JP6866892B2 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents
Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element Download PDFInfo
- Publication number
- JP6866892B2 JP6866892B2 JP2018509473A JP2018509473A JP6866892B2 JP 6866892 B2 JP6866892 B2 JP 6866892B2 JP 2018509473 A JP2018509473 A JP 2018509473A JP 2018509473 A JP2018509473 A JP 2018509473A JP 6866892 B2 JP6866892 B2 JP 6866892B2
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- Japan
- Prior art keywords
- liquid crystal
- solvent
- crystal alignment
- alignment agent
- mass
- 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.)
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- 239000004973 liquid crystal related substance Substances 0.000 title claims description 134
- 239000003795 chemical substances by application Substances 0.000 title claims description 79
- 239000002904 solvent Substances 0.000 claims description 98
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 38
- 229920000642 polymer Polymers 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 35
- 239000004642 Polyimide Substances 0.000 claims description 32
- 229920001721 polyimide Polymers 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 150000004985 diamines Chemical class 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 8
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 6
- 125000000962 organic group Chemical group 0.000 claims description 6
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 claims description 5
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 241000018344 Ehrlichia sp. 'CGE agent' Species 0.000 claims 1
- 239000000243 solution Substances 0.000 description 74
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- 239000000203 mixture Substances 0.000 description 27
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- 239000007787 solid Substances 0.000 description 23
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- 239000000463 material Substances 0.000 description 8
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
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- 238000001035 drying Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000000565 sealant Substances 0.000 description 5
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
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- 238000011156 evaluation Methods 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
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- 230000035484 reaction time Effects 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
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- 125000003545 alkoxy group Chemical group 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
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- OURNLUUIQWKTRH-UHFFFAOYSA-N oxirane;phenol Chemical compound C1CO1.OC1=CC=CC=C1.OC1=CC=CC=C1 OURNLUUIQWKTRH-UHFFFAOYSA-N 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
- JCMFJIHDWDKYIL-UHFFFAOYSA-N propyl 3-methoxypropanoate Chemical compound CCCOC(=O)CCOC JCMFJIHDWDKYIL-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
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- Chemical & Material Sciences (AREA)
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- Nonlinear Science (AREA)
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- Crystallography & Structural Chemistry (AREA)
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- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Medicinal Chemistry (AREA)
- Liquid Crystal (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、インクジェット成膜法に適し、かつ、塗布した際の寸法安定性の高い液晶配向剤、該液晶配向剤から得られる液晶配向膜、及び該液晶配向膜を具備する液晶表示素子に関する。 The present invention relates to a liquid crystal alignment agent suitable for an inkjet film forming method and having high dimensional stability when applied, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element provided with the liquid crystal alignment film.
液晶配向膜としては、ポリアミック酸(ポリアミド酸とも言われる。)などのポリイミド前駆体や可溶性ポリイミドの溶液を主成分とする液晶配向剤を塗布し焼成した、いわゆるポリイミド系の液晶配向膜が広く使用されている。
かかる液晶配向膜の成膜法としては、一般に、スピンコート、ディップコート、フレキソ印刷などが知られている。実用的には、フレキソ印刷が多く使用されている。しかし、フレキソ印刷では液晶パネルの品種違いにより様々な樹脂版が必要となること、製造工程ではその版交換が煩雑であるということ、成膜工程を安定させるためにダミー基板への成膜をしなければならないこと、版の製作が液晶表示パネルの製造コスト上昇の一因になるなどの問題がある。As the liquid crystal alignment film, a so-called polyimide-based liquid crystal alignment film in which a polyimide precursor such as polyamic acid (also referred to as polyamic acid) or a liquid crystal alignment agent containing a solution of soluble polyimide as a main component is applied and fired is widely used. Has been done.
As a method for forming such a liquid crystal alignment film, spin coating, dip coating, flexographic printing and the like are generally known. Practically, flexographic printing is often used. However, flexographic printing requires various resin plates depending on the type of liquid crystal panel, the plate replacement is complicated in the manufacturing process, and film formation is performed on a dummy substrate to stabilize the film formation process. There are problems such as having to make a plate and contributing to an increase in the manufacturing cost of the liquid crystal display panel.
そのため、印刷版を用いない液晶配向膜の成膜法として、インクジェット法が注目されている。インクジェット法は、基板に微細な液滴を滴下し、液の濡れ広がりにより成膜する方法である。印刷版を用いないだけでなく、自由に印刷のパターンを設定できるため、液晶表示素子の製造工程が簡素化できる。また、フレキソ印刷で必要であったダミー基板への成膜が不要となることで塗布液の無駄が少ないという利点がある。インクジェット法により、液晶パネルのコストダウン、生産効率の向上が期待される。 Therefore, the inkjet method is attracting attention as a method for forming a liquid crystal alignment film without using a printing plate. The inkjet method is a method in which fine droplets are dropped on a substrate and a film is formed by the wetting and spreading of the liquid. Not only does it not use a printing plate, but the printing pattern can be set freely, which simplifies the manufacturing process of the liquid crystal display element. Further, there is an advantage that the coating liquid is not wasted because the film formation on the dummy substrate, which is required for flexographic printing, is not required. The inkjet method is expected to reduce the cost of liquid crystal panels and improve production efficiency.
インクジェット法により形成される液晶配向膜は、塗布面内部の膜厚ムラが小さく、かつ塗布周辺部の成膜精度が高いことが要求される。一般的にインクジェット法により成膜した液晶配向膜は、塗布面内での膜厚の均一性と、塗布周辺部の成膜精度がトレードオフの関係にある。すなわち、通常、面内均一性の高い材料は、塗布周辺部の寸法安定性が低く、設定した寸法から、膜がはみ出してしまう。一方、塗布周辺部が直線となる材料は、塗布面内均一性が低くなってしまう。 The liquid crystal alignment film formed by the inkjet method is required to have a small film thickness unevenness inside the coating surface and a high film thickness accuracy in the coating peripheral portion. Generally, in a liquid crystal alignment film formed by an inkjet method, there is a trade-off relationship between the uniformity of the film thickness in the coated surface and the film forming accuracy in the peripheral portion of the coating. That is, usually, a material having high in-plane uniformity has low dimensional stability in the coating peripheral portion, and the film protrudes from the set dimensions. On the other hand, a material having a straight coating peripheral portion has low in-plane uniformity.
上記塗布周辺部の成膜精度を高めるため、特殊の構造物によって配向膜を所定の範囲に閉じ込める方法が提案されている(特許文献1〜3参照)。しかし、これらの方法は特殊の構造物が必要になるという難点を有する。 In order to improve the film formation accuracy of the coating peripheral portion, a method of confining the alignment film in a predetermined range by a special structure has been proposed (see Patent Documents 1 to 3). However, these methods have the disadvantage of requiring special structures.
近年、液晶表示素子の高精細化に伴い、多層配線のTFT設計が主流になりつつある。TFT設計では、下層の配線と上層の配線とを接続するため、基板上にコンタクトホール(C/Hとも称する)が形成される。これに伴い、配線構造やC/Hの影響で、液晶配向剤塗布時において、液の広がり性が阻害されやすくなる。その結果、C/H周辺やその他の部分にドット状のムラや筋状のムラのような、配向膜の厚みの不均一が生じ、液晶表示素子の表示が不均一となることがある。 In recent years, with the increase in definition of liquid crystal display elements, TFT design of multi-layer wiring is becoming mainstream. In the TFT design, a contact hole (also referred to as C / H) is formed on the substrate in order to connect the lower layer wiring and the upper layer wiring. Along with this, due to the influence of the wiring structure and C / H, the spreadability of the liquid is likely to be hindered when the liquid crystal alignment agent is applied. As a result, the thickness of the alignment film may be non-uniform, such as dot-like unevenness or streak-like unevenness around the C / H or other parts, and the display of the liquid crystal display element may be non-uniform.
また、インクジェット法で用いられる液晶配向剤は、インクジェットノズルからの配向剤吐出を安定に行う為に、低粘度であることが求められ、それに応じて液晶配向剤中の樹脂成分比率を少なく設定することがある。一方、液晶配向膜の周辺部の膜厚を均一にし、かつ液晶配向膜の幅を抑制するためには、液晶配向剤の低粘度を維持しながら、かつ液晶配向剤中の樹脂成分比率を増加させることが必要であり、そのような液晶配向剤が求められている。 Further, the liquid crystal alignment agent used in the inkjet method is required to have a low viscosity in order to stably discharge the alignment agent from the inkjet nozzle, and the resin component ratio in the liquid crystal alignment agent is set to be small accordingly. Sometimes. On the other hand, in order to make the thickness of the peripheral portion of the liquid crystal alignment film uniform and suppress the width of the liquid crystal alignment film, the resin component ratio in the liquid crystal alignment agent is increased while maintaining the low viscosity of the liquid crystal alignment agent. It is necessary to make such a liquid crystal alignment agent, and such a liquid crystal alignment agent is required.
本発明は、上記課題に鑑み、配線構造やC/Hの影響で生じる液晶配向膜の成膜不良や、液晶表示素子の表示が不均一となる不良を抑制することができ、かつ、液晶配向剤の粘度を低くしつつ、樹脂成分比率を大きくできる液晶配向剤、及びそれを用いた液晶配向膜を提供することにある。 In view of the above problems, the present invention can suppress defects in the formation of the liquid crystal alignment film caused by the influence of the wiring structure and C / H and defects in which the display of the liquid crystal display element becomes non-uniform, and the liquid crystal alignment can be suppressed. It is an object of the present invention to provide a liquid crystal alignment agent capable of increasing the resin component ratio while lowering the viscosity of the agent, and a liquid crystal alignment film using the same.
本発明者は上記課題の解決の為鋭意研究を重ねた結果、本発明を完成するに至ったものである。
本発明の要旨は、ポリイミド前駆体及びそのイミド化物であるポリイミドからなる群から選ばれる少なくとも1種の重合体と、下記A、B及びCグループに属する溶媒を含有する溶媒と、を含有することを特徴とする液晶配向剤。
Aグループ:N−メチル−2−ピロリドン(NMP)、N−エチル−2−ピロリドン(NEP)、γ‐ブチロラクトン(GBL)および1,3−ジメチルイミダゾリジノン(DMI)からなる群から選ばれる少なくとも1種の溶媒
Bグループ:ジプロピレングリコールジメチルエーテル(DME)
Cグループ:下記式(a)で表される化合物を含む溶媒
The gist of the present invention is to contain at least one polymer selected from the group consisting of a polyimide precursor and a polyimide which is an imidized product thereof, and a solvent containing a solvent belonging to the following groups A, B and C. A liquid crystal alignment agent characterized by.
Group A: At least selected from the group consisting of N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), γ-butyrolactone (GBL) and 1,3-dimethylimidazolidinone (DMI). One Solvent Group B: Dipropylene Glycol Dimethyl Ether (DME)
Group C: Solvent containing the compound represented by the following formula (a)
本発明によれば、配線構造やC/Hの影響で生じる液晶配向膜の成膜不良や、液晶表示素子の表示が不均一となる不良を抑制することができ、かつ、低粘度を維持しながら、かつ高樹脂成分比率を有することができるため、インクジェット法による成膜に好適なポリイミド系の液晶配向剤、それを用いた液晶配向膜、及び液晶表示素子が得られる。 According to the present invention, it is possible to suppress defects in the formation of a liquid crystal alignment film caused by the influence of the wiring structure and C / H, and defects in which the display of the liquid crystal display element becomes non-uniform, and maintain low viscosity. However, since it can have a high resin component ratio, a polyimide-based liquid crystal alignment agent suitable for film formation by an inkjet method, a liquid crystal alignment film using the same, and a liquid crystal display element can be obtained.
本発明の液晶配向剤は、ポリイミド前駆体及びそのイミド化物であるポリイミドからなる群から選ばれる少なくとも1種の重合体(以下、特定重合体ともいう。)と、下記する溶媒A,溶媒B、及び溶媒Cを含有する溶媒(以下、特定溶媒ともいう。)を含有する。 The liquid crystal aligning agent of the present invention comprises at least one polymer (hereinafter, also referred to as a specific polymer) selected from the group consisting of a polyimide precursor and a polyimide which is an imide thereof, and the following solvent A, solvent B, and the like. And a solvent containing a polymer C (hereinafter, also referred to as a specific solvent).
