JP7284581B2 - 重合性液晶材料および重合された液晶膜 - Google Patents
重合性液晶材料および重合された液晶膜 Download PDFInfo
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- JP7284581B2 JP7284581B2 JP2018560758A JP2018560758A JP7284581B2 JP 7284581 B2 JP7284581 B2 JP 7284581B2 JP 2018560758 A JP2018560758 A JP 2018560758A JP 2018560758 A JP2018560758 A JP 2018560758A JP 7284581 B2 JP7284581 B2 JP 7284581B2
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- 238000001228 spectrum Methods 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 230000008961 swelling Effects 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
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical group C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- NZNAAUDJKMURFU-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 NZNAAUDJKMURFU-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 150000004867 thiadiazoles Chemical group 0.000 description 1
- NMFKEMBATXKZSP-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2.S1C=CC2=C1C=CS2 NMFKEMBATXKZSP-UHFFFAOYSA-N 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229960000984 tocofersolan Drugs 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 150000003611 tocopherol derivatives Chemical class 0.000 description 1
- 235000019149 tocopherols Nutrition 0.000 description 1
- 125000006168 tricyclic group Chemical group 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-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
- 238000012795 verification Methods 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
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
- 239000011590 β-tocopherol Substances 0.000 description 1
- 235000007680 β-tocopherol Nutrition 0.000 description 1
- 239000002478 γ-tocopherol Substances 0.000 description 1
- QUEDXNHFTDJVIY-DQCZWYHMSA-N γ-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-DQCZWYHMSA-N 0.000 description 1
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 description 1
- 239000002446 δ-tocopherol Substances 0.000 description 1
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Description
