JP2006137856A - Polymerizable liquid crystal composition and cured product of the same - Google Patents
Polymerizable liquid crystal composition and cured product of the same Download PDFInfo
- Publication number
- JP2006137856A JP2006137856A JP2004328949A JP2004328949A JP2006137856A JP 2006137856 A JP2006137856 A JP 2006137856A JP 2004328949 A JP2004328949 A JP 2004328949A JP 2004328949 A JP2004328949 A JP 2004328949A JP 2006137856 A JP2006137856 A JP 2006137856A
- Authority
- JP
- Japan
- Prior art keywords
- group
- liquid crystal
- crystal composition
- polymerizable liquid
- diyl group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 119
- 239000000203 mixture Substances 0.000 title claims abstract description 104
- 239000003999 initiator Substances 0.000 claims abstract description 23
- 239000002516 radical scavenger Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims description 41
- -1 amine compound Chemical class 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- 125000004959 2,6-naphthylene group Chemical group [H]C1=C([H])C2=C([H])C([*:1])=C([H])C([H])=C2C([H])=C1[*:2] 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 claims description 4
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 4
- 101150065749 Churc1 gene Proteins 0.000 claims description 4
- 102100038239 Protein Churchill Human genes 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 230000006750 UV protection Effects 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 239000012071 phase Substances 0.000 description 48
- 239000010408 film Substances 0.000 description 40
- 239000000758 substrate Substances 0.000 description 37
- 239000004642 Polyimide Substances 0.000 description 25
- 229920001721 polyimide Polymers 0.000 description 25
- 239000008096 xylene Substances 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 150000001412 amines Chemical group 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 150000003738 xylenes Chemical class 0.000 description 10
- 230000001678 irradiating effect Effects 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 0 CC1(C)N(C)C(C)(C)CC(*CCCS(CC2)C*2C2CC(C)(*)N(C)C(C)(C)C2)C1 Chemical compound CC1(C)N(C)C(C)(C)CC(*CCCS(CC2)C*2C2CC(C)(*)N(C)C(C)(C)C2)C1 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CVSXFBFIOUYODT-UHFFFAOYSA-N 178671-58-4 Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)=C(C#N)C(=O)OCC(COC(=O)C(C#N)=C(C=1C=CC=CC=1)C=1C=CC=CC=1)(COC(=O)C(C#N)=C(C=1C=CC=CC=1)C=1C=CC=CC=1)COC(=O)C(C#N)=C(C=1C=CC=CC=1)C1=CC=CC=C1 CVSXFBFIOUYODT-UHFFFAOYSA-N 0.000 description 1
- 150000004786 2-naphthols Chemical class 0.000 description 1
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical class C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical class CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002999 depolarising effect Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- YBGZDTIWKVFICR-UHFFFAOYSA-N octinoxate Chemical compound CCCCC(CC)COC(=O)C=CC1=CC=C(OC)C=C1 YBGZDTIWKVFICR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000003232 pyrogallols Chemical class 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Diffracting Gratings Or Hologram Optical Elements (AREA)
- Liquid Crystal (AREA)
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Polarising Elements (AREA)
Abstract
Description
本発明は重合性を有する液晶組成物、及びこれの硬化物に関する。 The present invention relates to a polymerizable liquid crystal composition and a cured product thereof.
重合性官能基を有する液晶（以下、重合性液晶という）は、液晶としての性質とモノマーとしての性質を持つ。液晶としての性質を利用して配向させ、これに紫外線（UV）を照射すると、その配向状態を固定化した高分子を作製できる。液晶は種々の配向状態を容易に得ることが可能であるため、配向制御が必要な高分子、例えば位相差フィルム、偏光ビームスプリッター、光学的ローパスフィルター、ホログラム素子などの作製原料として有用である。 A liquid crystal having a polymerizable functional group (hereinafter referred to as a polymerizable liquid crystal) has properties as a liquid crystal and a property as a monomer. By aligning using the properties as a liquid crystal and irradiating it with ultraviolet light (UV), a polymer in which the alignment state is fixed can be produced. Since liquid crystal can easily obtain various alignment states, it is useful as a raw material for producing polymers that require alignment control, such as retardation films, polarizing beam splitters, optical low-pass filters, and hologram elements.
このような応用の際、耐UV性は重要である。耐UV性が良好でないと、UVへの暴露によって黄変や、位相差などの光学パラメータの変化を引き起こしてしまう。 In such applications, UV resistance is important. If UV resistance is not good, exposure to UV causes yellowing and changes in optical parameters such as phase difference.
通常のモノマーの技術分野では、モノマーに紫外線吸収剤を添加することによって耐UV性を向上させている。重合性液晶材料の技術分野でも、紫外線吸収剤の使用が技術文献１及び２に開示されている。しかしながら、紫外線吸収剤を添加すると、高分子を作製する際の紫外線照射において、重合・硬化が著しく阻害されるため、紫外線照射による重合を迅速に行うための光重合開始剤の添加量を、紫外線吸収剤を添加していない場合と比較して著しく増やす必要があるという問題があった。光重合開始剤の添加量の増加は、例えば、液晶温度範囲を狭くしたり、複屈折率が小さくしてしまう。また、重合性液晶組成物が重合しやすくなるため、保存安定性を悪化させてしまうという問題があった。 In the technical field of ordinary monomers, UV resistance is improved by adding an ultraviolet absorber to the monomers. Also in the technical field of polymerizable liquid crystal materials, the use of ultraviolet absorbers is disclosed in Technical Documents 1 and 2. However, when an ultraviolet absorber is added, polymerization and curing are significantly inhibited in ultraviolet irradiation when preparing a polymer. Therefore, the amount of photopolymerization initiator added for rapid polymerization by ultraviolet irradiation is reduced to ultraviolet rays. There was a problem that it was necessary to increase significantly compared with the case where no absorbent was added. An increase in the addition amount of the photopolymerization initiator, for example, narrows the liquid crystal temperature range or decreases the birefringence. Moreover, since the polymerizable liquid crystal composition is easily polymerized, there is a problem that storage stability is deteriorated.
本発明が解決しようとする課題は、重合性液晶組成物の紫外線による重合・硬化が著しく阻害されず、光重合開始剤の添加量を著しく増やす必要がなく、また、保存安定性を悪化させることなく重合性液晶組成物の硬化物の耐UV性を改善すること、及び耐UV性が改善した重合性液晶組成物の硬化物を提供することにある。 The problem to be solved by the present invention is that polymerization / curing of the polymerizable liquid crystal composition by ultraviolet rays is not significantly inhibited, it is not necessary to significantly increase the amount of photopolymerization initiator added, and storage stability is deteriorated. An object of the present invention is to improve the UV resistance of a cured product of a polymerizable liquid crystal composition and to provide a cured product of a polymerizable liquid crystal composition with improved UV resistance.
上記課題を解決するために鋭意検討した結果、重合性液晶組成物にラジカル捕獲剤を添加すれば良いことを見出した。即ち、本発明はラジカル捕獲剤を含有することを特徴とする重合性液晶組成物及び当該組成物の硬化物を提供する。 As a result of intensive studies in order to solve the above problems, it has been found that a radical scavenger may be added to the polymerizable liquid crystal composition. That is, the present invention provides a polymerizable liquid crystal composition containing a radical scavenger and a cured product of the composition.
本願発明の重合性液晶組成物は、光重合開始剤の添加量を著しく増やすこと無く当該組成物の硬化物の耐UV性を改善することが可能であり、位相差フィルム、偏光ビームスプリッター、光学的ローパスフィルター、ホログラム素子などの作製原料として有用である。 The polymerizable liquid crystal composition of the present invention can improve the UV resistance of a cured product of the composition without significantly increasing the addition amount of the photopolymerization initiator, and the retardation film, polarizing beam splitter, optical It is useful as a raw material for producing a typical low-pass filter and a hologram element.
ラジカル捕獲剤とはラジカル捕捉剤とも称し、反応中に生じるラジカルを効率よく捕らえるために用いられる化合物を指す。ラジカル捕獲剤の少量の添加により、ラジカル連鎖反応の反応速度を低下するか又は停止することが可能であり、ラジカル連鎖反応に起因する重合性液晶組成物の硬化物の分解反応を抑制することが可能となる。ラジカル捕獲剤はこの目的には安定なラジカルが一般に用いられる。 The radical scavenger is also referred to as a radical scavenger and refers to a compound used for efficiently capturing radicals generated during the reaction. By adding a small amount of a radical scavenger, the reaction rate of the radical chain reaction can be reduced or stopped, and the decomposition reaction of the cured product of the polymerizable liquid crystal composition resulting from the radical chain reaction can be suppressed. It becomes possible. As the radical scavenger, a stable radical is generally used for this purpose.
ラジカル捕獲剤は多くの種類が知られているが、重合性液晶組成物との親和性を考慮して選択することが好ましい。そのため、ラジカル捕獲剤の分子量は１０００以下であることが好ましく、８００以下がより好ましく、６００以下が特に好ましい。具体的にはメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ターシャーリーブチル基などの置換基を配したフェノール性水酸基を有する化合物、もしくはアミンをあげることができる。特に、嵩高い置換を配したアミンはヒンダードアミンと呼ばれており、本発明の用途に有用である。アミンとしては２級アミンが好ましく、３級アミンが特に好ましい。ヒンダードアミンの具体的な構造としては、一般式（I） Although many types of radical scavengers are known, it is preferable to select them in consideration of the affinity with the polymerizable liquid crystal composition. Therefore, the molecular weight of the radical scavenger is preferably 1000 or less, more preferably 800 or less, and particularly preferably 600 or less. Specifically, a compound having a phenolic hydroxyl group with a substituent such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a tertiary butyl group, or an amine can be given. In particular, amines with bulky substitutions are called hindered amines and are useful for the purposes of the present invention. As the amine, a secondary amine is preferable, and a tertiary amine is particularly preferable. The specific structure of the hindered amine has the general formula (I)
（式中、Rは水素原子もしくは炭素原子数１から５のアルキル基を表す。右端で連結するものとする）で表される部分構造を有していることが好ましい。このような化合物の具体的な例としては、式（I−１）および式（I−２）の化合物を例示することができる。 (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The partial structure is preferably connected at the right end). Specific examples of such compounds include compounds of formula (I-1) and formula (I-2).