<特定溶媒>
本発明の液晶配向剤に含有される溶媒は、上記溶媒A、溶媒B、及び溶媒Cを含有するが、以下に、それぞれについて説明する。
<溶媒A>
溶媒Aは、N−メチル−2−ピロリドン(NMP)、N−エチル−2−ピロリドン(NEP)、γ‐ブチロラクトン(GBL)、及び1,3−ジメチルイミダゾリジノン(DMI)からなる群から選ばれる少なくとも1種の溶媒である。溶媒Aは、液晶配向剤中の重合体を溶解させるものである。<Specific solvent>
The solvent contained in the liquid crystal alignment agent of the present invention contains the above-mentioned solvent A, solvent B, and solvent C, and each of them will be described below.
<Solvent A>
Solvent A is selected from the group consisting of N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), γ-butyrolactone (GBL), and 1,3-dimethylimidazolidinone (DMI). At least one solvent. Solvent A dissolves the polymer in the liquid crystal alignment agent.
なかでも、N−メチル−2−ピロリドン、N−エチル−2−ピロリドン、又はγ‐ブチロラクトン(GBL)が好ましく、より好ましくはN−メチル−2−ピロリドン(NMP)、又はγ‐ブチロラクトン(GBL)である。
本発明の液晶配向剤において、溶媒Aの含有量は、液晶配向剤の全質量に対し、20〜90質量%が好ましく、30〜80質量%がより好ましく、更に好ましくは、50〜80質量%である。Of these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyrolactone (GBL) is preferable, and N-methyl-2-pyrrolidone (NMP) or γ-butyrolactone (GBL) is more preferable. Is.
In the liquid crystal aligning agent of the present invention, the content of the solvent A is preferably 20 to 90% by mass, more preferably 30 to 80% by mass, still more preferably 50 to 80% by mass, based on the total mass of the liquid crystal aligning agent. Is.
<溶媒B>
溶媒Bは、ジプロピレングリコールジメチルエーテル(DME)である。溶媒Bは、液晶配向剤の塗布均一性の向上と低粘度化に寄与する溶媒である。
本発明の液晶配向剤において、溶媒Bの含有量は、液晶配向剤の全質量に対し、5〜50質量%が好ましく、10〜50質量%がより好ましい。<Solvent B>
Solvent B is dipropylene glycol dimethyl ether (DME). The solvent B is a solvent that contributes to improving the coating uniformity of the liquid crystal alignment agent and lowering the viscosity.
In the liquid crystal aligning agent of the present invention, the content of the solvent B is preferably 5 to 50% by mass, more preferably 10 to 50% by mass, based on the total mass of the liquid crystal aligning agent.
<溶媒C>
溶媒Cは、下記式(a)で表される化合物からなる。
式(a)中、R1、R2は,それぞれ独立して、直鎖又は分岐状の炭素数1〜8、好ましくは3〜8、より好ましくは3〜6のアルキル基である。但し、R1及びR2の炭素数の合計は4以上であり、好ましくは5〜12である。<Solvent C>
The solvent C is composed of a compound represented by the following formula (a).
In the formula (a), R 1 and R 2 are independently linear or branched alkyl groups having 1 to 8 carbon atoms, preferably 3 to 8 carbon atoms, and more preferably 3 to 6 carbon atoms. However, the total number of carbon atoms of R 1 and R 2 is 4 or more, preferably 5 to 12.
式(a)で表される溶媒Cは、具体的には、以下のa−1〜a−48が例示されるが、これらに限定されない。
溶媒Cは、なかでも、入手性と実用性の点から、a−22、a−13〜a−21、a−24、a−26、a−27、a−31、a−34、a−37、又はa−38が好ましく、a−22、又はa−37がより好ましい。
本発明の液晶配向剤において、溶媒Cの含有量は、液晶配向剤の全質量に対し、5〜40質量%が好ましく、10〜30質量%がより好ましい。Solvent C is, among others, a-22, a-13 to a-21, a-24, a-26, a-27, a-31, a-34, a- from the viewpoint of availability and practicality. 37 or a-38 is preferable, and a-22 or a-37 is more preferable.
In the liquid crystal aligning agent of the present invention, the content of the solvent C is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, based on the total mass of the liquid crystal aligning agent.
また、溶媒B及び溶媒Cの合計含有量が、液晶配向剤の全質量に対し、20〜50質量%が好ましく、20〜40質量%がより好ましい。また、その際、溶媒Bの含有量は、溶媒Cの含有量より大きいことが好ましく、特に、溶媒Cの含有量より、1〜20質量%大きいことがより好ましい。
本発明の液晶配向剤は、特定溶媒以外の溶媒を含有していてもよい。その例としては、ブチルセロソルブ、1−ブトキシ‐2−プロパノール、ブチルセロソルブアセタート、ジプロピレングリコールモノメチルエーテル、ダイアセトンアルコール、ジエチレングリコールジエチルエーテル、ジイソペンチルエーテル、プロピレングリコールジアセタート、ジイソブチルケトン、エチルカルビトールおよびジプロピレングリコールジメチルエーテル、ガンマバレロラクトンなどが挙げられる。特定溶媒以外の溶媒は、液晶配向剤の全質量に対し、50質量%以下が好ましく、20質量%以下がより好ましい。The total content of the solvent B and the solvent C is preferably 20 to 50% by mass, more preferably 20 to 40% by mass, based on the total mass of the liquid crystal aligning agent. At that time, the content of the solvent B is preferably larger than the content of the solvent C, and more preferably 1 to 20% by mass larger than the content of the solvent C.
The liquid crystal alignment agent of the present invention may contain a solvent other than the specific solvent. Examples include butyl cellosolve, 1-butoxy-2-propanol, butyl cellosolve acetate, dipropylene glycol monomethyl ether, diacetone alcohol, diethylene glycol diethyl ether, diisopentyl ether, propylene glycol diacetate, diisobutyl ketone, ethyl carbitol. And dipropylene glycol dimethyl ether, gamma valerolactone and the like. The solvent other than the specific solvent is preferably 50% by mass or less, more preferably 20% by mass or less, based on the total mass of the liquid crystal aligning agent.
<特定重合体>
本発明の液晶配向剤に含有される特定重合体であるポリイミド前駆体は、以下の式(1)で表わされる構造を有することが好ましい。
The polyimide precursor, which is a specific polymer contained in the liquid crystal alignment agent of the present invention, preferably has a structure represented by the following formula (1).
式(1)中、X1は、テトラカルボン酸誘導体由来の4価の有機基である。Y1はジアミン由来の2価の有機基である。R1は、水素原子又は炭素原子数1〜5のアルキレンである。加熱時のイミド化反応の進行のしやすさの観点から、R1は水素原子、メチル基、又はエチル基が好ましく、水素原子又はメチル基がより好ましい。
A1及びA2は、それぞれ独立して、水素原子又は、炭素数1〜5のアルキル基、炭素数2〜5のアルケニル基、又は炭素数2〜5のアルキニル基である。液晶配向性の観点から、A1及びA2は水素原子、又はメチル基が好ましい。In formula (1), X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative. Y 1 is a diamine-derived divalent organic group. R 1 is a hydrogen atom or an alkylene having 1 to 5 carbon atoms. From the viewpoint of easiness of the imidization reaction during heating, R 1 is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group.
A 1 and A 2 are independently hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, alkenyl groups having 2 to 5 carbon atoms, or alkynyl groups having 2 to 5 carbon atoms. From the viewpoint of liquid crystal orientation, A 1 and A 2 are preferably hydrogen atoms or methyl groups.
以下に、上記ポリイミド前駆体を製造する原料となる各成分について説明する。
<ジアミン>
ポリイミド前駆体の製造に用いられるジアミン成分は特に限定されないが、上記式(1)で表されるポリイミド前駆体の原料であるジアミンは、下記の式(2)で表される。
<Diamine>
The diamine component used in the production of the polyimide precursor is not particularly limited, but the diamine which is the raw material of the polyimide precursor represented by the above formula (1) is represented by the following formula (2).
式(2)中、A1及びA2は好ましい例も含めて、上記式(1)のA1及びA2と同様の定義である。Y1を例示すると、以下の(Y−1)〜(Y−170)が挙げられる。
なかでも、(Y−7)、(Y−8)、(Y−16)、(Y−17)、(Y−18)、(Y−20),(Y−21)、(Y−22)、(Y−28)、(Y−35)、(Y−38)、(Y−43)、(Y−48)、(Y−64),(Y−66)、(Y−71)、(Y−72)、(Y−76),(Y−77)、(Y−80)、(Y−81)、(Y−82)、(Y−83)、(Y156)、(Y−159)、(Y−160)、(Y−161)、(Y−162)(Y−168)、(Y−169)又は(Y−170)が好ましく、特には、(Y−7)、(Y−8)、(Y−16)、(Y−17)、(Y−18)、(Y−21)、(Y−22)、(Y−28)、(Y−38)、(Y−64),(Y−66)、(Y−72)、(Y−76),(Y−81)、(Y156)、(Y−159)、(Y−160)、(Y−161)、(Y−162)(Y−168)、(Y−169)又は(Y−170)が好ましい。
Among them, (Y-7), (Y-8), (Y-16), (Y-17), (Y-18), (Y-20), (Y-21), (Y-22). , (Y-28), (Y-35), (Y-38), (Y-43), (Y-48), (Y-64), (Y-66), (Y-71), ( Y-72), (Y-76), (Y-77), (Y-80), (Y-81), (Y-82), (Y-83), (Y156), (Y-159) , (Y-160), (Y-161), (Y-162) (Y-168), (Y-169) or (Y-170), especially (Y-7), (Y-170). 8), (Y-16), (Y-17), (Y-18), (Y-21), (Y-22), (Y-28), (Y-38), (Y-64) , (Y-66), (Y-72), (Y-76), (Y-81), (Y156), (Y-159), (Y-160), (Y-161), (Y- 162) (Y-168), (Y-169) or (Y-170) are preferred.
<テトラカルボン酸誘導体>
ポリイミド前駆体の製造に用いられるテトラカルボン酸誘導体は特に限定されないが、上記式(1)で表されるポリイミド前駆体の原料であるテトラカルボン酸誘導体成分としては、テトラカルボン酸二無水物だけでなく、その誘導体であるテトラカルボン酸、テトラカルボン酸ジハライド、テトラカルボン酸ジアルキルエステル、又はテトラカルボン酸ジアルキルエステルジハライドが挙げられる。<Tetracarboxylic acid derivative>
The tetracarboxylic acid derivative used for producing the polyimide precursor is not particularly limited, but the tetracarboxylic acid dianhydride which is the raw material of the polyimide precursor represented by the above formula (1) is only a tetracarboxylic dianhydride. Examples thereof include tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, and tetracarboxylic acid dialkyl ester dihalide, which are derivatives thereof.
テトラカルボン酸二無水物又はその誘導体としては、下記式(3)で表されものが好ましい。
式(3)中、X1は、脂環式構造を有する4価の有機基であり、その構造は特に限定されない。具体例としては、下記式(X1−1)〜(X1−44)が挙げられる。
式(X1−1)〜(X1−4)において、R3〜R23は、それぞれ独立して、水素原子、ハロゲン原子、炭素数1〜6のアルキル基、炭素数2〜6のアルケニル基、炭素数2〜6のアルキニル基、フッ素原子を含有する炭素数1〜6の1価の有機基、又はフェニル基である。液晶配向性の点から、R3〜R23は、水素原子、ハロゲン原子、メチル基、又はエチル基が好ましく、水素原子、又はメチル基がより好ましい。
なお、式(X1−1)の具体例としては、下記式(X1−1−1)〜(
X1−1−6)が挙げられる。液晶配向性及び光反応の感度の点から、(X1−1−1)が特に好ましい。In the formulas (X1-1) to (X1-4), R 3 to R 23 are independently hydrogen atom, halogen atom, alkyl group having 1 to 6 carbon atoms, alkenyl group having 2 to 6 carbon atoms, respectively. It is an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group. From the viewpoint of liquid crystal orientation, R 3 to R 23 are preferably a hydrogen atom, a halogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group.