L31は、-(Sp31-A32)を示し、
L32は、H、1~5個のC原子をもつ、アルキル、アルコキシ、チオアルキル、アルキルカルボニル、アルコキシカルボニル、アルキルカルボニルオキシまたはアルコキシカルボニルオキシ;またはF、Cl、CN、NO2、OCN、SCN、または1~4個の炭素原子をもつモノ-、オリゴ-またはポリフッ素化されたアルキルまたはアルコキシ;または-(Sp31-A31)を示し、
A31は、シリル、スルホ、スルホニル、ホルミル、アミン、イミン、ニトリル、メルカプト、ニトロ、ハロゲン、C1~12アルキル、C6~12アリール、C1~12アルコキシ、ヒドロキシル、またはこれらの基の組み合わせを含む群から選択される1以上の置換基を任意に有していてもよい、アリール基、ヘテロアリール基、(非芳香族)脂環式基またはヘテロ環基を示し、
R31は、H、または1~12個のC原子を有するアルキルを示す。
重合性液晶材料は、均一配向をもつ異方性ポリマー膜の調製のための先行技術において知られている。これらの膜は通常、重合性液晶混合物の薄い層を基体上へコーティングすること、混合物を配列させて均一配向にすること、および混合物を重合させることによって調製される。膜の配向は、プラナー(すなわち、ここで液晶分子は、層に対して実質的に平行に配列されている)、ホメオトロピック(層に対して直角または垂直である)、またはティルトであり得る。
重合性液晶(LC)材料は、室温では安定である一方、高温に供されると劣化し得る。例えば、ある期間加熱させられると、分散またはリターダンスなどの光学特性は減少し、そのため光学膜の性能は時間とともに劣化する。これは、とりわけ、低重合化度、およびポリマー中の対応する残留フリーラジカルの高含量、ポリマー収縮、および/または熱酸化的な劣化に起因し得る。
JP 5054456 B2は、1種以上の二反応性メソゲン化合物、およびCibaから入手可能なOxe02およびAdekaから入手可能なN-1919 (T)の市販の光開始剤を含む重合性液晶(LC)材料を記載する。
- 基体に対して好ましい接着を示し、
- VIS光に対して高度に透明であり、
- 時間とともに黄色く着色すること(黄変)の低減を呈し、および
- 高い温度での好ましい安定性または耐久性を示すべきであり、加えて、
- 均一に配列されたポリマー膜は、大量生産のための一般的に知られている適合性のある方法によって生産されるべきである
驚くべきことに、本発明の発明者らは、上の要求の目的の1以上、好ましくはすべてが、請求項1に記載の重合性LC材料を使用することによって、好ましくは同時に、達成され得ることを見出した。
それゆえ、本発明は、少なくとも1種の二反応性または多反応性のメソゲン化合物、および式CO-1で表される少なくとも1種の化合物を含む重合性LC材料に関する。
さらに、本発明はまた、対応する、重合性LC材料の生産方法にも関する。
本明細書に使用されるとき、用語「ポリマー」は、1以上の違うタイプの繰り返し単位(分子の最小構成単位)の主鎖を網羅する分子を意味するものと理解されるであろう。前記用語は、一般的に知られている用語「オリゴマー」、「コポリマー」、「ホモポリマー」等々を包含する。さらに、用語ポリマーは、ポリマー自体に加えて、開始剤からの残留物、触媒、およびかかるポリマーの合成に関与する他の要素も包含するものと理解されるであろう。前記ポリマーにおいて、かかる残留物は、それへと共有結合的に組み込まれないないものとして理解される。さらに、かかる残留物および他の要素は、重合後の精製プロセスの間中に通常取り除かれるものの、それらが一般に、容器間または溶媒間または分散媒体間で移されるときポリマーとともに残存するように、典型的にはポリマーとともに混合されているか、または共に混ざり合わされている。
用語「膜」および「層」は、機械的安定性をもつ、剛直なまたはフレキシブルな、自立したまたは独立した膜、ならびに支持基体上のまたは2基体間のコーティングまたは層を包含する。
可視光は、約400nmから約740nmまでの範囲の波長を有する電磁照射である。紫外(UV)光は、約200nmから約450nmまでの範囲の波長をもつ電磁照射である。
Ee=dθ/dA
として定義される。
放射露光または放射線量(He)は、時間(t)あたりの照射または照射力(Ee):
He=Ee・t
である。
用語「透明点」は、最も高い温度範囲をもつメソ相と、等方相との間の転移が生じる温度を意味する。
用語「プラナー構造」または「プラナー配向」は、光学軸が、膜面に対して実質的に平行であるところの膜を指す。
用語「Cプレート」は、一軸性複屈折材料の層を利用する光学的リターダーを指すが、その異常軸は、層の平面に対して垂直に配向する。
