求めた。
[A−1成分:ポリL−乳酸樹脂(PLLA)]
[製造例1−1]
L−ラクチド(株式会社武蔵野化学研究所製、光学純度100%)100重量部に対し、オクチル酸スズを0.005重量部加え、窒素雰囲気下、攪拌翼のついた反応機にて、180℃で2時間反応し、オクチル酸スズに対し1.2倍当量の燐酸を添加しその後、13.3Paで残存するラクチドを除去し、チップ化し、ポリL−乳酸樹脂を得た。
得られたポリL−乳酸樹脂の重量平均分子量は15.2万、融解エンタルピー(ΔHmh)は49J/g、融点(Tmh)は175℃、ガラス転移点(Tg)55℃、カルボキシル基含有量は14eq/tonであった。
[A−2成分:ポリD−乳酸樹脂の製造(PDLA)]
[製造例1−2]
製造例1−1のL−ラクチドのかわりにD−ラクチド(株式会社武蔵野化学研究所製、光学純度100%)を使用する以外は製造例1−1と同様の操作を行い、ポリD−乳酸樹脂を得た。得られたポリD−乳酸樹脂の重量平均分子量は15.1万、融解エンタルピー(ΔHmh)は48J/g、融点(Tmh)は175℃、ガラス転移点(Tg)55℃、カルボキシル基含有量は15eq/ton、であった。
[A−3成分:ステレオコンプレックスポリ乳酸樹脂の製造(scPLA)]
[製造例1−3]
製造例1−1および1−2で得られたPLLA,PDLAの各50重量部よりなるポリ乳酸樹脂計100重量部並びに燐酸−2,2’−メチレンビス(4,6−ジ−tert−ブチルフェニル)ナトリウム(アデカスタブNA−11:(株)ADEKA製)0.1重量部をブレンダーで混合後、110℃で5時間乾燥し、径30mmφのベント式二軸押出機[(株)日本製鋼所製TEX30XSST]に供給し、シリンダー温度250℃、スクリュー回転数250rpm、吐出量9kg/h、およびベント減圧度3kPaで溶融押出してペレット化し、ポリ乳酸樹脂1を得た。得られたステレオコンプレックスポリ乳酸樹脂の重量平均分子量は13万、融解エンタルピー(ΔHms)は56J/g、融点(Tms)は220℃、ガラス転移点(Tg)58℃、カルボキシル基含有量は17eq/ton、式(1)を用いて算出したステレオコンプレックス結晶化度は、100%であった。
結果をまとめて表1中に記載する。なお、表1中のΔHmsは、190℃以上250℃未満に現れる結晶融点の融解エンタルピーであり、ΔHmhは、190℃未満に現れる結晶融点の融解エンタルピーである。Tmsは、190℃以上250℃未満に現れる結晶融点であり、Tmhは、190℃未満に現れる結晶融点である。
下記の製造例に示す方法により、環状カルボジイミドの製造を行った。また製造例中における各値は下記の方法で求めた。
(1)環状カルボジイミド構造のNMRによる同定
合成した環状カルボジイミド化合物のNMRによる同定は、日本電子(株)製JNR−EX270を使用し、1H−NMR、13C−NMRによって確認した。尚、溶媒は重クロロホルムを用いた。
(2)環状カルボジイミドのカルボジイミド骨格のIRによる同定
合成した環状カルボジイミド化合物のカルボジイミド骨格の同定は、ニコレー(株)製Magna−750を使用し、FT−IRよってカルボジイミドに特徴的な2100〜2200cm−1の吸収ピークを確認することで行った。
[C−1成分:環状カルボジイミドの製造(CC1)]
[製造例2]
o−ニトロフェノール(0.11mol)と1,2−ジブロモエタン(0.05mol)、炭酸カリウム(0.33mol)、N,N−ジメチルホルムアミド(DMF)200mlを攪拌装置及び加熱装置を設置した反応装置にN2雰囲気下仕込み、130℃で12時間反応後、DMFを減圧により除去し、得られた固形物をジクロロメタン200mlに溶かし、水100mlで3回分液を行った。有機層を硫酸ナトリウム5gで脱水し、ジクロロメタンを減圧により除去し、中間生成物A(ニトロ体)を得た。
下記の実施例、比較例に示す方法により、ポリ乳酸樹脂(A成分)と添加剤との樹脂組成物ペレットの製造を行った。また実施例中における各値は下記の方法で求めた。
(1)成形性
ポリ乳酸系樹脂組成物を射出成形機(東芝機械(株)製:IS−150EN)、150mm×150mm、厚さ2mm、金型表面磨き#8000の金型を使用し、シリンダー温度230℃、金型温度90℃にて成形片を作成し、その成形可否と成形サイクル(射出時間と冷却時間の合計時間)を評価した。
(2)成形品表面外観
ポリ乳酸系樹脂組成物を射出成形機(東芝機械(株)製:IS−150EN)、150mm×150mm、厚さ2mm、金型表面磨き#8000の金型を使用し、シリンダー温度230℃、金型温度90℃にて成形片を作成した際の成形品表面にガス転写痕が見られたかどうかを目視にて判定し、ガス転写痕が見られなかった場合を○、ガス転写痕が見られた場合を×として評価した。
(3)耐加水分解性
ポリ乳酸系樹脂組成物を射出成形機(東芝機械(株)製:IS−150EN)を使用して、シリンダー温度230℃、金型温度90℃にて、厚さ4mmのISO測定用の成形片を作成した。次に、この成形片を80℃×95%RH条件にて200h、湿熱処理を行った。ISO527−1、ISO527−2に準拠して、引張試験を実施し、湿熱処理前の引張最大応力と湿熱処理後の引張最大応力から保持率[(湿熱処理後の引張最大応力/湿熱処理前の引張最大応力)×100]を算出した。
その他原料としては、以下のものを使用した。
(4)荷重たわみ温度
組成物を射出成形機(東芝機械(株)製:IS−150EN)を使用して、シリンダー温度230℃、金型温度120℃、成形サイクル70秒にて、厚み4mmのISO規格に準拠した試験片を成形し、温度23℃、相対湿度50%の環境下で24時間放置した後、ISO75−1および2に準拠して、荷重0.45MPaにて測定した。
(5)ノッチ付衝撃値
組成物を射出成形機(東芝機械(株)製:IS−150EN)を使用して、シリンダー温度230℃、金型温度120℃、成形サイクル70秒にて、厚み4mmのISO規格に準拠した試験片を成形し、温度23℃、相対湿度50%の環境下で24時間放置した後、ISO規格に準拠してノッチ付衝撃値を測定した。
B−1:ライオン(株)製 レオファットOC−0503M ポリオキシアルキレン脂肪
酸モノエステル[全酸価0.98mmgKOH/g]
B’−1:コハク酸とトリエチレングリコールモノメチルエーテルのジエステル[全酸価1.5mmgKOH/g]
C−2:BASFジャパン(株)製 ADR−4368CS [エポキシ基含有アクリル
−スチレン共重合体]
C−3:日清紡(株)製 カルボジライトLA−1 [脂肪族ポリカルボジイミド]
C−4:ラインケミージャパン(株)製 stabaxol−P[芳香族ポリカルボジイミド]
D−1:チバ・スペシャリティ・ケミカルズ(株)製 Irganox1076 [n−オクタデシル−3−(3’,5’−ジ−tert−ブチル−4’−ヒドロキシフェニル)プロピオネート]
D−2:(株)アデカ製 PEP−24G [ビス(2,4−ジ−tert−ブチルフェニル)ペンタエリスリトールジホスファイト]
E−1:三菱レイヨン(株)製 メタブレンS−2001 [シリコン系コアシェルゴム]
