TW202136433A - Polymerizable liquid crystal ink formulations - Google Patents

Abstract

The present invention relates to polymerizable liquid crystalline formulations and especially to an ink formulation for inkjet printing comprising 10 to 50% w/w of one or more polymerizable liquid crystalline compounds and 50 to 90% w/w of one or more organic solvents selected from the group of aliphatic ketones, cyclic ketones, alkyl ethers of ethylene glycol or propylene glycol, alkyl esters of menthyl or aromatic solvents.

Description

Polymerizable liquid crystal ink formulation

The present invention relates to polymerizable liquid crystal formulations and particularly to ink formulations for inkjet printing, which comprise one or more polymerizable liquid crystal compounds and 50 to 90% w/w One or more organic solvents selected from the group of aliphatic ketones, cyclic ketones, ethylene glycol or propylene glycol alkyl ethers, menthyl alkyl esters or aromatic solvents.

Flat liquid crystal displays exhibit good image quality, low cost, and good processability in a large area due to the stable supply chain of all their components. However, compared with light emitting diodes (LED) and organic light emitting diode displays (OLED), brightness and color gamut are generally poor. Compared with OLED panels, the larger layout including polarizers, absorptive color filters and optical films present in LCD panels is the main reason for the lower transmittance and color purity of LCD displays. This ultimately ends in energy-efficient devices . For reference, since the liquid crystal panel blocks or absorbs light, only about 30% of the light emitted from the backlight unit is felt by the user.

JP 4752581 B2 proposes a manufacturing method for an improved color filter. The method has a process of forming barriers on a substrate; a process of forming a multicolor pixel pattern with a certain barrier between the barriers by photolithography ; A process of forming an alignment film processed by alignment processing on the color pixel pattern; and by ink-jetting a liquid crystal phase shift layer on the alignment film by means of each block corresponding to the multi-color pixel pattern The process pattern, wherein the liquid crystal phase shift layer includes a plurality of liquid crystal phase shift regions corresponding to a multi-color pattern; the plurality of liquid crystal phase shift regions have a retardation to correct the retardation of the multi-color pixel pattern; and for each pixel The sum of the retardation of the multi-color pixel pattern and the retardation in the corresponding plurality of liquid crystal phase shift regions is characteristically and substantially the same.

However, the proposed process requires further processing steps in terms of generally known methods for mass production, such as the process of forming barriers on the substrate by photolithography.

Other attempts to improve light efficiency have been reported, such as color filterless LCD panels. This type of display has a backlight unit that includes a plurality of white, red, green, and blue light-emitting diodes arranged on a substrate, as described in, for example, US 8,928,841 B2.

A backlight unit comprising phosphor-converted white LEDs (which emits blue light, which is converted into yellow radiation by the phosphor material to provide the final white light) is described in, for example, KR 10-0946015 B1.

However, since the color filter absorbs light, the wide bandwidth of the yellow light used for conversion creates important restrictions, which prevent high brightness and color gamut. Therefore, by avoiding the parallax effect and increasing the overall brightness of the LCD display, a narrow bandwidth RGB emitter is a better option for increasing the color gamut.

In this regard, quantum materials (QM) are very suitable for solving the above shortcomings due to the following outstanding features: ● The central emission wavelength can be tuned by controlling the size of the nanoparticle ● Its FWHM is about 20 to 30 nm, which is mainly determined by the size ● Its photoluminescence efficiency is high, and ● The resulting device structure is simple.

On the one hand, these properties make it a good candidate to replace phosphor materials in backlight units, as described in, for example, Adv. Mater. 2010, Vol. 22, pages 3076 to 3080. On the other hand, these properties This makes it a good candidate to replace the conventional absorptive color filter, as described in, for example, CN 102944943 B. Both methods result in LCD displays with high transmittance and color gamut, resulting in excellent image quality, if the color of light is provided for conversion.

Polymerizable liquid crystal-based optical films or such as optical retarders, brightness enhancement films or reflective optical films are described in, for example, EP 0 940 707 B1, EP 0 888 565 B1 and GB 2 329 393 B1. Its high birefringence, favorable alignment control, and well-established processing in mass production make it an excellent material for improving display performance. A common method for mass production of these films includes the following steps: -For example, by inkjet printing to provide a continuous layer of polymerizable LC material on the substrate, -Polymerize the polymerizable components of the polymerizable LC material by photopolymerization, and -Remove the polymerized LC material from the substrate as needed and/or provide it on another substrate as needed.

Due to the above procedure, the polymerizable liquid crystal or reactive mesogen (RM)-based optical film is formed as a single layer provided in the display layout as a continuous film with different thicknesses throughout the layer.

其中(Δn)係薄膜之雙折射率，(d)係薄膜之厚度及λ係入射光束之波長。The optical retardation (δ(λ)) of this type of polymer film as a function of the incident beam wavelength (λ) is given by the following equation:

(Δn) is the birefringence of the film, (d) is the thickness of the film and λ is the wavelength of the incident light beam.

Therefore, the optical retardation of a given polymerized liquid crystal film is constant in the x-y plane. However, ideally, for each sub-pixel (RGB), for each color, different optical properties are required in the x-y plane of the polymer film. Furthermore, cholesterol optical films are generally used to enhance the brightness of the device. However, each color in this paper also requires different optical reflections of the polymer film.

Inkjet printing is a manufacturing technique used to deposit ink or materials on various substrates with micron-level precision (such as sub-pixel size). It can be used to create complex patterns, otherwise the patterns can only be generated by a more complex multi-step process using a photomask (such as a patterned retarder). In addition, it offers the potential to digitize the manufacturing process, which is currently limited to processes such as roll-to-roll large-area substrates. In addition, inkjet printing can be used to coat specific materials on specific locations on a given substrate or to achieve pixel-to-pixel printing.

A general challenge in inkjet printing is to control the thickness distribution of dry deposits, such as J. Sun, B. Bao, M. He, H. Zhou and Y. Song, ACS Appl. Mater. Interfaces, 2015, 7, 28086-28099 or P. Calvert, Chem. Mater., 2001, 13, 3299-3305.

Co-distributions are observed in the solid coffee ring effect of inkjet printing from solvents, such as D. Mampallil and HB Eral, Adv. Colloid Interface Sci., 2018, 252, 38-54; W. Han and Z. Lin, Angew Chemie-Int. Ed., 2012, 51, 1534-1546 or RD Deegan, O. Bakajin, TF Dupont, G. Huber, SR Nagel and TA Witten, Nature, 1997, 389, 827-829 are further described.

Then, the solvent is exhausted at the edge, and the solvent at the center of the dried droplet is driven to the edge. The solvent takes away the solute along with it and leaves a contour where the material accumulates at the edge after complete evaporation.

For non-polymerizable liquid crystal formulations, such as printing inks used in OLED applications, describe methods for solving the coffee ring effect problem, such as the use of mixed solvent systems and surfactants, such as, for example, T. Still, PJ Yunker, and AG Yodh, Langmuir, 2012, 28, 4984-4988 or C. Jiang, Z. Zhong, B. Liu, Z. He, J. Zou, L. Wang, J. Wang, J. Peng and Y. Cao, ACS Appl. Mater . Interfaces, 2016, 8, 26162–26168. In addition to these solutions, D. Soltman and V. Subramanian, Langmuir, 2008, 24, 2224-2231 recommend reducing the evaporation rate to prevent the unwanted solute transport.

However, in view of polymerizable liquid crystal formulations, a smooth surface profile and high alignment quality of liquid crystal molecules are required to produce good optical properties from inkjet printed optical films. In addition, the inventors have discovered non-polymerizable liquid crystal formulations used in inks and based on high boiling point solvents (such as γ-butyrolactone, cyclohexylbenzene, butyl benzoate, methyl benzoate, 1-methylnaphthalene, etc.) The common solvent system of materials is not suitable for use with polymerizable liquid crystal mixtures because of the extremely long time required for its evaporation. Such long evaporation times generally result in poor alignment quality of inkjet printed polymer films obtained from polymerizable liquid crystal formulations.

In addition, common solvents used in polymerizable liquid crystal mixtures (such as cyclohexanone, toluene, cyclopentanone, PGMEA, MIBK, etc.) prevent the use of inkjet printing technology due to the extremely fast evaporation of the solvent, so it is not suitable for inkjet printing In technology. Generally, the low boiling point solvents described above are generally not suitable for inkjet printing because the volume of each droplet is much smaller than the volume of standard paint. This leads to evaporation and subsequent crystallization on the print head, thereby blocking further printing.