Δn=ne-no
のとおりに定義され、式中neは、異常光屈折率であり、およびnoは、常光屈折率であり、および平均屈折率nav.は、以下の式:
nav.=((2no 2+ne 2)/3)1/2
によって与えられる。
平均屈折率nav.および常光屈折率noは、Abbe屈折計を使用して測定され得る。Δnは、次いで、上の等式から計算され得る。
すべての物理的特性は、"Merck Liquid Crystals, Physical Properties of Liquid Crystals", Status Nov. 1997, Merck KgaA、Germanyに従って決定されてきた、および決定されており、別段の明示的な言及がない限り、20℃の温度に対して与えられる。光学的異方性(Δn)は、589.3nmの波長にて決定される。
所定の一般式において別段の明示的な言及がない限り、以下の用語は、以下の意味を有する:
好ましいアルキニル基は、例えば、エチニル、プロピニル、ブチニル、ペンチニル、シクロペンチニル、ヘキシニル、シクロヘキシニル、ヘプチニル、シクロヘプチニル、オクチニル、シクロオクチニル等である。
好ましいアミノ基は、例えば、ジメチルアミノ、メチルアミノ、メチルフェニルアミノ、フェニルアミノ等である。
キノキサリンイミダゾール、ベンゾオキサゾール、ナフトオキサゾール、アントロオキサゾール、フェナントロオキサゾール、イソオキサゾール、ベンゾチアゾール、ベンゾフラン、イソベンゾフラン、ジベンゾフラン、キノリン、イソキノリン、プテリジン、ベンゾ-5,6-キノリン、ベンゾ-6,7-キノリン、ベンゾ-7,8-キノリン、ベンゾイソキノリン、アクリジン、フェノチアジン、フェノキサジン、ベンゾピリダジン、ベンゾピリミジン、キノキサリン、フェナジン、ナフチリジン、アザカルバゾール、ベンゾカルボリン、フェナントリジン、フェナントロリン、チエノ[2,3b]チオフェン、チエノ[3,2b]チオフェン、ジチエノチオフェン、イソベンゾチオフェン、ジベンゾチオフェン、ベンゾチアジアゾチオフェン等の縮合基、またはこれらの基の組み合わせである。ヘテロアリール基はまた、アルキル、アルコキシ、チオアルキル、フッ素、フルオロアルキル、またはさらなるアリールまたはヘテロアリールの基によっても置換されていてもよい。
は、好ましくは、
であり、
式中Lは、どの出現においても同一であるかまたは異なっており、以上以下において与えられる意味の1つを有し、好ましくはF、Cl、CN、NO2、CH3、C2H5、C(CH3)3、CH(CH3)2、CH2CH(CH3)C2H5、OCH3、OC2H5、COCH3、COC2H5、COOCH3、COOC2H5、CF3、OCF3、OCHF2、OC2F5またはP-Sp-、極めて好ましくはF、Cl、CN、CH3、C2H5、OCH3、COCH3、OCF3またはP-Sp-、最も好ましくはF、Cl、CH3、OCH3、COCH3またはOCF3である。
重合性基(P)は好ましくは、C=C二重結合またはC≡C三重結合、および開環を伴う重合に好適な基、例えば、オキセタンまたはエポキシド基等、を含有する群から選択される。
CH2=CW2-(O)k3-、CW1=CH-CO-(O)k3-、CW1=CH-CO-NH-、CH2=CW1-CO-NH-、CH3-CH=CH-O-、(CH2=CH)2CH-OCO-、(CH2=CH-CH2)2CH-OCO-、(CH2=CH)2CH-O-、(CH2=CH-CH2)2N-、(CH2=CH-CH2)2N-CO-、CH2=CW1-CO-NH-、CH2=CH-(COO)k1-Phe-(O)k2-、CH2=CH-(CO)k1-Phe-(O)k2-、Phe-CH=CH-からなる群から選択され、式中
W2は、H、または1~5個のC原子を有するアルキルを、とりわけH、メチル、エチルまたはn-プロピルを示し、
および
であり、式中W2は、H、または1~5個のC原子を有するアルキル、とりわけH、メチル、エチルまたはn-プロピルを示す。
とくに好ましいのは、以下の式から選択される多反応性重合性ラジカルである:
-X-アルキル-C(CH2Px)(CH2Py)-CH2Pz I*b
-X-アルキル-CHPxCHPy-CH2Pz I*c
-X-アルキル-C(CH2Px)(CH2Py)-CaaH2aa+1 I*d
-X-アルキル-CHPx-CH2Py I*e
-X-アルキル-CHPxPy I*f
-X-アルキル-CPxPy-CaaH2aa+1 I*g
-X-アルキル-C(CH2Pv)(CH2Pw)-CH2OCH2-C(CH2Px)(CH2Py)CH2Pz I*h
-X-アルキル-CH((CH2)aaPx)((CH2)bbPy) I*i
