JP7497179B2 - 耐衝撃性改良剤、これを含む耐衝撃性改良剤組成物、これらを含む合成樹脂組成物、およびその成形体 - Google Patents
耐衝撃性改良剤、これを含む耐衝撃性改良剤組成物、これらを含む合成樹脂組成物、およびその成形体 Download PDFInfo
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- JP7497179B2 JP7497179B2 JP2020049494A JP2020049494A JP7497179B2 JP 7497179 B2 JP7497179 B2 JP 7497179B2 JP 2020049494 A JP2020049494 A JP 2020049494A JP 2020049494 A JP2020049494 A JP 2020049494A JP 7497179 B2 JP7497179 B2 JP 7497179B2
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- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- RLMGYIOTPQVQJR-UHFFFAOYSA-N cyclohexane-1,3-diol Chemical compound OC1CCCC(O)C1 RLMGYIOTPQVQJR-UHFFFAOYSA-N 0.000 description 1
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- VZRUGPJUVWRHKM-UHFFFAOYSA-N dibutylhexamethylenediamine Chemical compound CCCCNCCCCCCNCCCC VZRUGPJUVWRHKM-UHFFFAOYSA-N 0.000 description 1
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- ZGWZLZBHNLDZOW-UHFFFAOYSA-N diethyl-(1,3,4-trimethylimidazol-2-ylidene)azanium Chemical compound CCN(CC)C=1N(C)C(C)=C[N+]=1C ZGWZLZBHNLDZOW-UHFFFAOYSA-N 0.000 description 1
- ZCGNNESZWJPBLW-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite 2-[2-(2-hydroxyphenyl)propan-2-yl]-3,4,5,6-tetra(tridecyl)phenol Chemical compound OP(O)OP(O)O.CCCCCCCCCCCCCC1=C(CCCCCCCCCCCCC)C(CCCCCCCCCCCCC)=C(O)C(C(C)(C)C=2C(=CC=CC=2)O)=C1CCCCCCCCCCCCC ZCGNNESZWJPBLW-UHFFFAOYSA-N 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- MFUGKPWEUBVBNA-UHFFFAOYSA-L dilithium;dibenzoate Chemical compound [Li+].[Li+].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 MFUGKPWEUBVBNA-UHFFFAOYSA-L 0.000 description 1
- VVOJOQPHGMSAAN-UHFFFAOYSA-L dilithium;dodecyl phosphate Chemical compound [Li+].[Li+].CCCCCCCCCCCCOP([O-])([O-])=O VVOJOQPHGMSAAN-UHFFFAOYSA-L 0.000 description 1
- RCRBCNZJGBTYDI-UHFFFAOYSA-L dilithium;terephthalate Chemical compound [Li+].[Li+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 RCRBCNZJGBTYDI-UHFFFAOYSA-L 0.000 description 1
- JJQMZTMEQGCDAA-UHFFFAOYSA-N dimethyl-(1,3,4-trimethylimidazol-2-ylidene)azanium Chemical compound CN(C)C=1N(C)C(C)=C[N+]=1C JJQMZTMEQGCDAA-UHFFFAOYSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-L dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [O-]P([O-])(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-L 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- QNFQYLRYCQTBEP-UHFFFAOYSA-L dipotassium;dibenzoate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 QNFQYLRYCQTBEP-UHFFFAOYSA-L 0.000 description 1
- GWTCIAGIKURVBJ-UHFFFAOYSA-L dipotassium;dodecyl phosphate Chemical compound [K+].[K+].CCCCCCCCCCCCOP([O-])([O-])=O GWTCIAGIKURVBJ-UHFFFAOYSA-L 0.000 description 1