（式中、R１は炭素原子数１１から２０のアルキル基を表す）
ラジカル捕獲剤の濃度は、重合性液晶組成物中で０．０１から０．５質量％の範囲であることが好ましい。
(Wherein R 1 represents an alkyl group having 11 to 20 carbon atoms)
The concentration of the radical scavenger is preferably in the range of 0.01 to 0.5% by mass in the polymerizable liquid crystal composition.
添加する光重合開始剤の濃度は、０．０１から７質量％が好ましい。光重合開始剤の添加濃度は、開始剤の種類や硬化プロセスによって変化するが、ラジカル捕獲剤を添加しない場合の最適濃度より、０．１〜２％増すのが好ましい。例えば、光重合開始剤として添加濃度が低くて良いアシルフォスフィンオキシド系化合物、例えば、商品名としてTPO（バスフ社製）、Irgacure-819（チバスペシャリティケミカルズ社製）などを使用する場合、添加濃度は０．０５から２質量％が好ましく、０．１から１．５質量％がさらに好ましく、０．２〜１質量％が特に好ましい。また、酸素阻害を受けにくく、重合の際の空気中でも硬化させることが可能な開始剤、例えば、商品名としてIrgacure-907（チバスペシャリティケミカルズ製などを使用する場合、添加濃度は２から７質量％が好ましく、３から６．５質量％がさらに好ましく、４〜６質量％が特に好ましい。 The concentration of the photopolymerization initiator to be added is preferably 0.01 to 7% by mass. The addition concentration of the photopolymerization initiator varies depending on the type of the initiator and the curing process, but it is preferably 0.1 to 2% higher than the optimum concentration when no radical scavenger is added. For example, when using an acyl phosphine oxide-based compound whose addition concentration may be low as a photopolymerization initiator, such as TPO (manufactured by Bassuf), Irgacure-819 (manufactured by Ciba Specialty Chemicals), etc. Is preferably 0.05 to 2% by mass, more preferably 0.1 to 1.5% by mass, and particularly preferably 0.2 to 1% by mass. In addition, an initiator that is not susceptible to oxygen inhibition and can be cured even in the air during polymerization, such as Irgacure-907 (made by Ciba Specialty Chemicals, Inc.), has an addition concentration of 2 to 7% by mass. 3 to 6.5% by mass is more preferable, and 4 to 6% by mass is particularly preferable.
本発明の重合性液晶組成物に含有される重合性液晶化合物としては、この技術分野で重合性液晶と認識されるものであれば特に制限なく使用することができる。このような重合性液晶化合物としては、一般式（II） The polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition of the present invention can be used without particular limitation as long as it is recognized as a polymerizable liquid crystal in this technical field. Such polymerizable liquid crystal compounds include those represented by the general formula (II)
（式中、A1、A2及びA3はそれぞれ独立的に、1,4-フェニレン基、1,4-シクロヘキシレン基、1,4-シクロヘキセニル基、テトラヒドロピラン-2,5-ジイル基、1,3-ジオキサン-2,5-ジイル基、テトラヒドロチオピラン-2,5-ジイル基、1,4-ビシクロ(2,2,2)オクチレン基、デカヒドロナフタレン-2,6-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基、フェナントレン-2,7-ジイル基、9,10-ジヒドロフェナントレン-2,7-ジイル基、1,2,3,4,4a,9,10a-オクタヒドロフェナントレン2,7-ジイル基又はフルオレン2,7-ジイル基を表し、該1,4-フェニレン基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基、フェナントレン-2,7-ジイル基、9,10-ジヒドロフェナントレン-2,7-ジイル基、1,2,3,4,4a,9,10a-オクタヒドロフェナントレン2,7-ジイル基及びフルオレン2,7-ジイル基は非置換であるか又は置換基として１個又は２個以上のF、Cl、CF3、OCF3又はCH3を有することができ、P1は反応性官能基を表し、S1は単結合、炭素原子数１〜１２のアルキレン基を表し、置換基として１個以上のF、Cl、CN、CH3またはCF3を有することができ、該アルキル基に存在する1個または2個以上のCH2基は、O原子が相互に直接結合しないものとしてO、CO又はCOOで置換されていてもよく、X1は、単結合、-O-、-COO-又は-OCO-を表し、Y1、及びY2はそれぞれ独立的に、単結合、-COO-、-OCO-、-CH＝N-、-N＝CH-、-C≡C-、-CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2O-、-OCH2CH2CH2-、-CH2O-、-OCH2-、-CF2O-、-OCF2-、-CH＝N-N＝CH-、-CF＝CF-、-CH＝CH-、-CH2CH2CH＝CH-、-CH＝CHCH2CH2-、-CH2CH＝CHCH2-、-CH=CHCOO-、-OCOCH=CH-、-CH2CH2COO-又は-OCOCH2CH2-を表し、Y3は単結合、-O-、-CO-、-COO-、-OCO-、-CH2-、-CH2O-、-OCH2-、-CONH-、-NHCO-、-CH2COO-又は-CH2OCO-を表し、Lは炭素原子数1〜18のアルキル基、炭素原子数2〜18のアルケニル基、ハロゲン原子、CN又はNCSを表し、該アルキル基又はアルケニル基は非置換であるか又は置換基として1個または2個以上のF、Cl、CN、CH3、又はCF3を有することができ、該アルキル基又はアルケニル基中に存在する1個または2個以上のCH2基は、O原子が相互に直接結合しないものとして、O、CO又はCOOで置換されていてもよく、もしくは、P1-S1-X1と同じ意味を表し、nは0、1、又は2を表す。）のような化合物を挙げることができる。一般式（II）のP1は反応性もしくは重合性官能基を表し、反応性もしくは重合性官能基として認識されるものであれば特に制限は無いが、下記の式（III-1）〜式（III-10）で表される構造から選択するのが好ましい。この中でも、式（III-1）、式（III-3）又は式（III-9）で表される構造が好ましく、式（III-1）で表される構造が特に好ましい。 Wherein A 1 , A 2 and A 3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group Pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6- Naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group or Represents a fluorene 2,7-diyl group, the 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl Group, 9,10-dihydrophenanthrene-2,7-diyl 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group and fluorene 2,7-diyl group are unsubstituted or have one or more F as substituents , Cl, CF 3 , OCF 3 or CH 3 , P 1 represents a reactive functional group, S 1 represents a single bond, an alkylene group having 1 to 12 carbon atoms, and one substituent One or two or more CH 2 groups present in the alkyl group can have the above F, Cl, CN, CH 3 or CF 3 , and O, CO Or X 1 represents a single bond, —O—, —COO— or —OCO—, and Y 1 and Y 2 each independently represent a single bond, —COO—, -OCO-, -CH = N-, -N = CH-, -C≡C-, -CH 2 CH 2- , -CH 2 CH 2 CH 2 CH 2- , -CH 2 CH 2 CH 2 O-, -OCH 2 CH 2 CH 2- , -CH 2 O-, -OCH 2- , -CF 2 O-, -OCF 2- , -CH = NN = CH-, -CF = CF-, -CH = CH- , -CH 2 CH 2 CH = CH-, -CH = CHCH 2 CH 2 —, —CH 2 CH═CHCH 2 —, —CH═CHCOO—, —OCOCH═CH—, —CH 2 CH 2 COO— or —OCOCH 2 CH 2 —, Y 3 represents a single bond, —O -, - CO -, - COO -, - OCO -, - CH 2 -, - CH 2 O -, - OCH 2 -, - CONH -, - NHCO -, - CH 2 COO- or -CH 2 OCO- L represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a halogen atom, CN or NCS, and the alkyl group or alkenyl group is unsubstituted or 1 as a substituent. Or two or more F, Cl, CN, CH 3 , or CF 3 , and one or more CH 2 groups present in the alkyl group or alkenyl group have an O atom As it is not directly bonded to, it may be substituted with O, CO or COO, or represents the same meaning as P 1 —S 1 —X 1, and n represents 0, 1, or 2. And the like. P 1 in the general formula (II) represents a reactive or polymerizable functional group and is not particularly limited as long as it is recognized as a reactive or polymerizable functional group, but the following formula (III-1) to formula It is preferable to select from the structure represented by (III-10). Among these, the structure represented by Formula (III-1), Formula (III-3), or Formula (III-9) is preferable, and the structure represented by Formula (III-1) is particularly preferable.
一般式（II）において、S1は炭素原子数１〜１２のアルキレン基が好ましく、炭素原子数2〜8のアルキレン基がさらに好ましく、3〜6のアルキレン基が特に好ましい。アルキレン基は、置換基として１個以上のF、Cl、CN、CH3またはCF3を有することができ、該アルキレン基に存在する1個または2個以上のCH2基は、O原子が相互に直接結合しないものとしてO、CO又はCOOで置換されていてもよい。 In the general formula (II), S 1 is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, and particularly preferably an alkylene group having 3 to 6 carbon atoms. An alkylene group can have one or more F, Cl, CN, CH 3 or CF 3 as substituents, and one or more CH 2 groups present in the alkylene group can have an O atom It may be substituted with O, CO, or COO as it does not directly bond to.