-X-アルキル-CHPxCHPy-CaaH2aa+1 I*k
式中
Xは、X’について示される意味の1つを有し、および
Pv~Pzは各々、相互に独立して、Pについて上に示される意味の1つを有する。
YxxおよびYyyは、各々相互に独立して、H、F、Cl、またはCNを示し、
X’は、好ましくは-O-、-S-、-CO-、-COO-、-OCO-、-O-COO-、-CO-NRxx-、-NRxx-CO-、-NRxx-CO-NRyy-または単結合である。
とりわけ好ましい基-X’-Sp’-は、-(CH2)p1-、-O-(CH2)p1-、-OCO-(CH2)p1-、-OCOO-(CH2)p1-であり、ここでp1は、1から12までの整数である。
- グラフトポリマー分子は、1以上の側鎖が、構造的にまたは配置的に、主鎖とは異なる分枝のポリマーである。
- スターポリマー分子は、単一の分枝点が、複数の線状の鎖またはアームを生じさせる、分枝のポリマー分子である。アームが同一である場合、スターポリマー分子は、規則性であると言われる。隣接するアームが、異なる繰り返しサブユニットから構成される場合、スターポリマー分子は、混合鎖であると言われる。
- 櫛型ポリマー分子は、2以上の3方向の分枝点および線状側鎖をもつ主鎖からなる。アームが同一である場合、櫛型ポリマー分子は、規則性であると言われる。
- ブラシ状ポリマー分子は、線状の、非分枝の側鎖をもつ主鎖からなり、前記側鎖において、分枝点の1以上が、4方向またはより大きい官能性を有する。
式CO-1で表される好ましいカルバゾールオキシムエステル光開始剤は、以下の式CO-2~CO-10、
式中、L31、L32、およびR31は、式CO-1の下、上に定義されるとおりの意味の1つを有する、
で表される化合物の群から選択される。
式中、L31、L32、およびR31は、式CO-1の下、上に定義されるとおりの意味の1つを有する、
から選択されるカルバゾールオキシムエステル光開始剤である。
式中、L31、L32、およびR31は、式CO-1の下、上に定義されるとおりの意味の1つを有する、
から選択されるカルバゾールオキシムエステル光開始剤である。
P1-Sp1-MG-Sp2-P2 DRM
から選択され、式中
Sp1およびSp2は、互いに独立して、スペーサー基または単結合を表し、および
MGは、棒状のメソゲン基であり、これは、好ましくは式MG
-(A1-Z1)n-A2- MG
から選択され、式中
Z1は、複数存在する場合、相互に独立して、-O-、-S-、-CO-、-COO-、-OCO-、-S-CO-、-CO-S-、-O-COO-、-CO-NR00-、-NR00-CO-、-NR00-CO-NR000、-NR00-CO-O-、-O-CO-NR00-、-OCH2-、-CH2O-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-CH2CH2-、-(CH2)n1、-CF2CH2-、-CH2CF2-、-CF2CF2-、-CH=N-、-N=CH-、-N=N-、-CH=CR00-、-CY1=CY2-、-C≡C-、-CH=CH-COO-、-OCO-CH=CH-または単結合を表し、
nは、1、2、3または4、好ましくは1または2、最も好ましくは2であり、
n1は、1から10までの整数、好ましくは1、2、3または4である。
P0は、複数存在する場合、相互に独立して、重合性基、好ましくはアクリル基、メタアクリル基、オキセタン基、エポキシ基、ビニル基、ヘプタジエン基、ビニルオキシ基、プロペニルエーテル基またはスチレン基であり、
xおよびyは、互いに独立して、0であるか、または同一のまたは異なる1から12までの整数であり、
zは各々、および独立して、0または1であるが、隣接するxまたはyが0のとき、zは0である。
P1-Sp1-MG-R MRM
から選択され、
Rは、F、Cl、Br、I、-CN、-NO2、-NCO、-NCS、-OCN、-SCN、-C(=O)NRxRy、-C(=O)X、-C(=O)ORx、-C(=O)Ry、-NRxRy、-OH、-SF5、任意に置換されていてもよいシリル、1~12個の、好ましくは1~6個のC原子をもつ直鎖または分枝のアルキル、アルコキシ、アルキルカルボニル、アルコキシカルボニル、アルキルカルボニルオキシまたはアルコキシカルボニルオキシであり、ここで1以上のH原子は、FまたはClによって任意に置き換えられていてもよく、
RxおよびRyは、互いに独立して、H、または1~12個のC原子をもつアルキルである。
好ましくは、式MRMで表される単反応性メソゲン化合物は、以下の式から選択される。
Z0は、-COO-、-OCO-、-CH2CH2-、-CF2O-、-OCF2-、-CH=CH-、-OCO-CH=CH-、-CH=CH-COO-、または単結合であり、