In view of these issues, there is a great need for polymerizable liquid crystal mixtures or ink formulations based on a high boiling point solvent system that, in addition to one or more polymerizable liquid crystal compounds, also includes better exhibiting slow evaporation rate and high annealing One or more solvents used in inkjet printing applications. In addition, even when printing in small areas (such as typical pixel or sub-pixel sizes), polymer films obtained from such formulations by inkjet printing should exhibit good alignment quality after polymerization.

Surprisingly, the inventors have discovered that certain families of solvents and combinations of solvents and polymerizable liquid crystal materials exhibit excellent jetting properties while still achieving high resolution and flat printing profile at the same time.

Therefore, the present invention relates to an ink formulation for inkjet printing, which contains 10 to 50% w/w of one or more polymerizable liquid crystal compounds and 50 to 90% w/w selected from aliphatic ketones, One or more organic solvents from the group of cyclic ketones, alkyl ethers of ethylene glycol or propylene glycol, alkyl esters of menthyl or aromatic solvents.

In addition, the present invention relates to a method by combining at least 10 to 50% w/w of one or more polymerizable liquid crystal compounds with 50 to 90% w/w selected from aliphatic ketones, cyclic ketones, ethylene glycol or A method for producing ink formulations by mixing one or more of the alkyl ethers of propylene glycol or aromatic solvents.

In addition, the present invention relates to the use of an ink formulation as described above and below in an inkjet printer.

In addition, the present invention relates to a polymer film that can be obtained by or by ink-jet printing the ink formulation as described above and below on a substrate and curing the ink formulation.

In addition, the present invention relates to a method of producing a polymer film, which includes the steps of ink-jet printing the ink formulation as described above and below on a substrate and curing the ink formulation.

In addition, the present invention relates to the use of a polymer film as described above and below as an optical film or in an optical component.

In addition, the present invention relates to an optical component comprising one or more polymer films obtainable from or from the ink formulations described above and below.

Another aspect of the present invention is the use of one or more optical components as described above and below in an optical device.

Another aspect of the present invention is an optical device comprising one or more optical components, the one or more optical components including one or more of which can be obtained from or from one or more of the ink formulations described above and below Polymer film.

The present invention relates to a polymerizable liquid crystal ink formulation for inkjet printing, which contains 10 to 50% w/w of one or more polymerizable liquid crystal compounds and 50 to 90% w/w selected from aliphatic ketones , Cyclic ketones, ethylene glycol or propylene glycol alkyl ethers, menthyl alkyl esters or one or more organic solvents from the group of aromatic solvents.

其中 P¹ 及P² 彼此獨立地表示可聚合的基團， Sp¹ 及Sp² 彼此獨立地為間隔基或單鍵，及 MG        為桿狀液晶原基團，其較佳係選自式MG

其中 A¹ 及A² 在多次出現時彼此獨立地表示芳族或脂環族基團，其視需要包含一或多個選自N、O及S之雜原子，且係視需要經L¹ 單-或多取代， L¹ 為P-Sp-、F、Cl、Br、I、-CN、-NO₂ 、-NCO、-NCS、-OCN、-SCN、-C(=O)NR⁰⁰ R⁰⁰⁰ 、-C(=O)OR⁰⁰ 、-C(=O)R⁰⁰ 、-NR⁰⁰ R⁰⁰⁰ 、-OH、-SF₅ 、視需要經取代之矽基、具有1至12個(較佳1至6個)C原子之芳基或雜芳基及具有1至12個(較佳1至6個)C原子之直鏈或分支鏈烷基、烷氧基、烷基羰基、烷氧基羰基、烷基羰基氧基或烷氧基羰基氧基，其中一或多個H原子係視需要經F或Cl置換， R⁰⁰ 及R⁰⁰⁰ 彼此獨立地表示H或具有1至12個C原子之烷基， Z¹ 在多次出現時彼此獨立地表示-O-、-S-、-CO-、-COO-、-OCO-、-S-CO-、-CO-S-、-O-COO-、-CO-NR⁰⁰ -、-NR⁰⁰ -CO-、-NR⁰⁰ -CO-NR⁰⁰⁰ 、-NR⁰⁰ -CO-O-、-O-CO-NR⁰⁰ -、-OCH₂ -、-CH₂ O-、-SCH₂ -、-CH₂ S-、-CF₂ O-、-OCF₂ -、-CF₂ S-、-SCF₂ -、-CH₂ CH₂ -、-(CH₂ )_n1 、-CF₂ CH₂ -、-CH₂ CF₂ -、-CF₂ CF₂ -、-CH=N-、-N=CH-、-N=N-、-CH=CR⁰⁰ -、-CY¹ =CY² -、-C≡C-、-CH=CH-COO-、-OCO-CH=CH-或單鍵， Y¹ 及Y² 彼此獨立地表示H、F、Cl或CN， n               為1、2、3或4，較佳係1或2，最佳係2， n1             為1至10之整數，較佳係1、2、3或4。Preferably, one or more polymerizable liquid crystal compounds used in the ink formulation of the present invention are selected from the dual-reactive or multi-reactive compounds of formula DRM

Wherein P ¹ and P ² independently represent a polymerizable group, Sp ¹ and Sp ² are independently a spacer or a single bond, and MG is a rod-shaped mesogen group, which is preferably selected from the formula MG

Wherein A ¹ and A ² represent an aromatic or alicyclic group independently of each other in multiple occurrences, which optionally contain one or more heteroatoms selected from N, O and S, and are optionally controlled by L ¹ Single- or multiple substitution, L ¹ is P-Sp-, F, Cl, Br, I, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C(=O)NR ⁰⁰ R ⁰⁰⁰ , -C(=O)OR ⁰⁰ , -C(=O)R ⁰⁰ , -NR ⁰⁰ R ⁰⁰⁰ , -OH, -SF ₅ , optionally substituted silyl groups, with 1 to 12 (preferably 1 To 6) C atoms of aryl or heteroaryl and 1 to 12 (preferably 1 to 6) C atoms of linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl , Alkylcarbonyloxy or alkoxycarbonyloxy, where one or more H atoms are replaced by F or Cl as necessary, R ⁰⁰ and R ⁰⁰⁰ independently represent H or an alkane with 1 to 12 C atoms Base, Z ¹ represents -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO- independently of each other when it appears multiple times , -CO-NR ⁰⁰ -, -NR ⁰⁰ -CO-, -NR ⁰⁰ -CO-NR ⁰⁰⁰ , -NR ⁰⁰ -CO-O-, -O-CO-NR ⁰⁰ -, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CH ₂ CH ₂ -, -(CH ₂ ) _n1 , -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH=N-, -N=CH-, -N=N-, -CH=CR ⁰⁰ -, -CY ¹ = CY ² -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or single bond, Y ¹ and Y ² independently represent H, F, Cl or CN, and n is 1. 2, 3 or 4, preferably 1 or 2, most preferably 2, n1 is an integer from 1 to 10, preferably 1, 2, 3 or 4.

The "polymerizable group" (P) is preferably selected from groups containing C=C double bonds or C≡C triple bonds, and groups suitable for ring-opening polymerization, such as, for example, oxetan Alkyl or epoxy groups.

、

、

、

、CH₂ =CW² -(O)_k3 -、CW¹ =CH-CO-(O)_k3 -、CW¹ =CH-CO-NH-、CH₂ =CW¹ -CO-NH-、CH₃ -CH=CH-O-、(CH₂ =CH)₂ CH-OCO-、(CH₂ =CH-CH₂ )₂ CH-OCO-、(CH₂ =CH)₂ CH-O-、(CH₂ =CH-CH₂ )₂ N-、(CH₂ =CH-CH₂ )₂ N-CO-、CH₂ =CW¹ -CO-NH-、CH₂ =CH-(COO)_k1 -Phe-(O)_k2 -、CH₂ =CH-(CO)_k1 -Phe-(O)_k2 -、Phe-CH=CH-組成之群， 其中 W¹ 表示H、F、Cl、CN、CF₃ 、苯基或具有1至5個C原子之烷基，特別是H、F、Cl或CH₃ ， W² 表示H或具有1至5個C原子之烷基，特別是H、甲基、乙基或正丙基， W³ 及W⁴ 各彼此獨立地表示H、Cl或具有1至5個C原子之烷基，Phe表示1,4-伸苯基，其係視需要經所以上所定義但不同於P-Sp之一或多個基團L取代，較佳之取代基L為F、Cl、CN、NO₂ 、CH₃ 、C₂ H₅ 、OCH₃ 、OC₂ H₅ 、COCH₃ 、COC₂ H₅ 、COOCH₃ 、COOC₂ H₅ 、CF₃ 、OCF₃ 、OCHF₂ 、OC₂ F₅ ，更佳苯基，及 k₁ 、k₂ 及k₃ 各彼此獨立地表示0或1，k₃ 較佳表示1，及k₄ 為1至10之整數。Preferably, the polymerizable group (P) is selected from CH ₂ =CW ¹ -COO-, CH ₂ =CW ¹ -CO-,

