JP2013047316A - ポリ乳酸樹脂組成物、成形品の製造方法、成形品、及び電子機器用ホルダー - Google Patents
ポリ乳酸樹脂組成物、成形品の製造方法、成形品、及び電子機器用ホルダー Download PDFInfo
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- JP2013047316A JP2013047316A JP2012025360A JP2012025360A JP2013047316A JP 2013047316 A JP2013047316 A JP 2013047316A JP 2012025360 A JP2012025360 A JP 2012025360A JP 2012025360 A JP2012025360 A JP 2012025360A JP 2013047316 A JP2013047316 A JP 2013047316A
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- Prior art keywords
- polylactic acid
- resin composition
- acid resin
- mass
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- Prior art date
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Abstract
【解決手段】本発明に係るポリ乳酸樹脂組成物は、ポリ乳酸と、ポリ乳酸以外の熱可塑性樹脂とを含有する。前記ポリ乳酸樹脂組成物中の前記ポリ乳酸の割合は4質量%以上10質量%未満の範囲である。前記ポリ乳酸の分散度が4.0以下である。
【選択図】なし
Description
本実施形態によるポリ乳酸樹脂組成物は、ポリ乳酸及びポリ乳酸以外の熱可塑性樹脂を含有する。更に、ポリ乳酸樹脂組成物中のポリ乳酸の割合は4質量%以上10質量%未満の範囲、好ましくは4〜7質量%の範囲であり、且つ、このポリ乳酸の分散度が4.0以下である。このポリ乳酸の重量平均分子量は7.0万以上であることが好ましい。
ポリ乳酸樹脂組成物が含有するポリ乳酸の重量平均分子量(Mw)は7.0万以上であることが好ましく、この場合、ポリ乳酸樹脂組成物の流動性と成形品の耐久性が射出成形材料として更に適したものになる。このポリ乳酸の重量平均分子量(Mw)と数平均分子量(Mn)との比である分散度(Mw/Mn)は4.0以下である。更に、ポリ乳酸樹脂組成物中のポリ乳酸の含有量は4質量%以上10質量%未満の範囲であり、好ましくは4〜7質量%の範囲である。
ポリ乳酸樹脂組成物中のポリ乳酸以外の熱可塑性樹脂は、ABS樹脂(アクリロニトリル・ブタジエン・スチレン共重合樹脂)、PC樹脂(ポリカーボネート樹脂)、PMMA樹脂(ポリメチルメタクリレート樹脂)、PP樹脂(ポリプロピレン樹脂)、LDPE樹脂(低密度ポリエチレン樹脂)のうち、少なくとも一種を含有することが好ましい。
ポリ乳酸樹脂組成物がABS樹脂を含有することで、成形品の耐久性、寸法安定性、耐衝撃性、耐熱性、並びにポリ乳酸樹脂組成物の成形時の成形性が高くなる。また、ABS樹脂をポリ乳酸で代替するという観点からは、ポリ乳酸樹脂組成物中のABS樹脂の含有量が低減し、それに伴ってABS樹脂中のブタジエン単位における不飽和二重結合の割合も低減する。このため、成形品の耐光性が向上することも期待される。
ポリ乳酸樹脂組成物がポリカーボネート樹脂を含有する場合、成形品の耐熱性及び耐衝撃性が向上する。
比粘度(ηSP)=(t−t0)/t …(a)
[t0は塩化メチレンの落下秒数、tは試料溶液の落下秒数]
ηSP/c=[η]+0.45×[η]2c(但し[η]は極限粘度) …(b)