A0は、複数存在する場合、相互に独立して、非置換であるか、または1、2、3または4個の基Lで置換された1,4-フェニレン、またはトランス-1,4-シクロヘキシレンであり、
wは、0または1であり、
およびここで、ベンゼン環およびナフタレン環は、加えて、1以上の同一であるかまたは異なっている基Lで置換され得る。
別の好ましい態様において、重合性LC材料は、2個より少ない重合性基を有する重合性メソゲン化合物を含有しない。
別の好ましい態様において、重合性LC材料は、アキラル材料である、すなわち、いずれのキラル重合性メソゲン化合物をも、他のキラル化合物をも含有しない。
これらの反応性シンナーはさらにまた、例えば、エポキシドまたはウレタン(メタ)アクリラートであってもよい。
かかるエポキシドおよびウレタン(メタ)アクリラートは、「混合形態」として上に列挙される化合物の中に包含されている。
かかる助剤はまた、例えば、FluorN(登録商標)561またはFluorN(登録商標)562としてCytonixからも入手可能である。
かかる助剤はまた、例えば、Tivida(登録商標)FL2300およびTivida(登録商標)FL2500としてCytonixからも入手可能である。
群c4)における助剤は、液晶組成物の総重量に基づいて、約0から3.0重量%まで、好ましくは約0から1.5重量%までの割合で任意に採用される。
これらの助剤は、これらの添加剤を含有する色素粒子の静電反発および/または立体障害を本質的に通して、色素分散を安定化させ、ここで後者のケースにおいて、助剤とその周囲の媒体(例えばバインダー)との相互作用が、主要な役割を果たす。
基体の、および例えばそれらのプリントまたはコーティングのために意図される、プリントインク、コーティング組成物およびペイントの、幅広く変動する物理的および化学的性質の観点から、接着促進システムの多様性は、驚くべきことではない。
2,6-ジ-tert-ブチル-4-メチルフェノール、2-tert-ブチル-4,6-ジメチルフェノール、2,6-ジ-tert-ブチル-4-エチルフェノール、2,6-ジ-tert-ブチル-4-n-ブチルフェノール、2,6-ジ-tert-ブチル-4-イソブチルフェノール、2,6-ジシクロペンチル-4-メチルフェノール、2-(α-メチルシクロヘキシル)-4,6-ジメチルフェノール、2,6-ジオクタデシル4-メチルフェノール、2,4,6-トリシクロヘキシルフェノール、2,6-ジ-tert-ブチル-4-メトキシメチルフェノール、線状または分枝の側鎖を有するノニルフェノール(例えば2,6-ジノニル-4-メチルフェノール、2,4-ジメチル-6-(1’-メチルウンデク-1’-イル)フェノール、2,4-ジメチル-6-(1’-メチルヘプタデク-1’-イル)フェノール、2,4-ジメチル-6-(1’-メチルトリデク-1’-イル)フェノールのノニフェノールおよびこれら化合物の混合物)などのアルキル化物フェノール、2,4-ジオクチルチオメチル-6-tert-ブチルフェノール、2,4-ジオクチルチオメチル-6-メチルフェノール、2,4-ジオクチルチオメチル-6-エチルフェノールおよび2,6-ジドデシルチオメチル-4-ノニルフェノールなどのアルキルチオメチルフェノール、
a) 1種以上の二反応性または多反応性の重合性メソゲン化合物、
b) 任意に1種以上の単反応性重合性メソゲン化合物、
c) 任意に1種以上の抗酸化剤添加剤、
d) 任意に1種以上の接着促進剤、
e) 任意に1種以上の界面活性剤、
f) 任意に1種以上の安定剤、
g) 任意に1種以上の単反応性、二反応性または多反応性の重合性非メソゲン化合物、
h) 光重合を開始させるために使用される波長で最大吸収を示す1種以上の染料、
i) 任意に1種以上の連鎖移動剤、
j) 任意に1種以上の安定剤、
k) 任意に1種以上の潤滑および流動助剤、および
l) 任意に1種以上の希釈剤
を含む。
a) 式CO-1で表される1種以上の光開始剤(好ましくは式CO-19~22で表される化合物、より好ましくは式CO-19で表される化合物から選択される)を、好ましくは0.1~10重量%の、極めて好ましくは0.5~8重量%の量で、
- 基体上に、以上以下に記載されるとおりの重合性LC材料の層を提供すること、
- 重合性LC材料を光重合化によって重合化すること、および
- 任意に、重合されたLC材料を基体から取り除くこと、および/または任意に、別の基体上にそれを提供すること
によって、ポリマー膜を調製する方法に関する。
重合性LC材料を好適な溶媒に溶解することもまた、可能である。