一般式（II）において、A1、A2及びA3としてはそれぞれ独立的に1,4-フェニレン基、1,4-シクロヘキシレン基、デカヒドロナフタレン-2,6-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基又は2,6-ナフチレン基が好ましく、1,4-フェニレン基又は1,4-シクロヘキシレン基がさらに好ましく、1,4-フェニレン基又は1,4-シクロヘキシレン基が特に好ましい。1,4-フェニレン基、デカヒドロナフタレン-2,6-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基及び2,6-ナフチレン基は1個又は2個以上のF、Cl、CF3、OCF3、CH3を置換基として有していても良い。 In the general formula (II), A 1 , A 2 and A 3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, decahydronaphthalene-2,6-diyl group, 1,2 1,4-tetrahydronaphthalene-2,6-diyl group or 2,6-naphthylene group is preferred, 1,4-phenylene group or 1,4-cyclohexylene group is more preferred, 1,4-phenylene group or 1 A 4-cyclohexylene group is particularly preferred. 1,4-phenylene group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group and 2,6-naphthylene group are one or more F, Cl, CF 3, OCF 3, CH 3 may have a substituent.
一般式（II）において、X1としては、単結合又は-O-が好ましく、-O-がさらに好ましい。 In the general formula (II), X 1 is preferably a single bond or —O—, more preferably —O—.
一般式（II）において、Y1及びY2としてはそれぞれ独立的に単結合、-COO-、-OCO-、-C≡C-、-CH2CH2-、-CH2CH2COO-又は-OCOCH2CH2-が好ましい。 In the general formula (II), Y 1 and Y 2 are each independently a single bond, —COO—, —OCO—, —C≡C—, —CH 2 CH 2 —, —CH 2 CH 2 COO— or -OCOCH 2 CH 2 -is preferred.
一般式（II）において、Y3は単結合、-O-、-COO-又は-OCO-が好ましい。 In the general formula (II), Y 3 is preferably a single bond, —O—, —COO— or —OCO—.
一般式（II）において、Lは、化合物として低い粘度が必要な場合には炭素原子数1〜5のアルキル基が好ましく、炭素原子数1〜3のアルキル基がより好ましい。反応により架橋密度を有する高分子を得ることが必要な場合には、P1-S1-X1と同じ意味であることが好ましい。 In the general formula (II), L is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms when low viscosity is required as a compound. When it is necessary to obtain a polymer having a crosslinking density by reaction, it is preferably the same as P 1 -S 1 -X 1 .
一般式（II）で表される化合物の中でも、P1がアクリロイルオキシ基、S1が単結合、X1が単結合の化合物は、重合性液晶組成物として室温での液晶性を付与しやすく、また粘度が低いため好ましい。具体的には式（II-A-1）〜（II-A-12）の化合物を挙げることができる。 Among the compounds represented by the general formula (II), a compound in which P 1 is an acryloyloxy group, S 1 is a single bond, and X 1 is a single bond is easy to impart liquid crystal properties at room temperature as a polymerizable liquid crystal composition. Moreover, it is preferable because of its low viscosity. Specific examples include compounds of formulas (II-A-1) to (II-A-12).
（式中、L'は炭素原子数1〜8のアルキル基を表す）
典型的な例としては、式（II-A-2）において、L'が3または5の化合物や、式（II-A-3）において、L'が3または5の化合物は、液晶温度がおよそ30〜60℃の範囲にあり、これらを混合することで室温での液晶性を確保しやすいため好ましい。また、式（II-A-1）において、L'が3または5の化合物は、液晶温度がおよそ40〜70℃の範囲にあり、複屈折率が約0.05と小さいという特徴があるため有用である。以上のような化合物は粘度が数10mPa・ｓと小さく、また、本発明の重合性液晶組成物の液晶温度範囲を室温付近に調節しやすいため、製造プロセス上、粘度を低く設定する必要がある場合には有効な材料系である。
(In the formula, L ′ represents an alkyl group having 1 to 8 carbon atoms)
As a typical example, a compound in which L ′ is 3 or 5 in the formula (II-A-2) or a compound in which L ′ is 3 or 5 in the formula (II-A-3) has a liquid crystal temperature of It is in the range of about 30 to 60 ° C., and mixing these is preferable because liquid crystallinity at room temperature is easily secured. In the formula (II-A-1), a compound having L ′ of 3 or 5 is useful because the liquid crystal temperature is in the range of about 40 to 70 ° C. and the birefringence is as small as about 0.05. is there. The above compounds have a viscosity as small as several tens of mPa · s, and the liquid crystal temperature range of the polymerizable liquid crystal composition of the present invention can be easily adjusted to around room temperature. Therefore, it is necessary to set the viscosity low in the manufacturing process. In some cases, it is an effective material system.
一般式（II）の化合物の中でも、P1がアクリロイルオキシ基、S2が炭素原子数2〜8のアルキレン基、X2が単結合、又は-O-、Lは炭素原子数1〜18のアルキル基、炭素原子数2〜18のアルケニル基、ハロゲン原子、CNを表す化合物は、硬化物に柔軟性を付与できる性質を持つ。具体的には式（II-B-1）〜（II-B-21）の化合物を挙げることができる。 Among the compounds of the general formula (II), P 1 is an acryloyloxy group, S 2 is an alkylene group having 2 to 8 carbon atoms, X 2 is a single bond, or —O—, and L is a carbon atom having 1 to 18 carbon atoms. A compound representing an alkyl group, an alkenyl group having 2 to 18 carbon atoms, a halogen atom, or CN has a property of imparting flexibility to the cured product. Specific examples include compounds of formulas (II-B-1) to (II-B-21).
（式中、uは2〜12の整数を表し、vは0または1を表し、Y3及びLは一般式（II）におけると同じ意味を表す）。 (In the formula, u represents an integer of 2 to 12, v represents 0 or 1, and Y 3 and L represent the same meaning as in the general formula (II)).
典型的な例としては、式（II-B-1）において、uが3から6の整数、vが１、Y3が単結合、LがCNの化合物や、式（II-B-4）において、uが3から6の整数、vが１、Y3が単結合、LがCNの化合物は、複屈折率が約0.2以上と大きいため、本発明の重合性液晶組成物の複屈折率の増大に有効である。また、これとは逆に、式（II-B-11）において、uが3から6の整数、vが１、Y3が単結合、Lがプロピル基やペンチル基の化合物は、本発明の重合性液晶材料の複屈折率の低減に有効である。以上のような化合物は、粘度が数10〜200mPa・s以下であり、かつ硬化物の柔軟性を付与できる性質を有するものの、硬化物の耐熱性を悪化させる傾向があるため、本発明の重合性液晶組成物中での最大濃度は50質量%以下、さらに好ましくは35質量%以下、特に好ましくは25質量%以下に設定するのが好ましい。 As a typical example, in the formula (II-B-1), u is an integer of 3 to 6, v is 1, Y 3 is a single bond, L is CN, and the formula (II-B-4) In the present invention, a compound in which u is an integer of 3 to 6, v is 1, Y 3 is a single bond, and L is CN has a large birefringence of about 0.2 or more. It is effective in increasing Conversely, in the formula (II-B-11), a compound in which u is an integer of 3 to 6, v is 1, Y 3 is a single bond, L is a propyl group or a pentyl group is This is effective for reducing the birefringence of the polymerizable liquid crystal material. The above compounds have a viscosity of several tens to 200 mPa · s or less and have the property of imparting flexibility of the cured product, but tend to deteriorate the heat resistance of the cured product. The maximum concentration in the liquid crystal composition is preferably set to 50% by mass or less, more preferably 35% by mass or less, and particularly preferably 25% by mass or less.
一般式（II）の化合物の中でも、P1がアクリロイルオキシ基、S1が炭素原子数2〜8のアルキレン基、LがP1-S1-X1と同じ意味を表す化合物は、分子内に2つの反応性もしくは重合性官能基を有するため反応により得られる高分子の機械的、熱的な安定性が高いために好ましい。具体的には式（II-C-1）〜（II-C-5）の化合物を挙げることができる。 Among the compounds of the general formula (II), P 1 is an acryloyloxy group, S 1 is an alkylene group having 2 to 8 carbon atoms, and L is the same as P 1 -S 1 -X 1 It has two reactive or polymerizable functional groups, and is preferable because of high mechanical and thermal stability of the polymer obtained by the reaction. Specific examples include compounds of formulas (II-C-1) to (II-C-5).
（式中、uは2〜12の整数を表し、vは0または1を表し、Y3及びLは一般式（II）におけると同じ意味を表す）。 (In the formula, u represents an integer of 2 to 12, v represents 0 or 1, and Y 3 and L represent the same meaning as in the general formula (II)).