[η]=1.23×10−4M0.83 …(c)
c=0.7 …(d)
(3)PMMA樹脂
ポリ乳酸樹脂組成物がポリメタクリル酸メチル樹脂(PMMA樹脂)を含有すると、成形品の寸法安定性、耐衝撃性、耐熱性が向上する。また、成形品の透明性が高くなると共に、成形品の耐候性が向上する。
ポリ乳酸樹脂組成物がポリプロピレン樹脂を含有すると、成形品の比重が低くなり、成形品の軽量化が期待できる。
ポリ乳酸樹脂組成物が低密度ポリエチレン樹脂を含有すると、成形品の電気的絶縁特性が良好となる。
ポリ乳酸樹脂組成物は、ポリカルボジイミド化合物やモノカルボジイミド化合物等のカルボジイミド化合物を含有することも好ましい。この場合、これらの化合物が、ポリ乳酸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発揮し、これにより成形品の高温高湿環境下での耐久性が更に向上する。
ポリ乳酸樹脂組成物は、メタクリル酸アルキルとアクリル酸アルキルとの共重合体を含有することも好ましい。この場合、成形品の耐衝撃性等の機械的特性が更に改善される。
ポリ乳酸樹脂組成物は、更にポリブチレンアジペートテレフタレートを含有することが好ましい。ポリブチレンアジペートテレフタレートは1,4−ブタンジオールとアジピン酸とテレフタル酸の共重合体であり、その具体例としてはBASF社製の商品名エコフレックスが挙げられる。
ポリ乳酸樹脂組成物がコアシェルゴムを含有することも好ましい。この場合、成形品の耐衝撃性等の機械的特性が更に向上する。コアシェルゴムは多層構造の重合体であって、重合体で構成される最内層(コア層)と、コア層を覆い且つコア層とは異種の重合体から構成される1以上の層(シェル層)とを有する。コアシェルゴムとしては、例えばゴム状重合体の存在下で、スチレン系単量体、シアン化ビニル系単量体などの単量体が重合してなる樹脂が挙げられる。
(X)ポリオルガノシロキサン粒子;
(Y)第1のビニル系単量体;
(Z)第2のビニル系単量体。
(Y−1)多官能性単量体100〜50質量%;
(Y−2)その他の共重合可能な単量体0〜50質量%。
ポリ乳酸樹脂組成物が、植物由来原料を含む原料から合成されたPET(植物由来PET)を含有することも好ましい。このような植物由来PETは、例えばテレフタル酸と、サトウキビなどの植物由来のエタノール(いわゆるバイオエタノール)から製造されたモノエチレングリコール(バイオモノエチレングリコール)を含むモノエチレングリコールとが、脱水縮合することで合成される。
ポリ乳酸樹脂組成物中には、上記以外の種々の熱可塑性樹脂が含まれてもよい。例えばポリ乳酸樹脂組成物が、ポリエチレンテレフタレート樹脂(PET樹脂)、ポリブチレンテレフタレート樹脂(PBT樹脂)、シクロヘキサンジメタノール共重合ポリエチレンテレフタレート樹脂(いわゆるPET−G樹脂)、ポリエチレンナフタレート樹脂、ポリブチレンナフタレート樹脂などの芳香族ポリエステル樹脂;環状ポリオレフィン樹脂;ポリカプロラクトン樹脂;ポリフッ化ビニリデン樹脂に代表される熱可塑性フッ素樹脂;ポリエチレン樹脂、エチレン−(α−オレフィン)共重合体樹脂などを含有してもよい。ポリ乳酸樹脂組成物中には前記のような樹脂が一種のみ含まれていてもよく、二種以上が含まれていてもよい。このような種々の熱可塑性樹脂により、成形品の耐衝撃性が更に向上し得る。これらの熱可塑性樹脂が使用される場合、その含有量は、ポリ乳酸樹脂組成物に対して3〜12質量%の範囲であることが好ましい。