,

,

,

, CH ₂ =CW ² -(O) _k3 -, CW ¹ =CH-CO-(O) _k3 -, CW ¹ =CH-CO-NH-, CH ₂ =CW ¹ -CO-NH-, CH _3- CH=CH-O-, (CH ₂ =CH) ₂ CH-OCO-, (CH ₂ =CH-CH ₂ ) ₂ CH-OCO-, (CH ₂ =CH) ₂ CH-O-, (CH ₂ = CH-CH ₂ ) ₂ N-, (CH ₂ =CH-CH ₂ ) ₂ N-CO-, CH ₂ =CW ¹ -CO-NH-, CH ₂ =CH-(COO) _k1 -Phe-(O) _k2 -, CH ₂ =CH-(CO) _k1 -Phe-(O) _k2 -, Phe-CH=CH-, where W ¹ represents H, F, Cl, CN, CF ₃ , phenyl or has An alkyl group with 1 to 5 C atoms, especially H, F, Cl or CH ₃ , W ² represents H or an alkyl group with 1 to 5 C atoms, especially H, methyl, ethyl or n-propyl , W ³ and W ⁴ each independently represent H, Cl or an alkyl group having 1 to 5 C atoms, and Phe represents 1,4-phenylene, which is defined as above but is different from P- Sp is substituted by one or more groups L, the preferred substituent L is F, Cl, CN, NO ₂ , CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , COCH ₃ , COC ₂ H ₅ , COOCH ₃ , COOC ₂ H ₅ , CF ₃ , OCF ₃ , OCHF ₂ , OC ₂ F ₅ , more preferably phenyl, and k ₁ , k ₂ and k ₃ each independently represent 0 or 1, and k ₃ preferably represents 1, and k ₄ are integers from 1 to 10.

及

， 其中W² 表示H或具有1至5個C原子之烷基，特別是H、甲基、乙基或正丙基， 更佳之可聚合的基團(P)為乙烯基氧基、丙烯酸酯、甲基丙烯酸酯、氟丙烯酸酯、氯丙烯酸酯、氧雜環丁烷及環氧化物，最佳係丙烯酸酯或甲基丙烯酸酯，特別是丙烯酸酯。Especially the polymerizable group P is CH ₂ =CH-COO-, CH ₂ =C(CH ₃ )-COO-, CH ₂ =CF-COO-, CH ₂ =CH-, CH ₂ =CH-O -, (CH ₂ =CH) ₂ CH-OCO-, (CH ₂ =CH) ₂ CH-O-,

and

, Where W ² represents H or an alkyl group having 1 to 5 C atoms, especially H, methyl, ethyl or n-propyl, more preferably the polymerizable group (P) is vinyloxy, acrylate , Methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide, preferably acrylate or methacrylate, especially acrylate.

Preferably, instead of one or more groups P-Sp-, all polyreactive polymerizable compounds and their sub-formulas contain one or more branched chain groups containing two or more polymerizable groups P Group (multi-reactive polymerizable group).

Suitable groups of this type and polymerizable compounds containing them are described in, for example, US 7,060,200 B1 or US 2006/0172090 A1.

其中 alkyl       表示單鍵或具有1至12個C原子之直鏈或分支鏈伸烷基，其中一或多個非相鄰CH₂ 基團可各彼此獨立地經-C(R^x )=C(R^x )-、-C≡C-、-N(R^x )-、-O-、-S-、-CO-、-CO-O-、-O-CO-、-O-CO-O-置換，置換方式為使得O及/或S原子彼此不直接連接，且其中(此外)一或多個H原子可經F、Cl或CN置換，其中R^x 具有以上所提及的含義中之一者，_aa 及_bb 各彼此獨立地表示0、1、2、3、4、5或6， X           具有針對X'所指示的含義中之一者，及 P^v 至P^z 各彼此獨立地具有以上針對P所指示的含義中之一者。Particularly preferred is a multi-reactive polymerizable group selected from the following formula:

Wherein alkyl represents a single bond or a straight or branched chain alkylene having 1 to 12 C atoms, wherein one or more non-adjacent CH ₂ groups can each independently pass through -C(R ^x )=C( R ^x )-, -C≡C-, -N(R ^x )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- Replacement, the replacement method is such that the O and/or S atoms are not directly connected to each other, and wherein (in addition) one or more H atoms can be replaced by F, Cl or CN, wherein R ^x has one of the meanings mentioned above , _Aa and _bb each independently represent 0, 1, 2, 3, 4, 5, or 6, X has one of the meanings indicated for X', and P ^v to P ^z each independently have the above For one of the meanings indicated by P.

The preferred spacer Sp is selected from the formula Sp'-X', so that the group "P-Sp-" conforms to the formula "P-Sp'-X'-", where Sp' represents 1 to 20 (preferably 1 Up to 12) C atoms, which are mono- or poly-substituted by F, Cl, Br, I or CN as necessary, and wherein (in addition) one or more non-adjacent CH ₂ groups may each be independent of each other Earth Jing -O-, -S-, -NH-, -NR ^xx -, -SiR ^xx R ^yy -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -NR ^xx -CO-O-, -O-CO-NR ^0xx -, -NR ^xx -CO-NR ^yy -, -CH=CH- or -C≡C- replacement, the replacement method is So that the O and/or S atoms are not directly connected to each other, X'represents -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR ^xx -, -NR ^xx -CO-, -NR ^xx -CO-NR ^yy -, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH=N-, -N=CH-, -N=N-, -CH =CR ^xx -, -CY ^xx =CY ^xx -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or single bond, R ^xx and R ^yy each independently represent H or An alkyl group having 1 to 12 C atoms, and Y ^xx and Y ^yy each independently represent H, F, Cl, or CN. X'is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR ^xx -, -NR ^xx -CO-, -NR ^xx -CO -NR ^{yy -or} single key.

Typical spacer Sp' is for example -(CH ₂ ) _p1 -, -(CH ₂ CH ₂ O) _q1 -CH ₂ CH ₂ -, -CH ₂ CH ₂ -S-CH ₂ CH ₂ -, -CH ₂ CH ₂ -NH-CH ₂ CH ₂ -or -(SiR ^xx R ^yy -O) _p1 -, where p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R ^xx and R ^yy have the above-mentioned meaning.

The plus is a group -X'-Sp'- _{- (CH 2) p1 -,} - O- (CH 2) p1 -, - OCO- (CH 2) p1 -, - OCOO- (CH 2) p1 - , Where p1 is an integer from 1 to 12.

Particularly preferred groups Sp' in each case are, for example, linear, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptyl, octyl, and nonyl , Decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene -N-methylimino ethylene, 1-methyl ethylene, ethylene, propylene and butenylene.

Preferred groups A ¹ and A ² include but are not limited to furan, pyrrole, thiophene, oxazole, thiazole, thiadiazole, imidazole, phenylene, cyclohexylene, bicyclooctyl, cyclohexenyl, pyridine , Pyrimidine, pyrazine, azulene, indane, pyridine, naphthalene, tetrahydronaphthalene, anthracene, phenanthrene and dithiophene and thiophene, all of which are unsubstituted or have 1, 2, 3 or 4 as defined above The group L is substituted.

Particularly preferred groups A ¹ and A ² are selected from 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, thiophene-2,5-diyl, naphthalene- 2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indan-2,5-diyl, dicyclooctyl or 1,4-cyclohexyl, of which One or two non-adjacent CH ₂ groups are optionally substituted with O and/or S, wherein these groups are unsubstituted or substituted with 1, 2, 3 or 4 groups L as defined above.

The particularly preferred group Z ¹ is independently selected from -COO-, -OCO-, -CH ₂ CH ₂ -, -CF ₂ O-, -OCF ₂ -, -C≡C each time it appears. -, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO-, or single bond.

其中 P⁰ 在多次出現時彼此獨立地為可聚合的基團，較佳係丙烯酸、甲基丙烯酸、氧雜環丁烷、環氧基、乙烯基、庚二烯、乙烯基氧基、丙烯基醚或苯乙烯基， L            在每次出現時相同或不同地具有式DRM中針對L¹ 所給出的含義中之一者，且在多次出現時較佳係彼此獨立地選自F、Cl、CN或具有1至5個C原子之視需要經鹵化之烷基、烷氧基、烷基羰基、烷氧基羰基、烷基羰基氧基或烷氧基羰基氧基， r            為0、1、2、3或4， x及y       彼此獨立地為0或1至12之相同或不同整數， z            分別且獨立地為0或1，若相鄰的x或y為0，則z為0。The excellent formula DRM dual-reactive mesogen compound is selected from the following formula:

Where P ⁰ is a polymerizable group independently of each other when it occurs multiple times, preferably acrylic acid, methacrylic acid, oxetane, epoxy, vinyl, heptadiene, vinyloxy, propylene A base ether or a styryl group, each occurrence of L has ^{one of the meanings given for L 1 in} the formula DRM the same or differently, and it is preferably selected independently of each other from F, Cl, CN or optionally halogenated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 5 C atoms, where r is 0, 1, 2, 3, or 4, x and y are independently 0 or the same or different integers from 1 to 12, z is 0 or 1, respectively and independently, if the adjacent x or y is 0, then z is 0 .

Especially preferred are compounds of formula DRMa1, DRMa2 and DRMa3, especially compounds of formula DRMa1.

In another preferred embodiment, one or more of the polymerizable compounds used in the ink formulation according to the present invention is selected from the group consisting of mono-reactive liquid crystal compounds of the formula MRM, P ¹ -Sp ¹ -MG-R MRM where P ^1. Sp ¹ and MG have the meanings given in the formula DRM, R F, Cl, Br, I, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C(=O)NR ^x R ^y , -C(=O)X, -C(=O)OR ^x , -C(=O)R ^y , -NR ^x R ^y , -OH, -SF ₅ , optionally substituted silyl , Linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12 (preferably 1 to 6) C atoms , Where one or more H atoms are replaced by F or Cl as necessary, X is halogen, preferably F or Cl, and R ^x and R ^y are independently H or an alkyl group having 1 to 12 C atoms .

其中P⁰ 、L、r、x、y及z係如式DRMa-1至式DRMe中所定義， R⁰ 為具有1個或更多個(較佳1至15個)C原子之烷基、烷氧基、硫基烷基、烷基羰基、烷氧基羰基、烷基羰基氧基或烷氧基羰基氧基或表示Y⁰ ， Y⁰ 為F、Cl、CN、NO₂ 、OCH₃ 、OCN、SCN、SF₅ 或具有1至4個C原子之單-、寡-或多氟化烷基或烷氧基， Z⁰ 為-COO-、-OCO-、-CH₂ CH₂ -、-CF₂ O-、-OCF₂ -、-CH=CH-、-OCO-CH=CH-、-CH=CH-COO-或單鍵， A⁰ 在多次出現時彼此獨立地為未經取代或經1、2、3或4個基團L取代之1,4-伸苯基，或反式1,4-伸環己基， u及v       彼此獨立地為0、1或2， w           為0或1， 且其中該等苯環及萘環可另外經一或多個相同或不同基團L取代。The preferred mono-reactive mesogen compound of formula MRM is selected from the following formulas.

Wherein P ⁰ , L, r, x, y and z are as defined in formula DRMa-1 to formula DRMe, R ⁰ is an alkyl group having 1 or more (preferably 1 to 15) C atoms, Alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy or represents Y ⁰ , Y ⁰ is F, Cl, CN, NO ₂ , OCH ₃ , OCN, SCN, SF ₅ or mono-, oligo- or polyfluorinated alkyl or alkoxy having 1 to 4 C atoms, Z ⁰ is -COO-, -OCO-, -CH ₂ CH ₂ -,- CF ₂ O-, -OCF ₂ -, -CH=CH-, -OCO-CH=CH-, -CH=CH-COO- or single bond, A ⁰ is unsubstituted or independently of each other in multiple occurrences 1,4-phenylene substituted by 1, 2, 3 or 4 groups L, or trans 1,4-cyclohexylene, u and v are independently 0, 1 or 2, and w is 0 or 1, and wherein the benzene ring and naphthalene ring may be additionally substituted with one or more same or different groups L.

More preferred are compounds of formulas MRM1, MRM2, MRM3, MRM4, MRM5, MRM6, MRM7, MRM9 and MRM10, especially compounds of formulas MRM1, MRM4, MRM6 and MRM7, and especially compounds of formulas MRM1 and MRM7.

The compounds of formula DRM, MRM and their sub-formulas can be similar to those known to those skilled in the art and described in standard works of organic chemistry (such as, for example, Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Thieme- Verlag, Stuttgart).

The compounds of formula DRM, MRM and their sub-formulas can preferably be used alone or in combination with each other.

Preferably, the polymerizable liquid crystal compound used includes one or more compounds selected from the formula DRM, more preferably one or more compounds selected from the formula DRM and one or more compounds of the formula MRM.

As for the polymerizable liquid crystal compound used as a whole, the ratio of the compounds of formula DRM, MRM and their sub-formulas is preferably in the range of 30 to 99.9% by weight, more preferably in the range of 40 to 99.9% by weight and even More preferably, it is in the range of 50 to 99.9% by weight.

In a preferred embodiment, with respect to the polymerizable liquid crystal compound used as a whole, the ratio of the bi-reactive polymerizable mesogen compound is preferably in the range of 5 to 99% by weight, more preferably 10 to 97% by weight. In the range of weight% and even more preferably in the range of 15 to 95 weight %.

In another preferred embodiment, with respect to the polymerizable liquid crystal compound used as a whole, if any, the proportion of the mono-reactive polymerizable mesogen compound is preferably in the range of 5 to 80% by weight, and more It is preferably in the range of 10 to 75% by weight and even more preferably in the range of 15 to 70% by weight.

In another preferred embodiment, if present, the proportion of the multi-reactive polymerizable mesogen compound in the entire polymerizable liquid crystal material according to the present invention is preferably in the range of 1 to 30% by weight, more preferably in the range of 1 to 30% by weight. In the range of 2 to 20% by weight and even more preferably in the range of 3 to 10% by weight.

In another preferred embodiment, the polymerizable LC material does not contain polymerizable mesogen compounds having more than two polymerizable groups.

In another preferred embodiment, the polymerizable LC material does not contain polymerizable mesogen compounds having less than two polymerizable groups.

Preferably, one or more organic solvents (preferably all selected solvents) are selected from a boiling point in the range of 60 to 380°C, preferably in the range of 100 to 340°C and most preferably in the range of 120 to 330°C. Solvents within the range.

Preferably, the one or more organic solvents (preferably all selected solvents) are selected from solvents with a melting point preferably below 25° C., which means that the selected solvent is liquid at room temperature.

Preferably, the one or more organic solvents (preferably all selected solvents) are selected from solvents having a viscosity of> 15 mPas, preferably> 20 mPas, more preferably> 25 mPas and most preferably> 50 mPas.

Preferably, the one or more organic solvents (preferably all the selected solvents) are selected from the polymerizable liquid crystal compound used therein and exhibit a solubility in the selected solvent of ≥5 g/l, preferably ≥10 g/l solvent.

Examples of preferred organic solvents and their boiling points (BP) and melting points (MP) are shown in Table 1 below. Table 1: Preferred solvents and their boiling point (BP) and melting point (MP). Solvent BP( ℃ ) MP( ℃ ) Cyclohexanone 155 Liquid at RT 3-phenoxy toluene 271 Liquid at RT Phenyl naphthalene 324 Liquid at RT Menthyl Isovalerate 260 Liquid at RT Bis(propylene glycol) methyl ether acetate 200 Liquid at RT Propylene glycol monomethyl ether acetate 145-146 Liquid at RT

The preferred organic solvent system or mixture is cyclohexanone: bis(propylene glycol) methyl ether acetate, cyclohexanone: propylene glycol monomethyl ether acetate or bis(propylene glycol) methyl ether acetate: propylene glycol monomethyl Combination of base ether acetate. The preferred mixture ratio of the organic solvent system is 2:1 to 1:2.

Formulations of the present invention has ^better. S in a range of viscosity between 0.8 and 50 mPa more preferably ^in. The range of 1 of s to 40 mPa, and most preferably 2 to 15 ^mPa. S of the range of.

