JP4685431B2 - 帯電防止性樹脂組成物 - Google Patents
帯電防止性樹脂組成物 Download PDFInfo
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- JP4685431B2 JP4685431B2 JP2004373039A JP2004373039A JP4685431B2 JP 4685431 B2 JP4685431 B2 JP 4685431B2 JP 2004373039 A JP2004373039 A JP 2004373039A JP 2004373039 A JP2004373039 A JP 2004373039A JP 4685431 B2 JP4685431 B2 JP 4685431B2
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- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- RQFLGKYCYMMRMC-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O RQFLGKYCYMMRMC-UHFFFAOYSA-N 0.000 description 1
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- AXRSHKZFNKUGQB-UHFFFAOYSA-N octyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC)OC1=CC=CC=C1 AXRSHKZFNKUGQB-UHFFFAOYSA-N 0.000 description 1
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- 239000012074 organic phase Substances 0.000 description 1
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- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- WWYDYZMNFQIYPT-UHFFFAOYSA-N ru78191 Chemical compound OC(=O)C(C(O)=O)C1=CC=CC=C1 WWYDYZMNFQIYPT-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 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
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
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- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- BXYHVFRRNNWPMB-UHFFFAOYSA-N tetramethylphosphanium Chemical compound C[P+](C)(C)C BXYHVFRRNNWPMB-UHFFFAOYSA-N 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
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- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- DMEUUKUNSVFYAA-UHFFFAOYSA-N trinaphthalen-1-ylphosphane Chemical compound C1=CC=C2C(P(C=3C4=CC=CC=C4C=CC=3)C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 DMEUUKUNSVFYAA-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
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-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
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-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