- LPZZAIMVFFLHQU-UHFFFAOYSA-L dipotassium;octyl phosphate Chemical compound [K+].[K+].CCCCCCCCOP([O-])([O-])=O LPZZAIMVFFLHQU-UHFFFAOYSA-L 0.000 description 1
- LRUDDHYVRFQYCN-UHFFFAOYSA-L dipotassium;terephthalate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 LRUDDHYVRFQYCN-UHFFFAOYSA-L 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
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- SPUXJWDKFVXXBI-UHFFFAOYSA-N tris(2-tert-butylphenyl) phosphate Chemical compound CC(C)(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)(C)C)OC1=CC=CC=C1C(C)(C)C SPUXJWDKFVXXBI-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- SGKKYCDALBXNCG-UHFFFAOYSA-N tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-5-methylphenyl] phosphite Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C(=CC(OP(OC=3C(=CC(SC=4C=C(C(O)=C(C)C=4)C(C)(C)C)=C(C)C=3)C(C)(C)C)OC=3C(=CC(SC=4C=C(C(O)=C(C)C=4)C(C)(C)C)=C(C)C=3)C(C)(C)C)=C(C=2)C(C)(C)C)C)=C1 SGKKYCDALBXNCG-UHFFFAOYSA-N 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
前記ジオール(a1)が、1,4-ブタンジオール、またはエチレングリコールの少なくとも一方であり、前記ジカルボン酸(a2)が、コハク酸、またはコハク酸を含有するジカルボン酸の混合物であることを特徴とするものである。
前記ポリエステル(a)の末端に有する水酸基またはカルボキシル基と、化合物(b)の末端に有する水酸基と、前記エポキシ化合物(D)のエポキシ基またはエポキシ基が反応することによって形成された水酸基、との反応により形成された、エステル結合またはエーテル結合を介して結合してなる構造を有することが好ましい。さらに、本発明の耐衝撃性改良剤においては、前記高分子化合物(E)が、前記ポリエステルのブロック(A)と、前記ポリエーテルのブロック(B)と、がエステル結合を介して繰り返し交互に結合してなる両末端にカルボキシル基を有するブロックポリマー(C)と、前記エポキシ化合物(D)と、がエステル結合を介して結合してなる構造を有することが好ましい。さらにまた、本発明の耐衝撃性改良剤においては、前記ポリエステル(a)が、両末端にカルボキシル基を有する構造であることが好ましい。また、本発明の耐衝撃性改良剤においては、前記化合物(b)が、ポリエチレングリコール、またはポリテトラメチレングリコールの少なくとも一方であることが好ましい。さらに、本発明の耐衝撃性改良剤においては、前記高分子化合物(E)の結晶化温度が20~70℃の範囲内であることが好ましい。さらにまた、本発明の耐衝撃性改良剤においては、前記高分子化合物(E)の前記ポリエステル(a)の数平均分子量が、ポリスチレン換算で1,000~10,000であることが好ましい。また、本発明の耐衝撃性改良剤においては、前記高分子化合物(E)の前記ブロックポリマー(C)の数平均分子量がポリスチレン換算で5,000~50,000であることが好ましい。
本発明の耐衝撃性改良剤は、ジオール(a1)とジカルボン酸(a2)が反応して得られるポリエステル(a)と、炭素原子数2~4のアルキレンオキシ基の群から選ばれる少なくとも一つの基を一つ以上有する両末端に水酸基を有する化合物(b)と、エポキシ基を2個以上有するエポキシ化合物(D)と、が反応して得られる高分子化合物(E)の1種以上を含有するものである。ここで炭素原子数2~4のアルキレンオキシ基とは、エチレンオキシ基、プロピレンオキシ基、ブチレンオキシ基が挙げられる。これらの中でも、耐衝撃性の点から、エチレンオキシ基、またはブチレンオキシ基の少なくとも一方が好ましい。ここで、エチレンオキシ基とは、下記一般式(1)で示される基であり、ブチレンオキシ基は下記一般式(2)で表される基である。
下記水酸基価測定方法で水酸基価を測定し、下記式で数平均分子量(以下「Mn」とも称する)を決定した。
数平均分子量=(56110×2)/水酸基価
<水酸基価測定法>
・試薬A(アセチル化剤)
(1)トリエチルホスフェート 1560mL
(2)無水酢酸 193mL
(3)過塩素酸(60%) 16g
上記試薬を(1)→(2)→(3)の順に混合する。
・試薬B
ピリジンと純水を体積比率で3:1に混合する。
・試薬C
500mLのイソプロピルアルコールにフェノールフタレイン液を2~3滴加え、1N-KOH水溶液で中性にする。
水酸基価[mgKOH/g]=56.11×f×(T-B)/S
f:1N-KOH水溶液のfactor
B:空試験滴定量[mL]
T:本試験滴定量[mL]
S:サンプル量[g]
数平均分子量(以下、「Mn」とも称する)は、ゲルパーミエーションクロマトグラフィー(GPC)法によって測定した。Mnの測定条件は以下の通りである。
装置 :日本分光(株)製GPC装置
溶媒 :クロロホルム
基準物質 :ポリスチレン
検出器 :示差屈折計(RI検出器)
カラム固定相:昭和電工(株)製Shodex LF-804
カラム温度 :40℃
サンプル濃度:1mg/1mL
流量 :0.8mL/min.