The viscosity of the formulation and solvent according to the present invention was measured with a Discovery AR3 type 1° cone-plate rotational rheometer (Thermo Scientific). The equipment can accurately control the temperature and shear rate. The viscosity is measured at a temperature of 25.0°C (+/-0.2°C) and a shear rate of ^{500 s -1.} Measure each sample three times and average the obtained measurements.

The formulation of the present invention preferably has a surface tension in the range of 15 to 70 mN/m, more preferably in the range of 10 to 50 mN/m, and most preferably in the range of 20 to 40 mN/m.

Preferably, the organic solvent blend contains a surface tension in the range of 15 to 70 mN/m, more preferably in the range of 10 to 50 mN/m, and most preferably in the range of 20 to 40 mN/m.

The surface tension can be measured using FTA (First Ten Angstrom) 1000 contact angle goniometer at 20°C. The details of the method can be obtained from First Ten Angstrom, such as "Surface Tension Measurements Using the Drop Shape Method" published by Roger P. Woodward, Ph.D. Preferably, the suspended drop method can be used to determine the surface tension. This measurement technique can disperse the droplets from the needle in the liquid or gas phase. The shape of the droplet depends on the relationship between surface tension, gravity and density difference. Using the hanging drop method, use https://www.kruss.de/services/education-theory/glossary/drop-shape-analysis to calculate the surface tension from the shadow image of the hanging drop. A commonly used and commercially available high-precision drop shape analysis tool (ie FTA1000 from First Ten Ångstrom) is used for all surface tension measurements. The surface tension is determined by the software FTA1000. All measurements are performed at room temperature (which is in the range between 20°C and 25°C). Standard operating procedures include the use of a new disposable droplet dispensing system (syringe and needle) to determine the surface tension of each formulation. Each droplet is measured for a duration of one minute and sixty measurements are taken and then averaged. For each formulation, three droplets are measured. The final value is an average of these measured values. The tool is cross-checked regularly for various liquids with well-known surface tension.

To prepare the brightness enhancement film, a liquid crystal ink formulation that is polymerizable with cholesterol is usually used. Therefore, in a preferred embodiment, a polymerizable liquid crystal ink formulation containing one or more opposing additives according to the present invention is used to induce the cholesterol phase.

The preferred opposing additives can be selected from opposing RM and opposing dopants, many of which are well-known to those skilled in the art and are commercially available.

Suitable non-polymerizable anti-palm compounds are, for example, anti-palp dopants, such as R- or S-811, R- or S-1011, R- or S-2011, R- or S-3011, R- or S-4011, R- or S-5011, or CB 15 (all available from Merck KGaA, Darmstadt, Germany).

其中P具有以上針對P⁰ 所給出的含義中之一者，Z⁰ 、u、v、x、y、R⁰ 及A係如以上所定義，及L¹ 及L² 彼此獨立地具有如以上所給出的L之含義中之一者。Suitable polymerizable antipodal compounds are, for example, the antipodal RM (R1) to (R10) listed below, or the polymerizable antipodal material Paliocolor® LC756 (from BASF AG, Ludwigshafen, Germany).

Where P has one of the meanings given ^{above for P 0 , Z 0} , u, v, x, y, R ⁰ and A are as defined above, and L ¹ and L ² independently of each other have the same as above One of the meanings of L given.

It is an excellent compound with high HTP, especially a compound containing a sorbitol group as described in WO 98/00428, a compound containing hydrogenated benzoin as described in, for example, GB 2,328,207, such as The anti-palpable binaphthyl derivatives described in WO 02/94805, the anti-palpable binaphthol acetal derivatives described in, for example, WO 02/34739, the antiplying properties described in, for example, WO 02/06265 TADDOL derivatives and opposing compounds having at least one fluorinated linking group and end or center opposing groups as described in, for example, WO 02/06196 or WO 02/06195.

Particularly preferred are those with HTP of 40 µm ^-1 or higher, 60 µm ^-1 or higher, and most preferably 80 µm ^-1 or higher.

Particularly preferred are polymerizable sorbitol (for example, they are of formula (R8) and (R9)) and polymerizable hydrogenated benzoin (for example, they are of formula (R10)).

其中P、Z⁰ 、A、L¹ 、L² 、v及x具有以上所給出的含義，R¹ 具有以上所給出的R⁰ 之含義中之一者或為P-Sp，R具有R⁰ 之含義中之一者，m為0、1、2或3及r1及r2為0、1、2、3或4。More preferred are non-polymerizable sorbitol and hydrogenated benzoin of the following formulas M1 and M2. More preferably, it is the palm-based binaphthol of the following formulas M3 and M4.

Wherein P, Z ⁰ , A, L ¹ , L ² , v and x have the meanings given above, R ¹ has one of the meanings of R ⁰ given above or is P-Sp, R has R ^{One of the meanings of 0} , m is 0, 1, 2, or 3, and r1 and r2 are 0, 1, 2, 3, or 4.

Very preferred is the compound of formula M3, wherein R ¹ is P-Sp. More preferably, it is a compound of formula M3, wherein m is 0 or 1, Z ⁰ is -COO-, -OCO- or a single bond, and A is 1,4-phenylene substituted ^{by 1 or 2 groups L 1 as necessary} Group, or trans-1,4-cyclohexylene.

The formulation with the palm-like additive preferably exhibits the cholesterol LC phase, and excellently exhibits the cholesterol LC phase at room temperature.

In another preferred embodiment, the formulation optionally contains selected from other polymerization initiators, antioxidants, surfactants, stabilizers, catalysts, sensitizers, inhibitors, chain transfer agents, and co-reactive monomers. , Reactive diluents, surface active compounds, lubricants, wetting agents, dispersants, hydrophobic agents, adhesives, flow enhancers, degassing or defoaming agents, degassing agents, diluents, reactive diluents, aids One or more additives in the group consisting of agents, colorants, dyes, pigments, and nanoparticles.

Lubricants and flow aids generally include silicon-free but also silicon-containing polymers (such as polyacrylates) or modifiers of low molecular weight polydialkylsiloxanes. The modification is that some of the alkyl groups have been replaced by various organic groups. Such organic groups are, for example, polyether, polyester or even long-chain (fluorinated) alkyl groups, the former being the most commonly used.

The polyether groups in the correspondingly modified polysiloxanes are usually established by ethylene oxide and/or propylene oxide units. Generally speaking, the higher the proportion of these alkylene oxide units in the modified polysiloxane, the more hydrophilic the resulting product.

Such additives can be selected from Tego, for example, TEGO® Glide 100, TEGO® Glide ZG 400, TEGO® Glide 406, TEGO® Glide 410, TEGO® Glide 411, TEGO® Glide 415, TEGO® Glide 420, TEGO® Glide 435, TEGO® Glide 440, TEGO® Glide 450, TEGO® Glide A 115, TEGO® Glide B 1484 (also used as defoamer and deaerator), TEGO® Flow ATF, TEGO® Flow 300, TEGO® Flow 460, TEGO® Flow 425 and TEGO® Flow ZFS 460 are commercially available. Suitable radiation curable lubricants and flow aids (which can also be used to improve scratch resistance) are the products TEGO® Rad 2100, TEGO® Rad 2200, TEGO® Rad 2500, TEGO® Rad 2600 and TEGO® Rad 2700, Likewise, they can be obtained from TEGO.

Such additives can also be obtained from BYK, such as BYK®-300 BYK®-306, BYK®-307, BYK®-310, BYK®-320, BYK®-333, BYK®-341, Byk® 354, Byk® 361, Byk®361N, BYK®388 obtained.

Such additives are also available as FC4430® from 3M, for example.

Such adjuvants are also available as FluorN®561 or FluorN®562 from Cytonix, for example.

Such adjuvants are also available as Tivida® FL 2300 and Tivida® FL 2500 from Merck KGaA, for example.

Relative to all solids or components other than the solvent present, these auxiliary agents are used in a proportion of about 0 to 3.0% by weight, preferably about 0 to 2.0% by weight, as necessary.

In another preferred embodiment, the formulation contains one or more specific antioxidant additives preferably selected from the Irganox® series (for example, the commercially available antioxidants Irganox® 1076 and Irganox® 1010, from Ciba, Switzerland).

In another preferred embodiment, the formulation comprises, for example, a commercially available Irgacure® or Darocure® (Ciba AG) series, especially Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 817, Irgacure 907, Irgacure 1300, Irgacure, Irgacure 2022, Irgacure 2100, Irgacure 2959 or Darcure TPO, and one or more selected from commercially available OXE02 (Ciba AG), NCI 930, N1919T (Adeka), SPI-03 or SPI-04 (Samyang) Photoinitiator.