- ZZLMAPIPKMCNJF-UHFFFAOYSA-H trizinc 5-sulfonatobenzene-1,3-dicarboxylate Chemical compound [Zn++].[Zn++].[Zn++].[O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O.[O-]C(=O)c1cc(cc(c1)S([O-])(=O)=O)C([O-])=O ZZLMAPIPKMCNJF-UHFFFAOYSA-H 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
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- 235000019871 vegetable fat Nutrition 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
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- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
<A成分:熱可塑性樹脂>
本発明のA成分の熱可塑性樹脂は、上記C成分以外のガラス転移温度(Tg)が115℃以上の熱可塑性樹脂であって、特に限定されるものではない。しかしながら、上記のとおりガラス転移温度(Tg)が130℃以上の熱可塑性樹脂が好ましい。かかる熱可塑性樹脂は高い加工温度を必要とする一方、B成分およびC成分の組み合わせは熱安定性に優れるからである。一方その上限は好ましくは250℃、より好ましくは230℃である。Tgは、JIS K7121に準拠した示差走査熱量計(DSC)測定により求められる値である。
(1)該ポリカーボネートを構成する2価フェノール成分100モル%中、BPMが20〜80モル%(より好適には40〜75モル%、さらに好適には45〜65モル%)であり、かつBCFが20〜80モル%(より好適には25〜60モル%、さらに好適には35〜55モル%)である共重合ポリカーボネート。
(2)該ポリカーボネートを構成する2価フェノール成分100モル%中、BPAが10〜95モル%(より好適には50〜90モル%、さらに好適には60〜85モル%)であり、かつBCFが5〜90モル%(より好適には10〜50モル%、さらに好適には15〜40モル%)である共重合ポリカーボネート。
(3)該ポリカーボネートを構成する2価フェノール成分100モル%中、BPMが20〜80モル%(より好適には40〜75モル%、さらに好適には45〜65モル%)であり、かつBis−TMCが20〜80モル%(より好適には25〜60モル%、さらに好適には35〜55モル%)である共重合ポリカーボネート。
(i)吸水率が0.05〜0.15%、好ましくは0.06〜0.13%であり、かつTgが120〜180℃であるポリカーボネート、あるいは
(ii)Tgが160〜250℃、好ましくは170〜230℃であり、かつ吸水率が0.10〜0.30%、好ましくは0.13〜0.30%、より好ましくは0.14〜0.27%であるポリカーボネート。
比粘度(ηSP)=(t−t0)/t0
[t0は塩化メチレンの落下秒数、tは試料溶液の落下秒数]
求められた比粘度(ηSP)から次の数式により粘度平均分子量Mを算出する。
ηSP/c=[η]+0.45×[η]2c(但し[η]は極限粘度)
[η]=1.23×10−4M0.83
c=0.7
本発明のB成分は、下記一般式(II)で示されるイオン性化合物である。
本発明の帯電防止性樹脂組成物は、上記のイオン性化合物と共に、スルホン酸塩基を有するポリエーテルエステルを併用することで、その相乗効果により従来の帯電防止性樹脂組成物にない特性を発揮する。ここでポリエーテルエステルとは、ポリエーテル単位をその繰り返し単位中に有するポリエステルであり、該ポリエステルは芳香族ジカルボン酸成分とグリコール成分からなるポリマーであり、該ポリエーテルは3量体以上のポリ(アルキレンオキサイド)グリコール成分をその繰り返し単位に有するポリマーをいう。該ポリエーテルの繰り返し単位は、−O−(RX−O)n−(ここでは、RXは炭素数1以上のアルキレン基を示し、nは3以上を示す)で示される単位である。尚、ポリエーテルエステル中にはジエチレングリコール成分を含むことができる。
次に、B成分およびC成分の含有量について説明する。B成分の含有量は、A成分の熱可塑性樹脂100重量部に対して0.01〜20重量部、好ましくは0.05〜10重量部、より好ましくは0.1〜5重量部、さらに好ましくは0.5〜3重量部の範囲である。B成分の含有量が0.01重量部未満では樹脂組成物の帯電防止効果が不十分となりやすく、20重量部を超えると機械的特性、耐熱性、および成形加工性が低下しやすい。C成分の含有量は、A成分100重量部に対して0.1〜50重量部、好ましくは5〜50重量部、より好ましくは10〜40重量部の範囲である。C成分の含有量が0.1重量部未満では帯電防止効果が不十分となりやすく、50重量部を超えると機械的特性、耐熱性、および成形加工性が低下しやすい。本発明のB成分およびC成分の相乗効果は、A成分に対して少量であっても発揮される。しかしながら、本発明の帯電防止性樹脂組成物は、表面固有抵抗値がより低い領域においてその特徴が発揮されることから、C成分の含有量はA成分100重量部に対して5重量部以上であることが好ましい。更にB成分とC成分との含有量の割合は、100重量部のC成分を基準としてB成分が好ましくは0.1〜50重量部、より好ましくは1〜25重量部、更に好ましくは2〜15重量部である。
