JP2008133445A - 樹脂組成物およびそれからなる成形品 - Google Patents
樹脂組成物およびそれからなる成形品 Download PDFInfo
- Publication number
- JP2008133445A JP2008133445A JP2007271914A JP2007271914A JP2008133445A JP 2008133445 A JP2008133445 A JP 2008133445A JP 2007271914 A JP2007271914 A JP 2007271914A JP 2007271914 A JP2007271914 A JP 2007271914A JP 2008133445 A JP2008133445 A JP 2008133445A
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- Prior art keywords
- acid
- resin
- preferable
- oxazoline
- weight
- 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
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- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 61
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- 239000000178 monomer Substances 0.000 description 30
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- 230000009477 glass transition Effects 0.000 description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 25
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 19
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 8
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 8
- 238000006467 substitution reaction Methods 0.000 description 8
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
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- 229940022769 d- lactic acid Drugs 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 7
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- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
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- 238000005259 measurement Methods 0.000 description 7
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- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
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- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 6
- 239000004609 Impact Modifier Substances 0.000 description 6
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 6
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 6
- 125000004018 acid anhydride group Chemical group 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
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- 125000000524 functional group Chemical group 0.000 description 6
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 6
- 150000003949 imides Chemical class 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
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- 229910052717 sulfur Inorganic materials 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical group CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 5
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- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 5
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