The concentration of the polymerization initiator as a whole in the formulation is preferably 0.5 to 10% by weight, extremely preferably 0.8 to 8% by weight, and more preferably 1 to 6% by weight, relative to all solids or components except the solvent present. %.

Preferably, in addition to one or more bi-reactive or multi-reactive polymerizable mesogen compounds and one or more solvents, the ink formulation also includes a) One or more mono-reactive polymerizable mesogen compounds, b) One or more photoinitiators, c) One or more antioxidant additives as needed, d) One or more stabilizers as needed, e) One or more lubricants and flow aids as needed.

More preferably, in addition to one or more (preferably two or more) dual-reactive polymerizable mesogen compounds (if present, relative to all components without solvent, the amount is preferably 10 to 90 % By weight, preferably 15 to 75% by weight, preferably selected from the compound of formula DRMa-1) and one or more solvents, the formulation also includes a) One or more (preferably two or more) mono-reactive polymerizable mesogen compounds as required, relative to all components without solvent, the amount is preferably 10 to 95% by weight. Preferably 25 to 85% by weight, preferably selected from compounds of formula MRM-1 and/or MRM-7, b) One or more (preferably one) photoinitiators as required, if present, relative to all components without solvent, the amount is preferably 1 to 10% by weight, and very preferably 2 to 7% by weight. c) One or more antioxidant additives as required, preferably selected from unsubstituted and substituted benzoic acid esters, especially Irganox® 1076, and if present, relative to all components without solvents, The amount is preferably 0.01 to 2% by weight, very preferably 0.05 to 1% by weight. d) One or more lubricants and flow aids as required, preferably selected from TEGO® Rad 2500, BYK®388, FC 4430 and/or Fluor N 562, and if present, relative to all solvent-free groups The amount is preferably 0.1% to 5%, very preferably 0.2 to 3% by weight.

In addition, the present invention relates to a method of combining at least 10 to 50% w/w (relative to the overall formulation) of one or more multi- or dual-reactive liquid crystal compounds and 50 to 90% w/w (relative to the overall formulation) A method of mixing one or more solvents selected from the group of aliphatic ketones, cyclic ketones, alkyl ethers of ethylene glycol or propylene glycol or aromatic solvents to produce ink formulations.

In addition, the present invention relates to the use of an ink formulation as described above and below in an inkjet printer. Suitable inkjet printers are known to those skilled in the art, such as the Dimatix® material printer series, Fujifilm, for example DMP-2800 or PiXDRO® LP 50 Meyer Burger.

In addition, the present invention relates to a method of producing a polymer film, which includes the steps of ink-jet printing the ink formulation as described above and below on a substrate and curing the ink formulation.

The area and thickness of the provided layer can vary for different purposes. Generally, a formulation having a thickness in the range of 500 nm to 2500 nm, preferably 1000 nm to 2000 nm, more preferably 1500 nm to 1900 nm is provided.

Generally, the provided area or print size ranges from 1 cm ² to 10 µm ² for use in color filters as described below. Preferably, the provided area or print size corresponds to the sub-pixel size and is usually The range of 1 mm to 0.01 mm is the minimum length in any pixel shape

Preferably, the appropriate droplet spacing is selected to be in the range of 100 µm to 10 µm, preferably 50 µm to 15 µm.

Suitable substrate materials or substrates are known by experts and described in the literature, such as, for example, conventional substrates used in the optical film industry, such as glass or plastic. Particularly suitable and preferred substrates for polymerization are polyesters, such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), polyvinyl alcohol (PVA), polycarbonate (PC ), triacetyl cellulose (TAC), or cycloolefin polymer (COP) or generally known color filter materials, especially triacetyl cellulose (TAC), cycloolefin polymer (COP) or general Known color filter material.

In a preferred embodiment, the process according to the present invention includes a process step (herein referred to as "annealing") in which the ink formulation can be allowed to stand for a period of time to uniformly redistribute the ink on the substrate.

Preferably, after printing, the ink is annealed for a period of time between 1 min and 3 h, preferably between 2 min and 1 h, and most preferably between 5 min and 30 min. The annealing is preferably performed at room temperature.

In an alternative embodiment, the annealing is performed at a high temperature, preferably higher than 20°C and lower than 140°C, more preferably higher than 40°C and lower than 100°C, and most preferably higher than 50°C and lower than 90°C conduct.

The polymerizable LC material (RM or reactive mesogen) of the ink formulation preferably exhibits a homogeneous alignment in the entire layer after curing or inkjet printing on the substrate. Preferably, the polymerizable LC material exhibits a uniform planar alignment or a uniform vertical alignment.

By comparing the surface energies of the RM layer and the substrate, the Friedel-Creagh-Kmetz rule can be used to predict whether the mixture adopts planar or vertical alignment: If γ _RM > γ _s , the reactive mesogen compound will exhibit vertical alignment, if γ _RM <γ _s , then the reactive mesogen compound will exhibit a homogeneous alignment.

When the surface energy of the substrate is relatively low, the intermolecular force between the reactive mesogens is stronger than the force across the RM-substrate interface. Therefore, the reactive mesogen is aligned perpendicular to the substrate (vertical alignment) to maximize the intermolecular force.

Vertical alignment can also be achieved by using amphoteric materials, which can be directly added to the polymerizable LC material, or the substrate can be processed in the form of a vertical alignment layer with these materials. The polar head of the amphoteric material is chemically bonded to the substrate, and the hydrocarbon tail point is perpendicular to the substrate. The intermolecular interaction between the amphiphilic material and the RM promotes vertical alignment. The commonly used amphoteric surfactants are described above.

Another method for promoting vertical alignment is to apply corona discharge treatment to the plastic substrate to generate alcohol or ketone functional groups on the surface of the substrate. These polar groups can interact with polar groups present in RM or surfactants to promote vertical alignment.

When the surface tension of the substrate is greater than the surface tension of the RM, the force across the interface dominates. If the reactive mesogen is aligned parallel to the substrate, the interface energy is minimized, so the long axis of the RM can interact with the substrate. One way to promote planar alignment is to coat the substrate with a polyimide layer, and then rub the alignment layer with a velvet cloth.

Other suitable planar alignment layers are known in the art, such as, for example, rubbing polyimides or alignment layers prepared by photo-alignment as described in US 5,602,661, US 5,389,698 or US 6,717,644.

Generally speaking, an overview of alignment technology is for example by I. Sage in "Thermotropic Liquid Crystals", edited by GW Gray, John Wiley & Sons, 1987, pages 75 to 77; and by T. Uchida and H. Seki in "Liquid Crystals-Applications and Uses Vol. 3", edited by B. Bahadur, World Scientific Publishing, Singapore 1992, pp. 1 to 63. A further overview of alignment materials and technologies is given by J. Cognard, Mol. Cryst. Liq. Cryst. 78, Supplement 1 (1981), pages 1 to 77.

To produce the polymer film according to the present invention, the polymerizable compound in the formulation is cured, polymerized or crosslinked (if a compound contains two or more polymerizable groups).

In a preferred preparation method, the formulation is printed on a substrate and then photopolymerized, for example by exposure to actinic radiation, as described in, for example, WO 01/20394, GB 2,315,072 or WO 98/04651.

The photopolymerization of the formulation is preferably achieved by exposing it to actinic radiation. Actinic radiation means irradiation with light (for example, UV light, IR light, or visible light), irradiation with X-rays or gamma rays, or irradiation with high-energy particles such as ions or electrons. Preferably, the polymerization is carried out by light radiation (especially with UV light). As the source of actinic radiation, for example, a single UV lamp or a group of UV lamps can be used. When using high lamp power, the curing time can be reduced. Another possible source of optical radiation is lasers, such as, for example, UV lasers, IR lasers or visible lasers.

The curing time especially depends on the reactivity of the polymerizable LC compound, the thickness of the printed layer, the type of polymerization initiator and the power of the UV lamp.

Generally, the curing time is preferably ≤ 5 minutes, extremely preferably ≤ 3 minutes, and most preferably ≤ 1 minute. For mass production, a short curing time of 30 seconds or less is preferred.

The suitable UV radiation power is preferably in ^{the range of 5 to 200 mWcm -2} , more preferably in the range of 50 to 175 mWcm ^-2 and most preferably in the range of 100 to 150 mWcm ^-2 .

Regarding the applied UV radiation as a function of time, a suitable UV dose is preferably in the range of 25 to 7200 mJcm ^-2 , more preferably 500 to 7200 mJcm ^-2 and most preferably 3000 to 7200 mJcm ^-2 .