D成分に使用されるリン系安定剤としては、亜リン酸、リン酸、亜ホスホン酸、ホスホン酸およびこれらのエステル、並びに第3級ホスフィンなどが例示される。
本発明のE成分であるヒンダードフェノール化合物としては、通常樹脂に配合される各種の化合物が使用できる。かかるヒンダードフェノール化合物としては、例えば、α−トコフェロール、ブチルヒドロキシトルエン、シナピルアルコール、ビタミンE、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、2−tert−ブチル−6−(3’−tert−ブチル−5’−メチル−2’−ヒドロキシベンジル)−4−メチルフェニルアクリレート、2,6−ジ−tert−ブチル−4−(N,N−ジメチルアミノメチル)フェノール、3,5−ジ−tert−ブチル−4−ヒドロキシベンジルホスホネートジエチルエステル、2,2’−メチレンビス(4−メチル−6−tert−ブチルフェノール)、2,2’−メチレンビス(4−エチル−6−tert−ブチルフェノール)、4,4’−メチレンビス(2,6−ジ−tert−ブチルフェノール)、2,2’−メチレンビス(4−メチル−6−シクロヘキシルフェノール)、2,2’−ジメチレン−ビス(6−α−メチル−ベンジル−p−クレゾール)、2,2’−エチリデン−ビス(4,6−ジ−tert−ブチルフェノール)、2,2’−ブチリデン−ビス(4−メチル−6−tert−ブチルフェノール)、4,4’−ブチリデンビス(3−メチル−6−tert−ブチルフェノール)、トリエチレングリコール−N−ビス−3−(3−tert−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオネート、1,6−へキサンジオールビス[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]、ビス[2−tert−ブチル−4−メチル6−(3−tert−ブチル−5−メチル−2−ヒドロキシベンジル)フェニル]テレフタレート、3,9−ビス{2−[3−(3−tert−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオニルオキシ]−1,1,−ジメチルエチル}−2,4,8,10−テトラオキサスピロ[5,5]ウンデカン、4,4’−チオビス(6−tert−ブチル−m−クレゾール)、4,4’−チオビス(3−メチル−6−tert−ブチルフェノール)、2,2’−チオビス(4−メチル−6−tert−ブチルフェノール)、ビス(3,5−ジ−tert−ブチル−4−ヒドロキシベンジル)スルフィド、4,4’−ジ−チオビス(2,6−ジ−tert−ブチルフェノール)、4,4’−トリ−チオビス(2,6−ジ−tert−ブチルフェノール)、2,2−チオジエチレンビス−[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]、2,4−ビス(n−オクチルチオ)−6−(4−ヒドロキシ−3,5−ジ−tert−ブチルアニリノ)−1,3,5−トリアジン、N,N’−ヘキサメチレンビス−(3,5−ジ−tert−ブチル−4−ヒドロキシヒドロシンナミド)、N,N’−ビス[3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオニル]ヒドラジン、1,1,3−トリス(2−メチル−4−ヒドロキシ−5−tert−ブチルフェニル)ブタン、1,3,5−トリメチル−2,4,6−トリス(3,5−ジ−tert−ブチル−4−ヒドロキシベンジル)ベンゼン、トリス(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)イソシアヌレート、トリス(3,5−ジ−tert−ブチル−4−ヒドロキシベンジル)イソシアヌレート、1,3,5−トリス(4−tert−ブチル−3−ヒドロキシ−2,6−ジメチルベンジル)イソシアヌレート、1,3,5−トリス2[3(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオニルオキシ]エチルイソシアヌレート、テトラキス[メチレン−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]メタン、トリエチレングリコール−N−ビス−3−(3−tert−