E−2:ロームアンドハース(株)製 パラロイドBPM500 [アクリル系コアシェルゴム]
E−3:日本エイアンドエル(株)製 AT−05 [アクリロニトリル−ブタジエン−スチレン共重合体]
E−4:住友化学(株)製 ボンドファスト7M [ポリエチン−グリシジルメタクリレート共重合体]
E−5:富士化成工業(株)製 TPAE−32 [ポリエーテルエステルアミドエラストマー
F−1:日東紡(株)製 3PE−937S(平均径13μm、カット長3mmのチョップドストランド)
G−1:協和化学工業(株)製 DHT−4A−2[焼成ハイドロタルサイト]
ポリ乳酸樹脂として製造例1−3で製造したポリ乳酸樹脂A−3成分を用いて、表2の組成をドライブレンドにて均一に予備混合した後、かかる予備混合物を第1供給口より供給し、溶融押出してペレット化した。ここで、第一供給口とは根元の供給口のことである。溶融押出は、サイドスクリューを備えた径30mmφのベント式二軸押出機[(株)日本製鋼所製TEX30XSST]を用い実施した。また、押出温度は、C1/C2〜C5/C6/C7〜C11/D=10℃/240℃/230℃/220℃/220℃とし、メインスクリュー回転数は150rpm、サイドスクリュー回転数は50rpm、吐出量は20kg/h、ベント減圧度は3kPaとした。なお、F−1を使用する組成においては、F−1を除く組成をドライブレンドにて均一に予備混合した後、かかる予備混合物を第1供給口より供給し、F−1成分を第2供給口から供給した。なお、ここで、第2供給口とはサイドスクリュウに備え付けた供給口のことである。
得られたペレットを100℃で5時間、熱風循環式乾燥機により乾燥し、射出成形機(東芝機械(株)製:IS−150EN)にて成形を実施し、評価を行った。結果を表2〜4に示す。
可塑剤(B−1成分)を含む実施例1〜3は、金型温度90℃で成形可能で、成形品表面外観に優れ、耐熱性に優れた材料であった。
<実施例4〜7>
可塑剤(B−1成分)に加え、末端封鎖剤(C成分)を含む実施例4〜7は、金型温度90℃で成形可能で、成形品表面外観に優れ、耐熱性、耐加水分解性に優れた材料であった。
<実施例8〜9>
可塑剤(B−1成分)、末端封鎖剤(C−1成分)、酸化防止剤(D成分)を含む実施例8〜9は、実施例4に比べさらに高い耐加水分解性を有していた。
<実施例10〜14>
可塑剤(B−1成分)、末端封鎖剤(C−1成分)、酸化防止剤(D−1成分)と衝撃改質剤(E成分)を含む実施例10〜14は、金型温度90℃で成形可能で、成形品表面外観、耐加水分解性、耐熱性に優れるとともに、更に耐衝撃性にも優れた材料であった。
<実施例15>
可塑剤(B−1成分)、末端封鎖剤(C−1成分)、酸化防止剤(D−1成分)と無機充填剤(F成分)を含むことで、金型温度90℃で成形可能で、成形品表面外観、耐加水分解性に優れるとともに、更に高い耐熱性と耐衝撃性を兼ね備えた材料であった。
<実施例16>
可塑剤(B−1成分)、末端封鎖剤(C−1成分)、酸化防止剤(D−1成分)とハイドロタルサイト(G成分)を含むことで、金型温度90℃で成形可能で、成形品表面外観、耐熱性に優れるとともに、更に高い耐加水分解性を有した材料であった。
可塑剤(B成分)を含まない比較例1は、金型温度90℃で成形出来なかった。
<比較例2>
可塑剤(B成分)を多く含む比較例2は、可塑剤のガス化による成形品表面のガス転写痕が見られ、耐熱性も悪い結果となった。
<比較例3>
可塑剤(B’−1成分)は、可塑剤の分子量が低いためにガス化しやすく、成形品表面にガス転写痕が見られた。