The photopolymerization is preferably carried out in an inert gas atmosphere, preferably in a heated nitrogen atmosphere, but polymerization in air is also possible.

The photopolymerization is preferably carried out at a temperature of 1 to 70°C, more preferably 5 to 50°C, even more preferably 15 to 30°C.

The polymerized LC film according to the present invention has good adhesion to plastic substrates (especially to TAC, COP and color filters). Therefore, it can be used as an adhesive or primer for subsequent LC layers, otherwise the LC layers will not adhere well to the substrate.

For example, the uniform homogeneous or plane-aligned polymer film of the present invention can be used as a retarder or compensation film or reflective film in LCDs to improve contrast and brightness and reduce chromaticity at large viewing angles. They can be used outside the switchable liquid crystal cell in the LCD, or between the substrates (usually glass substrates) that form the switchable liquid crystal cell and contain the switchable liquid crystal medium (in cell applications).

Therefore, the present invention also relates to the use of a polymer film as described above and below as an optical film or in an optical component.

其中(Δn)係薄膜之雙折射率，(d)係薄膜之厚度及λ係入射光束之波長。The optical retardation (δ(λ)) of the polymer film as a function of the incident beam wavelength (λ) is given by the following equation:

(Δn) is the birefringence of the film, (d) is the thickness of the film and λ is the wavelength of the incident light beam.

其中

為薄膜中光軸之入射角或傾斜角及

為對應之反射角。According to Snellius law, the birefringence as a function of the direction of the incident beam is defined as:

in

Is the incident angle or inclination angle of the optical axis in the film and

Is the corresponding reflection angle.

Based on these laws, the birefringence and the corresponding optical retardation depend on the thickness of the film and the tilt angle of the optical axis in the film (see Berek's compensator). Therefore, skilled experts know that different optical retardation or different birefringence can be caused by adjusting the thickness of the ink formulation or polymer film.

The birefringence (Δn) of the polymer film according to the present invention is preferably in the range of 0.01 to 0.30, more preferably in the range of 0.01 to 0.25 and even more preferably in the range of 0.01 to 0.16.

The optical retardation as a function of the thickness of the polymer film according to the present invention is less than 200 nm, preferably less than 180 nm and even more preferably less than 160 nm.

The polymer film of the present invention can also be used as an alignment film for other liquid crystal or RM materials. For example, they can be used in LCDs to induce or improve the alignment of a switchable liquid crystal medium, or to align subsequent layers of polymerizable LC materials coated thereon. In this way, a stack of polymerized LC films can be prepared.

In conclusion, the polymer film according to the present invention can be used for optical components in liquid crystal displays or projection systems (and especially reflective films with spatially varying reflection colors), such as polarizers, compensators, alignment layers, circular polarizers or Color filter.

Therefore, the present invention also relates to an optical component comprising one or more polymer films obtainable from or from the ink formulations described above and below.

In another preferred embodiment, the optical component comprises one or more (preferably two or more) polymer films that can be obtained from or from the ink formulations described above and below. The film is selected from A plate, C plate, biaxial polymer film or cholesterol polymer film or even any combination thereof.

Preferably, the present invention relates to a color filter comprising one or more (preferably two or more) polymer films obtainable from or from ink formulations as described above and below.

Preferably, the color filter includes a multi-color pixel pattern with a certain retardation, a polymer film on the multi-color pixel pattern, and the polymer film can be freely ink-jet printed to correspond to each of the multi-color pixel patterns. The ink formulation provided by a retardation is obtained, wherein the liquid crystal phase shift layer includes a plurality of liquid crystal phase shift regions corresponding to a multicolor pattern; the plurality of liquid crystal phase shift regions have a retardation for correcting the retardation of the multicolor pixel pattern Hysteresis; and for each pixel, the sum of the retardation of the multicolor pixel pattern and the retardation in the corresponding plurality of polymer film displacement regions is characteristically and substantially the same.

For this purpose, the color filter preferably includes a different birefringence for each sub-pixel (such as red, green and blue) of the color filter, which can be obtained from or from the ink formulations described above and below. Rate of one or more (preferably two or more) polymer films.

More preferably, the present invention relates to quantum material-based color filters comprising one or more (preferably two or more polymer films) obtainable from or from ink formulations as described above and below.

For this purpose, it is preferable that the color filter includes different reflection characteristics for each sub-pixel (such as red, green and blue) of the color filter, which can be obtained from or from the ink formulations described above and below. One or more (preferably two or more) cholesterol polymer films. For example, for each sub-pixel of the color filter, the red/green/blue CLC reflector has a left-handed and right-handed spiral orientation.

The polymer film according to the present invention can be used in transmissive or reflective displays. They can be used in conventional or QD-type OLED and LCD displays including pixel-color converter modules (PCC), especially LCDs in DAP (Alignment Phase Modification) or VA (Vertical Alignment) mode, such as (for example) ECB (electrically controlled birefringence), CSH (color super vertical), VAN or VAC (vertical alignment nematic or cholesterol) display, MVA (multi-domain vertical alignment) or PVA (patterned vertical alignment) display, used in bending mode or In hybrid displays, such as, for example, OCB (optically compensated bending cell or optically compensated birefringence), R-OCB (reflective OCB), HAN (hybrid alignment nematic), or pi-cell (π-cell) Display, also used in TN (Twisted Nematic), HTN (Highly Twisted Nematic) or STN (Super Twisted Nematic) mode display, used in AMD-TN (Active Matrix Drive TN) display, or used in IPS (In-plane switching) mode display (also known as "super TFT" display). Especially good series of VA, MVA, PVA, OCB and pi-cell displays.

Therefore, another aspect of the present invention is the use of one or more polymer films or optical components as described above and below in an optical device or an optical device containing one or more optical components, the one or more Each optical component includes one or more polymer films that can be obtained from or from one or more ink formulations as described above and below.

Many of the compounds or mixtures mentioned above and below are commercially available. All these compounds are known or can be prepared by methods known per se, such as in the literature, for example, standard works such as Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag As described in Stuttgart, it is precisely prepared under known and suitable reaction conditions for these reactions. Among them, variants that are known per se but not mentioned can also be used.

It should be understood that changes can be made to the foregoing embodiments of the present invention while still falling within the scope of the present invention. Unless otherwise specified, alternative features having the same, equivalent or similar purpose can replace each feature disclosed in this specification. Therefore, unless otherwise stated, each feature disclosed is only an example of a general series of equivalent or similar features.

All the features disclosed in this specification can be combined in any combination, except that at least some of these features and/or steps are mutually exclusive combinations. In particular, the preferred features of the present invention are applicable to all aspects of the present invention and can be used in any combination. Likewise, features described in optional combinations can be used alone (not in combination).

It should be understood that many of the features described above (especially the features of the preferred embodiment) are inventive in their own right and are not merely part of an embodiment of the present invention. In addition to or in place of any invention currently claimed, independent protection for these features can be sought.

23.59

23.59

9.32

37.79 RMM 2 ： 化合物 量 % w/w Irganox® 1076 0.08 Tego Rad ® 2500 0.05 Irgacure ® 907 5.00

3.65

15.00

15.00

8.14

20.00

33.08 RMM 3 ： 化合物 量 % w/w Irganox® 1076 0.08 Tego Rad® 2500 0.05 Irgacure® 907 5.00

3.05  

15.00

15.00

8.45

20.00

33.37 所使用的溶劑及溶劑系統 系統編號 溶劑 比 率 1 環己酮 - 2 3-苯氧基甲苯 - 3 苯基萘 - 4 異戊酸薄荷酯 - 5 二(丙二醇)甲基醚乙酸酯(DiPGMEA) - 6 丙二醇單甲基醚乙酸酯(PGMEA) - 7 環己酮: DiPGMEA 2:1 8 PGMEA: DiPGMEA 7:10 所使用的噴墨印表機： 1 Dimatix®材料印表機2800，Fujifilm 2 PiXDRO® LP 50，Meyer Burger。 一般程序： 藉由將對應之RMM與對應之溶劑系統(SS)混合來製備墨水調配物。然後以給定印刷尺寸(PD)及給定液滴間距(DS)來印刷墨水。然後在90℃下退火該層60秒並冷卻至室溫。然後用250至450 nm Omnicure燈在50 mW下於空氣中使該層固化120秒。在固化後確定雙折射率(Δn)及就膽固醇聚合物薄膜而言之中心反射波長(λ)及反射帶寬(dλ)。The present invention will now be described in more detail with reference to the following working examples, which are only illustrative and do not limit the scope of the present invention. Reactive mesogen mixture (RMM) used in the working example : Prepare the following reactive mesogen mixture according to the following table: RMM 1 : Compound Quantity % w/w Irganox ® 1076 0.08 FluorN ® 562 0.58 Irgacure ® 907 5.05