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオネート、トリエチレングリコール−N−ビス−3−(3−tert−ブチル−4−ヒドロキシ−5−メチルフェニル)アセテート、3,9−ビス[2−{3−(3−tert−ブチル−4−ヒドロキシ−5−メチルフェニル)アセチルオキシ}−1,1−ジメチルエチル]−2,4,8,10−テトラオキサスピロ[5,5]ウンデカン、テトラキス[メチレン−3−(3−tert−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオネート]メタン、1,3,5−トリメチル−2,4,6−トリス(3−tert−ブチル−4−ヒドロキシ−5−メチルベンジル)ベンゼン、およびトリス(3−tert−ブチル−4−ヒドロキシ−5−メチルベンジル)イソシアヌレートなどが例示される。
本発明の帯電防止性樹脂組成物は、上記A成分〜E成分以外にも、通常樹脂に配合される各種の添加剤を含むことができる。
本発明の帯電防止性樹脂組成物は、更にブルーイング剤を樹脂組成物中0.05〜3.0ppm(重量割合)含んでなることが好ましい。本発明の樹脂組成物は比較的黄色味を帯びやすいため、成形品に自然な透明感を付与するにはブルーイング剤の使用は非常に有効である。ここでブルーイング剤とは、橙色ないし黄色の光線を吸収することにより青色ないし紫色を呈する着色剤をいい、特に染料が好ましい。ブルーイング剤の配合により本発明の帯電防止性樹脂組成物は更に良好な色相を得る。ブルーイング剤の量が0.05ppm未満では色相の改善効果が不十分な場合がある一方、3.0ppmを超える場合には光線透過率が低下し適当ではない。より好ましいブルーイング剤の量は樹脂組成物中0.2〜2.0ppmの範囲である。ブルーイング剤としては代表例として、バイエル社のマクロレックスバイオレットBおよびマクロレックスブルーRR、並びにクラリアント社のポリシンスレンブルーRLSなどが挙げられる。
本発明の帯電防止性樹脂組成物には、その成形時の生産性向上や成形品の歪みの低減を目的として、更に離型剤を配合することが好ましい。かかる離型剤としては公知のものが使用できる。例えば、飽和脂肪酸エステル、不飽和脂肪酸エステル、ポリオレフィン系ワックス(ポリエチレンワックス、1−アルケン重合体など。酸変性などの官能基含有化合物で変性されているものも使用できる)、シリコーン化合物、フッ素化合物(ポリフルオロアルキルエーテルに代表されるフッ素オイルなど)、パラフィンワックス、蜜蝋などを挙げることができる。かかる離型剤は熱可塑性樹脂(A成分)100重量部に対して0.005〜2重量部が好ましい。
本発明の帯電防止性樹脂組成物は紫外線吸収剤を含有することができる。本発明の紫外線吸収剤としては、具体的にはベンゾフェノン系では、例えば、2,4−ジヒドロキシベンゾフェノン、2−ヒドロキシ−4−メトキシベンゾフェノン、2−ヒドロキシ−4−オクトキシベンゾフェノン、2−ヒドロキシ−4−ベンジロキシベンゾフェノン、2−ヒドロキシ−4−メトキシ−5−スルホキシベンゾフェノン、2−ヒドロキシ−4−メトキシ−5−スルホキシトリハイドライドレイトベンゾフェノン、2,2’−ジヒドロキシ−4−メトキシベンゾフェノン、2,2’,4,4’−テトラヒドロキシベンゾフェノン、2,2’−ジヒドロキシ−4,4’−ジメトキシベンゾフェノン、2,2’−ジヒドロキシ−4,4’−ジメトキシ−5−ソジウムスルホキシベンゾフェノン、ビス(5−ベンゾイル−4−ヒドロキシ−2−メトキシフェニル)メタン、2−ヒドロキシ−4−n−ドデシルオキシベンソフェノン、および2−ヒドロキシ−4−メトキシ−2’−カルボキシベンゾフェノンなどが例示される。
本発明の帯電防止性樹脂組成物は更に各種の染顔料を含有し多様な意匠性を発現する成形品を提供できる。例えば、蛍光増白剤を含むことにより発光色を生かしたより良好な意匠効果を付与することができる。また極微量の染顔料による微妙な着色のなされた帯電防止性樹脂組成物もまた提供可能である。
本発明の帯電防止性樹脂組成物には、上記D成分のリン系安定剤およびE成分のヒンダードフェノール系酸化防止剤以外の他の熱安定剤を配合することもできる。かかるその他の熱安定剤はD成分およびE成分のいずれかと併用されることが好ましく、特にD成分およびE成分と併用されることが好ましい。かかる他の熱安定剤としては、例えば3−ヒドロキシ−5,7−ジ−tert−ブチル−フラン−2−オンとo−キシレンとの反応生成物に代表されるラクトン系安定剤(かかる安定剤の詳細は特開平7−233160号公報に記載されている)が好適に例示される。かかる化合物はIrganox HP−136(商標、CIBA SPECIALTY CHEMICALS社製)として市販され、該化合物を利用できる。更に該化合物と各種のホスファイト化合物およびヒンダードフェノール化合物を混合した安定剤が市販されている。例えば上記社製のIrganox HP−2921が好適に例示される。本発明においてD成分およびE成分を熱可塑性樹脂に配合するため、かかる予め混合された安定剤を利用することもできる。ラクトン系安定剤の配合量は、A成分100重量部に対して好ましくは0.0005〜0.05重量部、より好ましくは0.001〜0.03重量部である。