ポリ乳酸樹脂組成物は、酸化防止剤を含有することが好ましい。この場合、成形品中のポリ乳酸の加水分解が更に抑制されることで、成形品の耐久性が更に向上する。酸化防止剤としては、2,2−メチレンビス−(4−メチル−6−t−ブチルフェノール)、3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロパン酸オクタデシル、及びビス(3−t−ブチル−4−ヒドロキシ−5−メチル−フェニル)ジシクロペンタジエンからなる群から選択される少なくとも一種が使用されることが好ましい。
ポリ乳酸樹脂組成物は充填材を含有してもよい。充填材としては、例えば、タルク、ワラストナイト、マイカ、クレー、モンモンリロナイト、スメクタイト、カオリン、ゼオライト(珪酸アルミニウム)、ゼオライトを酸処理及び加熱処理して得られる無水非晶質珪酸アルミニウムなどの無機充填材が挙げられる。特にタルク、ワラストナイトが好ましい。これらの充填剤のうち、一種のみが用いられても、二種以上が併用されてもよい。
ポリ乳酸樹脂組成物は、更に難燃剤を含有することも好ましい。この場合、成形品の難燃性が向上する。難燃剤としては、Br系難燃剤、有機リン系難燃剤、酸化アンチモンが用いられることが好ましい。ポリ乳酸樹脂組成物中のBr系難燃剤の含有量は、1〜30質量%であることが好ましく、有機リン系難燃剤の含有量は、1〜30質量%の範囲であることが好ましく、3〜12質量%の範囲であれば更に好ましい。また、酸化アンチモンの含有量は、0.1〜3質量%であることが好ましい。このような範囲において、ポリ乳酸樹脂組成物から形成される成形品の難燃性が向上する。
ポリ乳酸樹脂組成物は、更に含フッ素滴下防止剤を含有することも好ましい。含フッ素滴下防止剤は、成形品の燃焼時の溶融滴下を防止して難燃性を更に向上させるために使用される。
(1)PTFEの水性分散液と有機重合体の水性分散液または溶液とを混合し共沈殿を行い共凝集混合物を得る方法(特開昭60−258263号公報、特開昭63−154744号公報などに記載された方法);
(2)PTFEの水性分散液と乾燥した有機重合体粒子とを混合する方法(特開平4−272957号公報に記載された方法);
(3)PTFEの水性分散液と有機重合体粒子溶液を均一に混合し、この混合物からそれぞれの媒体を同時に除去する方法(特開平06−220210号公報、特開平08−188653号公報などに記載された方法);
(4)PTFEの水性分散液中で有機重合体を形成する単量体を重合する方法(特開平9−95583号公報に記載された方法);
(5)PTFEの水性分散液と有機重合体分散液を均一に混合後、更に該混合分散液中でビニル系単量体を重合し、その後混合物を得る方法(特開平11−29679号などに記載された方法)等が、挙げられる。
ポリ乳酸樹脂組成物は、本発明の目的に反せず、その効果を損なわない限りにおいて、必要に応じて、安定剤、紫外線吸収剤、滑剤、離型剤、可塑剤、帯電防止剤、無機および有機系抗菌剤等の、公知の添加剤を含有してもよい。これらの添加剤は、ポリ乳酸樹脂組成物の混練時に加えられても、成形時等に加えられてもよい。
ポリ乳酸樹脂組成物は、上記のようなポリ乳酸樹脂組成物の原料が任意の方法で混合、混練されることによって調製される。前記混合、混練にあたっては、例えば、二軸押出機、バンバリーミキサー、加熱ロール等が用いられるが、中でも二軸押出機による溶融混練が好ましい。
Lラクチド及びDラクチドの混合物を、金属重合触媒及びアルコールの存在下で、窒素雰囲気下、撹拌翼を備える反応機内で加熱することで反応させた後、反応機内を減圧して混合物中に残存するラクチドを除去した。更にこの混合物をチップ化することで、ポリ乳酸を調製した。このポリ乳酸の調製にあたり、LラクチドとDラクチドの配合比を変更することで、後述する組成を有するポリ乳酸D及びポリ乳酸Fを調製した。