As specific examples of the formula (X1-1), the following formulas (X1-1-1) to (
X1-1-6) can be mentioned. (X1-1-1) is particularly preferable from the viewpoint of liquid crystal orientation and sensitivity of photoreaction.
本発明のポリイミド前駆体及びポリイミドの原料であるテトラカルボン酸二無水物及びその誘導体としては、全テトラカルボン酸二無水物及びその誘導体1モルに対して、上記式(3)で表されるテトラカルボン酸二無水物又はその誘導体を60〜100モル%含むことが好ましい。良好な液晶配向性を有する液晶配向膜が得られるため、80〜100モル%がより好ましく、90〜100モル%がさらに好ましい。 The tetracarboxylic dianhydride and its derivative, which are the polyimide precursor of the present invention and the raw material of the polyimide, include the tetra represented by the above formula (3) with respect to 1 mol of the total tetracarboxylic dianhydride and its derivative. It preferably contains 60 to 100 mol% of carboxylic acid dianhydride or a derivative thereof. Since a liquid crystal alignment film having good liquid crystal orientation can be obtained, 80 to 100 mol% is more preferable, and 90 to 100 mol% is further preferable.
<ポリイミド前駆体>
<ポリアミック酸エステルの製造方法>
本発明に用いられるポリイミド前駆体の一つであるポリアミック酸エステルは、以下に示す(1)、(2)又は(3)の方法で製造できる。
(1)ポリアミック酸から製造する場合
ポリアミック酸エステルは、テトラカルボン酸二無水物とジアミンから得られるポリアミック酸をエステル化することによって合成できる。
具体的には、ポリアミック酸とエステル化剤を有機溶剤の存在下で−20℃〜150℃、好ましくは0℃〜50℃において、30分〜24時間、好ましくは1〜4時間反応させることによって合成できる。<Polyimide precursor>
<Manufacturing method of polyamic acid ester>
The polyamic acid ester, which is one of the polyimide precursors used in the present invention, can be produced by the methods (1), (2) or (3) shown below.
(1) When produced from polyamic acid A polyamic acid ester can be synthesized by esterifying a polyamic acid obtained from tetracarboxylic dianhydride and diamine.
Specifically, the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at −20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C. for 30 minutes to 24 hours, preferably 1 to 4 hours. Can be synthesized.
エステル化剤としては、精製によって容易に除去できるものが好ましく、N,N−ジメチルホルムアミドジメチルアセタール、N,N−ジメチルホルムアミドジエチルアセタール、N,N−ジメチルホルムアミドジプロピルアセタール、N,N−ジメチルホルムアミドジネオペンチルブチルアセタール、N,N−ジメチルホルムアミドジ−t−ブチルアセタール、1−メチル−3−p−トリルトリアゼン、1−エチル−3−p−トリルトリアゼン、1−プロピル−3−p−トリルトリアゼン、4−(4,6−ジメトキシ−1,3,5−トリアジンー2−イル)−4−メチルモルホリニウムクロリドなどが挙げられる。エステル化剤の使用量は、ポリアミック酸の繰り返し単位1モルに対して、2〜6モル当量が好ましい。 The esterifying agent is preferably one that can be easily removed by purification, and is preferably N, N-dimethylformamide dimethylacetal, N, N-dimethylformamide diethylacetal, N, N-dimethylformamide dipropylacetal, N, N-dimethylformamide. Dineopentylbutylacetal, N, N-dimethylformamide di-t-butylacetal, 1-methyl-3-p-tolyltriasel, 1-ethyl-3-p-tolyltriasel, 1-propyl-3-p Examples thereof include −triltriazene, 4- (4,6-dimethoxy-1,3,5-triazine-2-yl) -4-methylmorpholinium chloride and the like. The amount of the esterifying agent used is preferably 2 to 6 molar equivalents with respect to 1 mol of the repeating unit of the polyamic acid.
上記の反応に用いる溶媒は、ポリマーの溶解性からN,N−ジメチルホルムアミド、N−メチル−2−ピロリドン、又はγ−ブチロラクトンが好ましく、これらは1種又は2種以上を混合して用いてもよい。反応液中のポリマーの濃度は、ポリマーの析出が起こりにくく、かつ高分子量体が得やすいという観点から、1〜30質量%が好ましく、5〜20質量%がより好ましい。 The solvent used for the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone because of the solubility of the polymer, and these may be used alone or in combination of two or more. Good. The concentration of the polymer in the reaction solution is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, from the viewpoint that precipitation of the polymer is unlikely to occur and a high molecular weight polymer is easily obtained.
(2)テトラカルボン酸ジエステルジクロリドとジアミンとの反応により製造する場合
ポリアミック酸エステルは、テトラカルボン酸ジエステルジクロリドとジアミンから製造できる。具体的には、テトラカルボン酸ジエステルジクロリドとジアミンとを塩基と有機溶剤の存在下で−20℃〜150℃、好ましくは0℃〜50℃において、30分〜24時間、好ましくは1〜4時間反応させることによって製造できる。(2) When produced by reacting tetracarboxylic dianester dichloride with diamine The polyamic acid ester can be produced from tetracarboxylic dianester dichloride and diamine. Specifically, the tetracarboxylic dianester dichloride and diamine are mixed in the presence of a base and an organic solvent at −20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C. for 30 minutes to 24 hours, preferably 1 to 4 hours. It can be produced by reacting.
前記塩基には、ピリジン、トリエチルアミン、4−ジメチルアミノピリジンなどが使用できるが、反応が穏和に進行するためにピリジンが好ましい。塩基の使用量は、除去が容易な量で、かつ高分子量体が得やすいという観点から、テトラカルボン酸ジエステルジクロリドに対して、2〜4倍モルであることが好ましい。
上記の反応に用いる溶媒は、モノマーおよびポリマーの溶解性からN−メチル−2−ピロリドン、又はγ−ブチロラクトンが好ましく、これらは1種又は2種以上を混合して用いてもよい。反応液中のポリマー濃度は、ポリマーの析出が起こりにくく、かつ高分子量体が得やすいという観点から、1〜30質量%が好ましく、5〜20質量%がより好ましい。また、テトラカルボン酸ジエステルジクロリドの加水分解を防ぐため、ポリアミック酸エステルの合成に用いる溶媒はできるだけ脱水されていることが好ましく、窒素雰囲気中で、外気の混入を防ぐのが好ましい。Pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used as the base, but pyridine is preferable because the reaction proceeds mildly. The amount of the base used is preferably 2 to 4 times the molar amount of the tetracarboxylic dianester dichloride from the viewpoint that it can be easily removed and a high molecular weight substance can be easily obtained.
The solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone because of the solubility of the monomer and the polymer, and these may be used alone or in admixture of two or more. The polymer concentration in the reaction solution is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, from the viewpoint that the precipitation of the polymer is unlikely to occur and a high molecular weight polymer is easily obtained. Further, in order to prevent hydrolysis of the tetracarboxylic dianester dichloride, the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent the mixing of outside air in a nitrogen atmosphere.
(3)テトラカルボン酸ジエステルとジアミンからポリアミック酸エステルを製造する場合
ポリアミック酸エステルは、テトラカルボン酸ジエステルとジアミンを重縮合することにより製造できる。具体的には、テトラカルボン酸ジエステルとジアミンを縮合剤、塩基、及び有機溶剤の存在下で0℃〜150℃、好ましくは0℃〜100℃において、30分〜24時間、好ましくは3〜15時間反応させることによって製造できる。(3) When producing a polyamic acid ester from a tetracarboxylic dian ester and a diamine The polyamic acid ester can be produced by polycondensing a tetracarboxylic dian ester and a diamine. Specifically, tetracarboxylic diandies and diamines are mixed in the presence of a condensing agent, a base, and an organic solvent at 0 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C. for 30 minutes to 24 hours, preferably 3 to 15. It can be manufactured by reacting for a time.
前記縮合剤には、トリフェニルホスファイト、ジシクロヘキシルカルボジイミド、1−エチル−3−(3−ジメチルアミノプロピル)カルボジイミド塩酸塩、N,N’−カルボニルジイミダゾール、ジメトキシ−1,3,5−トリアジニルメチルモルホリニウム、O−(ベンゾトリアゾール−1−イル)−N,N,N’,N’−テトラメチルウロニウム テトラフルオロボラート、O−(ベンゾトリアゾール−1−イル)−N,N,N’,N’−テトラメチルウロニウムヘキサフルオロホスファート、(2,3−ジヒドロ−2−チオキソ−3−ベンゾオキサゾリル)ホスホン酸ジフェニルなどが使用できる。縮合剤の添加量は、テトラカルボン酸ジエステルに対して2〜3倍モルが好ましい。 The condensing agent includes triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy-1,3,5-triazi. Nylmethylmorpholinium, O- (benzotriazole-1-yl) -N, N, N', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazole-1-yl) -N, N , N', N'-tetramethyluronium hexafluorophosphate, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate and the like can be used. The amount of the condensing agent added is preferably 2 to 3 times the molar amount of the tetracarboxylic dianester.
前記塩基には、ピリジン、トリエチルアミンなどの3級アミンが使用できる。塩基の使用量は、除去が容易な量で、かつ高分子量体が得やすいという観点から、ジアミン成分に対して2〜4倍モルが好ましい。
また、上記反応において、ルイス酸を添加剤として加えることで反応が効率的に進行する。ルイス酸としては、塩化リチウム、臭化リチウムなどのハロゲン化リチウムが好ましい。ルイス酸の添加量はジアミン成分に対して0〜1.0倍モルが好ましい。A tertiary amine such as pyridine or triethylamine can be used as the base. The amount of the base used is preferably 2 to 4 times the molar amount of the diamine component from the viewpoint that it is easy to remove and a high molecular weight substance can be easily obtained.
Further, in the above reaction, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halide such as lithium chloride and lithium bromide is preferable. The amount of Lewis acid added is preferably 0 to 1.0 times the molar amount of the diamine component.
上記3つのポリアミック酸エステルの製造方法の中でも、高分子量のポリアミック酸エステルが得られるため、上記(1)又は上記(2)の製造法が特に好ましい。
上記のようにして得られるポリアミック酸エステルの溶液は、よく撹拌させながら貧溶媒に注入することで、ポリマーを析出させることができる。析出を数回行い、貧溶媒で洗浄後、常温あるいは加熱乾燥して精製されたポリアミック酸エステルの粉末を得ることができる。貧溶媒は、特に限定されないが、水、メタノール、エタノール、ヘキサン、ブチルセロソルブ、アセトン、トルエン等が挙げられる。Among the above three methods for producing a polyamic acid ester, the above method (1) or the above (2) is particularly preferable because a high molecular weight polyamic acid ester can be obtained.
The solution of the polyamic acid ester obtained as described above can be injected into a poor solvent with good stirring to precipitate a polymer. Precipitation is carried out several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.
<ポリアミック酸の製造方法>
本発明に用いられるポリイミド前駆体であるポリアミック酸は、以下に示す方法により製造できる。
具体的には、テトラカルボン酸二無水物とジアミンとを有機溶媒の存在下で−20℃〜150℃、好ましくは0℃〜50℃において、30分〜24時間、好ましくは1〜12時間反応させることによって合成できる。<Manufacturing method of polyamic acid>
The polyamic acid, which is a polyimide precursor used in the present invention, can be produced by the method shown below.
Specifically, the tetracarboxylic dianhydride and the diamine are reacted in the presence of an organic solvent at −20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C. for 30 minutes to 24 hours, preferably 1 to 12 hours. It can be synthesized by letting it.