以上のような化合物の中でも、式（II-C-3）の液晶温度範囲は約50〜70℃と、液晶温度範囲が約70〜140℃の上記（II-C-1）、（II-C-2）、（II-C-4）、（II-C-5）と低いため、本発明の重合性液晶組成物の液晶温度範囲を室温付近に設定することが容易であるため好ましい。また、得られる硬化物の機械的、熱的な安定性も高い。特に、vとしては1、かつuとしては3、4、6が好ましく、uとしては3,6がさらに好ましい。式（II-C-3）で表される化合物は、uが異なる複数の化合物を混合して用いるのが好ましく、例えば、vとしては1、かつuとしては3、及びvとしては1、uとしては6の化合物を混合して使用するのが好ましく、vとして1、かつuとしては3、vとして1、かつuとしては4、vとしては1、かつuとしては6の化合物を混合するのも好ましい。さらに、このような系に式（II-B-1）において、vとして1、uとして3から6の整数、Y3として単結合、LとしてCNを選択した化合物を添加すると、得られる高分子の耐熱性を向上させることができ、かつ粘度を低くすることができるので好ましい。この化合物の添加量は、30質量%以下が好ましく、25質量%以下がさらに好ましい。 Among these compounds, the liquid crystal temperature range of the formula (II-C-3) is about 50 to 70 ° C., and the liquid crystal temperature range is about 70 to 140 ° C. (II-C-1), (II- Since C-2), (II-C-4) and (II-C-5) are low, it is preferable because the liquid crystal temperature range of the polymerizable liquid crystal composition of the present invention can be easily set around room temperature. Further, the obtained cured product has high mechanical and thermal stability. In particular, v is 1 and u is preferably 3, 4, or 6, and u is more preferably 3,6. The compound represented by the formula (II-C-3) is preferably used by mixing a plurality of compounds having different u. For example, v is 1, and u is 3, and v is 1, u It is preferable to use a mixture of 6 compounds, and v is 1, and u is 3, v is 1, and u is 4, u is 1, and u is 6 It is also preferable. Furthermore, a polymer obtained by adding a compound in which formula (II-B-1) in the formula (II-B-1) is selected as v, an integer of 3 to 6 as u, a single bond as Y 3 and CN as L is added to such a system It is preferable because the heat resistance can be improved and the viscosity can be lowered. The amount of this compound added is preferably 30% by mass or less, and more preferably 25% by mass or less.
また、この他にも、重合性液晶化合物として式（IV−１）から（IV−５）のような化合物を使用することができる。このように、重合性官能基が一つの分子に3つ以上有する化合物を添加すると、重合速度の向上や高分子の耐熱性の向上が可能なため、好ましい。
（式中、uは2〜12の整数を表し、vは0または1を表す）
また、本発明の重合性液晶組成物には、その保存安定性を向上させるために、安定剤を添加することもできる。使用できる安定剤としては、例えば、ヒドロキノン、ヒドロキノンモノアルキルエーテル類、第三ブチルカテコール類、ピロガロール類、チオフェノール類、ニトロ化合物類、β−ナフチルアミン類、β−ナフトール類、ニトロソ化合物等が挙げられる。安定剤を使用する場合の添加量は、液晶組成物に対して０．００５〜１質量％の範囲が好ましく、０．０２〜０．５質量％がさらに好ましく、０．０３〜０．１質量％が特に好ましい。
(In the formula, u represents an integer of 2 to 12, and v represents 0 or 1)
In addition, a stabilizer can be added to the polymerizable liquid crystal composition of the present invention in order to improve its storage stability. Examples of the stabilizer that can be used include hydroquinone, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, and nitroso compounds. . When the stabilizer is used, the amount added is preferably 0.005 to 1% by mass, more preferably 0.02 to 0.5% by mass, and 0.03 to 0.1% by mass with respect to the liquid crystal composition. % Is particularly preferred.
次に本発明の硬化物について説明する。本発明の重合性液晶組成物を重合させることによって製造される硬化物は種々の用途に利用できる。例えば、本発明の重合性液晶組成物を、配向させない状態で重合させた場合、光散乱板、偏光解消板、モアレ縞防止板として利用可能である。また、本発明の重合性液晶組成物を配向させた状態において、重合させることにより製造された硬化物は、物理的性質に異方性を有しており、有用である。このような硬化物は、例えば、本発明の重合性液晶組成物を、布等でラビング処理した基板、もしくは有機薄膜を形成した基板表面を布等でラビング処理した基板、あるいはＳｉＯ２ を斜方蒸着した配向膜を有する基板上に塗布した後、本発明の重合性液晶組成物を重合させることによって製造することができる。 Next, the cured product of the present invention will be described. The cured product produced by polymerizing the polymerizable liquid crystal composition of the present invention can be used for various applications. For example, when the polymerizable liquid crystal composition of the present invention is polymerized without being oriented, it can be used as a light scattering plate, a depolarizing plate, or a moire fringe prevention plate. In addition, a cured product produced by polymerizing the polymerizable liquid crystal composition of the present invention in an aligned state has anisotropy in physical properties and is useful. Such a cured product is, for example, a substrate obtained by rubbing the polymerizable liquid crystal composition of the present invention with a cloth, or a substrate obtained by rubbing the surface of a substrate on which an organic thin film has been formed with a cloth, or an oblique SiO 2 layer . It can be manufactured by polymerizing the polymerizable liquid crystal composition of the present invention after coating on a substrate having a deposited alignment film.
重合性液晶組成物を基板上に塗布する際の方法としては、スピンコーティング、ダイコーティング、エクストルージョンコーティング、ロールコーティング、ワイヤーバーコーティング、グラビアコーティング、スプレーコーティング、ディッピング、プリント法等を挙げることができる。またコーティングの際、重合性液晶組成物に有機溶媒を添加しても良い。有機溶媒としては、酢酸エチル、テトラヒドロフラン、トルエン、ヘキサン、メタノール、エタノール、ジメチルホルムアミド、塩化メチレン、イソプロパノール、アセトン、メチルエチルケトン、アセトニトリル、セロソルブ類を挙げることができる。これらは単独でも、組み合わせて用いても良く、その蒸気圧と重合性液晶組成物の溶解性を考慮し、適宜選択すれば良い。また、その添加量は９０重量％以下が好ましい。添加した有機溶媒を揮発させる方法としては、自然乾燥、加熱乾燥、減圧乾燥、減圧加熱乾燥を用いることができる。重合性液晶組成物の塗布性をさらに向上させるためには、基板上にポリイミド薄膜等の中間層を設けることも有効である。基板上にポリイミド薄膜等の中間層を設けるのは、重合性液晶組成物を重合させて得られる重合体と基板の密着性が良くない場合に、密着性を向上させる手段としても有効である。 Examples of the method for applying the polymerizable liquid crystal composition on the substrate include spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spray coating, dipping, and printing. . Further, an organic solvent may be added to the polymerizable liquid crystal composition during coating. Examples of the organic solvent include ethyl acetate, tetrahydrofuran, toluene, hexane, methanol, ethanol, dimethylformamide, methylene chloride, isopropanol, acetone, methyl ethyl ketone, acetonitrile, and cellosolves. These may be used alone or in combination, and may be appropriately selected in consideration of the vapor pressure and the solubility of the polymerizable liquid crystal composition. The amount added is preferably 90% by weight or less. As a method for volatilizing the added organic solvent, natural drying, heat drying, reduced pressure drying, or reduced pressure heat drying can be used. In order to further improve the applicability of the polymerizable liquid crystal composition, it is also effective to provide an intermediate layer such as a polyimide thin film on the substrate. Providing an intermediate layer such as a polyimide thin film on the substrate is also effective as means for improving the adhesion when the polymer obtained by polymerizing the polymerizable liquid crystal composition and the substrate are not good in adhesion.
基板の形状としては、平板の他に、曲面を構成部分として有していても良い。基板を構成する材料は、有機材料、無機材料を問わずに用いることができる。基板の材料となる有機材料としては、例えば、ポリエチレンテレフタレート、ポリカーボネート、ポリイミド、ポリアミド、ポリメタクリル酸メチル、ポリスチレン、ポリ塩化ビニル、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリアリレート、ポリスルホン、トリアセチルセルロース、セルロース、ポリエーテルエーテルケトン等が挙げられ、また、無機材料としては、例えば、シリコン、ガラス、方解石等が挙げられる。 As a shape of the substrate, in addition to a flat plate, a curved surface may be included as a constituent part. The material which comprises a board | substrate can be used regardless of an organic material and an inorganic material. Examples of the organic material used as the substrate material include polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone, and triacetyl. Cellulose, cellulose, polyetheretherketone and the like can be mentioned, and examples of the inorganic material include silicon, glass and calcite.
これらの基板を布等でラビングすることによって適当な配向性を得られない場合、公知の方法に従ってポリイミド薄膜又はポリビニルアルコール薄膜等の有機薄膜を基板表面に形成し、これを布等でラビングしても良い。また、通常のツイステッド・ネマチック（ＴＮ）素子又はスーパー・ツイステッド・ネマチック（ＳＴＮ）素子で使用されているプレチルト角を与えるポリイミド薄膜は、硬化物内部の分子配向構造を更に精密に制御することができることから、特に好ましい。 When appropriate orientation cannot be obtained by rubbing these substrates with a cloth or the like, an organic thin film such as a polyimide thin film or a polyvinyl alcohol thin film is formed on the substrate surface according to a known method, and this is rubbed with a cloth or the like. Also good. In addition, the polyimide thin film that gives a pretilt angle used in a normal twisted nematic (TN) element or a super twisted nematic (STN) element can control the molecular orientation structure inside the cured product more precisely. Are particularly preferred.