Dラクチド(株式会社武蔵野化学研究所製、光学純度99%以上)100重量部に対し、オクチル酸スズを0.006重量部、オクタデシルアルコール0.37重量部を加え、窒素雰囲気下、撹拌翼のついた反応機にて、190℃で2時間反応し、その後、エステル交換抑制剤(ジヘキシルホスホノエチルアセテートDHPA)0.01重量部を加えた後、減圧して残存するラクチドを除去し、チップ化し、ポリ−D−乳酸を得た。得られたポリ−D−乳酸の重量平均分子量は13万、ガラス転移点(Tg)60℃、融点は170℃であった。
各実施例及び比較例について、下記表に示す成分を用い、樹脂成分については予め乾燥処理を施した上で、これらの成分をタンブラーで10分間混合した。得られた混合物を二軸押出機で、ダイス付近温度190℃、投入口付近温度200℃の条件で押し出してストランドを得た。
各実施例及び比較例につき、樹脂組成物の射出成形時に一点ゲートの金型を用い、成形品の寸法を60mm×60mm×2mmとした。この場合の金型への樹脂組成物の射出後、金型から成形品を変形が生じることなく取り出すことが可能となるまでに要した保持時間(冷却時間)を測定し、これを成形サイクルの指標とした。
各実施例及び比較例につき、樹脂組成物の射出成形時に1点ゲートの金型を用い、成形品の寸法を60mm×60mm×2mmとした。各実施例及び比較例において100個のサンプルについて試験をおこなった。
各実施例において、組成物の調製時にカーボンブラック(三菱化学株式会社製のカーボンブラックMA600B)を、下記表に示される原料成分の総量100質量部に対して1質量部の割合で配合した。
各実施例及び比較例で得られた成形品のノッチ付きのシャルピー衝撃値を、ISO 179に従って測定した。
各実施例及び比較例における成形品の荷重たわみ温度を、ISO 75−1及び75−2に従って測定した。測定荷重は0.45MPaとした。
各実施例及び比較例で得られた成形品を60℃、95%RHの雰囲気下に3000時間曝露した後、この成形品の引張強度を、ISO 179に従って測定した。曝露処理が施される前の成形品の引張強度に対する、曝露処理が施された後の成形品の引張強度の比率(引張強度の保持率)を導出し、これを耐久性の指標とした。
成形品を80℃の雰囲気下に48時間曝露する処理を施した。処理前の成形品と処理後の成形品の外観を目視で観察して比較した。
成形品に対し、UL94に従った燃焼試験を実施することで、難燃性のクラスを評価した。下記表に試験に供した成形品の厚み、並びに難燃性のクラスを示す。
成形品を80℃の雰囲気下に48時間曝露する処理を施した。処理前の成形品の寸法(a)及び処理後の成形品の寸法(b)から、次の式により成形収縮率を算出した。
[評価結果]
以上の評価試験の結果を、各実施例及び比較例における配合組成と共に下記表に示す。
・ポリ乳酸A:Nature Works LLC社製、商品名NatureWorks3001D、D−乳酸単位の割合1.5モル%、重量平均分子量6.4万、数平均分子量2.6万、分散度2.5。
・ポリ乳酸B:Nature Works LLC社製、商品名NatureWorks4032D、D−乳酸単位の割合1.9モル%。
・ポリ乳酸C:Nature Works LLC社製、商品名NatureWorks4060D、D−乳酸単位の割合11.5モル%、重量平均分子量8.6万、数平均分子量2.1万、分散度4.1。
・ポリ乳酸D:製造例1で得られたポリ乳酸、D−乳酸単位の割合1.9モル%、重量平均分子量7.5万、数平均分子量3.1万、分散度2.4、ISO ASTM D1238に規定されるメルトフローレート(190℃ 2.16kg)5.0g/10分。
・ポリ乳酸E:製造例2で得られたステレオコンプレックス型ポリ乳酸、重量平均分子量9.8万、数平均分子量3.6万、分散度2.7。
・ポリ乳酸F:製造例1で得られたポリ乳酸、L−乳酸単位の割合99.7モル%以上。
・植物由来PET:豊田通商株式会社販売、商品名EastPET PW1、植物由来MEG含有率5〜30%。
・PBAT:ポリブチレンアジペートテレフタレート。