上記の反応に用いる有機溶媒は、モノマーおよびポリマーの溶解性からN,N−ジメチルホルムアミド、N−メチル−2−ピロリドン、又はγ−ブチロラクトンが好ましく、これらは1種又は2種以上を混合して用いてもよい。ポリマーの濃度は、ポリマーの析出が起こりにくく、かつ高分子量体が得やすいという観点から、1〜30質量%が好ましく、5〜20質量%がより好ましい。 The organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone because of the solubility of the monomer and the polymer, and these are one or a mixture of two or more. You may use it. The concentration of the polymer is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, from the viewpoint that precipitation of the polymer is unlikely to occur and a high molecular weight polymer is easily obtained.
上記のようにして得られたポリアミック酸は、反応溶液をよく撹拌させながら貧溶媒に注入することで、ポリマーを析出させて回収することができる。また、析出を数回行い、貧溶媒で洗浄後、常温あるいは加熱乾燥することで精製されたポリアミック酸の粉末を得ることができる。貧溶媒は、特に限定されないが、水、メタノール、エタノール、ヘキサン、ブチルセロソルブ、アセトン、トルエン等が挙げられる。 The polyamic acid obtained as described above can be recovered by precipitating a polymer by injecting the reaction solution into a poor solvent while stirring well. Further, the purified polyamic acid powder can be obtained by performing precipitation several times, washing with a poor solvent, and then drying at room temperature or by heating. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.
<ポリイミドの製造方法>
本発明に用いられるポリイミドは、前記ポリアミック酸エステル又はポリアミック酸をイミド化することにより製造できる。ポリアミック酸エステルからポリイミドを製造する場合、前記ポリアミック酸エステル溶液、又はポリアミック酸エステル樹脂粉末を有機溶媒に溶解させて得られるポリアミック酸溶液に塩基性触媒を添加する化学的イミド化が簡便である。化学的イミド化は、比較的低温でイミド化反応が進行し、イミド化の課程で重合体の分子量低下が起こりにくいので好ましい。<Polyimide manufacturing method>
The polyimide used in the present invention can be produced by imidizing the polyamic acid ester or polyamic acid. When polyimide is produced from a polyamic acid ester, chemical imidization in which a basic catalyst is added to the polyamic acid ester solution or the polyamic acid solution obtained by dissolving the polyamic acid ester resin powder in an organic solvent is convenient. Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer is unlikely to decrease during the imidization process.
化学的イミド化は、イミド化させたいポリアミック酸エステルを、有機溶媒中において塩基性触媒存在下で撹拌することにより行うことができる。有機溶媒としては前述した重合反応時に用いる溶媒を使用できる。塩基性触媒としてはピリジン、トリエチルアミン、トリメチルアミン、トリブチルアミン、トリオクチルアミン等を挙げることができる。中でもトリエチルアミンは反応を進行させるのに充分な塩基性を有するので好ましい。 Chemical imidization can be performed by stirring the polyamic acid ester to be imidized in an organic solvent in the presence of a basic catalyst. As the organic solvent, the solvent used in the above-mentioned polymerization reaction can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, triethylamine is preferable because it has sufficient basicity to allow the reaction to proceed.
イミド化反応を行うときの温度は、−20℃〜140℃、好ましくは0℃〜100℃であり、反応時間は1〜100時間で行うことができる。塩基性触媒の量はアミック酸エステル基の0.5〜30モル倍、好ましくは2〜20モル倍である。得られる重合体のイミド化率は、触媒量、温度、反応時間を調節することで制御できる。イミド化反応後の溶液には、添加した触媒等が残存しているので、得られたイミド化重合体を回収し、有機溶媒で再溶解して、本発明の液晶配向剤とすることが好ましい。 The temperature at which the imidization reaction is carried out is −20 ° C. to 140 ° C., preferably 0 ° C. to 100 ° C., and the reaction time can be 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times, that of the amic acid ester group. The imidization rate of the obtained polymer can be controlled by adjusting the amount of catalyst, the temperature, and the reaction time. Since the added catalyst and the like remain in the solution after the imidization reaction, it is preferable to recover the obtained imidized polymer and redissolve it in an organic solvent to obtain the liquid crystal aligning agent of the present invention. ..
ポリアミック酸からポリイミドを製造する場合、ジアミン成分とテトラカルボン酸二無水物との反応で得られた前記ポリアミック酸の溶液に触媒を添加する化学的イミド化が簡便である。化学的イミド化は、比較的低温でイミド化反応が進行し、イミド化の過程で重合体の分子量低下が起こりにくいので好ましい。
化学的イミド化は、イミド化させたい重合体を、有機溶媒中において塩基性触媒と酸無水物の存在下で攪拌することにより行うことができる。有機溶媒としては前述した重合反応時に用いる溶媒を使用することができる。塩基性触媒としてはピリジン、トリエチルアミン、トリメチルアミン、トリブチルアミン、トリオクチルアミン等を挙げることができる。中でもピリジンは反応を進行させるのに適度な塩基性を持つので好ましい。また、酸無水物としては無水酢酸、無水トリメリット酸、無水ピロメリット酸等を挙げることができ、中でも無水酢酸を用いると反応終了後の精製が容易となるので好ましい。When polyimide is produced from a polyamic acid, it is convenient to chemically imidize by adding a catalyst to the solution of the polyamic acid obtained by the reaction of a diamine component and a tetracarboxylic dianhydride. Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer is unlikely to decrease during the imidization process.
Chemical imidization can be carried out by stirring the polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride. As the organic solvent, the solvent used in the above-mentioned polymerization reaction can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for advancing the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like. Among them, acetic anhydride is preferable because it facilitates purification after the reaction is completed.
イミド化反応を行うときの温度は、−20℃〜140℃、好ましくは0℃〜100℃であり、反応時間は1〜100時間で行うことができる。塩基性触媒の量はアミック酸基の0.5〜30モル倍、好ましくは2〜20モル倍であり、酸無水物の量はアミック酸基の1〜50モル倍、好ましくは3〜30モル倍である。得られる重合体のイミド化率は、触媒量、温度、反応時間を調節することで制御することができる。 The temperature at which the imidization reaction is carried out is −20 ° C. to 140 ° C., preferably 0 ° C. to 100 ° C., and the reaction time can be 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times, that of the amic acid group, and the amount of acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times that of the amic acid group. It is double. The imidization rate of the obtained polymer can be controlled by adjusting the amount of catalyst, the temperature, and the reaction time.
ポリアミック酸エステル又はポリアミック酸のイミド化反応後の溶液には、添加した触媒等が残存しているので、以下に述べる手段により、得られたイミド化重合体を回収し、有機溶媒で再溶解して、本発明の液晶配向剤とすることが好ましい。
上記のようにして得られるポリイミドの溶液は、よく撹拌させながら貧溶媒に注入することで、重合体を析出させることができる。析出を数回行い、貧溶媒で洗浄後、常温あるいは加熱乾燥して精製されたポリアミック酸エステルの粉末を得ることができる。
前記貧溶媒は、特に限定されないが、メタノール、アセトン、ヘキサン、ブチルセルソルブ、ヘプタン、メチルエチルケトン、メチルイソブチルケトン、エタノール、トルエン、ベンゼン等が挙げられる。Since the added catalyst and the like remain in the solution after the imidization reaction of the polyamic acid ester or polyamic acid, the obtained imidized polymer is recovered by the means described below and redissolved in an organic solvent. Therefore, it is preferable to use the liquid crystal aligning agent of the present invention.
The polyimide solution obtained as described above can be injected into a poor solvent with good stirring to precipitate a polymer. Precipitation is carried out several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
The poor solvent is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellsolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.
<液晶配向剤>
本発明の液晶配向剤は、特定重合体が特定溶媒を含む溶媒中に溶解された溶液の形態を有する。本発明に記載のポリイミド前駆体及びポリイミドの分子量は、重量平均分子量で2,000〜500,000が好ましく、より好ましくは5,000〜300,000であり、さらに好ましくは、10,000〜100,000である。また、数平均分子量は、好ましくは、1,000〜250,000であり、より好ましくは、2,500〜150,000であり、さらに好ましくは、5,000〜50,000である。<Liquid crystal alignment agent>
The liquid crystal alignment agent of the present invention has the form of a solution in which a specific polymer is dissolved in a solvent containing a specific solvent. The molecular weight of the polyimide precursor and the polyimide described in the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, still more preferably 10,000 to 100, in terms of weight average molecular weight. It is 000. The number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and even more preferably 5,000 to 50,000.
本発明に用いられる液晶配向剤の重合体の濃度は、形成させようとする塗膜の厚みの設定によって適宜変更することができるが、均一で欠陥のない塗膜を形成させるという点から1重量%以上であることが好ましく、溶液の保存安定性の点からは10重量%以下とすることが好ましい。 The concentration of the polymer of the liquid crystal aligning agent used in the present invention can be appropriately changed by setting the thickness of the coating film to be formed, but is 1 weight from the viewpoint of forming a uniform and defect-free coating film. % Or more, and preferably 10% by weight or less from the viewpoint of storage stability of the solution.
<その他の溶媒>
本発明の液晶配向剤には、上記溶媒A、B及びC以外の溶媒(以下、その他の溶媒ともいう。)を含有できる。その他の溶媒としては、ポリイミド前駆体及びポリイミドを溶解させる溶媒(良溶媒ともいう)や、液晶配向剤を塗布した際の液晶配向膜の塗膜性や表面平滑性を向上させる溶媒(貧溶媒ともいう)を含有させても良い。<Other solvents>
The liquid crystal alignment agent of the present invention may contain a solvent other than the above solvents A, B and C (hereinafter, also referred to as other solvents). Other solvents include a solvent that dissolves the polyimide precursor and polyimide (also called a good solvent), and a solvent that improves the coating film property and surface smoothness of the liquid crystal alignment film when a liquid crystal alignment agent is applied (also called a poor solvent). May be contained.
下記に、その他の溶媒の具体例を挙げるが、これらの例に限定されるものではない。
良溶媒としては、例えば、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、ジメチルスルホキシド、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、3−メトキシーN,N−ジメチルプロパンアミド(IPME)又は4−ヒドロキシ−4−メチル−2−ペンタノンなどを挙げることができる。Specific examples of other solvents are given below, but the present invention is not limited to these examples.
Good solvents include, for example, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N, N-dimethylpropanamide (IPME) or 4-hydroxy-. 4-Methyl-2-pentanone and the like can be mentioned.