次いで、この溶液は、基体上に、例えばスピンコーティング、プリンティング、または他の知られている技術によって、コーティングまたはプリントされ、および溶媒は、重合前に溶媒中は留去される。ほとんどのケースにおいて、溶媒の蒸発を容易にするために、混合物を加熱することが好適である。
RM層および基体の表面エネルギーを比較することによって、混合物が、均一のプラナー配列または均一のホメオトロピック配列を採択するであろうかを予測するために、Friedel-Creagh-Kmetz則:
γRM>γSの場合、反応性メソゲン化合物は、ホメオトロピック配列を表示するであろうし、γRM<γSの場合、反応性メソゲン化合物は、ホメオトロピック配列を表示するであろう、
が使用され得る。
光重合化は、好ましくは1から70℃までの、より好ましくは5~50℃の、なおより好ましくは15~30℃の温度にて実行される。
入射ビームの波長(λ)の関数としての、ポリマー膜の光学リターデーション(δ(λ))は、以下の式(7):
δ(λ)=(2πΔn・d)/λ (7)
により与えられ、式中(Δn)は、膜の複屈折であり、(d)は、膜の厚さであり、およびλは、入射ビームの波長である。
Δn=sinΘ/sinΨ (8)
のとおりに定義され、式中sinΘは、膜における入射角または光学軸のティルト角であり、sinΨは、対応する反射角である。
本発明に従うポリマー膜の厚さの関数としての光学リターデーションは、200nm未満、好ましくは180nm未満、なおより好ましくは150nm未満である。
殊のほかインセル適用に関し、本発明に従うポリマー膜は、高温安定性を呈する。それゆえ、ポリマー膜は、最大300℃まで、好ましくは最大250℃まで、より好ましくは最大230℃までの温度安定性を呈する。
以下のホスト混合物H-1を調製する。
Irganox1076(登録商標)は、市販されている安定剤である(Ciba AG, Basel, Switzerland)。FluorN 562は、市販されていある界面活性剤である(Cytonix, USA)。
** 本発明に従う式CO-21で表される化合物は、TR-PBG-304として、Changzhou Tronly New Electronic Materials CO., Ltd, Chinaから市販されているものである。
5.00%の種々の光開始剤(cf. 表2)を、上に記載のホスト混合物H-1のバルク中へドープすることによって、試験混合物を調製する。各場合において、混合物を、25%~30%個体の範囲内で、PGMEAに溶解させる。各混合物を、基体としての原板上に、1000rpmで30sec.スピンコーティングする。次いで、コーティングされた膜を、80℃の高温にて1分間アニールし、および250~450nmのオムニキュアにおいて、N2雰囲気下(8sec.、150mW)で夫々硬化する。
** Adeka, Japanから入手可能なN1919Tでの比較例。
*** 本発明に従う式CO-21およびCO-25で表される化合物は、TR-PBG-304およびTR-PBG-314として夫々、Changzhou Tronly New Electronic Materials CO., Ltd, Chinaから市販されているものである。
5.60%の種々の光開始剤(cf. 表3)を、上に記載のホスト混合物H-2のバルク中へドープすることによって、試験混合物を調製する。各場合において、混合物を、25%~30%固体の範囲内で、メチルエチルケトン/メチルイソブチルケトン/シクロヘキサノン(1:1:1)に溶解させる。各混合物を、基体としての原板上に、2000rpmで30sec.スピンコーティングする。次いで、コーティングされた膜を、50℃の高温にて1分間アニールし、および250~450nmのオムニキュアにおいて、N2雰囲気下(1.8s、150mW)で夫々硬化する。
** 本発明に従う式CO-25で表される化合物は、TR-PBG-314として、Changzhou Tronly New Electronic Materials CO., Ltd, Chinaから市販されているものである。
*** 本発明に従う式CO-25で表される化合物は、TR-PBG-314として、Changzhou Tronly New Electronic Materials CO., Ltd, Chinaから市販されているものである。
Claims (14)
- 少なくとも1種の二反応性または多反応性のメソゲン化合物および式CO-1
L31は、-(Sp31-A32)を示し、
L32は、H、1~5個以上のC原子をもつ、アルキル、アルコキシ、チオアルキル、アルキルカルボニル、アルコキシカルボニル、アルキルカルボニルオキシまたはアルコキシカルボニルオキシ;またはF、Cl、CN、NO2、OCN、SCN、または1~4個の炭素原子をもつモノ-、オリゴ-またはポリフッ素化されたアルキルまたはアルコキシ;または-(Sp31-A31)を示し、