本発明の重合性液晶組成物を硬化させる方法としては、紫外線又を照射することによって重合させる方法が好ましい。紫外線を使用する場合、偏光光源を用いても良いし、非偏光光源を用いても良い。また、液晶組成物を２枚の基板間に挟持させて状態で重合を行う場合には、少なくとも照射面側の基板は活性エネルギー線に対して適当な透明性が与えられていなければならない。また、光照射時にマスクを用いて特定の部分のみを重合させた後、電場や磁場または温度等の条件を変化させることにより、未重合部分の配向状態を変化させて、さらに紫外線を照射して重合させるという手段を用いても良い。また、照射時の温度は、本発明の液晶組成物の液晶状態が保持される温度範囲内であることが好ましい。特に、光重合によって重合体を製造しようとする場合には、意図しない熱重合の誘起を避ける意味からも可能な限り室温に近い温度、即ち、典型的には２５℃での温度で重合させることが好ましい。紫外線線の強度は、０．１ｍＷ／ｃｍ２〜２Ｗ／ｃｍ２が好ましい。強度が０．１ｍＷ／ｃｍ２以下の場合、光重合を完了させるのに多大な時間が必要になり生産性が悪化してしまい、２Ｗ／ｃｍ２以上の場合、重合性液晶組成物が劣化してしまう危険がある。 As a method of curing the polymerizable liquid crystal composition of the present invention, a method of polymerizing by irradiating with ultraviolet rays is preferable. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. Further, when the polymerization is carried out with the liquid crystal composition sandwiched between two substrates, at least the substrate on the irradiation surface side must be given appropriate transparency to the active energy rays. Moreover, after polymerizing only a specific part using a mask at the time of light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as an electric field, a magnetic field, or temperature, and ultraviolet rays are further irradiated. A means for polymerization may be used. Moreover, it is preferable that the temperature at the time of irradiation is in the temperature range in which the liquid crystal state of the liquid crystal composition of the present invention is maintained. In particular, in the case of producing a polymer by photopolymerization, the polymerization is carried out at a temperature as close to room temperature as possible from the viewpoint of avoiding unintentional induction of thermal polymerization, that is, typically at a temperature of 25 ° C. Is preferred. The intensity of the ultraviolet rays is preferably 0.1 mW / cm 2 to 2 W / cm 2 . When the strength is 0.1 mW / cm 2 or less, a great amount of time is required to complete the photopolymerization, and the productivity deteriorates. When the strength is 2 W / cm 2 or more, the polymerizable liquid crystal composition deteriorates. There is a risk that
重合によって得られた本発明の重合体は、初期の特性変化を軽減し、安定的な特性発現を図ることを目的として熱処理を施すこともできる。熱処理の温度は５０〜２５０℃の範囲で、また熱処理時間は３０秒〜１２時間の範囲が好ましい。 The polymer of the present invention obtained by polymerization can be subjected to heat treatment for the purpose of reducing initial characteristic changes and achieving stable characteristic expression. The heat treatment temperature is preferably in the range of 50 to 250 ° C., and the heat treatment time is preferably in the range of 30 seconds to 12 hours.
このような方法によって製造される本発明の重合体は、基板から剥離して単体で用いても、剥離せずに用いても良い。また、得られた重合体を積層しても、他の基板に貼り合わせて用いてもよい。 The polymer of the present invention produced by such a method may be peeled off from the substrate and used alone or without peeling. Further, the obtained polymer may be laminated or bonded to another substrate for use.
以下、実施例を挙げて本発明を更に詳述するが、本発明はこれらの実施例に限定されるものではない。また、以下の実施例及び比較例の組成物における「%」は『質量%』を意味する。位相差は波長589nmで測定した。
（実施例１）
式（a）の化合物50%
EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. Further, “%” in the compositions of the following examples and comparative examples means “mass%”. The phase difference was measured at a wavelength of 589 nm.
Example 1
50% of the compound of formula (a)
を0.1%添加した本発明の重合性液晶組成物（A1）を調製した。次に重合性液晶組成物（A1）を33%含有するキシレン溶液を調製した。このキシレン溶液を3cm角のポリイミド配向膜付きガラス基板にスピンコート（3000回転/分、30秒）した。スピンコートされた重合性液晶組成物（A1）は、ポリイミドのラビング方向に配向しているのが確認できた。スピンコートした基板に窒素気流下で24mW/cm2の紫外線を80秒照射して、重合性液晶組成物（A1）を硬化させた。この硬化膜の位相差を測定したところ、154.7nmであった。この硬化膜を150℃で1時間加熱し、冷却してから位相差を測定したところ、154.1nmであった。150℃で1時間加熱しても、位相差の変化は5%以内であったので、紫外線照射によって十分に硬化したと考えられる。この硬化膜に78mW/cm2の紫外線を500秒（紫外線量39J/cm2）、1000秒（通算紫外線量78J/cm2）、2000秒（通算紫外線照射量156J/cm2）曝露した時の位相差を測定したところ、それぞれ99.5nm、98.7nm、56.7nmであった。つまり、39J/cm2曝露したときには硬化直後の位相差に対して64.3%の大きさの位相差が保持されており、78J/cm2曝露したときには硬化直後の位相差に対して63.8%の大きさの位相差が保持されており、156J/cm2曝露したときには硬化直後の位相差に対して56.7%の大きさの位相差が保持されていることがわかった。 A polymerizable liquid crystal composition (A1) of the present invention with 0.1% added was prepared. Next, a xylene solution containing 33% of the polymerizable liquid crystal composition (A1) was prepared. This xylene solution was spin coated (3000 rpm / 30 seconds) on a 3 cm square glass substrate with a polyimide alignment film. It was confirmed that the spin-coated polymerizable liquid crystal composition (A1) was aligned in the polyimide rubbing direction. The polymerizable liquid crystal composition (A1) was cured by irradiating the spin-coated substrate with an ultraviolet ray of 24 mW / cm 2 for 80 seconds under a nitrogen stream. The retardation of the cured film was measured and found to be 154.7 nm. When this cured film was heated at 150 ° C. for 1 hour and cooled, the phase difference was measured and found to be 154.1 nm. Even when heated at 150 ° C. for 1 hour, the change in phase difference was within 5%, so it is considered that the film was sufficiently cured by ultraviolet irradiation. When this cured film was exposed to 78mW / cm 2 of UV for 500 seconds (UV dose 39J / cm 2 ), 1000 seconds (total UV dose 78J / cm 2 ), 2000 seconds (total UV dose 156J / cm 2 ) When the phase difference was measured, they were 99.5 nm, 98.7 nm, and 56.7 nm, respectively. That is, when exposed to 39 J / cm 2, a phase difference of 64.3% is retained with respect to the phase difference immediately after curing, and when exposed to 78 J / cm 2, it is 63.8% larger than the phase difference immediately after curing. It was found that the phase difference of 56.7% was maintained with respect to the phase difference immediately after curing when exposed to 156 J / cm 2 .
（比較例１）
実施例１で調製した重合性液晶組成物（A）99.8％に光重合開始剤ルシリンTPO（バスフ社製）0.2%、重合性液晶組成物（B）を調製した。次に重合性液晶組成物（B）を33%含有するキシレン溶液を調製した。このキシレン溶液を3cm角のポリイミド配向膜付きガラス基板にスピンコート（3000回転/分、30秒）した。スピンコートされた重合性液晶組成物（B）は、ポリイミドのラビング方向に配向しているのが確認できた。スピンコートした基板に窒素気流下で24mW/cm2の紫外線を80秒照射して、重合性液晶組成物（B）を硬化させた。この硬化膜の位相差を測定したところ、157.4nmであった。この硬化膜を150℃で1時間加熱し、冷却してから位相差を測定したところ、152.8nmであった。150℃で1時間加熱しても、位相差の変化は5%以内であったので、紫外線照射によって十分に硬化したと言える。この硬化膜に78mW/cm2の紫外線を500秒（紫外線量39J/cm2）、1000秒（通算紫外線量78J/cm2）、2000秒（通算紫外線照射量156J/cm2）曝露した時の位相差を測定したところ、それぞれ44.2nm、15.6nm、0nmであった。つまり、39J/cm2曝露したときには硬化直後の位相差に対して28.1%の大きさの位相差が保持されており、78J/cm2曝露したときには硬化直後の位相差に対して9.9%の大きさの位相差が保持されており、156J/cm2曝露したときには硬化直後の位相差は全く消失したことがわかった。
実施例１と比較例１との比較から、ヒンダードアミンを用いると硬化性を犠牲にすることなく、UV曝露時の位相差の変化を抑制できていることがわかる。
(Comparative Example 1)
The polymerizable liquid crystal composition (A) prepared in Example 1 was 99.8%, the photopolymerization initiator Lucillin TPO (manufactured by Basf) 0.2%, and the polymerizable liquid crystal composition (B) were prepared. Next, a xylene solution containing 33% of the polymerizable liquid crystal composition (B) was prepared. This xylene solution was spin coated (3000 rpm / 30 seconds) on a 3 cm square glass substrate with a polyimide alignment film. It was confirmed that the spin-coated polymerizable liquid crystal composition (B) was aligned in the polyimide rubbing direction. The polymerizable liquid crystal composition (B) was cured by irradiating the spin-coated substrate with ultraviolet rays of 24 mW / cm 2 for 80 seconds under a nitrogen stream. The retardation of the cured film was measured and found to be 157.4 nm. When this cured film was heated at 150 ° C. for 1 hour and cooled, the phase difference was measured and found to be 152.8 nm. Even when heated at 150 ° C. for 1 hour, the change in phase difference was within 5%, so it can be said that the film was sufficiently cured by ultraviolet irradiation. When this cured film was exposed to 78mW / cm 2 of UV for 500 seconds (UV dose 39J / cm 2 ), 1000 seconds (total UV dose 78J / cm 2 ), 2000 seconds (total UV dose 156J / cm 2 ) When the phase difference was measured, they were 44.2 nm, 15.6 nm, and 0 nm, respectively. In other words, when exposed to 39 J / cm 2, a phase difference of 28.1% is maintained with respect to the phase difference immediately after curing, and when exposed to 78 J / cm 2, it is 9.9% greater than the phase difference immediately after curing. It was found that the phase difference immediately after curing disappeared when exposed to 156 J / cm 2 .