本発明の帯電防止性樹脂組成物は熱線吸収能を有する化合物を含有することができる。本発明の帯電防止性樹脂組成物は、光透過性を有することから熱線吸収能を有する化合物の配合は、室内の高温化を抑制することができる。かかる樹脂組成物は、特に車両用樹脂窓ガラスや樹脂窓サッシガラスの用途において好適である。
本発明の帯電防止性樹脂組成物には、光拡散剤を配合して光拡散効果を付与することができる。かかる光拡散剤としては高分子微粒子、低屈折率の無機微粒子、およびこれらの複合物等が例示される。かかる高分子微粒子は、既に熱可塑性樹脂の光拡散剤として公知の微粒子である。より好適には粒径数μmのアクリル架橋粒子およびポリオルガノシルセスキオキサンに代表されるシリコーン架橋粒子などが例示される。光拡散剤の形状は球形、円盤形、柱形、および不定形などが例示される。かかる球形は、完全球である必要はなく変形しているものを含み、かかる柱形は立方体を含む。好ましい光拡散剤は球形であり、その粒径は均一であるほど好ましい。光拡散剤の含有量は、A成分100重量部に対して好ましくは0.005〜20重量部、より好ましくは0.01〜10重量部、更に好ましくは0.01〜3重量部である。尚、光拡散剤は2種以上を併用することができる。
本発明の帯電防止性樹脂組成物には、光高反射用白色顔料を配合して光反射効果を付与することができる。かかる白色顔料としては二酸化チタン(特にシリコーンなど有機表面処理剤により処理された二酸化チタン)顔料が特に好ましい。かかる光高反射用白色顔料の含有量は、A成分100重量部に対して3〜30重量部が好ましく、8〜25重量部がより好ましい。尚、光高反射用白色顔料は2種以上を併用することができる。
本発明の帯電防止性樹脂組成物には、本発明の目的が損なわれない量の難燃剤を使用することができる。難燃剤としては、例えば、臭素化エポキシ樹脂、臭素化ポリスチレン、臭素化ポリカーボネート、臭素化ポリアクリレート、モノホスフェート化合物、ホスフェートオリゴマー化合物、ホスホネートオリゴマー化合物、ホスホニトリルオリゴマー化合物、ホスホン酸アミド化合物、有機スルホン酸金属塩(例えばパーフルオロアルカンスルホン酸カリウム塩やジフェニルスルホンスルホン酸カリウム塩など)、並びにシリコーン系難燃剤などが挙げられる。かかる難燃剤はそれぞれ熱可塑性樹脂に対する公知の量を配合することができる。
本発明の帯電防止性樹脂組成物およびその成形品には、A成分〜E成分および上記各成分以外にも、本発明の目的を損なわない範囲において、架橋ゴム、無機系蛍光体(例えばアルミン酸塩を母結晶とする蛍光体)、流動改質剤、結晶核剤、無機および有機の抗菌剤、光触媒系防汚剤(例えば微粒子酸化チタン、微粒子酸化亜鉛)、およびフォトクロミック剤などの各種公知の樹脂用添加剤が含まれていてもよい。
本発明の帯電防止性樹脂組成物の製造に当たっては、その製造方法は特に限定されるものではない。しかしながらその成形品において樹脂中に帯電防止剤が均質に分散することが重要であることから、本発明の樹脂組成物は、A成分中にB成分およびC成分、並びにそれ以外の成分を溶融混練して製造されることが好ましい。
上記の如く得られた本発明の帯電防止性樹脂組成物は通常上記の如く製造されたペレットを射出成形して各種製品を製造することができる。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。また成形はコールドランナー方式およびホットランナー方式のいずれも選択することができる。
(i)帯電防止性能:長さ50mm×幅50mm×厚さ2.0mm、表面の算術平均粗さ(Ra)が0.03μmの平滑平板の試験片を射出成形により製造した。かかる試験片は成形直後より23℃、湿度50%の環境にて一週間調整された。その後、試験片の表面固有抵抗値(Ω)を東亜電波工業(株)製SM−8210極超絶縁計により測定した。数値が小さいほど帯電防止性能が優れていることを示す。
(i)マスターペレットの製造:下記に示す100重量部のC成分(TJP−101)に対して、5重量部のB−1成分(ION−B)またはB−2成分(ION−T)を配合したマスターペレットをベント式二軸押出機((株)日本製鋼所製:TEX30XSST(完全かみ合い、同方向回転、2条ネジスクリュー)を用いて製造した。C成分はスクリュー根元の第1供給口より供給され、B−1成分またはB−2成分は液注装置を用いて上記所定量となるよう供給された。かかる液注装置の供給ノズルは第1供給口の次のシリンダブロックに配置された。シリンダ温度およびダイス温度は180℃、ベントの真空度は3kPaであった。スクリュー回転数150rpm、吐出量は18.9kgに設定した。ダイスからのストランドは冷風のゾーンを通して一旦ひき取られた後、ペレタイザーを用いてペレット化された。