<比較例4>
可塑剤(B’−2成分)は、可塑剤のR1部分のアルキル鎖長が長すぎるために、樹脂との馴染みが悪く、可塑化効果が悪いため、成形サイクルが長くなった。
<比較例5>
可塑剤(B’−3成分)は、可塑剤のR1部分のアルキル鎖長が長く、エチレングリコールの繰り返し数(n)が大きいために、樹脂との馴染みが悪く、可塑化効率が悪いため、成形サイクルが長くなった。また、全酸価も大きいため耐加水分解性も悪い結果となった。
Claims (12)
- (A)(A−1)主としてL−乳酸単位からなるポリ−L乳酸(A−1成分)および(A−2)主としてD−乳酸単位からなるポリ−D乳酸(A−2成分)を含有し、A−1成分とA−2成分との重量比が10:90〜90:10の範囲にあるポリ乳酸(A成分)100重量部に対し、下記一般式(1)で表される(B)可塑剤(B成分)を0.5〜10重量部含有する組成物。
(式中、R1は炭素数17〜22の直鎖もしくは分岐のアルキル基を表し、R2は炭素数1〜3のアルキル基を表し、nは5〜20の範囲であり、AOはエチレングリコール、プロピレングリコール、ブチレングリコールから選ばれる少なくとも一種を表し、単独でも共重合であっても良い。) - ポリ−L乳酸(A−1成分)はL−乳酸単位を90モル%以上含有し、ポリ−D乳酸(A−2成分)はD−乳酸単位を90モル%以上含有する請求項1に記載の組成物。
- ポリ乳酸(A成分)は、示差走査熱量計(DSC)測定の昇温過程における融解エンタルピーを用いて下記式(2)で表されるステレオコンプレックス結晶化度が80%以上である請求項1または2に記載の組成物。
(2)ステレオコンプレックス結晶化度=△Hms/(△Hms+△Hmh)×100
[但し、式(2)中、△Hmhと△Hmsは、それぞれ示差走査熱量計(DSC)の昇温過程において、190℃未満に現れる結晶融点の融解エンタルピー(△Hmh)、および190℃以上250℃未満に現れる結晶融点の融解エンタルピー(△Hms)である。] - 可塑剤(B成分)は全酸価が3mgKOH/g以下である請求項1〜3のいずれか1項に記載の組成物。
- ポリ乳酸(A成分)100重量部に対し、(C)エポキシ化合物、カルボジイミド化合物からなる群より選ばれる少なくとも一種の末端封鎖剤(C成分)0.01〜10重量部を含む請求項1〜4のいずれか1項に記載の組成物。
- ポリ乳酸(A成分)100重量部に対し、(D)ヒンダートフェノール系化合物、ホスファイト系化合物、ホスホナイト系化合物、およびチオエーテル系化合物からなる群より選ばれる少なくとも一種の酸化防止剤(D成分)0.01〜2重量部を含む請求項1〜5のいずれか1項に記載の組成物。
- ポリ乳酸(A成分)100重量部に対して、(E)衝撃改質剤(E成分)2〜100重量部を含む請求項1〜6のいずれか1項に記載の組成物。
- ポリ乳酸(A成分)100重量部に対して、(F)無機充填剤(F成分)0.1〜100重量部を含む請求項1〜7のいずれか1項に記載の組成物。
- ポリ乳酸(A成分)100重量部に対して、(G)ハイドロタルサイト(G成分)0.01〜0.3重量部を含む請求項1〜8のいずれか1項に記載の組成物。
- 請求項1〜9のいずれか1項に記載の組成物からなる成形品。
- 射出成形、熱成形、ブロー成形または発泡成形により成形した請求項10に記載の成形品。
- 自動車部品、電気・電子部品、電気機器外装部品、OA外装部品である請求項10または11に記載の成形品。
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