貧溶媒の具体例としては、例えば、エタノール、イソプロピルアルコール、1−ブタノール、2−ブタノール、イソブチルアルコール、tert−ブチルアルコール、1−ペンタノール、2−ペンタノール、3−ペンタノール、2−メチル−1−ブタノール、イソペンチルアルコール、tert−ペンチルアルコール、3−メチル−2−ブタノール、ネオペンチルアルコール、1−ヘキサノール、2−メチル−1−ペンタノール、2−メチル−2−ペンタノール、2−エチル−1−ブタノール、1−ヘプタノール、2−ヘプタノール、3−ヘプタノール、1−オクタノール、2−オクタノール、2−エチル−1−ヘキサノール、シクロヘキサノール、1−メチルシクロヘキサノール、2−メチルシクロヘキサノール、3−メチルシクロヘキサノール、1,2−エタンジオール、1,2−プロパンジオール、1,3−プロパンジオール、1,2−ブタンジオール、1,3−ブタンジオール、1,4−ブタンジオール、2,3−ブタンジオール、1,5−ペンタンジオール、2−メチル−2,4−ペンタンジオール、2−エチル−1,3−ヘキサンジオール、ジプロピルエーテル、ジブチルエーテル、ジヘキシルエーテル、ジオキサン、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジブチルエーテル、1,2−ブトキシエタン、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールジブチルエーテル、2−ペンタノン、3−ペンタノン、2−ヘキサノン、2−ヘプタノン、4−ヘプタノン、3−エトキシブチルアセタート、1−メチルペンチルアセタート、2−エチルブチルアセタート、2−エチルヘキシルアセタート、エチレングリコールモノアセタート、エチレングリコールジアセタート、プロピレンカーボネート、エチレンカーボネート、2−(メトキシメトキシ)エタノール、ブチルセロソルブ、エチレングリコールモノイソアミルエーテル、エチレングリコールモノヘキシルエーテル、2−(ヘキシルオキシ)エタノール、フルフリルアルコール、ジエチレングリコール、プロピレングリコール、1−ブトキシ‐2−プロパノール、1−(ブトキシエトキシ)プロパノール、プロピレングリコールモノメチルエーテルアセタート、ジプロピレングリコール、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、トリプロピレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテルアセタート、エチレングリコールモノエチルエーテルアセタート、エチレングリコールモノブチルエーテルアセタート、エチレングリコールモノアセタート、エチレングリコールジアセタート、ジエチレングリコールモノエチルエーテルアセタート、ダイアセトンアルコール、プロピレングリコールジアセタート、ジイソペンチルエーテル、ジエチレングリコールモノブチルエーテルアセタート、2−(2−エトキシエトキシ)エチルアセタート、ジエチレングリコールアセタート、トリエチレングリコール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、乳酸メチル、乳酸エチル、酢酸メチル、酢酸エチル、酢酸n−ブチル、酢酸プロピレングリコールモノエチルエーテル、ピルビン酸メチル、ピルビン酸エチル、3−メトキシプロピオン酸メチル、3−エトキシプロピオン酸メチルエチル、3−メトキシプロピオン酸エチル、3−エトキシプロピオン酸、3−メトキシプロピオン酸、3−メトキシプロピオン酸プロピル、3−メトキシプロピオン酸ブチル、乳酸メチルエステル、乳酸エチルエステル、乳酸n−プロピルエステル、乳酸n−ブチルエステル、乳酸イソアミルエステル、ジイソブチルケトン、エチルカルビトール等が挙げられる。 Specific examples of the poor solvent include, for example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-. 1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl -1-Butanol, 1-Heptanol, 2-Heptanol, 3-Heptanol, 1-Octanol, 2-Octanol, 2-Ethylene-1-hexanol, Cyclohexanol, 1-Methylcyclohexanol, 2-Methylcyclohexanol, 3- Methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3- Butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol Diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone , 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetylate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- (methoxy) Methoxy) ethanol, butyl cellosolve, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, 1-butoxy-2-propanol, 1- (butoxyethoxy) propanol , Ethylene glycol monomethyl ether acetate, dipropylene glycol, zip Lopyrene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetator Diethylene glycol monoethyl ether acetate, diacetone alcohol, propylene glycol diacetate, diisopentyl ether, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, 3-methoxypropionic acid Methyl, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate ester, ethyl lactate ester , Lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester, diisobutylketone, ethylcarbitol and the like.
また、貧溶媒としては、下記式[D−1]〜式[D−3]で示される溶媒が挙げられる。
本発明の液晶配向剤には、エポキシ基、イソシアネート基、オキセタン基又はシクロカーボネート基を有する架橋性化合物、ヒドロキシル基、ヒドロキシアルキル基及び低級アルコキシアルキル基からなる群より選ばれる少なくとも1種の置換基を有する架橋性化合物、又は重合性不飽和結合を有する架橋性化合物を含んでいても良い。これら置換基や重合性不飽和結合は、架橋性化合物中に2個以上有する必要がある。 The liquid crystal alignment agent of the present invention contains at least one substituent selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group. It may contain a crosslinkable compound having a polymerizable unsaturated bond or a crosslinkable compound having a polymerizable unsaturated bond. It is necessary to have two or more of these substituents and polymerizable unsaturated bonds in the crosslinkable compound.
エポキシ基又はイソシアネート基を有する架橋性化合物としては、例えば、ビスフェノールアセトングリシジルエーテル、フェノールノボラックエポキシ樹脂、クレゾールノボラックエポキシ樹脂、トリグリシジルイソシアヌレート、テトラグリシジルアミノジフェニレン、テトラグリシジル−m−キシレンジアミン、テトラグリシジル−1,3−ビス(アミノエチル)シクロヘキサン、テトラフェニルグリシジルエーテルエタン、トリフェニルグリシジルエーテルエタン、ビスフェノールヘキサフルオロアセトジグリシジルエーテル、1,3−ビス(1−(2,3−エポキシプロポキシ)−1−トリフルオロメチル−2,2,2−トリフルオロメチル)ベンゼン、4,4−ビス(2,3−エポキシプロポキシ)オクタフルオロビフェニル、トリグリシジル−p−アミノフェノール、テトラグリシジルメタキシレンジアミン、2−(4−(2,3−エポキシプロポキシ)フェニル)−2−(4−(1,1−ビス(4−(2,3−エポキシプロポキシ)フェニル)エチル)フェニル)プロパン又は1,3−ビス(4−(1−(4−(2,3−エポキシプロポキシ)フェニル)−1−(4−(1−(4−(2,3−エポキシプロポキシ)フェニル)−1−メチルエチル)フェニル)エチル)フェノキシ)−2−プロパノールなどが挙げられる。 Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidyl aminodiphenylene, tetraglycidyl-m-xylene diamine, and tetra. Glycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenylglycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy)- 1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidylmethoxylenidamine, 2 -(4- (2,3-epoxypropoxy) phenyl) -2- (4- (1,1-bis (4- (2,3-epoxypropoxy) phenyl) ethyl) phenyl) propane or 1,3-bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1-(4- (1- (4- (2,3-epoxypropoxy) phenyl) -1-methylethyl) phenyl) ethyl) ) Phenoxy) -2-propanol and the like.
オキセタン基を有する架橋性化合物は、下記式[4A]で示されるオキセタン基を少なくとも2個有する化合物である。
シクロカーボネート基を有する架橋性化合物としては、下記式[5A]で示されるシクロカーボネート基を少なくとも2個有する架橋性化合物である。
ヒドロキシル基及びアルコキシル基からなる群より選ばれる少なくとも1種の置換基を有する架橋性化合物としては、例えば、ヒドロキシル基又はアルコキシル基を有するアミノ樹脂、例えば、メラミン樹脂、尿素樹脂、グアナミン樹脂、グリコールウリル−ホルムアルデヒド樹脂、スクシニルアミド−ホルムアルデヒド樹脂又はエチレン尿素−ホルムアルデヒド樹脂などが挙げられる。具体的には、アミノ基の水素原子がメチロール基又はアルコキシメチル基又はその両方で置換されたメラミン誘導体、ベンゾグアナミン誘導体、又はグリコールウリルを用いることができる。このメラミン誘導体又はベンゾグアナミン誘導体は、2量体又は3量体であってもよい。これらはトリアジン環1個当たり、メチロール基又はアルコキシメチル基を平均3〜6個有するものが好ましい。 Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group, for example, a melamine resin, a urea resin, a guanamine resin, and a glycol uryl. -Formaldehyde resin, succinylamide-formaldehyde resin or ethylene urea-formaldehyde resin and the like. Specifically, a melamine derivative, a benzoguanamine derivative, or glycoluryl in which the hydrogen atom of the amino group is substituted with a methylol group, an alkoxymethyl group, or both can be used. The melamine derivative or benzoguanamine derivative may be a dimer or a trimer. These preferably have an average of 3 to 6 methylol groups or alkoxymethyl groups per triazine ring.
上記のメラミン誘導体又はベンゾグアナミン誘導体の例としては、市販品のトリアジン環1個当たりメトキシメチル基が平均3.7個置換されているMX−750、トリアジン環1個当たりメトキシメチル基が平均5.8個置換されているMW−30(以上、三和ケミカル社製)やサイメル300、301、303、350、370、771、325、327、703、712などのメトキシメチル化メラミン、サイメル235、236、238、212、253、254などのメトキシメチル化ブトキシメチル化メラミン、サイメル506、508などのブトキシメチル化メラミン、サイメル1141のようなカルボキシル基含有メトキシメチル化イソブトキシメチル化メラミン、サイメル1123などのメトキシメチル化エトキシメチル化ベンゾグアナミン、サイメル1123−10などのメトキシメチル化ブトキシメチル化ベンゾグアナミン、サイメル1128などのブトキシメチル化ベンゾグアナミン、サイメル1125−80のようなカルボキシル基含有メトキシメチル化エトキシメチル化ベンゾグアナミン(以上、三井サイアナミド社製)が挙げられる。また、グリコールウリルの例として、サイメル1170などのブトキシメチル化グリコールウリル、サイメル1172などのメチロール化グリコールウリルなど、パウダーリンク1174などのメトキシメチロール化グリコールウリル等が挙げられる。 Examples of the above-mentioned melamine derivative or benzoguanamine derivative include MX-750 in which an average of 3.7 methoxymethyl groups are substituted per triazine ring on the market, and an average of 5.8 methoxymethyl groups per triazine ring. MW-30 (all manufactured by Sanwa Chemical Co., Ltd.) and methoxymethylated melamines such as Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Cymel 235, 236, Methoxymethylated butoxymethylated melamines such as 238, 212, 253, 254, butoxymethylated melamines such as Cymel 506, 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamines such as Cymel 1141, methoxy such as Cymel 1123. Methylated ethoxymethylated benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80 (above, Mitsui Sianamid Co., Ltd.). Examples of glycol uril include butoxymethylated glycol uril such as Cymel 1170, methylolated glycol uril such as Cymel 1172, and methoxymethylated glycol uril such as Powder Link 1174.
ヒドロキシル基又はアルコキシル基を有するベンゼン又はフェノール性化合物としては、例えば、1,3,5−トリス(メトキシメチル)ベンゼン、1,2,4−トリス(イソプロポキシメチル)ベンゼン、1,4−ビス(sec−ブトキシメチル)ベンゼン又は2,6−ジヒドロキシメチル−p−tert−ブチルフェノールが挙げられる。
より具体的には、国際公開公報WO2011/132751号(2011.10.27公開)の62〜66頁に掲載される、式[6−1]〜式[6−48]の架橋性化合物が挙げられる。Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, and 1,4-bis (1,4-bis). Benz-butoxymethyl) benzene or 2,6-dihydroxymethyl-p-tert-butylphenol can be mentioned.
More specifically, the crosslinkable compounds of formulas [6-1] to [6-48], which are published in International Publication No. WO2011 / 132751 (published 2011.10.27), are listed on pages 62 to 66. Be done.
重合性不飽和結合を有する架橋性化合物としては、例えば、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、トリ(メタ)アクリロイルオキシエトキシトリメチロールプロパン又はグリセリンポリグリシジルエーテルポリ(メタ)アクリレートなどの重合性不飽和基を分子内に3個有する架橋性化合物、更に、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、ブチレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、エチレンオキサイドビスフェノールA型ジ(メタ)アクリレート、プロピレンオキサイドビスフェノール型ジ(メタ)アクリレート、1,6−へキサンジオールジ(メタ)アクリレート、グリセリンジ(メタ)アクリレート、ペンタエリスリトールジ(メタ)アクリレート、エチレングリコールジグリシジルエーテルジ(メタ)アクリレート、ジエチレングリコールジグリシジルエーテルジ(メタ)アクリレート、フタル酸ジグリシジルエステルジ(メタ)アクリレート又はヒドロキシピバリン酸ネオペンチルグリコールジ(メタ)アクリレートなどの重合性不飽和基を分子内に2個有する架橋性化合物、加えて、2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、2−ヒドロキシブチル(メタ)アクリレート、2−フェノキシ−2−ヒドロキシプロピル(メタ)アクリレート、2−(メタ)アクリロイルオキシ−2−ヒドロキシプロピルフタレート、3−クロロ−2−ヒドロキシプロピル(メタ)アクリレート、グリセリンモノ(メタ)アクリレート、2−(メタ)アクリロイルオキシエチルリン酸エステル又はN−メチロール(メタ)アクリルアミド等の重合性不飽和基を分子内に1個有する架橋性化合物等が挙げられる。 Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylpropantri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) acryloyloxyethoxytrimethylol. Crosslinkable compounds having three polymerizable unsaturated groups in the molecule, such as propane or glycerin polyglycidyl ether poly (meth) acrylate, as well as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di. (Meta) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A Type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether 2 polymerizable unsaturated groups in the molecule such as di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate or neopentyl glycol di (meth) acrylate hydroxypivalate In addition, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2 -(Meta) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate or N-methylol (meth) ) Examples thereof include a crosslinkable compound having one polymerizable unsaturated group such as acrylamide in the molecule.