注入量 :100μL
結晶化温度は示差走査熱量測定器(DSC)を用いて測定する。試料を、アルミニウムパンに3±1mg量り取り、室温(25℃)から10℃/分の速度で130℃まで昇温し、5分間保持後、10℃/分の速度で0℃まで冷却して得られたチャートにおいて、吸熱のピークトップとなる温度を結晶化温度とする。
本発明の耐衝撃性改良剤組成物は、本発明の耐衝撃性改良剤に対し、さらに、アニオン性界面活性剤の1種以上が配合されてなるものである。
本発明の合成樹脂組成物は、合成樹脂に対し、本発明の耐衝撃性改良剤、または本発明の耐衝撃性改良剤組成物が配合されてなるものである。合成樹脂としては、熱可塑性樹脂が好ましい。
炭素原子数5~15のものが挙げられ、例えば、1,2,3,4-テトラメチルイミダゾリニウム、1,3-ジメチルイミダゾリニウム;
炭素原子数5~15のものが挙げられ、例えば、1,3-ジメチルイミダゾリウム、1-エチル-3-メチルイミダゾリウム;
炭素原子数6~15のものが挙げられ、例えば、1,3-ジメチル-1,4,5,6-テトラヒドロピリミジニウム、1,2,3,4-テトラメチル-1,4,5,6-テトラヒドロピリミジニウム;
炭素原子数6~20のものが挙げられ、例えば、1,3-ジメチル-1,4-ジヒドロピリミジニウム、1,3-ジメチル-1,6-ジヒドロピリミジニウム、8-メチル-1,8-ジアザビシクロ[5,4,0]-7,9-ウンデカジエニウム、8-メチル-1,8-ジアザビシクロ[5,4,0]-7,10-ウンデカジエニウム。
炭素原子数8~15のものが挙げられ、例えば、2-ジメチルアミノ-1,3,4-トリメチルイミダゾリニウム、2-ジエチルアミノ-1,3,4-トリメチルイミダゾリニウム;
炭素原子数8~15のものが挙げられ、例えば、2-ジメチルアミノ-1,3,4-トリメチルイミダゾリウム、2-ジエチルアミノ-1,3,4-トリメチルイミダゾリウム;
炭素原子数10~20のものが挙げられ、例えば、2-ジメチルアミノ-1,3,4-トリメチル-1,4,5,6-テトラヒドロピリミジニウム、2-ジエチルアミノ-1,3-ジメチル-4-エチル-1,4,5,6-テトラヒドロピリミジニウム;
炭素原子数10~20のものが挙げられ、例えば、2-ジメチルアミノ-1,3,4-トリメチル-1,4-ジヒドロピリミジニウム、2-ジメチルアミノ-1,3,4-トリメチル-1,6-ジヒドロピリミジニウム、2-ジエチルアミノ-1,3-ジメチル-4-エチル-1,4-ジヒドロピリミジニウム、2-ジエチルアミノ-1,3-ジメチル-4-エチル-1,6-ジヒドロピリミジニウム。
下記の製造例に従い、本発明の耐衝撃性改良剤である高分子化合物(E)を製造した。また、下記の製造例において、化合物(b)の数平均分子量は、下記<水酸基価からの数平均分子量の算出方法>で算出し、化合物(b)以外の数平均分子量は、下記<ポリスチレン換算による数平均分子量の測定方法>で算出した。
下記水酸基価測定方法で水酸基価を測定し、下記式で数平均分子量を決定した。
数平均分子量=(56110×2)/水酸基価
<水酸基価測定法>
・試薬A(アセチル化剤)
(1)トリエチルホスフェート 1560mL
(2)無水酢酸 193mL
(3)過塩素酸(60%) 16g
上記試薬を(1)→(2)→(3)の順に混合する。
・試薬B
ピリジンと純水を体積比率で3:1に混合する。
・試薬C
500mLのイソプロピルアルコールにフェノールフタレイン液を2~3滴加え、1N-KOH水溶液で中性にする。
水酸基価[mgKOH/g]=56.11×f×(T-B)/S
f:1N-KOH水溶液のfactor
B:空試験滴定量[mL]
T:本試験滴定量[mL]
S:サンプル量[g]
数平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)法によって測定した。Mnの測定条件は以下の通りである。
装置 :日本分光(株)製GPC装置
溶媒 :クロロホルム
基準物質 :ポリスチレン
検出器 :示差屈折計(RI検出器)
カラム固定相:昭和電工(株)製Shodex LF-804
カラム温度 :40℃
サンプル濃度:1mg/1mL
流量 :0.8mL/min.
