JP5348577B2 - 熱可塑性エラストマ樹脂組成物および成形体 - Google Patents
熱可塑性エラストマ樹脂組成物および成形体 Download PDFInfo
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- JP5348577B2 JP5348577B2 JP2006335286A JP2006335286A JP5348577B2 JP 5348577 B2 JP5348577 B2 JP 5348577B2 JP 2006335286 A JP2006335286 A JP 2006335286A JP 2006335286 A JP2006335286 A JP 2006335286A JP 5348577 B2 JP5348577 B2 JP 5348577B2
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- UHHKSVZZTYJVEG-UHFFFAOYSA-N oxepane Chemical compound C1CCCOCC1 UHHKSVZZTYJVEG-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical class C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
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- 229920005906 polyester polyol Polymers 0.000 description 1
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Description
前記グラフト共重合体(組成物)(B)のゴム質重合体がジエン系ゴム質重合体であること、
前記ポリエステルブロック共重合体(A)成分における高融点結晶性重合体セグメント(a1)が、ポリブチレンテレフタレート単位を主たる構成成分とするものであること、
前記ポリエステルブロック共重合体(A)成分における低融点セグメント(a2)が、ポリ(テトラメチレンオキシド)グリコール単位を主たる構成成分とするものであることが、いずれも好ましい条件として挙げられる。
ゴム質重合体の所定量M(g)にアセトンを加え、4時間還流した。この溶液を9000rpmで30分間遠心分離後、不溶分を濾過した。この不溶分を60℃で5時間減圧乾燥し、重量N(g)を測定し、グラフト率を次式で算出した。
グラフト率=100×(N−M×L)/(M×L)
ここで、Lはゴム質重合体中のゴムの含有率を表す。
ASTM D−2240にしたがって測定した。
JIS K7113にしたがって、引張破断強度と引張破断伸度を測定した。
ABS樹脂として、”トヨラック”タイプ500(東レ(株)製)を使用してJIS K7113で定められたJIS2号型ダンベル試験片を射出成形により作成し、この試験片を中央で半分の長さに切断し、その試験片の一方を、JIS2号型ダンベル試験片を成形するための金型内キャビティにセットした後、評価用エラストマ樹脂組成物を用いてシリンダー温度220℃、型温50℃で射出成形した。得られた成形品を室温にて1日放置した後、歪み速度20mm/分で引っ張って接合部分強度を測定し、ABS樹脂に対する接着力とした。
縦125mm、横70mm、厚さ2mmの角板を70℃の30%水酸化ナトリウム水溶液に3分間浸漬し、さらに70℃の20%塩酸水溶液に2分間浸漬した後、流水中で十分洗浄して粗表面化した試験片を得た。この粗表面化した試験片につき、以下に示す方法によりメッキ処理を施した。
1.センシタイジング:試験片を塩化第一スズ30g、塩酸(38%)60ccおよび水1000ccからなる溶液に25℃で2〜5分間浸漬。
2.水洗
3.アクチベーティング:試験片を塩化パラジウム0.1g、塩酸(38%)10ccおよび水1000ccからなる溶液に25℃で1〜3分間浸漬。
4.水洗
5.無電解銅メッキ:試験片を硫酸銅(5%水和物)10g、ホルマリン(37%)40cc、水酸化ナトリウム10g、ロッシエル塩20gおよび水1000ccからなる化学銅メッキ液(pH10.0〜11.5)に25〜30℃で10分間浸漬。
6.水洗
7.電気メッキ:試験片を濃硫酸50g、硫酸銅(5%水和物)200g、光沢剤(UBAC)4ccおよび水1000ccからなる酸性銅メッキ浴中におき、温度25〜30℃、電気密度4A/dm2の条件下に60分間電気メッキして厚み約60μmの銅メッキを形成した。
JIS2号ダンベル試験片をスーパーキセノンウェザーメーター(スガ試験機(株)製)内に設置し、キセノンランプ照射条件下で、63℃×102分、23℃×18分雨有りのサイクルにて100時間処理した後、表面外観を観察した。表面外観の判定としては良好なものを○、表面にひび割れなどの不良が観察されたものを×とした。
[ポリエステルブロック共重合体(A−1)の製造]