表に記載の各成分からなる樹脂組成物のペレットを製造し、上記加工法にて試験片、およびシート状部材を作成した。評価結果を表1〜3に示す。尚、表中の各成分の内容は下記の通りである。
PC−50WP:ビスフェノールAとホスゲンから界面縮重合法により製造された粘度平均分子量23,500のポリカーボネート樹脂パウダー(帝人化成(株)製:パンライトL−1250WP(商品名))
PC−BCF:下記方法により製造された9,9−ビス(3−メチル−4−ヒドロキシフェニル)フルオレン(“BCF”と略称)およびビスフェノールA(“BPA”と略称)からなる芳香族ポリカーボネート樹脂パウダー
PEN:ポリエチレンナフタレート樹脂(帝人化成(株)製:テオネックスTN8770(商品名)、該樹脂はそのジカルボン酸成分が2,6−ナフタレンジカルボン酸成分92モル%およびテレフタル酸成分8モル%の合計100モル%からなり、IV値が0.7、ガラス転移温度が115℃である)
PAR:ポリアリレート樹脂(ユニチカ(株)製:UポリマーU−100(商品名))
(B−1成分)
ION−B:一般式(II)においてカウンターイオンがBF4 −であるアンモニウム塩(日清紡績(株)製:イオン性液体B(商品名))
(B−2成分)
ION−T:一般式(II)においてカウンターイオンが(CF3SO2)2N−であるアンモニウム塩(日清紡績(株)製:イオン性液体T(商品名))
(B成分との比較用)
DBS−P:ドデシルベンゼンスルホン酸テトラブチルホスホニウム塩(竹本油脂(株)製:TCS−101(商品名))
DBS−Na:ドデシルベンゼンスルホン酸ナトリウム塩(竹本油脂(株)製)
TJP−101:スルホン酸塩基を有するポリエーテルエステル(竹本油脂(株)製;TJP−101(商品名)、かかるポリエーテルエステルは、(C1)スルホン酸塩基を持たない芳香族ジカルボン酸成分、(C2)上記一般式(III)で表されるスルホン酸塩基で置換された芳香族ジカルボン酸成分、(C3)炭素数2〜10のグリコール成分、および(C4)数平均分子量200〜50,000のポリ(アルキレンオキシド)グリコール成分からなるポリエーテルエステルである。ここで、(C1)を誘導するためのジカルボン酸は2,6−ナフタレンジカルボン酸、(C2)を誘導するためのジカルボン酸は5−ナトリウムスルホイソフタル酸、(C3)を誘導するためのグリコール成分はエチレングリコールおよび1,6−ヘキサンジオール、並びに(C4)を誘導するためのグリコール成分は数平均分子量2,000のポリ(エチレンオキシド)グリコールである。上記(C1)および(C2)の合計100モル%中、(C1)は88モル%、(C2)は12モル%である。エチレングリコールと1,6−ヘキサンジオールとの合計100モル%中、エチレングリコールは10モル%、1,6−ヘキサンジオールは90モル%である。更に上記(C4)のポリ(エチレンオキシド)グリコールは、ポリエーテルエステル100重量%中30重量%である。またポリエーテルエステル中におけるスルホン酸ナトリウム塩基の濃度は2.9×10−4モル/gであり、かつフェノール/テトラクロロエタン(重量比40/60)の混合溶媒中30℃で測定した還元粘度(濃度1.2g/dl)は1.35である。
BCM−B:上記の製法で作成された上記TJP−101とION−Bとからなるマスターペレット
BCM−T:上記の製法で作成された上記TJP−101とION−Tとからなるマスターペレット
(D成分およびE成分)
D−PEP8:(旭電化工業(株)製:アデカスタブPEP−8(商品名))
E−AO80:3,9−ビス[2−{3−(3−tert−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオニルオキシ}−1,1−ジメチルエチル]−2,4,8,10−テトラオキサスピロ[5,5]ウンデカン(旭電化工業(株)製:アデカスタブAO−80(商品名))
Claims (7)
- 上記C成分は、(C1)スルホン酸塩基を持たない芳香族ジカルボン酸成分、(C2)上記一般式(III)で表されるスルホン酸塩基で置換された芳香族ジカルボン酸成分、(C3)炭素数2〜10のグリコール成分、および(C4)数平均分子量200〜50,000のポリ(アルキレンオキシド)グリコール成分を有するポリエーテルエステルである請求項2に記載の帯電防止性樹脂組成物。
- 上記A成分は、ポリカーボネート樹脂である請求項1〜3のいずれか1項に記載の帯電防止性樹脂組成物。
- さらに100重量部のA 成分を基準として、0.0001〜1重量部のリン系安定剤(D成分)および/またはヒンダードフェノール系酸化防止剤(E成分)を配合してなる請求項1〜請求項4のいずれか1項に記載の帯電防止性樹脂組成物。
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