注入量 :100μL
セパラブルフラスコ中で、酸化防止剤(テトラキス[3-(3,5-ジ第三ブチル-4-ヒドロキシフェニル)プロピオニルオキシメチル]メタン、アデカスタブAO-60(株)ADEKA製)0.2g存在下、1,4-ブタンジオール122g(1.35モル)と、コハク酸168g(1.42モル)を、140℃から190℃まで徐々に昇温しながら常圧で3時間重合して、ポリエステル(a)-1を得た。得られたポリエステル(a)-1の数平均分子量は3,000であった。
示差走査熱量測定器(Perkin社製Diamond DSC)を用いて結晶化温度を測定する。試料を、ペレットを細かく切断し、アルミニウムパンに3±1mg量り取り、室温(25℃)から10℃/分の速度で130℃まで昇温し、5分間保持後、10℃/分の速度で0℃まで冷却して得られたチャートにおいて、吸熱のピークトップとなる温度を結晶化温度とした。
製造例1と同様にして得られたブロックポリマー(C)-1の400gに、エポキシ基を2個以上有するエポキシ化合物(D)-2として、水素添加ビスフェノールAジグリシジルエーテル(エポキシ当量215g/eq)4gを仕込み、220℃で5時間、減圧下で重合した後、製造例1と同様にして、本発明の耐衝撃性改良剤である高分子化合物(E)-2のペレットを400g得た。得られた高分子化合物(E)-2のペレットを、製造例1と同様にして、結晶化温度を測定した。
製造例1と同様にして得られたブロックポリマー(C)-1の400gに、エポキシ基を2個以上有するエポキシ化合物(D)-3として、ジシクロペンタジエンジメタノールジグリシジルエーテル(エポキシ当量170g/eq)3gを仕込み、220℃で5時間、減圧下で重合した後、製造例1と同様にして、本発明の耐衝撃性改良剤である高分子化合物(E)-3のペレットを400g得た。得られた高分子化合物(E)-3のペレットを、製造例1と同様にして、結晶化温度を測定した。
セパラブルフラスコ中で、酸化防止剤(テトラキス[3-(3,5-ジ第三ブチル-4-ヒドロキシフェニル)プロピオニルオキシメチル]メタン、アデカスタブAO-60(株)ADEKA製)0.2g存在下、1,4-ブタンジオール58g(0.65モル)と、コハク酸91g(0.77モル)を、140℃から190℃まで徐々に昇温しながら常圧で3時間重合して、ポリエステル(a)-2を得た。得られたポリエステル(a)-2の数平均分子量は1,000であった。
セパラブルフラスコ中で、酸化防止剤(テトラキス[3-(3,5-ジ第三ブチル-4-ヒドロキシフェニル)プロピオニルオキシメチル]メタン、アデカスタブAO-60(株)ADEKA製)0.2g存在下、エチレングリコール100g(1.61モル)と、コハク酸199g(1.69モル)を、140℃から190℃まで徐々に昇温しながら常圧で3時間重合して、ポリエステル(a)-3を得た。得られたポリエステル(a)-3の数平均分子量は3,000であった。
セパラブルフラスコ中で、酸化防止剤(テトラキス[3-(3,5-ジ第三ブチル-4-ヒドロキシフェニル)プロピオニルオキシメチル]メタン、アデカスタブAO-60(株)ADEKA製)0.2g存在下、1,4-ブタンジオール101g(1.12モル)と、エチレングリコール17g(0.28モル)と、コハク酸173g(1.47モル)を、140℃から190℃まで徐々に昇温しながら常圧で3時間重合して、ポリエステル(a)-4を得た。得られたポリエステル(a)-4の数平均分子量は3,000であった。
セパラブルフラスコ中で、酸化防止剤(テトラキス[3-(3,5-ジ第三ブチル-4-ヒドロキシフェニル)プロピオニルオキシメチル]メタン、アデカスタブAO-60(株)ADEKA製)0.2g存在下、1,4-ブタンジオール120g(1.33モル)と、コハク酸149g(1.26モル)と、アジピン酸21g(0.14モル)を、140℃から190℃まで徐々に昇温しながら常圧で3時間重合して、ポリエステル(a)-5を得た。得られたポリエステル(a)-5の数平均分子量は3,000であった。