・ABS樹脂A:アクリロニトリル単位割合20.5質量%、スチレン単位割合69質量%、ブタジエン単位割合10.5質量%、バルク重合による合成品、平均粒径0.46μm、ISO 1133に規定されるメルトフローレート(220℃ 10kg)が32g/10分、ISO179に規定されるシャルピー衝撃強度(ノッチ有)が14kJ/m2。
・ABS樹脂B:アクリロニトリル単位割合22質量%、スチレン単位割合58質量%、ブタジエン単位割合18質量%、乳化重合による合成品、平均粒径0.30μm、ISO 1133に規定されるメルトフローレート(220℃ 10kg)が29g/10分、ISO179に規定されるシャルピー衝撃強度(ノッチ有)が21kJ/m2。
・ABS樹脂C:アクリロトリル単位割合24質量%、スチレン単位割合62質量%、ブタジエン単位割合14.5質量%、乳化重合による合成品、平均粒径0.30μm、ISO 1133に規定されるメルトフローレート(220℃ 10kg)が16g/10分、ISO179に規定されるシャルピー衝撃強度(ノッチ有)が15kJ/m2。
・リサイクルABS樹脂A:家電製品の廃棄物から回収したABS樹脂。
・リサイクルABS樹脂B:ABS樹脂A(50質量%)とリサイクルABS樹脂A(50質量%)との混合物。
・難燃ABS樹脂A:アクリロニトリル単位割合15質量%、スチレン単位割合43質量%、ブタジエン単位割合15質量%、テトラブロモビスフェノールA17%質量%、酸化アンチモン6%質量%、乳化およびバルク重合による合成品、平均粒径0.10および0.30μm。
・難燃ABS樹脂B:ダイセルポリマー株式会社製、VF512、燃焼性UL−94 1.5mm厚みでV−2、ISO 1133に規定されるメルトフローレート(220℃ 10kg)が35g/10分、ISO179に規定されるシャルピー衝撃強度(ノッチ有)が18kJ/m2。
・難燃ABS樹脂C:ダイセルポリマー株式会社製、VF790、燃焼性UL−94 1.7mm厚みでV−2、ISO 1133に規定されるメルトフローレート(220℃ 10kg)が26g/10分、ISO179に規定されるシャルピー衝撃強度(ノッチ有)が20kJ/m2。
・ポリカーボネートABS樹脂:東レ株式会社製、品番PX10。
・ポリカーボネート樹脂:ISO ASTM D1238に規定されるメルトフローレート(300℃ 1.2kg)22g/10分、ISO 306に規定される荷重たわみ温度128℃。
・PMMA1:アクリルポリメチルメタクリレート、ISO ASTM D1238に規定されるメルトフローレート(230℃ 3.8kg)16g/10分、ISO 306に規定される荷重たわみ温度78℃。
・PMMA2:アクリルポリメチルメタクリレート、ISO ASTM D1238に規定されるメルトフローレート(230℃ 3.8kg)1.8g/10分、ISO 306に規定される荷重たわみ温度87℃。
・ポリプロピレン樹脂:プライムポリマー株式会社、品番J−466HP。
・低密度ポリエチレン樹脂:旭化成ケミカルズ株式会社、品番サンテックLD。
・カルボジイミド化合物A:イソシアネート基を有するカルボジイミド化合物、ポリ(4,4’−ジシクロヘキシルメタンカルボジイミド)、カルボジイミド当量248、カルボジイミド基:イソシアネート基のモル比15:2、日清紡ケミカル株式会社製 LA−1。
・カルボジイミド化合物B:イソシアネート基を有さないカルボジイミド化合物、カルボジイミド当量262、日清紡ケミカル株式会社製、HMV−15CA。
・エラストマー:メタクリル酸アルキルとアクリル酸アルキルとの共重合体、三菱レイヨン株式会社製の商品名メタブレンC223A。
・有機過酸化物:日本油脂株式会社製の商品名パーヘキサ25B。
Claims (24)
- ポリ乳酸と、ポリ乳酸以外の熱可塑性樹脂とを含有し、