Sp31は、スペーサー基または単結合を示し、
A31は、各々および独立して、シリル、スルホ、スルホニル、ホルミル、アミン、イミン、ニトリル、メルカプト、ニトロ、ハロゲン、C1~12アルキル、C6~12アリール、C1~12アルコキシ、ヒドロキシル、またはこれらの基の組み合わせを含む群から選択される1以上の置換基を任意に有していてもよい、アリール基、ヘテロアリール基、(非芳香族)脂環式基またはヘテロ環基を示し、
A32は、各々および独立して、シリル、スルホ、スルホニル、ホルミル、アミン、イミン、ニトリル、メルカプト、ニトロ、ハロゲン、C1~12アルキル、C6~12アリール、C1~12アルコキシ、ヒドロキシル、またはこれらの基の組み合わせを含む群から選択される1以上の置換基を任意に有していてもよい、アリール基、ヘテロアリール基、(非芳香族)脂環式基またはヘテロ環基を示し、および
R31は、H、または1~12個のC原子を有するアルキルを示す、
前記重合性LC材料。 - 少なくとも1種の二反応性または多反応性のメソゲン化合物が、式DRM
P1-Sp1-MG-Sp2-P2 DRM
から選択され、式中
P1およびP2は、互いに独立して、重合性基を示し、
Sp1およびSp2は、互いに独立して、スペーサー基または単結合であり、および
MGは、棒状のメソゲン基であり、前記基は、好ましくは式MG
-(A1-Z1)n-A2- MG
から選択され、式中
A1およびA2は、複数存在する場合、相互に独立して、芳香族基、または脂環式基を示し、前記基は、N、OおよびSから選択される1以上のヘテロ原子を任意に含有していてもよく、およびL1によって任意に単置換または多置換されていてもよく、
L1は、P-Sp-、F、Cl、Br、I、-CN、-NO2、-NCO、-NCS、-OCN、-SCN、-C(=O)NR00R000、-C(=O)OR00、-C(=O)R00、-NR00R000、-OH、-SF5、任意に置換されていてもよいシリル、1~12個のC原子をもつアリールまたはヘテロアリール、1~12個のC原子をもつ直鎖または分枝のアルキル、アルコキシ、アルキルカルボニル、アルコキシカルボニル、アルキルカルボニルオキシまたはアルコキシカルボニルオキシであり、ここで1個以上のH原子が、FまたはClによって任意に置き換えられていてもよく、
Pは重合性基であり、
Spはスペーサー基であり、
R00およびR000は、互いに独立して、H、または1~12個のC原子をもつアルキルを示し、
Z1は、複数存在する場合、相互に独立して、-O-、-S-、-CO-、-COO-、-OCO-、-S-CO-、-CO-S-、-O-COO-、-CO-NR00-、-NR00-CO-、-NR00-CO-NR000-、-NR00-CO-O-、-O-CO-NR00-、-OCH2-、-CH2O-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-CH2CH2-、-(CH2)n1-、-CF2CH2-、-CH2CF2-、-CF2CF2-、-CH=N-、-N=CH-、-N=N-、-CH=CR00-、-CY1=CY2-、-C≡C-、-CH=CH-COO-、-O-CO-CH=CH-または単結合を示し、
Y1およびY2は、互いに独立して、H、F、ClまたはCNを示し、
nは、1、2、3または4であり、および
n1は、1から10までの整数である、
請求項1に記載の重合性LC材料。 - 少なくとも1種の二反応性のメソゲン化合物が、以下の式
P0は、複数存在する場合、相互に独立して、アクリル基、メタアクリル基、オキセタン基、エポキシ基、ビニル基、ヘプタジエン基、ビニルオキシ基、プロペニルエーテル基、またはスチレン基であり、
Lは、各々が同一の存在であるかまたは異なって存在するとき、式DRMにおいてL1に与えられる意味の1つを有し、
rは0、1、2、3または4であり、
xおよびyは、互いに独立して、0であるか、または1から12までの同一のまたは異なる整数であり、
zは、各々および独立して、0または1であるが、ただし隣接するxまたはyが、0である場合、zは0である、
請求項2に記載の重合性LC材料。 - 式MRM
P1-Sp1-MG-R MRM
式中P1、Sp1、およびMGは、式DRMにおいて与えられるとおりの意味を有し、
Rは、F、Cl、Br、I、-CN、-NO2、-NCO、-NCS、-OCN、-SCN、-C(=O)NRxRy、-C(=O)X、-C(=O)ORx、-C(=O)Ry、-NRxRy、-OH、-SF5、任意に置換されていてもよいシリル、1~12個のC原子をもつ直鎖または分枝のアルキル、アルコキシ、アルキルカルボニル、アルコキシカルボニル、アルキルカルボニルオキシ、またはアルコキシカルボニルオキシであり、ここで1個以上のH原子が、FまたはClによって任意に置き換えられていてもよく、