セパラブルフラスコ中で、酸化防止剤(テトラキス[3-(3,5-ジ第三ブチル-4-ヒドロキシフェニル)プロピオニルオキシメチル]メタン、アデカスタブAO-60(株)ADEKA製)0.2g存在下、1,4-ブタンジオール118g(1.31モル)と、コハク酸130g(1.10モル)と、アジピン酸40g(0.28モル)を、140℃から190℃まで徐々に昇温しながら常圧で3時間重合して、ポリエステル(a)-6を得た。得られたポリエステル(a)-6の数平均分子量は3,000であった。
セパラブルフラスコ中で、酸化防止剤(テトラキス[3-(3,5-ジ第三ブチル-4-ヒドロキシフェニル)プロピオニルオキシメチル]メタン、アデカスタブAO-60(株)ADEKA製)0.2g存在下、1,4-ブタンジオール116g(1.28モル)と、コハク酸144g(1.22モル)と、セバシン酸27g(0.14モル)を、140℃から190℃まで徐々に昇温しながら常圧で3時間重合して、ポリエステル(a)-7を得た。得られたポリエステル(a)-7の数平均分子量は3,000であった。
セパラブルフラスコ中で、酸化防止剤(テトラキス[3-(3,5-ジ第三ブチル-4-ヒドロキシフェニル)プロピオニルオキシメチル]メタン、アデカスタブAO-60(株)ADEKA製)0.2g存在下、1,4-ブタンジオール110g(1.22モル)と、コハク酸122g(1.04モル)と、セバシン酸52g(0.26モル)を、140℃から190℃まで徐々に昇温しながら常圧で3時間重合して、ポリエステル(a)-8を得た。得られたポリエステル(a)-8の数平均分子量は3,000であった。
セパラブルフラスコ中で、酸化防止剤(テトラキス[3-(3,5-ジ第三ブチル-4-ヒドロキシフェニル)プロピオニルオキシメチル]メタン、アデカスタブAO-60(株)ADEKA製)0.2g存在下、1,4-ブタンジオール105g(1.17モル)と、コハク酸103g(0.87モル)と、セバシン酸75g(0.37モル)を、140℃から190℃まで徐々に昇温しながら常圧で3時間重合して、ポリエステル(a)-9を得た。得られたポリエステル(a)-9の数平均分子量は3,000であった。
セパラブルフラスコ中で、酸化防止剤(テトラキス[3-(3,5-ジ第三ブチル-4-ヒドロキシフェニル)プロピオニルオキシメチル]メタン、アデカスタブAO-60(株)ADEKA製)0.2g存在下、1,4-ブタンジオール115g(1.27モル)と、コハク酸143g(1.21モル)と、2,6-ナフタレンジカルボン酸29g(0.13モル)を、140℃から190℃まで徐々に昇温しながら常圧で3時間重合して、ポリエステル(a)-10を得た。得られたポリエステル(a)-10の数平均分子量は3,000であった。
セパラブルフラスコ中で、酸化防止剤(テトラキス[3-(3,5-ジ第三ブチル-4-ヒドロキシフェニル)プロピオニルオキシメチル]メタン、アデカスタブAO-60(株)ADEKA製)0.2g存在下、1,4-ブタンジオール119g(1.32モル)と、コハク酸171g(1.45モル)を、140℃から190℃まで徐々に昇温しながら常圧で3時間重合して、ポリエステル(a)-11を得た。得られたポリエステル(a)-11の数平均分子量は2,000であった。
表1~8に記載した配合量(質量部)に基づいてブレンドした各実施例の樹脂組成物を用いて、下記に示す試験片作製条件に従い、試験片を得た。得られた試験片を用いて、下記に従い、シャルピー衝撃強度の測定を行い、耐衝撃性の評価を行った。結果を表1~8に示す。同様にして、下記の表8に示す配合で、比較例の樹脂組成物を調製し、評価を行った。結果を表8に示す。
表1~8に示す配合量に基づいてポリカーボネート/ABS樹脂組成物を、(株)池貝製2軸押出機(PCM30,60mesh入り)を用いて、250℃、15kg/時間の条件で造粒し、ペレットを得た。得られたペレットを、横型射出成形機(NEX80:日精樹脂工業(株)製)を用い、樹脂温度250℃、金型温度50℃の加工条件で成形し、試験片(80mm×10mm×4mm)を得た。ポリカーボネート/ABSは、ポリカーボネート/ABS=7/3(質量比)であり、メルトフローレート=40g/10min(ISO1133、260℃×5.00kg)を使用した。