前記ポリ乳酸の割合が4質量%以上10質量%未満の範囲であり、
前記ポリ乳酸の分散度が4.0以下であるポリ乳酸樹脂組成物。 - 前記ポリ乳酸の重量平均分子量が7.0万以上である請求項1に記載のポリ乳酸樹脂組成物。
- 前記ポリ乳酸の割合が4〜7質量%の範囲である請求項1又は2に記載のポリ乳酸樹脂組成物。
- 前記熱可塑性樹脂がABS樹脂を含有する請求項1乃至3のいずれか一項に記載のポリ乳酸樹脂組成物。
- 前記ABS樹脂が、使用済みの製品から再生されたABS樹脂を含有する請求項4に記載のポリ乳酸樹脂組成物。
- 前記ABS樹脂が、難燃ABS樹脂を含有する請求項4又は5に記載のポリ乳酸樹脂組成物。
- ポリメタクリル酸メチル樹脂を更に含有する請求項4乃至6のいずれか一項に記載のポリ乳酸樹脂組成物。
- 前記ABS樹脂の平均粒径が0.3μm以下である請求項4乃至7のいずれか一項に記載のポリ乳酸樹脂組成物。
- 前記ABS樹脂のISO 1133に規定されるメルトフローレート(220℃ 10kg)が15〜35g/10分、ISO179に規定されるシャルピー衝撃強度(ノッチ有)が10〜30KJ/m2である請求項4乃至8のいずれか以降に記載のポリ乳酸樹脂組成物。
- ポリカーボネート樹脂を更に含有する請求項4乃至9のいずれか一項に記載のポリ乳酸樹脂組成物。
- 前記熱可塑性樹脂がポリカーボネート樹脂を含有する請求項1乃至3のいずれか一項に記載のポリ乳酸樹脂組成物。
- 前記熱可塑性樹脂がポリメチルメタクリレート樹脂を含有する請求項1乃至3のいずれか一項に記載のポリ乳酸樹脂組成物。
- 前記熱可塑性樹脂がポリプロピレン樹脂を含有する請求項1乃至3のいずれか一項に記載のポリ乳酸樹脂組成物。
- 前記熱可塑性樹脂が低密度ポリエチレン樹脂を含有する請求項1乃至3のいずれか一項に記載のポリ乳酸樹脂組成物。
- ポリブチレンアジペートテレフタレート及び有機過酸化物を更に含有する請求項1乃至14のいずれか一項に記載のポリ乳酸樹脂組成物。
- メタクリル酸アルキルとアクリル酸アルキルとの共重合体を更に含有する請求項1乃至15のいずれか一項に記載のポリ乳酸樹脂組成物。
- カルボジイミド化合物を更に含有する請求項1乃至16のいずれか一項に記載のポリ乳酸樹脂組成物。
- 前記カルボジイミド化合物が、イソシアネート基を有さない請求項17に記載のポリ乳酸樹脂組成物。
- コアシェルゴムを更に含有する請求項1乃至18のいずれか一項に記載のポリ乳酸樹脂組成物。
- 60℃95%RHの雰囲気下3000時間曝露される場合の引張強度の保持率が80%以上である成形品が形成される請求項1乃至19のいずれか一項に記載のポリ乳酸樹脂組成物。
- 請求項1乃至20のいずれか一項に記載のポリ乳酸樹脂組成物を準備し、前記ポリ乳酸樹脂組成物を成形する成形品の製造方法。
- 請求項1乃至21のいずれか一項に記載のポリ乳酸樹脂組成物を成形することにより形成される成形品。
- 60℃95%RHの雰囲気下3000時間曝露される場合の引張強度の保持率が80%以上である請求項22に記載の成形品。
- 請求項4乃至10のいずれか一項に記載のポリ乳酸樹脂組成物を成形することにより形成される電子機器用ホルダー。
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JP2016199654A (ja) * | 2015-04-09 | 2016-12-01 | 東洋スチレン株式会社 | スチレン系樹脂組成物及び成形体 |
CN117603567A (zh) * | 2023-12-18 | 2024-02-27 | 广州洛民塑料有限公司 | 一种新型可降解塑料折叠箩及其制造方法 |
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