更に、下記式[7A]で示される化合物を用いることもできる。
本発明の液晶配向剤における、架橋性化合物の含有量は、全ての重合体成分100質量部に対して、0.1〜150質量部が好ましい。なかでも、架橋反応が進行し目的の効果を発現させるためには、0.1〜100質量部が好ましい。より好ましいのは、1〜50質量部である。 The content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all the polymer components. Among them, 0.1 to 100 parts by mass is preferable in order for the cross-linking reaction to proceed and the desired effect to be exhibited. More preferred is 1 to 50 parts by mass.
本発明の液晶配向剤は、液晶配向剤を塗布した際の液晶配向膜の膜厚の均一性や表面平滑性を向上させる化合物を含有することができる。
液晶配向膜の膜厚の均一性や表面平滑性を向上させる化合物としては、フッ素系界面活性剤、シリコーン系界面活性剤、ノ二オン系界面活性剤などが挙げられる。
具体的には、例えば、エフトップEF301、EF303、EF352(以上、トーケムプロダクツ社製)、メガファックF171、F173、R−30(以上、大日本インキ社製)、フロラードFC430、FC431(以上、住友スリーエム社製)、アサヒガードAG710、サーフロンS−382、SC101、SC102、SC103、SC104、SC105、SC106(以上、旭硝子社製)などが挙げられる。The liquid crystal alignment agent of the present invention can contain a compound that improves the uniformity of the film thickness and the surface smoothness of the liquid crystal alignment film when the liquid crystal alignment agent is applied.
Examples of the compound for improving the uniformity of the film thickness and the surface smoothness of the liquid crystal alignment film include a fluorine-based surfactant, a silicone-based surfactant, and a nonion-based surfactant.
Specifically, for example, Ftop EF301, EF303, EF352 (above, manufactured by Tochem Products Co., Ltd.), Megafuck F171, F173, R-30 (above, manufactured by Dainippon Ink Co., Ltd.), Florard FC430, FC431 (above, Sumitomo 3M Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (all manufactured by Asahi Glass Co., Ltd.) and the like.
界面活性剤の使用量は、液晶配向剤に含有される全ての重合体成分100質量部に対して、好ましくは0.01〜2質量部、より好ましくは0.01〜1質量部である。
更に、液晶配向剤には、液晶配向膜中の電荷移動を促進して素子の電荷抜けを促進させる化合物として、国際公開公報WO2011/132751号(2011.10.27公開)の69〜73頁に掲載される、式[M1]〜式[M156]で示される窒素含有複素環アミンを添加することもできる。このアミンは、液晶配向剤に直接添加しても構わないが、濃度0.1〜10質量%、好ましくは1〜7質量%の溶液にしてから添加することが好ましい。この溶媒は、特定重合体を溶解させるならば特に限定されない。The amount of the surfactant used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment agent.
Further, as a liquid crystal aligning agent, as a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge removal of the element, see pages 69 to 73 of International Publication No. WO2011 / 132751 (published 2011.10.27). The nitrogen-containing heterocyclic amines represented by the formulas [M1] to [M156] described above can also be added. This amine may be added directly to the liquid crystal alignment agent, but it is preferably added after making a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. This solvent is not particularly limited as long as it dissolves the specific polymer.
本発明の液晶配向剤には、上記の貧溶媒、架橋性化合物、樹脂被膜又は液晶配向膜の膜厚の均一性や表面平滑性を向上させる化合物及び電荷抜けを促進させる化合物の他に、液晶配向膜と基板との密着性を向上させる目的のシランカップリング剤、さらには塗膜を焼成する際にポリイミド前駆体の加熱によるイミド化を効率よく進行させる目的のイミド化促進剤等を含有せしめても良い。 In addition to the above-mentioned poor solvent, crosslinkable compound, compound that improves the uniformity and surface smoothness of the film thickness and surface smoothness of the resin film or liquid crystal alignment film, and the compound that promotes charge loss, the liquid crystal alignment agent of the present invention includes liquid crystal. It contains a silane coupling agent for the purpose of improving the adhesion between the alignment film and the substrate, and an imidization accelerator for the purpose of efficiently advancing imidization by heating the polyimide precursor when firing the coating film. You may.
<液晶配向膜・液晶表示素子>
本発明の液晶配向膜は、上記の液晶配向剤を基板に塗布し、乾燥、焼成して得られる膜である。本発明の液晶配向剤を塗布する基板としては透明性の高い基板であれば特に限定されず、ガラス基板、窒化珪素基板、アクリル基板やポリカーボネート基板などのプラスチック基板等を用いることもできる。その際、液晶を駆動させるためのITO電極などが形成された基板を用いると、プロセスの簡素化の点から好ましい。また、反射型の液晶表示素子では、片側の基板のみにならばシリコンウエハーなどの不透明な物でも使用でき、この場合の電極にはアルミニウムなどの光を反射する材料も使用できる。<Liquid crystal alignment film / liquid crystal display element>
The liquid crystal alignment film of the present invention is a film obtained by applying the above liquid crystal alignment agent to a substrate, drying and firing. The substrate on which the liquid crystal alignment agent of the present invention is applied is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can also be used. At that time, it is preferable to use a substrate on which an ITO electrode or the like for driving the liquid crystal is formed from the viewpoint of simplifying the process. Further, in the reflective liquid crystal display element, an opaque object such as a silicon wafer can be used if only one side of the substrate is used, and a material that reflects light such as aluminum can also be used for the electrode in this case.
液晶配向剤の塗布方法は、工業的には、スクリーン印刷、オフセット印刷、フレキソ印刷又はインクジェット法などで行う方法が一般的である。その他の塗布方法としては、ディップ法、ロールコータ法、スリットコータ法、スピンナー法又はスプレー法などが知られている。
なかでも、本発明の液晶配向剤は、上記したように、重合体の含有成分比率や重合体の分子量を高く維持しながら液晶配向剤の低粘度にできるため、インクジェット法による塗布、成膜法が好適に使用できる。Industrially, the liquid crystal alignment agent is generally applied by screen printing, offset printing, flexographic printing, an inkjet method, or the like. As other coating methods, a dip method, a roll coater method, a slit coater method, a spinner method, a spray method and the like are known.
Among them, as described above, the liquid crystal alignment agent of the present invention can reduce the viscosity of the liquid crystal alignment agent while maintaining a high content ratio of the polymer and the molecular weight of the polymer. Can be preferably used.
液晶配向剤を基板上に塗布した後は、ホットプレート、熱循環型オーブン又はIR(赤外線)型オーブンなどの加熱手段により、溶媒を蒸発させて液晶配向膜とすることができる。液晶配向剤を塗布した後の乾燥、焼成工程は、任意の温度と時間を選択することができる。通常は、含有される溶媒を十分に除去するために50〜120℃で1〜10分焼成し、その後、150〜300℃で5〜120分焼成する条件が挙げられる。焼成後の液晶配向膜の厚みは、薄すぎると液晶表示素子の信頼性が低下する場合があるので、5〜300nmが好ましく、10〜200nmがより好ましい。
本発明の液晶配向剤は、基板上に塗布、焼成した後、ラビング処理や光配向処理などで配向処理をし、また、垂直配向用途などでは配向処理無しで、液晶配向膜として用いることができる。ラビング処理や光配向処理などで配向処理では、既知の方法や装置を使用できる。After the liquid crystal alignment agent is applied onto the substrate, the solvent can be evaporated to form a liquid crystal alignment film by a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven. Any temperature and time can be selected for the drying and firing steps after applying the liquid crystal alignment agent. Usually, in order to sufficiently remove the contained solvent, the condition of firing at 50 to 120 ° C. for 1 to 10 minutes and then firing at 150 to 300 ° C. for 5 to 120 minutes can be mentioned. If the thickness of the liquid crystal alignment film after firing is too thin, the reliability of the liquid crystal display element may decrease. Therefore, the thickness is preferably 5 to 300 nm, more preferably 10 to 200 nm.
The liquid crystal alignment agent of the present invention can be applied as a liquid crystal alignment film on a substrate, fired, and then subjected to alignment treatment by rubbing treatment, photoalignment treatment, or the like, and can be used as a liquid crystal alignment film without orientation treatment in vertical alignment applications. .. Known methods and devices can be used in the alignment process such as rubbing process and photo-alignment process.
液晶セルの作製方法の一例として、パッシブマトリクス構造の液晶表示素子を例にとり説明する。なお、画像表示を構成する各画素部分にTFT(Thin Film Transistor)などのスイッチング素子が設けられたアクティブマトリクス構造の液晶表示素子であってもよい。
具体的には、透明なガラス製の基板を準備し、一方の基板の上にコモン電極を、他方の基板の上にセグメント電極を設ける。これらの電極は、例えばITO電極とすることができ、所望の画像表示ができるようパターニングされている。次いで、各基板の上に、コモン電極とセグメント電極を被覆するようにして絶縁膜を設ける。絶縁膜は、例えば、ゾル−ゲル法によって形成されたSiO2−TiO2の膜とすることができる。As an example of a method for manufacturing a liquid crystal cell, a liquid crystal display element having a passive matrix structure will be described as an example. A liquid crystal display element having an active matrix structure in which a switching element such as a TFT (Thin Film Transistor) is provided in each pixel portion constituting the image display may be used.
Specifically, a transparent glass substrate is prepared, and a common electrode is provided on one substrate and a segment electrode is provided on the other substrate. These electrodes can be, for example, ITO electrodes and are patterned so as to display a desired image. Next, an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode. The insulating film can be, for example, a film of SiO 2- TiO 2 formed by the sol-gel method.
次に、各基板の上に液晶配向膜を形成し、一方の基板に他方の基板を互いの液晶配向膜面が対向するようにして重ね合わせ、周辺をシール剤で接着する。シール剤には、基板間隙を制御するために、通常、スペーサーを混入しておき、また、シール剤を設けない面内部分にも、基板間隙制御用のスペーサーを散布しておくことが好ましい。シール剤の一部には、外部から液晶を充填可能な開口部を設けておく。次いで、シール剤に設けた開口部を通じて、2枚の基板とシール剤で包囲された空間内に液晶材料を注入し、その後、この開口部を接着剤で封止する。注入には、真空注入法を用いてもよいし、大気中で毛細管現象を利用した方法を用いてもよい。液晶材料は、ポジ型液晶材料やネガ型液晶材料のいずれを用いてもよいが、好ましいのは、ネガ型液晶材料である。次に、偏光板の設置を行う。具体的には、2枚の基板の液晶層とは反対側の面に一対の偏光板を貼り付ける。 Next, a liquid crystal alignment film is formed on each substrate, the other substrate is superposed on one substrate so that the liquid crystal alignment film surfaces face each other, and the periphery is bonded with a sealant. It is preferable that a spacer is usually mixed in the sealant in order to control the substrate gap, and that the spacer for controlling the substrate gap is also sprayed on the in-plane portion where the sealant is not provided. A part of the sealing agent is provided with an opening in which the liquid crystal can be filled from the outside. Next, the liquid crystal material is injected into the space surrounded by the two substrates and the sealant through the opening provided in the sealant, and then the opening is sealed with an adhesive. For injection, a vacuum injection method may be used, or a method utilizing a capillary phenomenon in the atmosphere may be used. As the liquid crystal material, either a positive type liquid crystal material or a negative type liquid crystal material may be used, but a negative type liquid crystal material is preferable. Next, the polarizing plate is installed. Specifically, a pair of polarizing plates are attached to the surfaces of the two substrates opposite to the liquid crystal layer.