本発明は、(A)ポリ乳酸樹脂、(B)メタクリル系樹脂および(C)屈折率が1.45〜1.50の範囲である熱可塑性樹脂を配合してなる、透明性および耐熱性に優れた樹脂組成物およびそれからなる成形品に関するものである。
【解決手段】
(A)ポリ乳酸樹脂、(B)メタクリル系樹脂および(C)屈折率が1.45〜1.50の範囲である熱可塑性樹脂を配合してなる樹脂組成物であり、前記(C)屈折率が1.45〜1.50の範囲である熱可塑性樹脂がセルロース系樹脂であることが好ましく、(A)ポリ乳酸樹脂と(B)メタクリル系樹脂の重量比が、70/30〜10/90であることがより好ましく、厚み1mmに成形したときにヘイズ10%以下である樹脂組成物とすることができる。
【選択図】 なし
Description
(1)(A)ポリ乳酸樹脂、(B)メタクリル系樹脂および(C)屈折率が1.45〜1.50の範囲である熱可塑性樹脂を配合してなる樹脂組成物、
(2)前記(C)屈折率が1.45〜1.50の範囲である熱可塑性樹脂がセルロース系樹脂である(1)に記載の樹脂組成物、
(3)(A)ポリ乳酸樹脂と(B)メタクリル系樹脂の重量比が、70/30〜10/90である(1)〜(2)のいずれかに記載の樹脂組成物、
(4)(A)ポリ乳酸樹脂および(B)メタクリル系樹脂の合計量と(C)屈折率が1.45〜1.50の範囲である熱可塑性樹脂の重量比が、99/1〜1/99である(1)〜(3)のいずれかに記載の樹脂組成物、
(5)厚み1mmに成形したときにヘイズ10%以下である(1)〜(4)のいずれかに記載の樹脂組成物、および
(6)(1)〜(5)のいずれかに記載の樹脂組成物からなる成形品、である。
(a)ガラス転移温度の差が10℃以上
(b)シンジオタクチシチーの差が3%以上
Λm =(λ/2)/sin(θm /2)
により計算することができる。
(c)屈折率が1.45〜1.50
(d)ガラス転移温度が30℃以下の構成成分を含む
(A)ポリ乳酸樹脂
(A−1)ポリL乳酸樹脂(D体1.2%、重量平均分子量20万、融点172℃)
(A−2)ポリL乳酸樹脂(D体1.2%、重量平均分子量16万、融点172℃)
(A−3)ポリ乳酸ステレオコンプレックス(重量平均分子量15万、融点210℃)。
(B)メタクリル系樹脂
(B−1)ポリメチルメタクリレート樹脂(住友化学工業製“スミペックス”MHF、重量平均分子量9.5万、分子量分布2.8、ガラス転移温度115℃、シンジオタクチシチー47%)
(B−2)ポリメチルメタクリレート樹脂(住友化学工業製“スミペックス”LG35、重量平均分子量10万、分子量分布3.0、ガラス転移温度90℃、シンジオタクチシチー39%)
(B−3)グルタル酸無水物単位含有メタクリル系樹脂。
(C)屈折率が1.45〜1.50の範囲である熱可塑性樹脂
(C−1)セルロースアセテートプロピオネート(イーストマンケミカル製“CAP”アセテート置換度0.1、プロピオネート置換度2.6、屈折率1.48)
(C−2)セルローストリアセテート(ダイセル化学工業製LT−35、アセテート置換度2.93、屈折率1.48)
(C−3)ポリ4−メチルペンテン−1(三井化学製“TPX”RT18、屈折率1.46)。
(D)相溶化剤
(D−1)有機アルミニウム化合物(アセトアルコキシアルミニウムジイソプロピレート、味の素ファインテクノ製“プレンアクト”AL−M)
(D−2)有機チタン化合物(チタンテトライソプロポキシド、東京化成工業製)。
(E)耐衝撃改良剤
(E−1)グラフト共重合体(コア:アクリル酸メチル/メタクリル酸メチル共重合体、シェル:アクリル酸メチル/メタクリル酸メチル共重合体、屈折率1.48、ゴム層のTg−34℃)[参考例3]
(E−2)クラレ製“パラフェイス”ME−120(コア:アクリル系重合体、シェル:メタクリル酸メチル共重合体、屈折率1.468、ゴム層のTg−50℃)
(E−3)カネカ製“カネエース”M511(コア:ブタジエン/スチレン重合体、シェル:メタクリル酸メチル重合体、屈折率1.518、ゴム層のTg−100℃)。
(F)反応性化合物
(F−1)グリシジル基含有アクリル系共重合体(日本油脂製“マープルーフ”G2050M、重量平均分子量21万、分子量分布2.2)
(F−2)ポリカルボジイミド(日清紡製“カルボジライト”HMV−8CA、重量平均分子量2000)。
(G)無機粒子
(G−1)12−アミノドデカン酸塩酸塩で交換されたモンモリロナイト。
L−ラクチド100重量部、エチレングリコール0.2重量部を撹拌装置のついた反応容器中で、窒素雰囲気下、170℃で均一に溶解させた後、オクチル酸錫0.01重量部を加えた後、2時間重合反応させた。重合反応終了後、反応物をクロロホルムに溶解させ、メタノール(クロロホルムの5倍量)中で撹拌しながら沈殿させ、モノマーを完全に除去して、重量平均分子量4万のポリ−L−乳酸(P11)を得た。P11の重量平均分子量は5万であった。
容量が20リットルで、バッフルおよびファウドラ型撹拌翼を備えたステンレス製オートクレーブに、メタクリル酸メチル/アクリルアミド共重合体(特公昭45−24151号公報記載)0.05部をイオン交換水165部に溶解した溶液を400rpmで撹拌し、系内を窒素ガスで置換した。次に、下記混合物質を反応系を撹拌しながら添加し、60℃に昇温し懸濁重合を開始した。
メタクリル酸 10重量部
メタクリル酸メチル 80重量部
スチレン 10重量部
t−ドデシルメルカプタン 0.3重量部
2,2’−アゾビスイソブチロニトリル 0.4重量部。
メタクリル酸単位:0.5重量%
メタクリル酸メチル単位:77.5重量%
グルタル酸無水物単位:13.0重量%
スチレン単位:9.0重量%。
還流冷却器付き反応容器に、脱イオン水300重量部、ステアリン酸ナトリウム1.0重量部およびN−ラウロイルザルコシン酸ナトリウム0.1重量部を仕込み、70℃で30分間撹拌した後、過硫酸カリウム0.01重量部を添加し、窒素雰囲気下で撹拌後、メタクリル酸メチル50重量部、アクリル酸メチル2重量部およびメタクリル酸アリル0.15重量部からなる混合物を60分かけて連続的に添加し、80℃で60分間保持して、コア層重合体を得た。次いで、過硫酸カリウム0.01重量部を添加した後、アクリル酸ブチル58重量部、スチレン12重量部およびメタクリル酸アリル1重量部からなる混合物を60分かけて連続的に添加し、70℃で30分間保持して、シェル層(第2層)を重合させた。次いで、過硫酸カリウム0.01重量部を添加した後、メタクリル酸メチル29重量部およびアクリル酸メチル1重量部からなる混合物を60分かけて連続的に添加し、70℃で60分間保持して、シェル層(第3層)を重合させ、グラフト共重合体を作成した。このラテックスを硫酸で凝固し、苛性ソーダで中和した後、50℃温水で水洗脱水を3回繰り返し、固形分を80℃12時間乾燥して、3層構造の多層構造重合体(E−1)の粉体を得た。E−1に関し、屈折率は1.48、ゴム層のTgは−34℃であった。