From the comparison between Example 1 and Comparative Example 1, it can be seen that when hindered amine is used, the change in phase difference upon UV exposure can be suppressed without sacrificing curability.
（比較例２）
実施例１で調製した重合性液晶組成物（A）99.7％に光重合開始剤ルシリンTPO（バスフ社製）0.2%、紫外線吸収剤Uvinul-3039（バスフ社製）
(Comparative Example 2)
Polymerizable liquid crystal composition (A) prepared in Example 1 99.7%, photopolymerization initiator Lucillin TPO (manufactured by Basf) 0.2%, UV absorber Uvinul-3039 (manufactured by Basf)
を0.1%添加した重合性液晶組成物（C）を調製した。次に重合性液晶組成物（C）を33%含有するキシレン溶液を調製した。このキシレン溶液を3cm角のポリイミド配向膜付きガラス基板にスピンコート（3000回転/分、30秒）した。スピンコートされた重合性液晶組成物（C）は、ポリイミドのラビング方向に配向しているのが確認できた。スピンコートした基板に窒素気流下で24mW/cm2の紫外線を80秒照射して、重合性液晶組成物（C）を硬化させた。この硬化膜の位相差を測定したところ、160.4nmであった。この硬化膜を150℃で1時間加熱し、冷却してから位相差を測定したところ、118.2nmであった。150℃で1時間加熱による位相差の変化は5%以上あったので、紫外線照射によって十分に硬化しなかった。この硬化膜に78mW/cm2の紫外線を500秒（紫外線量39J/cm2）、1000秒（通算紫外線量78J/cm2）、2000秒（通算紫外線照射量156J/cm2）曝露した時の位相差を測定したところ、それぞれ72.5nm、57.8nm、43.1nmであった。つまり、39J/cm2曝露したときには硬化直後の位相差に対して45.2%の大きさの位相差が保持されており、78J/cm2曝露したときには硬化直後の位相差に対して36.0%の大きさの位相差が保持されており、156J/cm2曝露したときには156J/cm2曝露したときには硬化直後の位相差に対して26.9%の大きさの位相差が保持されていることがわかった。 A polymerizable liquid crystal composition (C) with 0.1% added was prepared. Next, a xylene solution containing 33% of the polymerizable liquid crystal composition (C) was prepared. This xylene solution was spin coated (3000 rpm / 30 seconds) on a 3 cm square glass substrate with a polyimide alignment film. It was confirmed that the spin-coated polymerizable liquid crystal composition (C) was aligned in the polyimide rubbing direction. The polymerizable liquid crystal composition (C) was cured by irradiating the spin-coated substrate with ultraviolet rays of 24 mW / cm 2 for 80 seconds under a nitrogen stream. The retardation of the cured film was measured and found to be 160.4 nm. When this cured film was heated at 150 ° C. for 1 hour and cooled, the phase difference was measured and found to be 118.2 nm. Since the change in phase difference by heating at 150 ° C. for 1 hour was 5% or more, it was not sufficiently cured by ultraviolet irradiation. When this cured film was exposed to 78mW / cm 2 of UV for 500 seconds (UV dose 39J / cm 2 ), 1000 seconds (total UV dose 78J / cm 2 ), 2000 seconds (total UV dose 156J / cm 2 ) When the phase difference was measured, they were 72.5 nm, 57.8 nm, and 43.1 nm, respectively. That is, when exposed to 39 J / cm 2, a phase difference of 45.2% of the phase difference immediately after curing is maintained, and when exposed to 78 J / cm 2, it is 36.0% larger than the phase difference immediately after curing. are the phase difference is maintained, when 156j / cm 2 exposure has been found that the phase difference of 26.9% in size are held with respect to the phase difference immediately after curing when 156j / cm 2 exposure.
（比較例３）
実施例１で調製した重合性液晶組成物（A）99.7％に光重合開始剤ルシリンTPO（バスフ社製）0.2%、紫外線吸収剤Uvinul-3008（バスフ社製）
(Comparative Example 3)
Polymerizable liquid crystal composition (A) prepared in Example 1 (99.7%), photopolymerization initiator Lucillin TPO (manufactured by Basf) 0.2%, UV absorber Uvinul-3008 (manufactured by Basf)
0.1%を添加した重合性液晶組成物（D）を調製した。次に重合性液晶組成物（D）を33%含有するキシレン溶液を調製した。このキシレン溶液を3cm角のポリイミド配向膜付きガラス基板にスピンコート（3000回転/分、30秒）した。スピンコートされた重合性液晶組成物（D）は、ポリイミドのラビング方向に配向しているのが確認できた。スピンコートした基板に窒素気流下で24mW/cm2の紫外線を80秒照射したものの、重合性液晶組成物（D）は硬化しなかった。 A polymerizable liquid crystal composition (D) added with 0.1% was prepared. Next, a xylene solution containing 33% of the polymerizable liquid crystal composition (D) was prepared. This xylene solution was spin-coated (3000 rpm / 30 seconds) on a 3 cm square glass substrate with a polyimide alignment film. It was confirmed that the spin-coated polymerizable liquid crystal composition (D) was aligned in the polyimide rubbing direction. Although the spin-coated substrate was irradiated with ultraviolet rays of 24 mW / cm 2 for 80 seconds under a nitrogen stream, the polymerizable liquid crystal composition (D) was not cured.
（比較例４）
実施例１で調製した重合性液晶組成物（A）99.7％に光重合開始剤ルシリンTPO（バスフ社製）0.2%、紫外線吸収剤Uvinul-3030（バスフ社製）
(Comparative Example 4)
99.7% of the polymerizable liquid crystal composition (A) prepared in Example 1, 0.2% of photopolymerization initiator Lucillin TPO (manufactured by Basf), UV absorber Uvinul-3030 (manufactured by Basf)
（比較例５）
実施例１で調製した重合性液晶組成物（A）99.7％、光重合開始剤ルシリンTPO（バスフ社製）0.2%、紫外線吸収剤Uvinul-3088（バスフ社製）
(Comparative Example 5)
Polymerizable liquid crystal composition (A) prepared in Example 1 (99.7%), photopolymerization initiator Lucillin TPO (manufactured by Basf) 0.2%, UV absorber Uvinul-3088 (manufactured by Basf)
（実施例２）
式（a）の化合物35%
(Example 2)
35% of the compound of formula (a)
（実施例３）
式（a）の化合物45%
(Example 3)
45% of the compound of formula (a)
実施例１から３、比較例１から５の比較から、耐UV性を改善する目的で紫外線吸収剤を使用した場合、耐UV性改善効果はあるものの、硬化性が悪化してしまうことがわかる。また耐UV性改善硬化も、紫外線吸収剤を使用するより、ヒンダードアミンを使用した方が優れていることがわかる。 From the comparison of Examples 1 to 3 and Comparative Examples 1 to 5, it can be seen that when an ultraviolet absorber is used for the purpose of improving UV resistance, the curability deteriorates although there is an effect of improving UV resistance. . Also, it can be seen that the UV-resistant curing is superior to using a hindered amine rather than using an ultraviolet absorber.
（実施例４）
実施例１で調製した重合性液晶組成物（A）94.8％に、光重合開始剤Irgacure-907（チバスペシャリティケミカルズ製）5%、ヒンダードアミンLS-765（三共ライフテック株式会社製）を0.2%添加した本発明の重合性液晶組成物（I）を調製した。次に重合性液晶組成物（I）を33%含有するキシレン溶液を調製した。このキシレン溶液を3cm角のポリイミド配向膜付きガラス基板にスピンコート（3000回転/分、30秒）した。スピンコートされた重合性液晶組成物（I）は、ポリイミドのラビング方向に配向しているのが確認できた。スピンコートした基板に空気中で24mW/cm2の紫外線を80秒照射して、重合性液晶組成物（I）を硬化させた。この硬化膜の位相差を測定したところ、120.2nmであった。この硬化膜を150℃で1時間加熱し、冷却してから位相差を測定したところ、115.4nmであった。150℃で1時間加熱しても、位相差の変化は5%以内であったので、紫外線照射によって十分に硬化したと考えられる。この硬化膜に78mW/cm2の紫外線を2000秒（紫外線量156J/cm2）曝露した時の位相差を測定したところ、90.2nmであった。つまり、78J/cm2曝露したときには硬化直後の位相差に対して75.0%の大きさの位相差が保持されていることがわかった。
Example 4
Addition of 5% of photopolymerization initiator Irgacure-907 (manufactured by Ciba Specialty Chemicals) and 0.2% of hindered amine LS-765 (manufactured by Sankyo Lifetech Co., Ltd.) to 94.8% of the polymerizable liquid crystal composition (A) prepared in Example 1 The polymerizable liquid crystal composition (I) of the present invention was prepared. Next, a xylene solution containing 33% of the polymerizable liquid crystal composition (I) was prepared. This xylene solution was spin coated (3000 rpm / 30 seconds) on a 3 cm square glass substrate with a polyimide alignment film. It was confirmed that the spin-coated polymerizable liquid crystal composition (I) was aligned in the polyimide rubbing direction. The polymerizable liquid crystal composition (I) was cured by irradiating the spin-coated substrate with ultraviolet rays of 24 mW / cm 2 in air for 80 seconds. The retardation of the cured film was measured and found to be 120.2 nm. When this cured film was heated at 150 ° C. for 1 hour and cooled, the phase difference was measured and found to be 115.4 nm. Even when heated at 150 ° C. for 1 hour, the change in phase difference was within 5%, so it is considered that the film was sufficiently cured by ultraviolet irradiation. When the cured film was exposed to 78 mW / cm 2 of ultraviolet rays for 2000 seconds (ultraviolet ray amount 156 J / cm 2 ), the phase difference was measured and found to be 90.2 nm. In other words, it was found that when exposed to 78 J / cm 2, a phase difference of 75.0% was maintained with respect to the phase difference immediately after curing.