23.59

23.59

9.32

37.79 RMM 2 : Compound Quantity % w/w Irganox® 1076 0.08 Tego Rad ® 2500 0.05 Irgacure ® 907 5.00

3.65

15.00

15.00

8.14

20.00

33.08 RMM 3 : Compound Quantity % w/w Irganox® 1076 0.08 Tego Rad® 2500 0.05 Irgacure® 907 5.00

3.05

15.00

15.00

8.45

20.00

33.37 Solvent and solvent system used System number Solvent Ratio 1 Cyclohexanone - 2 3-phenoxy toluene - 3 Phenyl naphthalene - 4 Menthyl Isovalerate - 5 Di(propylene glycol) methyl ether acetate (DiPGMEA) - 6 Propylene glycol monomethyl ether acetate (PGMEA) - 7 Cyclohexanone: DiPGMEA 2:1 8 PGMEA: DiPGMEA 7:10 Inkjet printer used: 1 Dimatix® Material Printer 2800, Fujifilm 2 PiXDRO® LP 50, Meyer Burger. General procedure: Prepare the ink formulation by mixing the corresponding RMM with the corresponding solvent system (SS). The ink is then printed with a given printing size (PD) and a given droplet spacing (DS). The layer was then annealed at 90°C for 60 seconds and cooled to room temperature. The layer was then cured for 120 seconds in the air with a 250 to 450 nm Omnicure lamp at 50 mW. After curing, determine the birefringence (Δn) and the central reflection wavelength (λ) and reflection bandwidth (dλ) of the cholesterol polymer film.

Working example Non-cholesterol polymer film: serial number RMM SS Solid content [%] PD Printer DS [µm] Δ n 1 1 8 30 1 cm x 1 cm 1 36 0.151 2 1 7 40 500 µm x 500 µm 1 35 0.152 3 1 7 40 500 µm x 500 µm 1 40 0.150 4 1 7 40 500 µm x 500 µm 1 45 0.153 5 1 7 40 500 µm x 500 µm 1 50 0.150 6 1 7 40 200 µm x 200 µm 1 45 0.152 7 1 7 40 200 µm x 200 µm 1 50 0.153 8 1 7 40 200 µm x 200 µm 1 55 0.153 9 1 7 40 200 µm x 200 µm 1 60 0.151 10 1 7 40 200 µm x 200 µm 1 80 0.151 11 1 7 40 200 µm x 200 µm 1 85 0.151 12 1 7 40 2.5 cm x 2.5 cm 1 60 0.152 13 1 7 40 2.5 cm x 2.5 cm 1 60 0.151 14 1 7 40 2.5 cm x 2.5 cm 1 60 0.150 15 1 7 40 100 µm x 300 µm 1 30 0.153 16 1 7 40 100 µm x 300 µm 1 34 0.150 Cholesterol polymer film: serial number RMM SS Solid content [%] PD Printer DS[µm] λ dλ 17 2 8 40 4 mm x 4 mm 1 15 532 83 18 2 8 40 4 mm x 4 mm 1 20 530 74 19 2 8 40 4 mm x 4 mm 1 25 522 57 twenty one 2 8 15 8 mm x 8 mm 2 16 533 53 twenty two 3 8 15 4 mm x 4 mm 2 16 634 65

Claims (16)

An ink formulation for inkjet printing, which contains 10 to 50% w/w of one or more polymerizable liquid crystal compounds and 50 to 90% w/w selected from aliphatic ketones, cyclic ketones, and ethylene two One or more organic solvents from the group of alkyl ethers of alcohol or propylene glycol, alkyl esters of menthyl or aromatic solvents. If the ink formulation of claim 1 contains one or more polymerizable liquid crystal compounds, the one or more polymerizable liquid crystal compounds are selected from the dual-reactive or multi-reactive compounds of formula DRM P ¹ -Sp ¹ -MG- Sp ² -P ² DRM wherein P ¹ and P ² independently represent a polymerizable group, Sp ¹ and Sp ² are independently a spacer or a single bond, and MG is a rod-shaped mesogen group, which is preferably Is selected from the formula MG, -(A ¹ -Z ¹ ) _n -A ² -MG where A ¹ and A ² represent an aromatic or alicyclic group independently of each other in multiple occurrences, which optionally contain one or Multiple heteroatoms selected from N, O and S, and are mono- or multi-substituted ^{by L 1 as necessary, L 1} is P-Sp-, F, Cl, Br, I, -CN, -NO ₂ ,- NCO, -NCS, -OCN, -SCN, -C(=O)NR ⁰⁰ R ⁰⁰⁰ , -C(=O)OR ⁰⁰ , -C(=O)R ⁰⁰ , -NR ⁰⁰ R ⁰⁰⁰ , -OH,- SF ₅ , optionally substituted silyl groups, aryl or heteroaryl groups having 1 to 12 C atoms, and straight or branched chain alkyl groups, alkoxy groups, and alkylcarbonyl groups having 1 to 12 C atoms, Alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, in which one or more H atoms are replaced by F or Cl as necessary, R ⁰⁰ and R ⁰⁰⁰ independently represent H or have 1 to 12 The alkyl group of C atom, Z ¹ represents -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-,- O-COO-, -CO-NR ⁰⁰ -, -NR ⁰⁰ -CO-, -NR ⁰⁰ -CO-NR ⁰⁰⁰ , -NR ⁰⁰ -CO-O-, -O-CO-NR ⁰⁰ -, -OCH _2- , -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CH ₂ CH ₂ -, -(CH ₂ ) _n1 , -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH=N-, -N=CH-, -N=N-, -CH=CR ⁰⁰ -, -CY ¹ =CY ² -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or single bond, Y ¹ and Y ² independently represent H, F, Cl or CN, n is 1, 2, 3, or 4, n1 is an integer from 1 to 10, and P represents polymerizable The combined group, Sp represents a spacer group. The ink formulation of claim 1 or 2, wherein the one or more polymerizable compounds are selected from mono-reactive liquid crystal compounds of formula MRM, P ¹ -Sp ¹ -MG-R MRM where P ¹ , Sp ¹ and MG It has the meaning given in the formula DRM in claim 2, RF, Cl, Br, I, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C(=O)NR ^x R ^y , -C(=O)X, -C(=O)OR ^x , -C(=O)R ^y , -NR ^x R ^y , -OH, -SF ₅ , optionally substituted silyl, with A straight or branched chain alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group with 1 to 12 C atoms, where one or more H atoms are based on It needs to be replaced by F or Cl, X is halogen, preferably F or Cl, and R ^x and R ^y are independently H or an alkyl group having 1 to 12 C atoms. Such as the ink formulation of any one of claims 1 to 3, which contains one or more opposing additives. The ink formulation of any one of claims 1 to 4, which contains one or more photoinitiators. A method for producing ink formulations by combining at least 10 to 50% w/w of one or more polymerizable liquid crystal compounds and 50 to 90% w/w selected from aliphatic ketones, cyclic ketones, One or more solvents from the group of alkyl ethers of ethylene glycol or propylene glycol, alkyl esters of menthyl or aromatic solvents are mixed. A use of the ink formulation of any one of claims 1 to 5 in an inkjet printer. A polymer film can be obtained by or by ink-jet printing the ink formulation of any one of claims 1 to 5 on a substrate and curing the ink formulation. A method for producing a polymer film, the method comprising the steps of ink-jet printing the ink formulation of any one of claims 1 to 5 on a substrate and curing the ink formulation. A use of the polymer film of claim 8 as an optical film or in an optical component. An optical component comprising one or more polymer films as claimed in Claim 8. The optical component of claim 11, wherein the optical component comprises one or more polymer films as in claim 8, and the one or more polymer films are selected from the group consisting of A plate, C plate, biaxial polymer film or cholesterol Polymer film or any combination thereof. The optical component of claim 11 or 12, wherein the optical component includes one or more polymer film color filters as in claim 8. The optical component according to any one of claims 11 to 13, wherein the optical component includes one or more polymer films as claimed in claim 8 quantum material-based color filter. A use of one or more optical components in an optical device as in any one of claims 11 to 14. An optical device comprising one or more optical components as claimed in Claim 11, the one or more optical components comprising one or more polymer films as claimed in Claim 8.