Na型モンモリロナイト(クニミネ工業:“クニピアF”、陽イオン交換容量120m当量/100g)100gを温水10リットルに攪拌分散し、ここに12−アミノドデカン酸塩酸塩30.2g(陽イオン交換容量と等量)を溶解させた温水2Lを添加して1時間攪拌し、生じた沈殿の濾別、温水洗浄を3回行い、得られた固体を80℃で真空乾燥することで、有機変性層状珪酸塩である12−アミノドデカン酸塩酸塩で交換されたモンモリロナイト(G−1)を得た。
150℃でプレス成形し、厚さ0.5mmのシートとした後、5mm×20mmの大きさの試験片を切り出し、アッベ屈折計(アタゴ製DR−M2)によって、23℃、589nm波長における屈折率を測定した。
ゲルパーミエーションクロマトグラフィー(GPC)により測定した標準PMMA換算の重量平均分子量の値である。溶媒にヘキサフルオロイソプロパノールを用い、流速0.5mL/minとし、試料濃度1mg/mLの溶液を0.1mL注入して測定した。
50m×50m×1mmおよび3mmの成形品を用いて、日本電色工業製ヘイズメーターNDH−300Aを用いて、JIS−K7105に従い、ヘイズを測定した。
127mm×12.7mm×3mmの短冊状成形品を用いて、ASTM D648に従い、荷重たわみ温度(荷重0.45MPa)を測定した。
ASTM1号ダンベル成形品を用いて、ASTM D638に従い、引張試験を行った。
3mm厚ノッチ付き成形品を用いて、ASTM D256に従い、アイゾット衝撃強度を測定した。
ASTM1号ダンベル成形品を、70℃、相対湿度95%の恒温恒湿槽中で100時間処理した後、引張強度を測定し引張強度保持率を求めた。引張強度保持率が大きいほど、耐加水分解性に優れると言える。
表1、表2に示すように原料を配合し、30mmφ二軸押出機を用いて、シリンダー温度220℃で溶融混練し、ペレット状の樹脂組成物を得た。
表3に示すように原料を配合し、30mmφ二軸押出機を用いて、シリンダー温度220℃で溶融混練し、ペレット状の樹脂組成物を得た。
表4に示すように原料を配合し、30mmφ二軸押出機を用いて、シリンダー温度220℃で溶融混練し、ペレット状の樹脂組成物を得た。
Claims (6)
- (A)ポリ乳酸樹脂、(B)メタクリル系樹脂および(C)屈折率が1.45〜1.50の範囲である熱可塑性樹脂を配合してなる樹脂組成物。
- 前記(C)屈折率が1.45〜1.50の範囲である熱可塑性樹脂がセルロース系樹脂である請求項1に記載の樹脂組成物。
- (A)ポリ乳酸樹脂と(B)メタクリル系樹脂の重量比が、70/30〜10/90である請求項1〜2のいずれか1項に記載の樹脂組成物。
- (A)ポリ乳酸樹脂および(B)メタクリル系樹脂の合計量と(C)屈折率が1.45〜1.50の範囲である熱可塑性樹脂の重量比が、99/1〜1/99である請求項1〜3のいずれか1項に記載の樹脂組成物。
- 厚み1mmに成形したときにヘイズ10%以下である請求項1〜4のいずれか1項に記載の樹脂組成物。
- 請求項1〜5のいずれか1項に記載の樹脂組成物からなる成形品。
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JP2019059829A (ja) * | 2017-09-26 | 2019-04-18 | 富士ゼロックス株式会社 | 樹脂組成物および樹脂成形体 |
JP2019059828A (ja) * | 2017-09-26 | 2019-04-18 | 富士ゼロックス株式会社 | 樹脂組成物およびその樹脂成形体 |
WO2019064624A1 (ja) * | 2017-09-26 | 2019-04-04 | 富士ゼロックス株式会社 | 樹脂組成物および樹脂成形体 |
US10584232B2 (en) * | 2017-09-26 | 2020-03-10 | Fuji Xerox Co., Ltd. | Resin composition and resin molded article thereof |
CN109553807B (zh) * | 2017-09-26 | 2022-09-13 | 伊士曼化工公司 | 树脂组合物及其树脂成型体 |
CN109553808B (zh) * | 2017-09-26 | 2022-09-13 | 伊士曼化工公司 | 树脂组合物及其树脂成型体 |
WO2019064626A1 (ja) * | 2017-09-26 | 2019-04-04 | 富士ゼロックス株式会社 | 樹脂組成物および樹脂成形体 |
CN109553807A (zh) * | 2017-09-26 | 2019-04-02 | 富士施乐株式会社 | 树脂组合物及其树脂成型体 |
US20190092929A1 (en) * | 2017-09-26 | 2019-03-28 | Fuji Xerox Co., Ltd. | Resin composition and resin molded article thereof |
US20190092930A1 (en) * | 2017-09-26 | 2019-03-28 | Fuji Xerox Co., Ltd. | Resin composition and resin molded body thereof |
WO2019171610A1 (ja) * | 2018-03-06 | 2019-09-12 | 富士ゼロックス株式会社 | 樹脂組成物および樹脂成形体 |
WO2019171611A1 (ja) * | 2018-03-06 | 2019-09-12 | 富士ゼロックス株式会社 | 樹脂組成物および樹脂成形体 |
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