Xは、ハロゲン、好ましくはFまたはClであり、および
RxおよびRyは、互いに独立して、H、または1~12個のC原子をもつアルキルである、
から選択される、少なくとも1種の単反応性のメソゲン化合物を含む、請求項2に記載の重合性LC材料。 - 少なくとも1種の単反応性のメソゲン化合物が、以下の式
P 0 は、複数存在する場合、相互に独立して、アクリル基、メタアクリル基、オキセタン基、エポキシ基、ビニル基、ヘプタジエン基、ビニルオキシ基、プロペニルエーテル基、またはスチレン基であり、
Lは、各々が同一の存在であるかまたは異なって存在するとき、式DRMにおいてL 1 に与えられる意味の1つを有し、
rは0、1、2、3または4であり、
xおよびyは、互いに独立して、0であるか、または1から12までの同一のまたは異なる整数であり、
zは、各々および独立して、0または1であるが、ただし隣接するxまたはyが、0である場合、zは0である、
R0は、1以上、好ましくは1~15個のC原子をもつアルキル、アルコキシ、チオアルキル、アルキルカルボニル、アルコキシカルボニル、アルキルカルボニルオキシ、またはアルコキシカルボニルオキシであるか、またはY0を示し、
Y0は、F、Cl、CN、NO2、OCH3、OCN、SCN、SF5、または1~4個のC原子をもつ、モノ-、オリゴ-、またはポリフッ素化アルキルまたはアルコキシであり、
Z0は、-COO-、-OCO-、-CH2CH2-、-CF2O-、-OCF2-、-CH=CH-、-OCO-CH=CH、-CH=CH-COO-、または単結合であり、
A0は、複数存在する場合、相互に独立して、非置換であるかまたは1、2、3または4基のLで置換された1,4-フェニレン、またはトランス-1,4-シクロヘキシレンであり、
uおよびvは、互いに独立して、0、1または2であり、
wは、0または1であり、および
ここでベンゼン環およびナフタレン環は加えて、1以上の同一のまたは異なる基Lで置換され得る、
請求項4に記載の重合性LC材料。 - 二反応性または多反応性のメソゲン化合物の割合が、5から90重量%までの範囲にある、請求項1~5のいずれか一項に記載の重合性LC材料。
- 単反応性のメソゲン化合物の割合が、5から80重量%までの範囲にある、請求項4または5に記載の重合性LC材料。
- 1種以上の抗酸化剤を含む、請求項1~7のいずれか一項に記載の重合性LC材料。
- 界面活性剤、さらなる安定剤、触媒、増感剤、阻害剤、連鎖移動剤、共反応モノマー、反応性シンナー、界面活性化合物、潤滑剤、湿滑剤、分散剤、疎水化剤、接着剤、流動性改善剤、脱泡または消泡剤、脱気剤、希釈剤、反応性希釈剤、助剤、着色料、染料、色素およびナノ粒子からなる群から選択される1以上の添加剤を任意に含む、請求項1~8のいずれか一項に記載の重合性LC材料。
- 式CO-1で表される1種以上の化合物を、少なくとも1種の二反応性または多反応性のメソゲン化合物と混合するステップを含む、請求項1~9のいずれか一項に記載の重合性LC材料の調製のためのプロセス。
- - 請求項1~9のいずれか一項に記載の重合性LC材料の層を基体上へ提供すること、
- 重合性LC材料を光重合すること、および
- 任意に、重合したLC材料を基体から取り除くこと、および/または任意に、それを別の基体上へ提供すること
による、ポリマー膜の調製のためのプロセス。 - 重合前に、式CO-1で表される少なくとも1種の化合物を添加することによって、少なくとも1種の二反応性または多反応性のメソゲン化合物を含む、請求項1~9のいずれか一項に記載の重合性LC材料から得られるポリマー膜の耐久性を増大させる方法。
- 液晶ディスプレイ、3Dディスプレイ、プロジェクションシステム、偏光子、補償板、配向層、円偏光子、カラーフィルター、装飾画像、液晶色素、空間的に変動する反射色をもつ反射膜、多色画像、偽造不可能な文書の、光学用途、電気光学用途、情報ストレージ用途、装飾用途および保安用途における、請求項1~9のいずれか一項に記載の重合性LC材料の使用。
- 請求項1~9のいずれか一項に記載の重合性LC材料を含む、光学コンポーネントまたは光学デバイス、偏光子、パターン化リターダー、補償板、配向層、円偏光子、カラーフィルター、装飾画像、液晶レンズ、液晶色素、空間的に変動する反射色をもつ反射膜、装飾用または情報ストレージ用の多色画像。
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