テレフタル酸50.5部、1,4−ブタンジオール43.8部および数平均分子量約1400のポリ(テトラメチレンオキシド)グリコール35.4部を、チタンテトラブトキシド0.04部とモノ−n−ブチル−モノヒドロキシスズオキサイド0.02部を共にヘリカルリボン型攪拌翼を備えた反応容器に仕込み、190〜225℃で3時間加熱し、反応水を系外に流出させながらエステル化反応を行った。反応混合物にテトラ−n−ブチルチタネート0.2部を追添加し、”イルガノックス”1098(チバガイギー社製ヒンダードフェノール系酸化防止剤)0.05部を添加した後、245℃に昇温し、次いで、50分かけて系内の圧力を27Paの減圧とし、その条件下で1時間50分重合を行った。得られたポリマを水中にストランド状で吐出し、カッティングによりペレットとした。
テレフタル酸59.3部、1,4−ブタンジオール51.4部および数平均分子量約1400のポリ(テトラメチレンオキシド)グリコール22.9部を、チタンテトラブトキシド0.04部とモノ−n−ブチル−モノヒドロキシスズオキサイド0.02部を共にヘリカルリボン型攪拌翼を備えた反応容器に仕込み、190〜225℃で3時間加熱し、反応水を系外に流出させながらエステル化反応を行った。反応混合物にテトラ−n−ブチルチタネート0.15部を追添加し、”イルガノックス”1098(チバガイギー社製ヒンダードフェノール系酸化防止剤)0.05部を添加した後、245℃に昇温し、次いで、50分かけて系内の圧力を27Paの減圧とし、その条件下で1時間50分重合を行った。得られたポリマを水中にストランド状で吐出し、カッティングによりペレットとした。
ポリブタジエンラテックス(ゴム粒子径0.25μm、ゲル含有率80%)60重量部(固形分換算)の存在下で、スチレン70%、アクリルニトリル20%、メタクリル酸10%からなる単量体混合物40重量部を4時間にわたって連続滴下して乳化重合した。得られたグラフト共重合体は硫酸マグネシウムで凝固し、苛性ソーダで中和、洗浄、濾過、乾燥してパウダー状のゴム質重合体を得た。本ゴム質重合体のグラフト率は36%であった。
ポリブタジエンラテックス60重量部(固形分換算)の存在下で、スチレン70%、アクリルニトリル30%からなる単量体混合物40重量部を4時間にわたって連続滴下して乳化重合した。得られた重合体は硫酸マグネシウムで凝固し、苛性ソーダで中和、洗浄、濾過、乾燥してパウダー状のゴム質重合体を得た。本ゴム質重合体のグラフト率は39%であった。
ポリブタジエンラテックス45重量部(固形分換算)の存在下で、スチレン70%、アクリルニトリル20%、メタクリル酸10%からなる単量体混合物55重量部を4時間にわたって連続滴下して乳化重合した。得られた重合体は硫酸マグネシウムで凝固し、苛性ソーダで中和、洗浄、濾過、乾燥してパウダー状のゴム質重合体を得た。本ゴム質重合体のグラフト率は38%であった。
下記実施例において、”トヨラック”タイプ100(東レ(株)製)を使用した。
参考例で得られたポリエステルブロック共重合体(A−1)、(A−2)に、グラフト共重合体(B−1)、(B−2)、(B−3)を、表1に示す配合比率(重量%)でV−ブレンダーを用いて混合し、直径45mmで3条ネジタイプのスクリューを有する2軸押出機を用いて220℃で溶融混練し、ペレット化した。
Claims (6)
- 主として結晶性芳香族ポリエステル単位からなる高融点結晶性重合体セグメント(a1)と、主として脂肪族ポリエーテル単位及び/又は脂肪族ポリエステル単位からなる低融点重合体セグメント(a2)とを主たる構成成分とするポリエステルブロック共重合体(A)55〜99重量%と、ゴム質重合体40〜85重量部の存在下に芳香族ビニル単量体50〜90wt%、シアン化ビニル単量体9〜50wt%、アクリル酸及び/またはメタクリル酸0.1〜20wt%からなる単量体混合物15〜60重量部(上記ゴム質重合体との総和が100重量部)をグラフト共重合してなるグラフト共重合体または該グラフト共重合体と残りの単量体が共重合したグラフト共重合体(組成物)(B)1〜45重量%とからなることを特徴とする熱可塑性エラストマ樹脂組成物。
- 前記ゴム質重合体がジエン系ゴム質重合体であることを特徴とする請求項1記載の熱可塑性エラストマ樹脂組成物。
- 前記ポリエステルブロック共重合体(A)成分における高融点結晶性重合体セグメント(a1)が、ポリブチレンテレフタレート単位を主たる構成成分とするものであることを特徴とする請求項1または2に記載の熱可塑性エラストマ樹脂組成物。
- 前記ポリエステルブロック共重合体(A)成分における低融点セグメント(a2)が、ポリ(テトラメチレンオキシド)グリコール単位を主たる構成成分とするものであることを特徴とする請求項1〜3のいずれか1項に記載の熱可塑性エラストマ樹脂組成物。
- 請求項1〜4のいずれか1項に記載の熱可塑性エラストマ樹脂組成物を成形したことを特徴とする成形体。
- 成形体の表面に、請求項1〜4以外の熱可塑性エラストマ樹脂組成物、金属膜、塗料から選択される1種以上が付着していることを特徴とする請求項5に記載の成形体。
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