（比較例６）
実施例１で調製した重合性液晶組成物（A）95％に、光重合開始剤Irgacure-907（チバスペシャリティケミカルズ製）5%を添加した重合性液晶組成物（J）を調製した。次に重合性液晶組成物（J）を33%含有するキシレン溶液を調製した。このキシレン溶液を3cm角のポリイミド配向膜付きガラス基板にスピンコート（3000回転/分、30秒）した。スピンコートされた重合性液晶組成物（J）は、ポリイミドのラビング方向に配向しているのが確認できた。スピンコートした基板に空気中で24mW/cm2の紫外線を80秒照射して、重合性液晶組成物（J）を硬化させた。この硬化膜の位相差を測定したところ、125.9nmであった。この硬化膜を150℃で1時間加熱し、冷却してから位相差を測定したところ、120.0nmであった。150℃で1時間加熱しても、位相差の変化は5%以内であったので、紫外線照射によって十分に硬化したと考えられる。この硬化膜に78mW/cm2の紫外線を2000秒（紫外線量156J/cm2）曝露した時の位相差を測定したところ、84.8nmであった。つまり、156J/cm2曝露したときには硬化直後の位相差に対して67.4%の大きさの位相差が保持されていることがわかった。
(Comparative Example 6)
A polymerizable liquid crystal composition (J) prepared by adding 5% of a photopolymerization initiator Irgacure-907 (manufactured by Ciba Specialty Chemicals) to 95% of the polymerizable liquid crystal composition (A) prepared in Example 1 was prepared. Next, a xylene solution containing 33% of the polymerizable liquid crystal composition (J) was prepared. This xylene solution was spin coated (3000 rpm / 30 seconds) on a 3 cm square glass substrate with a polyimide alignment film. It was confirmed that the spin-coated polymerizable liquid crystal composition (J) was aligned in the polyimide rubbing direction. The polymerizable liquid crystal composition (J) was cured by irradiating the spin-coated substrate with ultraviolet rays of 24 mW / cm 2 in air for 80 seconds. It was 125.9 nm when the phase difference of this cured film was measured. When this cured film was heated at 150 ° C. for 1 hour and cooled, the phase difference was measured and found to be 120.0 nm. Even when heated at 150 ° C. for 1 hour, the change in phase difference was within 5%, so it is considered that the film was sufficiently cured by ultraviolet irradiation. The phase difference when this cured film was exposed to 78 mW / cm 2 of ultraviolet rays for 2000 seconds (ultraviolet ray amount 156 J / cm 2 ) was 84.8 nm. That is, it was found that when exposed to 156 J / cm 2, a phase difference of 67.4% was maintained with respect to the phase difference immediately after curing.
実施例４、比較例６の比較から、ヒンダードアミンの添加により硬化性を犠牲にせずに耐UV性を改善できているのがわかる。
From the comparison between Example 4 and Comparative Example 6, it can be seen that the addition of hindered amine can improve UV resistance without sacrificing curability.
Claims (8)
A cured product of the polymerizable liquid crystal composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004328949A JP4792731B2 (en) | 2004-11-12 | 2004-11-12 | Polymerizable liquid crystal composition and cured product of the composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004328949A JP4792731B2 (en) | 2004-11-12 | 2004-11-12 | Polymerizable liquid crystal composition and cured product of the composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006137856A true JP2006137856A (en) | 2006-06-01 |
| JP4792731B2 JP4792731B2 (en) | 2011-10-12 |
Family
ID=36618871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004328949A Active JP4792731B2 (en) | 2004-11-12 | 2004-11-12 | Polymerizable liquid crystal composition and cured product of the composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4792731B2 (en) |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007016207A (en) * | 2005-06-10 | 2007-01-25 | Chisso Corp | Polymerizable liquid crystal composition |
| JP2008019290A (en) * | 2006-07-10 | 2008-01-31 | Adeka Corp | Polymeric composition |
| JP2010189282A (en) * | 2009-02-16 | 2010-09-02 | Dic Corp | Polyfunctional polymerizable compound |
| JP2012087197A (en) * | 2010-10-19 | 2012-05-10 | Fujifilm Corp | Alkali resistance improver, photocurable liquid crystal composition, optical film, polarizing plate and liquid crystal display |
| CN102977896A (en) * | 2011-09-02 | 2013-03-20 | Jsr株式会社 | Method for manufacturing liquid crystal display component |
| WO2014024648A1 (en) * | 2012-08-08 | 2014-02-13 | Jnc株式会社 | Liquid crystal composition and liquid crystal display element |
| JP2014505745A (en) * | 2010-12-10 | 2014-03-06 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Liquid crystal medium and electro-optic display |
| JP2014505746A (en) * | 2010-12-07 | 2014-03-06 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Liquid crystal medium and electro-optic display |
| US8895776B2 (en) | 2008-03-18 | 2014-11-25 | Arena Pharmaceuticals, Inc. | Modulators of the prostacyclin (PGI2) receptor useful for the treatment of disorders related thereto |
| US8940891B2 (en) | 2008-12-08 | 2015-01-27 | Arena Pharmaceuticals, Inc. | Modulators of the prostacyclin (PGI2) receptor useful for the treatment of disorders related thereto |
| US8962879B2 (en) | 2012-11-14 | 2015-02-24 | E I Du Pont De Nemours And Company | Perfluoropolyvinyl modified aryl intermediates/monomers |
| US9012478B2 (en) | 2008-11-26 | 2015-04-21 | Arena Pharmaceuticals, Inc. | Pyrazolyl substituted carbonic acid derivatives as modulators of the prostacyclin (PGI2) receptor useful for the treatment of disorders related thereto |
| US9145356B2 (en) | 2012-11-14 | 2015-09-29 | E I Du Pont De Nemours And Company | Perfluoropolyvinyl modified aryl intermediates and monomers |
| US9193702B2 (en) | 2013-10-31 | 2015-11-24 | E I Du Pont De Nemours And Company | Fluorinated aryl epoxide compounds |
| US9365476B2 (en) | 2012-11-14 | 2016-06-14 | E I Du Pont De Nemours And Company | Aryl compounds modified with perfluorovinyl ethers |
| KR20170012364A (en) * | 2014-09-19 | 2017-02-02 | 디아이씨 가부시끼가이샤 | Polymerizable composition and film using same |
| JP2017031428A (en) * | 2014-09-05 | 2017-02-09 | Dic株式会社 | Liquid crystal composition and liquid crystal element using the same |
| WO2018116901A1 (en) * | 2016-12-19 | 2018-06-28 | Dic株式会社 | Polymerizable composition, and optical isomer produced using same |
| US10537546B2 (en) | 2014-10-23 | 2020-01-21 | Arena Pharmaceuticals, Inc. | Method of treating conditions related to the PGI2 receptor |
| JP2020125408A (en) * | 2019-02-05 | 2020-08-20 | 富士フイルム株式会社 | Polymerizable liquid crystal composition, optically anisotropic film, optical film, polarizing plate and image display device |
| US11123298B2 (en) | 2017-03-01 | 2021-09-21 | Arena Pharmaceuticals, Inc. | Compositions comprising PGI2-receptor agonists and processes for the preparation thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0695083A (en) * | 1992-09-09 | 1994-04-08 | Matsushita Electric Ind Co Ltd | Liquid crystal optical element |
| JPH1087740A (en) * | 1996-09-11 | 1998-04-07 | Toray Ind Inc | Production of vinylic polymer |
| JP2000271194A (en) * | 1999-03-24 | 2000-10-03 | Tomey Corp | Disinfecting method of contact lens |
| JP2001328949A (en) * | 2000-05-22 | 2001-11-27 | Tadashi Tanabe | Pharmaceutical composition containing prostacyclin synthetase gene |
| JP2002069450A (en) * | 2000-08-29 | 2002-03-08 | Dainippon Ink & Chem Inc | Polimerizable liquid crystal composition |
-
2004
- 2004-11-12 JP JP2004328949A patent/JP4792731B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0695083A (en) * | 1992-09-09 | 1994-04-08 | Matsushita Electric Ind Co Ltd | Liquid crystal optical element |
| JPH1087740A (en) * | 1996-09-11 | 1998-04-07 | Toray Ind Inc | Production of vinylic polymer |
| JP2000271194A (en) * | 1999-03-24 | 2000-10-03 | Tomey Corp | Disinfecting method of contact lens |
| JP2001328949A (en) * | 2000-05-22 | 2001-11-27 | Tadashi Tanabe | Pharmaceutical composition containing prostacyclin synthetase gene |
| JP2002069450A (en) * | 2000-08-29 | 2002-03-08 | Dainippon Ink & Chem Inc | Polimerizable liquid crystal composition |
Cited By (41)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007016207A (en) * | 2005-06-10 | 2007-01-25 | Chisso Corp | Polymerizable liquid crystal composition |
| JP2008019290A (en) * | 2006-07-10 | 2008-01-31 | Adeka Corp | Polymeric composition |
| US8895776B2 (en) | 2008-03-18 | 2014-11-25 | Arena Pharmaceuticals, Inc. | Modulators of the prostacyclin (PGI2) receptor useful for the treatment of disorders related thereto |
| US10668033B2 (en) | 2008-03-18 | 2020-06-02 | Arena Pharmaceuticals, Inc. | Modulators of the prostacyclin (PGI2) receptor useful for the treatment of disorders related thereto |
| US11098034B2 (en) | 2008-11-26 | 2021-08-24 | Arena Pharmaceuticals, Inc. | Pyrazolyl substituted carbonic acid derivatives as modulators of the prostacyclin (PGI2) receptor useful for the treatment of disorders related thereto |
| US9012478B2 (en) | 2008-11-26 | 2015-04-21 | Arena Pharmaceuticals, Inc. | Pyrazolyl substituted carbonic acid derivatives as modulators of the prostacyclin (PGI2) receptor useful for the treatment of disorders related thereto |
| US10689372B2 (en) | 2008-11-26 | 2020-06-23 | Arena Pharmaceuticals, Inc. | Pyrazolyl substituted carbonic acid derivatives as modulators of the prostacyclin (PGI2) receptor useful for the treatment of disorders related thereto |