以下に実施例を挙げ、本発明を更に詳しく説明するが、本発明はこれらに限定されるものではない。下記で用いる略語は、以下のとおりである。
DA−1:1,5−ビス(4−アミノフェノキシ)ペンタン
DA−2:4,4’−ジアミノジフェニルメタン
DA−3:4,4’−ジアミノジフェニルアミン、CA−1:ピロメリット酸二無水物
CA−2:1,2,3,4−シクロブタンテトラカルボン酸二無水物
CA−3:3,4−ジカルボキシ−1,2,3,4−テトラヒドロ−1−ナフタレンコハク酸二無水物
NMP:N−メチル−2−ピロリドン、GBL:γブチロラクトン、
BCS:ブチルセロソルブ、PB :1−ブトキシ‐2−プロパノール
DME:ジプロピレングリコールジメチルエーテル
DPM:ジプロピレングリコールモノメチルエーテル
DAA:ダイアセトンアルコール、DEDG:ジエチレングリコールジエチルエーテル
DIBC:2,6−ジメチル‐4−ヘプタノール
AD−1:下記式の化合物
DA-1: 1,5-bis (4-aminophenoxy) pentane DA-2: 4,4'-diaminodiphenylmethane DA-3: 4,4'-diaminodiphenylamine, CA-1: pyromellitic dianhydride CA -2: 1,2,3,4-cyclobutanetetracarboxylic dianhydride CA-3: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride NMP: N -Methyl-2-pyrrolidone, GBL: γbutyrolactone,
BCS: Butyl cellosolve, PB: 1-butoxy-2-propanol DME: Dipropylene glycol dimethyl ether DPM: Dipropylene glycol monomethyl ether DAA: Dipropylene alcohol, DEDG: Diethylene glycol diethyl ether DIBC: 2,6-dimethyl-4-heptanol AD- 1: Compound of the following formula
<粘度の測定>
ポリアミック酸、液晶配向剤などの粘度は、E型粘度計(東機産業社製)を使用し、温度25℃で測定した。
<固形分濃度の測定>
溶液1.0gをアルミニウム製カップに測りとり、200℃、2時間の条件で加熱処理した後、カップの上に残存している固体量を計測し、溶液の固形分濃度を測定した。<Measurement of viscosity>
The viscosities of the polyamic acid, the liquid crystal alignment agent, etc. were measured at a temperature of 25 ° C. using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.).
<Measurement of solid content concentration>
1.0 g of the solution was measured in an aluminum cup, heat-treated at 200 ° C. for 2 hours, and then the amount of solid remaining on the cup was measured to measure the solid content concentration of the solution.
[ポリアミック酸A1の製造]
撹拌装置付きおよび窒素導入管付きの2000mlフラスコにDA−1を171.8g入れ、NMP1676gを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を水冷下で撹拌しながらCA−1を113.8g加え、さらに固形分濃度が12重量%になるようにNMPを加え、窒素雰囲気下、50度で加熱しながら20時間撹拌し、ポリアミック酸(A1)の溶液(粘度:90mPa・s)を得た。このポリアミック酸(A1)溶液1.0gをアルミ二ウム製カップに測りとり、200℃2時間の条件で処理した際の固形分濃度は11.2重量%であった。[Manufacturing of polyamic acid A1]
171.8 g of DA-1 was placed in a 2000 ml flask equipped with a stirrer and a nitrogen introduction tube, 1676 g of NMP was added, and the mixture was stirred and dissolved while feeding nitrogen. 113.8 g of CA-1 was added to this diamine solution while stirring under water cooling, NMP was further added so that the solid content concentration became 12% by weight, and the mixture was stirred under a nitrogen atmosphere at 50 ° C. for 20 hours. A solution of polyamic acid (A1) (viscosity: 90 mPa · s) was obtained. When 1.0 g of this polyamic acid (A1) solution was measured in an aluminum cup and treated under the condition of 200 ° C. for 2 hours, the solid content concentration was 11.2% by weight.
[ポリアミック酸溶液a1の製造]
ポリアミック酸(A1)溶液535.7gに対して、NMPを264.3g、およびBCS200.0g加え、固形分濃度の濃度が6.0重量%のポリアミック酸溶液(a1)溶液を得た。
[ポリアミック酸溶液a2の製造]
ポリアミック酸(A1)溶液535.7gに対して、NMPを264.3g、およびPB200.0g加え、固形分濃度の濃度が6.0重量%のポリアミック酸溶液(a2)溶液を得た。
[ポリアミック酸溶液a3の製造]
ポリアミック酸(A1)溶液535.7gに対して、NMPを264.3g、およびDME200.0g加え、固形分濃度の濃度が6.0重量%のポリアミック酸溶液(a3)を得た。[Manufacturing of polyamic acid solution a1]
264.3 g of NMP and 200.0 g of BCS were added to 535.7 g of the polyamic acid (A1) solution to obtain a polyamic acid solution (a1) solution having a solid content concentration of 6.0% by weight.
[Manufacturing of polyamic acid solution a2]
264.3 g of NMP and 200.0 g of PB were added to 535.7 g of the polyamic acid (A1) solution to obtain a polyamic acid solution (a2) solution having a solid content concentration of 6.0% by weight.
[Manufacturing of polyamic acid solution a3]
264.3 g of NMP and 200.0 g of DME were added to 535.7 g of the polyamic acid (A1) solution to obtain a polyamic acid solution (a3) having a solid content concentration of 6.0% by weight.
[ポリアミック酸A2の製造]
撹拌装置付き及び窒素導入管付きの2000mlフラスコにDA−1を100.8g及びDA−5を34.9g入れ、NMP1337gを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を水冷下で撹拌しながらCA−1を92.2g加え、さらに固形分濃度が12重量%になるようにNMPを加え、窒素雰囲気下、50℃に加熱しながら20時間撹拌し、ポリアミック酸(A2)の溶液(粘度:520mmPa・s)を得た。[Manufacturing of polyamic acid A2]
100.8 g of DA-1 and 34.9 g of DA-5 were placed in a 2000 ml flask equipped with a stirrer and a nitrogen introduction tube, 1337 g of NMP was added, and the mixture was stirred and dissolved while feeding nitrogen. 92.2 g of CA-1 was added to this diamine solution while stirring under water cooling, NMP was further added so that the solid content concentration became 12% by weight, and the mixture was stirred under a nitrogen atmosphere at 50 ° C. for 20 hours. A solution of polyamic acid (A2) (viscosity: 520 mmPa · s) was obtained.
[ポリアミック酸B1の製造]
撹拌装置付きおよび窒素導入管付きの2000ml四つ口フラスコにDA−3を87.7g入れ、NMPとGBLが各50重量%の比率でブレンドされた溶媒(以下溶媒1)1052.5gを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を水冷下で撹拌しながらCA−2を70.1gと溶媒1を382.7g加えて、窒素雰囲気下、水冷下で3時間攪拌した。その後、DA−2を21.8gと溶媒1を191.3g加えて攪拌した。DA−2が溶解した後、CA−3を33.0gと溶媒1を287.0g加えて、再び窒素雰囲気下、水冷下で3時間攪拌することで、固形分濃度が9.8重量%のポリアミック酸(B1)の溶液(粘度:65mPa・s)を得た。このポリアミック酸(B1)溶液1.0gをアルミ二ウム製カップに測りとり、200℃2時間の条件で処理した際の固形分濃度は9.8重量%であった。[Manufacturing of polyamic acid B1]
87.7 g of DA-3 was placed in a 2000 ml four-necked flask equipped with a stirrer and a nitrogen introduction tube, and 1052.5 g of a solvent (hereinafter referred to as solvent 1) in which NMP and GBL were blended in a ratio of 50% by weight each was added. The mixture was dissolved by stirring while sending nitrogen. While stirring this diamine solution under water cooling, 70.1 g of CA-2 and 382.7 g of solvent 1 were added, and the mixture was stirred under water cooling under a nitrogen atmosphere for 3 hours. Then, 21.8 g of DA-2 and 191.3 g of solvent 1 were added and stirred. After DA-2 was dissolved, 33.0 g of CA-3 and 287.0 g of solvent 1 were added, and the mixture was stirred again under a nitrogen atmosphere and water cooling for 3 hours to bring the solid content concentration to 9.8% by weight. A solution of polyamic acid (B1) (viscosity: 65 mPa · s) was obtained. When 1.0 g of this polyamic acid (B1) solution was measured in an aluminum cup and treated under the condition of 200 ° C. for 2 hours, the solid content concentration was 9.8% by weight.
[ポリアミック酸B2の製造]
撹拌装置付きおよび窒素導入管付きの2000ml四つ口フラスコにDA−3を95.6g及びDA−4を18.2g入れ、NMPを967g加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を水冷下で撹拌しながらCA−2を54.8gとNMPを276g加えて、窒素雰囲気下、水冷下で3時間攪拌した。その後、CA−4を75.0gと、固形分濃度が15重量%となるようにNMPを加えて、窒素雰囲気下、50℃に加熱しながら、12時間攪拌し、ポリアミック酸(B2)溶液(粘度:302mmPa・s)を得た。[Manufacturing of polyamic acid B2]
95.6 g of DA-3 and 18.2 g of DA-4 were placed in a 2000 ml four-necked flask equipped with a stirrer and a nitrogen introduction tube, 967 g of NMP was added, and the mixture was stirred and dissolved while sending nitrogen. While stirring this diamine solution under water cooling, 54.8 g of CA-2 and 276 g of NMP were added, and the mixture was stirred under water cooling under a nitrogen atmosphere for 3 hours. Then, 75.0 g of CA-4 and NMP were added so that the solid content concentration was 15% by weight, and the mixture was stirred for 12 hours under a nitrogen atmosphere while heating at 50 ° C. to obtain a polyamic acid (B2) solution (B2). Viscosity: 302 mmPa · s) was obtained.
[実施例1]
ポリアミック酸(B1)溶液153.4gを測りとり、その溶液へ、NMPを1.3g、3−グリシドキシプロピルトリエトキシシランが1.3重量%入ったGBL溶液を38.5g、GBLを95.9g、DMEを53.5g、及びDIBCを50.0g加え、室温で1時間撹拌した。その後、a3を107.5g加えて、さらに1時間撹拌することで、固形分:NMP:GBL:DME:DIBCの比率が、4.3:30:40.7:15:10(重量%)の溶液(C1)を500.0g得た。[Example 1]
Weigh 153.4 g of a polyamic acid (B1) solution, and add 1.3 g of NMP and 1.3% by weight of 3-glycidoxypropyltriethoxysilane to the solution, 38.5 g of GBL solution, and 95 of GBL. .9 g, 53.5 g of DME, and 50.0 g of DIBC were added, and the mixture was stirred at room temperature for 1 hour. Then, by adding 107.5 g of a3 and stirring for another 1 hour, the ratio of solid content: NMP: GBL: DME: DIBC was 4.3: 30: 40.7: 15: 10 (% by weight). 500.0 g of the solution (C1) was obtained.
[実施例2]
ポリアミック酸(B1)溶液153.4gを測りとり、その溶液へ、NMPを1.3g、及び3−グリシドキシプロピルトリエトキシシランが1.3重量%入ったGBL溶液を38.5g、GBLを120.9g、DME28.5g及びDIBC50.0gを加え、室温で1時間撹拌した。その後、a3を107.5g加えて、さらに1時間撹拌することで、固形分:NMP:GBL:DME:DIBC=4.3:30:40.7:10:10(重量%)の溶液(C2)を500.0g得た。[Example 2]
Weigh 153.4 g of a polyamic acid (B1) solution, and add 1.3 g of NMP and 38.5 g of GBL solution containing 1.3% by weight of 3-glycidoxypropyltriethoxysilane to the solution. 120.9 g, 28.5 g of DME and 50.0 g of DIBC were added, and the mixture was stirred at room temperature for 1 hour. Then, 107.5 g of a3 was added, and the mixture was further stirred for 1 hour to obtain a solution (C2) having a solid content: NMP: GBL: DME: DIBC = 4.3: 30: 40.7: 10: 10 (% by weight). ) Was obtained in an amount of 500.0 g.
[実施例3]
12重量%のポリアミック酸(A2)溶液33.3gと、15重量%のポリアミック酸(B2)溶液106.6gとの混合液を30分撹拌した後、これに対し、NMPを11.1g、3−グリシドキシプロピルトリエトキシシランが1.0重量%入ったNMP溶液20.0g、GBLを204.0g、DMEを75.0g及びDIBCを50.0g加え、室温で3時間撹拌することで、A2とB2のポリマー固形分比が2:8であり、固形分:NMP:GBL:DME:DIBC=4.2:30:40.8:15:10(重量%)の溶液(C8)を500.0g得た。[Example 3]
A mixture of 33.3 g of a 12 wt% polyamic acid (A2) solution and 106.6 g of a 15 wt% polyamic acid (B2) solution was stirred for 30 minutes, and then 11.1 g of NMP and 3 -Add 20.0 g of NMP solution containing 1.0% by weight of glycidoxypropyltriethoxysilane, 204.0 g of GBL, 75.0 g of DME and 50.0 g of DIBC, and stir at room temperature for 3 hours. The polymer solid content ratio of A2 and B2 is 2: 8, and a solution (C8) of solid content: NMP: GBL: DME: DIBC = 4.2: 30: 40.8: 15:10 (% by weight) is 500. 0.0 g was obtained.
[実施例4]
12重量%のポリアミック酸(A2)溶液33.3gと、15重量%のポリアミック酸(B2)溶液106.6gとの混合液を30分撹拌した後、これに対し、NMPを5.1g、3−グリシドキシプロピルトリエトキシシランが1.0重量%入ったNMP溶液20.0g、AD−1が10重量%入ったNMP溶液を6.0g、GBLを204.0g、DMEを75.0g及びDIBCを50.0g加え、室温で3時間撹拌することで、A2とB2のポリマー固形分比が2:8であり、固形分:NMP:GBL:DME:DIBC=4.2:30:40.8:15:10(重量%)の溶液(C9)を500.0g得た。[Example 4]
A mixture of 33.3 g of a 12 wt% polyamic acid (A2) solution and 106.6 g of a 15 wt% polyamic acid (B2) solution was stirred for 30 minutes, and then 5.1 g of NMP was added to the mixture. -NMP solution containing 1.0% by weight of glycidoxypropyltriethoxysilane, 6.0 g of NMP solution containing 10% by weight of AD-1, 204.0 g of GBL, 75.0 g of DME and By adding 50.0 g of DIBC and stirring at room temperature for 3 hours, the polymer solid content ratio of A2 and B2 was 2: 8, and the solid content: NMP: GBL: DME: DIBC = 4.2: 30: 40. 500.0 g of a 8:15:10 (% by weight) solution (C9) was obtained.
[比較例1]
ポリアミック酸(B1)溶液153.4gを測りとり、その溶液へ、NMPを1.3g、3−グリシドキシプロピルトリエトキシシランが1.3重量%入ったGBL溶液を38.5g、GBLを145.9g及びDME53.5gを加え、室温で1時間撹拌した。その後、a3を107.5g加えて、さらに1時間撹拌することで、固形分:NMP:GBL:DME=4.3:30:50.7:15(重量%)の溶液(C3)を500.0g得た。[Comparative Example 1]
Weigh 153.4 g of a polyamic acid (B1) solution, and add 1.3 g of NMP and 1.3% by weight of 3-glycidoxypropyltriethoxysilane to the solution, 38.5 g of GBL solution, and 145 of GBL. .9 g and 53.5 g of DME were added, and the mixture was stirred at room temperature for 1 hour. Then, 107.5 g of a3 was added, and the mixture was further stirred for 1 hour to obtain a solution (C3) having a solid content: NMP: GBL: DME = 4.3: 30: 50.7: 15 (% by weight). I got 0g.
[比較例2]
ポリアミック酸(B1)溶液153.4gを測りとり、その溶液へ、NMPを1.3g、3−グリシドキシプロピルトリエトキシシランが1.3重量%入ったGBL溶液を38.5g、GBLを145.9g及びBCS53.5gを加え、室温で1時間撹拌した。その後、a1を107.5g加えて、さらに1時間撹拌することで、固形分:NMP:GBL:BCS=4.3:30:50.7:15(重量%)の溶液(C4)を500.0g得た。[Comparative Example 2]
Weigh 153.4 g of a polyamic acid (B1) solution, and add 1.3 g of NMP and 1.3% by weight of 3-glycidoxypropyltriethoxysilane to the solution, 38.5 g of GBL solution, and 145 of GBL. .9 g and 53.5 g of BCS were added, and the mixture was stirred at room temperature for 1 hour. Then, 107.5 g of a1 was added, and the mixture was further stirred for 1 hour to obtain a solution (C4) having a solid content: NMP: GBL: BCS = 4.3: 30: 50.7: 15 (% by weight). I got 0g.
[比較例3]
ポリアミック酸(B1)溶液153.4gを測りとり、その溶液へ、NMPを1.3g、3−グリシドキシプロピルトリエトキシシランが1.3重量%入ったGBL溶液を38.5g、GBLを95.9g、BCS53.5g及びDPM50.0gを加え、室温で1時間撹拌した。その後、a1を107.5g加えて、さらに1時間撹拌することで、固形分:NMP:GBL:BCS:DPM=4.3:30:40.7:15:10(重量%)の溶液(C5)を500.0g得た。[Comparative Example 3]
Weigh 153.4 g of a polyamic acid (B1) solution, and add 1.3 g of NMP and 1.3% by weight of 3-glycidoxypropyltriethoxysilane to the solution, 38.5 g of GBL solution, and 95 of GBL. .9 g, 53.5 g of BCS and 50.0 g of DPM were added, and the mixture was stirred at room temperature for 1 hour. Then, 107.5 g of a1 was added, and the mixture was further stirred for 1 hour to obtain a solution (C5) of solid content: NMP: GBL: BCS: DPM = 4.3: 30: 40.7: 15: 10 (% by weight). ) Was obtained in an amount of 500.0 g.
[比較例4]
ポリアミック酸(B1)溶液153.4gを測りとり、その溶液へ、NMPを1.3g、3−グリシドキシプロピルトリエトキシシランが1.3重量%入ったGBL溶液を38.5g、GBLを95.9g、DME53.5g及びDPM50.0gを加え、室温で1時間撹拌した。その後、a3を107.5g加えて、さらに1時間撹拌することで、固形分:NMP:GBL:DME:DPM=4.3:30:40.7:15:10(重量%)の溶液(C6)を500.0g得た。[Comparative Example 4]
Weigh 153.4 g of a polyamic acid (B1) solution, and add 1.3 g of NMP and 1.3% by weight of 3-glycidoxypropyltriethoxysilane to the solution, 38.5 g of GBL solution, and 95 of GBL. .9 g, 53.5 g of DME and 50.0 g of DPM were added, and the mixture was stirred at room temperature for 1 hour. Then, 107.5 g of a3 was added, and the mixture was further stirred for 1 hour to obtain a solution (C6) of solid content: NMP: GBL: DME: DPM = 4.3: 30: 40.7: 15: 10 (% by weight). ) Was obtained in an amount of 500.0 g.
[比較例5]
ポリアミック酸(B1)溶液153.4gを測りとり、その溶液へ、NMPを1.3g、3−グリシドキシプロピルトリエトキシシランが1.3重量%入ったGBL溶液を38.5g、GBLを95.9g、PB53.5g及びDPM50.0gを加え、室温で1時間撹拌した。その後、a2を107.5g加えて、さらに1時間撹拌することで、固形分:NMP:GBL:PB:DPM=4.3:30:40.7:15:10(重量%)の溶液(C7)を500.0g得た。[Comparative Example 5]
Weigh 153.4 g of a polyamic acid (B1) solution, and add 1.3 g of NMP and 1.3% by weight of 3-glycidoxypropyltriethoxysilane to the solution, 38.5 g of GBL solution, and 95 of GBL. .9 g, 53.5 g of PB and 50.0 g of DPM were added, and the mixture was stirred at room temperature for 1 hour. Then, 107.5 g of a2 was added, and the mixture was further stirred for 1 hour to obtain a solution (C7) having a solid content: NMP: GBL: PB: DPM = 4.3: 30: 40.7: 15: 10 (% by weight). ) Was obtained in an amount of 500.0 g.
実施例1〜4及び比較例1〜5については、孔径1μmのフィルターで濾過した後、粘度を測定し、表2に示した。その後、以下の塗布性評価を実施した。
[インクジェット塗布性評価]
上記で調製した実施例1〜4及び比較例1〜5について、インクジェット塗布装置(石井表記社製)を用いて、TFT基板上に塗布した。塗布条件は、ノズル間ピッチ127μm、塗布速度250mm/sec、ディスペンス量70pL、塗布面積36×36mmで行った。また、塗布は、110℃のホットプレート上で1分仮乾燥を行った後、230℃で15分の条件でIRオーブンで焼成した際に、塗膜の厚みが120nmとなる条件で塗布した。For Examples 1 to 4 and Comparative Examples 1 to 5, the viscosity was measured after filtering with a filter having a pore size of 1 μm, and is shown in Table 2. Then, the following coatability evaluation was carried out.
[Evaluation of inkjet coatability]
Examples 1 to 4 and Comparative Examples 1 to 5 prepared above were coated on a TFT substrate using an inkjet coating device (manufactured by Ishii Notation Co., Ltd.). The coating conditions were a nozzle-to-nozzle pitch of 127 μm, a coating speed of 250 mm / sec, a spread amount of 70 pL, and a coating area of 36 × 36 mm. Further, the coating was carried out under the condition that the thickness of the coating film was 120 nm when the film was temporarily dried on a hot plate at 110 ° C. for 1 minute and then fired in an IR oven at 230 ° C. for 15 minutes.
[塗膜の評価方法]
塗布された基板を110℃で仮乾燥した塗膜について、コンタクトホールや配線の影響で発生するドットやスジ状のムラ程度を比較して、以下の4段階で評価した。
目視で全面に顕著なムラが確認できるものをLv4、目視で部分的にムラが確認できるものをLv3、ムラが目視では見えないものをLv2、光学顕微鏡でもムラが全くないものをLv1とした。[Evaluation method of coating film]
The coating film temporarily dried at 110 ° C. on the coated substrate was evaluated in the following four stages by comparing the degree of dot and streak-like unevenness generated due to the influence of contact holes and wiring.
Lv4 was used to visually confirm remarkable unevenness on the entire surface, Lv3 was used to visually confirm partial unevenness, Lv2 was used to visually confirm unevenness, and Lv1 was used to obtain no unevenness even with an optical microscope.
また、クロムが表面に蒸着されたガラス基板上にも塗布を行い、塗膜端部の色調変化(膜厚ムラ)がある部分の幅を、ノギスで測長し、Haloサイズとして評価した。なお、Haloサイズは値が小さいほど、良好な塗膜であるとされる。
さらに、塗膜幅を実測し、設定塗布領域に対して、実測値と設定値の差を寸法安定性として評価した。なお、この評価では、値が小さいものほど良好な塗膜であるとされる。
これらの結果を表1、2に示す。Further, the coating was also applied to a glass substrate on which chromium was vapor-deposited on the surface, and the width of a portion having a color tone change (film thickness unevenness) at the edge of the coating film was measured with a caliper and evaluated as a Halo size. The smaller the Halo size, the better the coating film.
Further, the coating film width was actually measured, and the difference between the measured value and the set value was evaluated as dimensional stability with respect to the set coating region. In this evaluation, the smaller the value, the better the coating film.
These results are shown in Tables 1 and 2.
Claims (14)
溶媒A:N−メチル−2−ピロリドン、N−エチル−2−ピロリドン、γ‐ブチロラクトン及びジメチルイミダゾリジノンからなる群から選ばれる少なくとも1種。
溶媒B:ジプロピレングリコールジメチルエーテル
溶媒C:下記式(a)で表される化合物
Solvent A: At least one selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone and dimethylimidazolidinone.
Solvent B: Dipropylene glycol dimethyl ether Solvent C: Compound represented by the following formula (a)
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