ISO179-1(ノッチ付)に準拠して測定した。
測定は試験片10枚を測定し、平均値を算出した。
*2:ポリカーボネート/ABS=7/3(質量比)、メルトフローレート=40g/10min(ISO1133、260℃×5.00kg)
*3:ポリテトラフルオロエチレン
Claims (15)
- ジオール(a1)とジカルボン酸(a2)が反応して得られるポリエステル(a)と、炭素原子数2~4のアルキレンオキシ基の群から選ばれる少なくとも一つの基を一つ以上有する両末端に水酸基を有する化合物(b)と、エポキシ基を2個以上有するエポキシ化合物(D)と、が反応して得られる高分子化合物(E)の1種以上を含有する耐衝撃性改良剤であって、
前記ジオール(a1)が、1,4-ブタンジオール、またはエチレングリコールの少なくとも一方であり、前記ジカルボン酸(a2)が、コハク酸、またはコハク酸を含有するジカルボン酸の混合物であることを特徴とする耐衝撃性改良剤。 - 前記炭素原子数2~4のアルキレンオキシ基の群から選ばれる少なくとも一つの基が、エチレンオキシ基、またはブチレンオキシ基の少なくとも一方である請求項1記載の耐衝撃性改良剤。
- 前記高分子化合物(E)が、前記ポリエステル(a)から構成されるポリエステルのブロック(A)と、前記化合物(b)から構成されるポリエーテルのブロック(B)とを有し、
前記ポリエステル(a)の末端に有する水酸基またはカルボキシル基と、化合物(b)の末端に有する水酸基と、前記エポキシ化合物(D)のエポキシ基またはエポキシ基が反応することによって形成された水酸基、との反応により形成された、エステル結合またはエーテル結合を介して結合してなる構造を有する請求項1または2記載の耐衝撃性改良剤。 - 前記高分子化合物(E)が、前記ポリエステルのブロック(A)と、前記ポリエーテルのブロック(B)と、がエステル結合を介して繰り返し交互に結合してなる両末端にカルボキシル基を有するブロックポリマー(C)と、前記エポキシ化合物(D)と、がエステル結合を介して結合してなる構造を有する請求項3記載の耐衝撃性改良剤。
- 前記ポリエステル(a)が、両末端にカルボキシル基を有する構造である請求項1~4のうちいずれか一項記載の耐衝撃性改良剤。
- 前記化合物(b)が、ポリエチレングリコール、またはポリテトラメチレングリコールの少なくとも一方である請求項1~5のうちいずれか一項記載の耐衝撃性改良剤。
- 前記高分子化合物(E)の結晶化温度が20~70℃の範囲内である請求項1~6のうちいずれか一項記載の耐衝撃性改良剤。
- 前記高分子化合物(E)の前記ポリエステル(a)の数平均分子量が、ポリスチレン換算で1,000~10,000である請求項1~7のうちいずれか一項記載の耐衝撃性改良剤。
- 前記高分子化合物(E)の前記ブロックポリマー(C)の数平均分子量がポリスチレン換算で5,000~50,000である請求項4記載の耐衝撃性改良剤。
- 請求項1~9のうちいずれか一項記載の耐衝撃性改良剤に対し、さらにアニオン性界面活性剤が配合されていることを特徴とする耐衝撃性改良剤組成物。
- 合成樹脂に対し、請求項1~9のうちいずれか一項記載の耐衝撃性改良剤が配合されていることを特徴とする合成樹脂組成物。
- 合成樹脂に対し、請求項10記載の耐衝撃性改良剤組成物が配合されていることを特徴とする合成樹脂組成物。
- 前記合成樹脂が、ポリカーボネート樹脂およびアクリロニトリル-ブタジエン-スチレン樹脂からなる群から選ばれる1種以上である請求項11または12記載の合成樹脂組成物。
- さらに、ポリテトラフルオロエチレンが配合されている請求項11~13のうちいずれか一項記載の合成樹脂組成物。
- 請求項11~14のうちいずれか一項記載の合成樹脂組成物からなることを特徴とする成形体。
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