| US10214518B2 (en) | 2008-11-26 | 2019-02-26 | Arena Pharmaceuticals, Inc. | Pyrazolyl substituted carbonic acid derivatives as modulators of the prostacyclin (PGI2) receptor useful for the treatment of disorders related thereto |
| US9663500B2 (en) | 2008-11-26 | 2017-05-30 | Arena Pharmaceuticals, Inc. | Pyrazolyl substituted carbonic acid derivatives as modulators of the prostacyclin (PGI2) receptor useful for the treatment of disorders related thereto |
| US10138210B2 (en) | 2008-12-08 | 2018-11-27 | Arena Pharmaceuticals, Inc. | Substituted pyridazines as prostacyclin receptor modulators |
| US8940891B2 (en) | 2008-12-08 | 2015-01-27 | Arena Pharmaceuticals, Inc. | Modulators of the prostacyclin (PGI2) receptor useful for the treatment of disorders related thereto |
| US10793529B2 (en) | 2008-12-08 | 2020-10-06 | Arena Pharmaceuticals, Inc. | Substituted pyridazines and 1,2,4-triazines as prostacyclin receptor modulators |
| JP2010189282A (en) * | 2009-02-16 | 2010-09-02 | Dic Corp | Polyfunctional polymerizable compound |
| JP2012087197A (en) * | 2010-10-19 | 2012-05-10 | Fujifilm Corp | Alkali resistance improver, photocurable liquid crystal composition, optical film, polarizing plate and liquid crystal display |
| JP2014505746A (en) * | 2010-12-07 | 2014-03-06 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Liquid crystal medium and electro-optic display |
| JP2014505745A (en) * | 2010-12-10 | 2014-03-06 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Liquid crystal medium and electro-optic display |
| CN102977896A (en) * | 2011-09-02 | 2013-03-20 | Jsr株式会社 | Method for manufacturing liquid crystal display component |
| KR101908964B1 (en) | 2011-09-02 | 2018-10-17 | 제이에스알 가부시끼가이샤 | Manufacturing method for liquid crystal display device, polymer composition, and the liquid crystal display device |
| TWI564635B (en) * | 2011-09-02 | 2017-01-01 | Jsr股份有限公司 | Polymer composition, liquid crystal display device and fabricating method thereof |
| WO2014024648A1 (en) * | 2012-08-08 | 2014-02-13 | Jnc株式会社 | Liquid crystal composition and liquid crystal display element |
| US8968597B2 (en) | 2012-08-08 | 2015-03-03 | Jnc Corporation | Liquid crystal composition and liquid crystal display device |
| JPWO2014024648A1 (en) * | 2012-08-08 | 2016-07-25 | Jnc株式会社 | Liquid crystal composition and liquid crystal display element |
| US8962879B2 (en) | 2012-11-14 | 2015-02-24 | E I Du Pont De Nemours And Company | Perfluoropolyvinyl modified aryl intermediates/monomers |
| US9365476B2 (en) | 2012-11-14 | 2016-06-14 | E I Du Pont De Nemours And Company | Aryl compounds modified with perfluorovinyl ethers |
| US9145356B2 (en) | 2012-11-14 | 2015-09-29 | E I Du Pont De Nemours And Company | Perfluoropolyvinyl modified aryl intermediates and monomers |
| US9193702B2 (en) | 2013-10-31 | 2015-11-24 | E I Du Pont De Nemours And Company | Fluorinated aryl epoxide compounds |
| JPWO2016035667A1 (en) * | 2014-09-05 | 2017-04-27 | Dic株式会社 | Liquid crystal composition and liquid crystal display device using the same |
| CN106661455A (en) * | 2014-09-05 | 2017-05-10 | Dic株式会社 | Liquid crystal composition and liquid crystal display element using same |
| JP2017031428A (en) * | 2014-09-05 | 2017-02-09 | Dic株式会社 | Liquid crystal composition and liquid crystal element using the same |
| KR20170012364A (en) * | 2014-09-19 | 2017-02-02 | 디아이씨 가부시끼가이샤 | Polymerizable composition and film using same |
| KR101955952B1 (en) * | 2014-09-19 | 2019-03-08 | 디아이씨 가부시끼가이샤 | Polymerizable composition and film using same |
| US10688076B2 (en) | 2014-10-23 | 2020-06-23 | Arena Pharmaceuticals, Inc. | Method of treating conditions related to the PGI2 receptor |
| US11000500B2 (en) | 2014-10-23 | 2021-05-11 | Arena Pharmaceuticals, Inc. | Method of treating conditions related to the PGI2 receptor |
| US10537546B2 (en) | 2014-10-23 | 2020-01-21 | Arena Pharmaceuticals, Inc. | Method of treating conditions related to the PGI2 receptor |
| US11426377B2 (en) | 2014-10-23 | 2022-08-30 | Arena Pharmaceuticals, Inc. | Method of treating conditions related to the PGI2 receptor |
| US11826337B2 (en) | 2014-10-23 | 2023-11-28 | Arena Pharmaceuticals, Inc. | Method of treating conditions related to the PGI2 receptor |
| WO2018116901A1 (en) * | 2016-12-19 | 2018-06-28 | Dic株式会社 | Polymerizable composition, and optical isomer produced using same |
| US11123298B2 (en) | 2017-03-01 | 2021-09-21 | Arena Pharmaceuticals, Inc. | Compositions comprising PGI2-receptor agonists and processes for the preparation thereof |
| US11826471B2 (en) | 2017-03-01 | 2023-11-28 | Arena Pharmaceuticals, Inc. | Compositions comprising PGI2-receptor agonists and processes for the preparation thereof |
| JP2020125408A (en) * | 2019-02-05 | 2020-08-20 | 富士フイルム株式会社 | Polymerizable liquid crystal composition, optically anisotropic film, optical film, polarizing plate and image display device |
| JP7042761B2 (en) | 2019-02-05 | 2022-03-28 | 富士フイルム株式会社 | Polymerizable liquid crystal composition, optically anisotropic film, optical film, polarizing plate and image display device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4792731B2 (en) | 2011-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4792731B2 (en) | Polymerizable liquid crystal composition and cured product of the composition | |
| JP6728581B2 (en) | Light-absorption anisotropic film, three-dimensional light-absorption anisotropic film, and method for producing the same | |
| JP4595498B2 (en) | Organosilicon compound-containing polymerizable liquid crystal composition | |
| KR101802218B1 (en) | Liquid crystal alignment film | |
| US7541071B2 (en) | Liquid-crystalline (METH) acrylate derivatives and composition containing them | |
| JP4788123B2 (en) | Photopolymerizable liquid crystal composition, polymer thereof or polymer composition and optically anisotropic film | |
| JP7379443B2 (en) | Manufacturing method of long retardation film | |
| CN103360257B (en) | Polymerizable biphenyl compound | |
| KR20150068892A (en) | Polymerizable liquid crystal composition and optically anisotropic substance having twist alignment | |
| US20070128379A1 (en) | Homeotropically aligned liquid crystal film and process for producing the same | |
| JP2019168714A (en) | Manufacturing method of long circular polarizing plate, and long circular polarizing plate | |
| CN112740084B (en) | Polarizing film and method for producing same | |
| JP2009514024A (en) | Highly transparent cholesteric liquid crystal film | |
| JP4924865B2 (en) | Polymerizable liquid crystal compound, polymerizable liquid crystal composition and polymer thereof | |
| JP2005272561A (en) | Polymerizable liquid crystal composition and polymer of the same | |
| KR20170103775A (en) | Polymerizable liquid crystal composition, and optically anisotropic body, phase difference film, antireflective film, and liquid crystal display element fabricated using same | |
| CN101792391B (en) | Polymerizable biphenyl compound | |
| JP4984842B2 (en) | Homeotropic alignment liquid crystal film and method for producing the same | |
| JP2006342332A (en) | Cyclic ether polymerizable liquid crystal composition, homeotropically aligned liquid crystal film and method for producing homeotropically aligned liquid crystal film | |
| JP2015529343A (en) | Optical film and display element including the same | |
| CN114149397B (en) | Dibenzofurane-based polymerizable compound, preparation method and application thereof | |
| JP4232441B2 (en) | Photopolymerizable liquid crystal composition and optical element using the same | |
| JP2020042149A (en) | Liquid crystal film, optical laminate, circularly polarizing plate, and organic electroluminescence display device | |
| WO2019163611A1 (en) | Liquid crystal cured layer, production method therefor, optical film, polarizing plate, and display device | |
| JP5051417B2 (en) | Photoinitiator and polymerizable composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20071022 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20091030 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20091105 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091225 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20101224 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110127 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110222 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110318 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110414 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110610 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110628 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110711 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4792731 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140805 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |