Polymerizable liquid crystal material and polymerized liquid crystal film

文档序号：1835885 发布日期：2021-11-12 浏览：20次中文

阅读说明：本技术 可聚合液晶材料及经聚合的液晶膜 (Polymerizable liquid crystal material and polymerized liquid crystal film ) 是由崔榕岘尹铉轸 B·施纳特温克尔于 2020-03-16 设计创作，主要内容包括：本发明涉及可聚合LC材料,其包含一种或多种二反应性或多反应性介晶化合物及一种或多种式UVI化合物(式UVI),其中各个基团具有如权利要求中所给出的含义之一。此外,本发明还涉及其制备方法,可由对应可聚合LC材料获得的具有改良的热耐久性及UV稳定性的聚合物膜,涉及制备此聚合物膜的方法,及涉及此聚合物膜及所述可聚合LC材料用于光学、电光、装饰或安全装置的用途。(The present invention relates to a polymerisable LC material comprising one or more di-or multireactive mesogenic compounds and one or more compounds of formula UVI (formula UVI),)

1. A polymerisable LC material comprising at least one di-or multireactive mesogenic compound and one or more compounds of formula UVI,

wherein the individual radicals have the following meanings:

R¹to R⁵Each independently selected from the group consisting of H, -alkyl, -OH, -alkylaryl, -alkylheteroaryl, -cycloalkyl, cycloheteroalkyl, alkenyl, aryl, and-SO₃H, and is selected from the group consisting of

R⁶And R⁷Each independently represents a hydrogen atom, a hydroxyl group or a halogen atom, or R⁶And R⁷Forming an optionally substituted cycloalkyl or cycloheteroalkyl ring.

2. Polymerizable LC material according to claim 1, wherein the compound of formula UVI is selected from the following subformulae:

wherein

R¹To R⁵Each independently selected from the group consisting of H, -alkyl, -OH, -alkylaryl, -alkylheteroaryl, -cycloalkyl, cycloheteroalkyl, alkenyl, aryl, and-SO₃H, and is selected from the group consisting of

R⁶And R⁷Each independently represents a hydrogen atom, a hydroxyl group or a halogen atom,

R⁸to R¹³Each independently is a group selected from the group consisting of H, alkyl, aryl, heteroaryl, alkylaryl, alkylheteroaryl, alkenyl, and alkynyl,

X¹represents O or S, and

R¹⁴and R¹⁵Selected from the group consisting of H, -C (═ O) R⁸Alkyl, alkenyl, alkynyl, aryl, cycloalkyl, heteroaryl and cycloheteroalkyl.

3. Polymerizable LC material according to claim 1 or 2, wherein the compound of formula UVI is selected from the following subformulae:

wherein

R²To R⁵Each independently selected from the group consisting of H, -alkyl, -OH, -alkylaryl, -alkylheteroaryl, -cycloalkyl, cycloheteroalkyl, alkenyl, aryl, and-SO₃H, and is selected from the group consisting of

R⁶And R⁷Each independently represents a hydrogen atom, a hydroxyl group or a halogen atom,

R⁸to R¹³Each independently is a group selected from the group consisting of H, alkyl, aryl, heteroaryl, alkylaryl, alkylheteroaryl, alkenyl, and alkynyl,

X¹represents O or S, and is represented by,

and is

R¹⁴And R¹⁵Selected from the group consisting of H, -C (═ O) R⁸Alkyl, alkenyl, alkynyl, aryl, cycloalkyl, heteroaryl and cycloheteroalkyl.

4. Polymerizable LC material according to one or more of claims 1 to 3, wherein the compound of formula UVI is selected from the following subformulae:

wherein

R²And R⁴Each independently selected from the group consisting of H, -alkyl, -OH, -alkylaryl, -alkylheteroaryl, -cycloalkyl, cycloheteroalkyl, alkenyl, aryl, and-SO₃H, and is selected from the group consisting of

R⁶And R⁷Each independently represents a hydrogen atom or a hydroxyl groupA radical or a halogen atom,

R⁸to R¹³Each independently is a group selected from the group consisting of H, alkyl, aryl, heteroaryl, alkylaryl, alkylheteroaryl, alkenyl, and alkynyl,

X¹represents O or S, and is represented by,

and is

R¹⁴And R¹⁵Selected from the group consisting of H, -C (═ O) R⁸Alkyl, alkenyl, alkynyl, aryl, cycloalkyl, heteroaryl and cycloheteroalkyl.

5. Polymerizable LC material according to one or more of claims 1 to 4, wherein the compound of formula UVI is selected from the group of compounds wherein R²And R⁴Each independently represents an alkylaryl group, especially an alkylphenyl group, or an alkyl group, especially a linear or branched alkyl group having from 5 to 15 carbon atoms, of which one or more- (CH)₂) The-group may be substituted with-COO-, -OCO-in such a way that no two oxygen atoms are linked together.

6. Polymerisable LC material according to one or more of claims 1 to 5, wherein the compound of formula UVI is selected from the group of compounds of the following subformula

。

7. Polymerisable LC material according to one or more of claims 1 to 6, wherein the at least one di-or multireactive mesogenic compound is selected from the group of compounds of formula DRM

P¹-Sp¹-MG-Sp²-P² DRM

Wherein

P¹And P²Earth surface independent of each otherA polymerizable group is shown, and a polymerizable group is shown,

Sp¹and Sp²Independently of one another, are a spacer group or a single bond, and

MG is a rod-like mesogenic group, preferably selected from the group consisting of

-(A¹-Z¹)_n-A²- MG

Wherein

A¹And A²In each case independently of one another, an aromatic or cycloaliphatic radical, which optionally contains one or more heteroatoms selected from N, O and S, and optionally via L¹One or more of mono-substitution or multi-substitution,

L¹is P-Sp-, F, Cl, Br, I, -CN, -NO₂、-NCO、-NCS、-OCN、-SCN、-C(＝O)NR⁰⁰R⁰⁰⁰、-C(＝O)OR⁰⁰、-C(＝O)R⁰⁰、-NR⁰⁰R⁰⁰⁰、-OH、-SF₅Optionally substituted silyl, aryl or heteroaryl having 1 to 12C atoms, straight-chain or branched alkyl having 1 to 12C atoms, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, wherein one or more H atoms are optionally replaced by F or Cl,

R⁰⁰and R⁰⁰⁰Independently of one another, H or alkyl having 1 to 12C atoms,

Z¹in the case of multiple occurrence represent independently of each other-O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR-⁰⁰-、-NR⁰⁰-CO-、-NR⁰⁰-CO-NR⁰⁰⁰、-NR⁰⁰-CO-O-、-O-CO-NR⁰⁰-、-OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-CH₂CH₂-、-(CH₂)_n1、-CF₂CH₂-、-CH₂CF₂-、-CF₂CF₂-、-CH＝N-、-N＝CH-、-N＝N-、-CH＝CR⁰⁰-、-CY¹＝CY²-, -C.ident.C-, -CH-COO-, -OCO-CH-or a single bond,

Y¹and Y²H, F, Cl or CN are represented independently of each other,

n is 1,2,3 or 4, and

n1 is an integer from 1 to 10.

8. Polymerizable LC material according to one or more of claims 1 or 7, wherein the at least one di-reactive mesogenic compound is selected from the following formulae:

wherein

P⁰Independently of one another in the case of a plurality of occurrences, is acryloyl, methacryloyl, oxetanyl, epoxy, vinyl, heptadiene, vinyloxy, propenyl ether or styryl,

l has L in Targeted DRM, the same or different at each occurrence¹One of the meanings given is as follows,

r is 0, 1,2,3 or 4,

x and y are independently of each other 0 or the same or different integers from 1 to 12,

z is each and independently 0 or 1, wherein if the adjacent x or y is 0, then z is 0.

9. Polymerisable LC material according to one or more of claims 1 to 8, comprising at least one mono-reactive mesogenic compound selected from the group consisting of formula MRM,

P¹-Sp¹-MG-R MRM

wherein P is¹、Sp¹And MG has the meaning as given in DRM,

r is F, Cl, Br, I, -CN, -NO₂、-NCO、-NCS、-OCN、-SCN、-C(＝O)NR^xR^y、-C(＝O)X、-C(＝O)OR^x、-C(＝O)R^y、-NR^xR^y、-OH、-SF₅Optionally substituted silyl, straight-chain or branched alkyl having 1 to 12C atoms, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, in which one or more H atoms are optionally replaced by F or Cl,

x is halogen, preferably F or Cl, and

R^xand R^yIndependently of one another, H or alkyl having 1 to 12C atoms.

10. Polymerizable LC material according to one or more of claims 1 to 9, wherein the at least one mono-reactive mesogenic compound is selected from the following formulae:

wherein P is⁰L, r, x, y and z are as defined in claim 8,

R⁰is alkyl, alkoxy, sulfanyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 or more, preferably 1 to 15, C atoms, or represents Y⁰，

Y⁰Is F, Cl, CN, NO₂、OCH₃、OCN、SCN、SF₅Or mono-fluoro having 1 to 4C atoms,An oligo-or polyfluoroalkyl or alkoxy group,

R⁰¹and R⁰²Is H, alkyl, alkoxy, sulfanyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 or more, preferably 1 to 15, C atoms, or represents Y⁰，

Z⁰is-COO-, -OCO-, -CH₂CH₂-、-CF₂O-、-OCF₂-, -CH-, -OCO-CH-, -CH-COO-or a single bond,

A⁰independently of one another in multiple occurrences, is unsubstituted or substituted by 1,2,3 or 4 radicals L, or trans-1, 4-cyclohexylene,

u and v are independently of one another 0, 1 or 2,

w is 0 or 1, and

wherein the benzene and naphthalene rings may additionally be substituted by one or more identical or different radicals L.

11. Polymerisable LC material according to one or more of claims 1 to 10, comprising one or more compounds of the formula ND,

wherein

U^1,2Independently of one another, are selected from

a and nIncluding its mirror image, in which the ring U¹And U²Each bonded to a group- (B) via an axial bond_q-, and one or two of these rings are not adjacent CH₂Optionally substituted by O and/or S, and the ring U¹And U²Optionally substituted with one or more groups L,

l has L in Targeted DRM, the same or different at each occurrence¹One of the meanings given is as follows,

Q^1,2independently of one another, is CH or SiH,

Q³is C or Si, and is characterized in that,

each occurrence of B is independently of the other-C.ident.C-, -CY¹＝CY²-or an optionally substituted aromatic or heteroaromatic group,

Y^1,2independently of one another, H, F, Cl, CN or R⁰，

q is an integer from 1 to 10, preferably 1,2,3,4, 5,6 or 7,

A^1-4independently of one another, from a non-aromatic, aromatic or heteroaromatic carbocyclic or heterocyclic radical, optionally via one or more radicals R⁵Is substituted, and wherein- (A)¹-Z¹)_m-U¹-(Z²-A²)_n-and- (A)³-Z³)_o-U²-(Z⁴-A⁴)_pEach free of more aromatic groups than non-aromatic groups and preferably free of more than one aromatic group,

Z^1-4independently of one another, -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR⁰-、-NR⁰-CO-、-NR⁰-CO-NR⁰⁰-、-OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-CH₂CH₂-、-(CH₂)₃-、-(CH₂)₄-、-CF₂CH₂-、-CH₂CF₂-、-CF₂CF₂-、-CH＝CH-、-CY¹＝CY²-、-CH＝N-、-N＝CH-、-N＝N-、-CH＝CR⁰-、-C≡C-、-CH＝CH-COO-、-OCO-CH＝CH-、CR⁰R⁰⁰Or a single bond, or a mixture of single bonds,

R⁰and R⁰⁰Independently of one another, H or alkyl having 1 to 12C atoms,

m and n are each independently of the other 0, 1,2,3 or 4,

o and p are independently of one another 0, 1,2,3 or 4,

R^1-5independently of one another, are identical or different radicals selected from: H. halogen, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C (═ O) NR⁰R⁰⁰、-C(＝O)X⁰、-C(＝O)R⁰、-NH₂、-NR⁰R⁰⁰、-SH、-SR⁰、-SO₃H、-SO₂R⁰、-OH、-NO₂、-CF₃、-SF₅P-Sp-, optionally substituted silyl, or carbyl or hydrocarbyl radicals having 1 to 40C atoms which are optionally substituted and optionally contain one or more heteroatoms, or represents P or P-Sp-, or is substituted by P or P-Sp-, wherein the compound contains at least one group R^1-5The group represents P or P-Sp-or is substituted by P or P-Sp-,

p is a polymerizable group, and P is a polymerizable group,

sp is a spacer group or a single bond.

12. Polymerisable LC material according to one or more of claims 1 to 11, wherein the proportion of the di-or multireactive polymerisable mesogenic compound is in the range of 5 to 99 wt.%.

13. Polymerisable LC material according to one or more of claims 1 to 12, wherein the proportion of the mono-reactive polymerisable mesogenic compound is in the range of 5 to 80 wt.%.

14. Polymerizable LC material according to one or more of claims 1 to 13, optionally comprising one or more additives selected from the group consisting of: surfactants, additional stabilizers, catalysts, sensitizers, inhibitors, chain transfer agents, co-reactive monomers, reactive visbreakers, surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, flow improvers, deaerators or defoamers, deaerators, diluents, reactive diluents, auxiliaries, colorants, dyes, pigments and nanoparticles.

15. A method for the preparation of a polymerisable LC material according to one or more of claims 1 to 14, comprising the step of mixing one or more compounds of formula UVI with at least one di-or multireactive mesogenic compound.

16. A method of making a polymer film by:

-providing a layer of a polymerizable LC material according to one or more of claims 1 to 14 onto a substrate,

photopolymerising the polymerisable LC material, and

-optionally removing the polymerized LC material from the substrate and/or optionally providing it onto another substrate.

17. Polymer film obtainable from a polymerisable LC material according to one or more of claims 1 to 14 by a process comprising the steps of:

-providing the layer of polymerisable LC material onto a substrate,

photopolymerising the LC material, and

-optionally removing the polymerized LC material from the substrate and/or optionally providing it onto another substrate.

18. A polymer film according to claim 17, characterized in that the LC material is homogeneously aligned.

19. Use of a polymer film according to claim 17 or 18 or a polymerisable LC material according to one or more of claims 1 to 14 in optical, electrooptical, information storage, decorative and security applications, such as liquid crystal displays, 3D displays, projection systems, polarizers, compensators, alignment layers, circular polarizers, colour filters, decorative images, liquid crystal pigments, reflective films having spatially different reflective colours, multicolour images, non-counterfeitable documents such as identification cards or credit cards or banknotes.

20. Optical component or device, polarizer, patterned retarder, compensator, alignment layer, circular polarizer, color filter, decorative image, liquid crystal lens, liquid crystal pigment, reflective film having spatially different reflective colors, multicolor image for decoration or information storage comprising at least one polymer film according to claim 17 or 18 or a polymerizable LC material according to one or more of claims 1 to 14.

Technical Field

The present invention relates to a polymerisable LC material comprising one or more di-or multireactive mesogenic compounds and one or more compounds of formula UVI,

wherein each group has one of the meanings given in the claims. Furthermore, the present invention relates to a process for the preparation thereof, a polymer film with improved thermal durability and UV stability obtainable from the corresponding polymerisable LC material, to a process for the preparation of such a polymer film, and to the use of such a polymer film and the polymerisable LC material for optical, electrooptical, decorative or security devices.

Background and Prior Art

Polymerizable liquid crystal materials are known in the art for the preparation of anisotropic polymer films with uniform orientation. These films are typically prepared by applying a thin layer of a polymerizable liquid crystal mixture to a substrate, aligning the mixture in a uniform orientation, and polymerizing the mixture. The orientation of the film may be planar, i.e. in which the liquid crystal molecules are oriented substantially parallel to the layer, homeotropic (at right angles or perpendicular to the layer) or tilted.

Such optical films are described, for example, in EP 0940707B 1, EP 0888565B 1 and GB 2329393B 1.

Polymerizable Liquid Crystal (LC) materials, while stable at room temperature, can degrade when subjected to increased temperatures. For example, when heated for a certain period of time, optical properties such as dispersion or retardation are degraded, and thus, the properties of the optical film are degraded with time. In particular, this can be attributed to a low degree of polymerization and a correspondingly high content of residual free radicals in the polymer, shrinkage of the polymer and/or thermo-oxidative degradation.

Thermo-oxidative degradation is the destruction of a polymer network catalyzed by oxidation at high temperatures. It is well known that antioxidant additives or simply antioxidants can be used to reduce the temperature experienced by polymersThermal oxidative degradation in time. This is particularly important when the optical film is used in-cell applications due to high temperatures. In particular, the optical films must survive when annealing the polyimide in the LC cell. In this regard, documents WO 2009/86911A 1 and JP 5354238B 1 describe compositions comprising commercially available antioxidants1076.

The above-described materials have significant disadvantages, such as the UV stability or thermal durability of the resulting polymer films still being not high enough, their transparency to visible light being limited, they requiring the use of further additives, or their bandwidth of application being limited, due to the LC material used.

Thus, there is still a need for new and preferably improved polymerizable liquid crystalline materials or mixtures which do not show the disadvantages of the prior art materials or, if so, show them only to a lesser extent.

Advantageously, such polymerisable LC materials should preferably be suitable for the preparation of different, uniformly aligned polymer networks such as polymer films or polymer network LC applications, and in particular, should simultaneously:

exhibits advantageous adhesion to the substrate,

-is highly transparent to visible light,

exhibit a reduced yellow coloration (yellowing) over time and

exhibit advantageous high-temperature stability or durability, and furthermore

Exhibit advantageous high thermal and/or UV stability or durability, and furthermore,

homogeneously aligned polymer films should be produced by compatible, well-known methods for mass production.

Other objects of the present invention will be immediately apparent to those skilled in the art from the following detailed description.

Surprisingly, the inventors of the present invention have found that by using a polymerisable LC material according to claim 1, one or more, preferably all, of the above required objects can be achieved, preferably simultaneously.

Summary of The Invention

The present invention relates to a polymerisable LC material comprising at least one di-or multireactive mesogenic compound and one or more compounds of formula UVI,

wherein the individual radicals have the following meanings:

R⁶And R⁷Each independently represents a hydrogen atom, a hydroxyl group or a halogen atom, or R⁶And R⁷Forming an optionally substituted cycloalkyl or cycloheteroalkyl ring.

In addition, the invention also relates to a corresponding method for producing a polymerisable LC material.

The invention further relates to a polymer network or polymer film obtainable, preferably obtained, from a polymerisable LC material as described above and below, and a method of producing a polymer film as described above and below.

The present invention further relates to a method of increasing the UV stability of a polymer film obtainable, preferably obtained, from a polymerisable LC material as described above and below by adding a compound of formula UVI to the LC material prior to polymerisation.

The invention further relates to the use of a polymer network or a polymer film or a polymerisable LC material as described above and below for optical, electrooptical, information storage, decorative and security applications, such as liquid crystal displays, projection systems, polarizers, compensators, alignment layers, circular polarizers, color filters, decorative images, liquid crystal pigments, reflective films having a spatially different reflective colour, multicolour images, non-counterfeitable documents like identification cards or credit cards or bank notes.

The invention also relates to an optical component or device, a polarizer, a patterned retarder, a compensator, an alignment layer, a circular polarizer, a color filter, a decorative image, a liquid crystal lens, a liquid crystal pigment, a reflective film having a spatially varying reflective color, a multicolored image for decoration or information storage comprising at least one polymer network or polymer film or polymerizable LC material as described above and below.

The invention further relates to a liquid crystal display comprising at least one polymer network or polymer film or polymerizable LC material or optical component as described above and below.

The invention further relates to an authentication, verification or security marking, a coloured or multicoloured image for security purposes, an unforgeable article or document of value (such as an identification card or credit card or banknote) comprising at least one polymer network or polymer film or polymerisable LC material or optical component as described above and below.

Terms and definitions

As used herein, the term "polymer" will be understood to refer to a molecule comprising a backbone of one or more different types of repeating units (the smallest constitutional unit of the molecule), and includes the well-known terms "oligomer", "copolymer", "homopolymer", and the like. Furthermore, it is to be understood that the term polymer comprises, in addition to the polymer itself, residues from initiators, catalysts and other elements accompanying the synthesis of such polymers, wherein such residues are understood not to be covalently incorporated therein. In addition, such residues and other elements, although typically removed during post-polymerization purification, are typically mixed or blended with the polymer such that they typically remain in the polymer as it is transferred between vessels or between solvent or dispersion media.

The term "(meth) acrylic polymer" as used in the present invention includes polymers derived from acrylic monomers, polymers obtainable from methacrylic monomers, and corresponding copolymers obtainable from mixtures of such monomers.

The term "polymerization" refers to a chemical process by which a plurality of polymerizable groups or polymer precursors (polymerizable compounds) comprising such polymerizable groups are bonded together to form a polymer.

The term "film" or "layer" includes rigid or flexible, self-supporting or free-standing films with mechanical stability, as well as coatings or layers on a supporting substrate or between two substrates.

The term "liquid crystal" or (LC) relates to a material having a liquid crystalline mesophase in some temperature range (thermotropic LC) or in some concentration range in solution (lyotropic LC). They necessarily contain mesogenic compounds.

The terms "mesogenic compound" and "liquid crystal compound" refer to a compound comprising one or more rod-shaped (rod or plate/lath shaped) or disc-shaped (disc shaped) mesogenic groups. The term "mesogenic group" refers to a group that has the ability to induce liquid crystal phase (or mesophase) behavior. The compounds comprising mesogenic groups do not necessarily have to exhibit a liquid crystalline mesophase themselves. They may also exhibit a liquid crystalline mesophase only in mixtures with other compounds, or when mesogenic compounds or materials or mixtures thereof are polymerized. The liquid crystal mesophase comprises a low molecular weight non-reactive liquid crystalline compound, a reactive or polymerizable liquid crystalline compound and a liquid crystalline polymer.

The rod-like mesogenic groups typically comprise a mesogenic core consisting of one or more aromatic or non-aromatic cyclic groups connected to each other directly or via a linking group, optionally comprising end groups attached to the ends of the mesogenic core, and optionally comprising one or more side groups attached to the long side of the mesogenic core, wherein these end groups and side groups are typically selected from e.g. carbon-based (carbyl) or hydrocarbyl groups, polar groups (such as halogen, nitro, hydroxyl, etc.) or polymerizable groups.

The term "reactive mesogen" refers to a polymerisable mesogenic or liquid crystalline compound, preferably a monomeric compound. These compounds can be used as pure compounds or as mixtures of reactive mesogens with other compounds acting as photoinitiators, inhibitors, surfactants, stabilizers, chain transfer agents, non-polymerizable compounds, etc.

Polymerizable compounds having one polymerizable group are also referred to as "mono-reactive" compounds, compounds having two polymerizable groups are also referred to as "di-reactive" compounds, and compounds having more than two polymerizable groups are also referred to as "multi-reactive" compounds. Compounds that do not contain polymerizable groups are also referred to as "non-reactive or non-polymerizable" compounds.

The term "non-mesogenic compound or material" refers to a compound or material that does not contain mesogenic groups as defined above.

Visible light is electromagnetic radiation having a wavelength in the range of about 400nm to about 740 nm. Ultraviolet (UV) light is electromagnetic radiation having a wavelength in the range of about 200nm to about 450 nm.

Irradiance (E)_e) Or radiant power is defined as the power per unit area (dA) of electromagnetic radiation (do θ) incident on the surface:

E_e＝dθ/dA。

radiation exposure or radiation dose (H)_e) For irradiation or radiation power (E) per time (t)_e)：

H_e＝E_e·t。

All temperatures, for example the melting point T (C, N) or T (C, S) of the liquid crystal, the transition T (S, N) from smectic (S) to nematic (N) phase and the clearing point T (N, I) are given in degrees celsius. All temperature differences are given in degrees of difference.

The term "clearing point" refers to the temperature of the transition between the occurrence of the mesophase and the isotropic phase having the highest temperature range.

The term "director" is known from the prior art and refers to the preferred direction of orientation of the long molecular axis (in the case of rod-shaped compounds) or the short molecular axis (in the case of discotic compounds) of the liquid crystal or RM molecules. In the case of such uniaxial ordering of anisotropic molecules, the director is the anisotropy axis.

The term "alignment" or "orientation" relates to the alignment (orientational ordering) of anisotropic units (e.g. small molecules or fragments of large molecules) of a material in a uniform direction (referred to as the "alignment direction"). In an alignment layer of a liquid crystal material or RM material, the liquid crystal director coincides with the alignment direction such that the alignment direction corresponds to the direction of the anisotropy axis of the material.

The term "homogeneously aligned" or "homogeneously aligned" of a liquid crystal or RM material, for example in a layer of the material, means that the long molecular axes (in the case of calamitic compounds) or the short molecular axes (in the case of discotic compounds) of the liquid crystal or RM molecules are oriented substantially in the same direction. In other words, the lines of the liquid crystal directors are parallel.

The term "homeotropic structure" or "homeotropic orientation" refers to a film in which the optical axis is substantially perpendicular to the plane of the film.

The term "planar structure" or "planar orientation" refers to a film in which the optical axis is substantially parallel to the plane of the film.

The term "negative (optical) dispersion" refers to a birefringent or liquid crystal material or layer exhibiting reverse birefringence dispersion, wherein the magnitude of the birefringence (Δ n) increases with increasing wavelength (λ), i.e., | Δ n (450) | < | Δ n (550) |, or Δ n (450)/Δ n (550) <1, where Δ n (450) and Δ n (550) are the birefringence of the material measured at wavelengths of 450nm and 550nm, respectively. Conversely, "positive (optical) dispersion" refers to a material or layer having | Δ n (450) | > | Δ n (550) | or Δ n (450)/Δ n (550) > 1. See also, for example, A.Uchiyama, T.Yatabe "Control of wave length Dispersion of Bireframing for organic polycarbonate Films connecting Positive and Negative Bireframing Units". J.appl.Phys. Vol.42, p.6941-6945 (2003).

Since the optical retardation at a given wavelength is defined as the product of birefringence and layer thickness as described above [ R (λ) ═ Δ n (λ) · d ], the optical dispersion can be expressed as "birefringence dispersion" by the ratio Δ n (450)/Δ n (550), or "retardation dispersion" by the ratio R (450)/R (550), where R (450) and R (550) are the retardation of the material measured at wavelengths of 450nm and 550nm, respectively. Since the layer thickness d does not vary with wavelength, R (450)/R (550) is equal to Δ n (450)/Δ n (550). Thus, a material or layer having negative or reverse (reverse) dispersion has R (450)/R (550) <1 or | R (450) | < | R (550) |, and a material or layer having positive or normal dispersion has R (450)/R (550) >1 or | R (450) | > | R (550) |.

In the present invention, unless otherwise specified, "optical dispersion" refers to delay dispersion, i.e., the ratio R (450)/R (550).

The term "high dispersion" means that the absolute value of the dispersion shows a large deviation from 1, while the term "low dispersion" means that the absolute value of the dispersion shows a small deviation from 1. Thus, "high negative dispersion" means a dispersion value significantly less than 1, and "low negative dispersion" means a dispersion value only slightly less than 1.

The retardation (R (λ)) of a material can be measured using a spectroscopic ellipsometer, such as the M2000 spectroscopic ellipsometer of j.a. The instrument is capable of measuring the optical retardation in nanometers of a birefringent material (e.g., quartz) typically in the wavelength range of 370nm to 2000 nm. The dispersion of the material (R (450)/R (550) or Δ n (450)/Δ n (550)) can be calculated from this data.

The methods for making these measurements were proposed by N.Singh, N.2006, 10 at the national physical laboratory (London, UK) and are entitled "Spectroscopic Ellipsometry, Part1-Theory and Fundamentals, Part 2-Practical samples and Part 3-measurements". Test procedures described in accordance with the delay Measurement (RetMeas) Manual (2002) and WVASE (Woollam variable angle spectroscopic ellipsometer) guidelines (2002) published by j.a. Woollam corporation (lincoln, nebraska, usa). This method was used to determine the retardation of the materials, films and devices described in this invention unless otherwise indicated.

The term "a-plate" refers to an optical retarder utilizing a layer of uniaxially birefringent material with its extraordinary axis oriented parallel to the plane of the layer.

The term "C-plate" refers to an optical retarder utilizing a layer of uniaxially birefringent material with its extraordinary axis oriented perpendicular to the plane of the layer.

In a/C-plates comprising an optically uniaxially birefringent liquid crystal material with a uniform orientation, the optical axis of the film is given by the direction of the extraordinary axis. An a (or C) plate comprising an optically uniaxial birefringent material with positive birefringence is also referred to as a "positive a (or C) plate" or "+ a (or + C) plate".

An a (or C) plate, e.g. a discotic anisotropic material, comprising a film of an optically uniaxial birefringent material with negative birefringence is also referred to as "negative a (or C) plate" or "-a (or C) plate", depending on the orientation of the discotic material. Films made from cholesteric rod material with reflection bands in the UV part of the spectrum also have the optical properties of a negative C-plate.

The birefringence Δ n is defined as follows

Δn＝n_e-n_o

Wherein n is_eExtraordinary refractive index and n_oIs the ordinary refractive index, and the average refractive index n_av.Given by the equation:

n_av.＝((2n_o ²+n_e ²)/3)^1/2

average refractive index n_av.And ordinary refractive index n_oCan be measured using an Abbe refractometer. Δ n can then be calculated from the above equation.

As used herein, plural forms of terms, as the context clearly dictates otherwise, are understood herein to include the singular form, and vice versa.

Unless explicitly stated otherwise, all Physical Properties have been determined according to or according to "Merck Liquid Crystals, Physical Properties of Liquid Crystals" Status 1997, 11 months, Merck KGaA, Germany and are given for a temperature of 20 ℃. The optical anisotropy (. DELTA.n) was measured at a wavelength of 589.3 nm.

If questionable, the definitions as given in c.tschierske, g.pelzl and s.diele, angelw.chem.2004, 116,6340-6368 will apply.

Unless otherwise indicated, in a given formula, the following terms have the following meanings:

"carbyl" means a monovalent or polyvalent organic group containing at least one carbon atom, free of other atoms (such As-C ≡ C-) or optionally containing one or more other atoms such As N, O, S, P, Si, Se, As, Te, or Ge (e.g. carbonyl, etc.). "hydrocarbyl" means a carbonyl group that additionally contains one or more H atoms and optionally one or more heteroatoms, such As N, O, S, P, Si, Se, As, Te, or Ge.

The carbyl or hydrocarbyl group may be a saturated or unsaturated group. Unsaturated groups are, for example, aryl, alkenyl or alkynyl groups. Carbyl or hydrocarbyl groups having greater than 3C atoms can be straight chain, branched, and/or cyclic and can contain spiro-linked or fused rings.

Preferred carbyl and hydrocarbyl radicals are optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy having 1 to 40C atoms, preferably 1 to 25C atoms, particularly preferably 1 to 18C atoms, optionally substituted aryl or aryloxy having 6 to 40C atoms, preferably 6 to 25C atoms, or optionally substituted alkylaryl, arylalkyl, alkylaryloxy, arylalkyloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy having 6 to 40C atoms, preferably 6 to 25C atoms.

Other preferred carbyl and hydrocarbyl radicals are C₁-C₄₀Alkyl radical, C₂-C₄₀Alkenyl radical, C₂-C₄₀Alkynyl, C₃-C₄₀Allyl radical, C₄-C₄₀Alkyldienyl radical, C₄-C₄₀Polyalkenyl radical, C₆-C₄₀Aryl radical, C₆-C₄₀Alkylaryl group, C₆-C₄₀Arylalkyl radical, C₆-C₄₀Alkylaryloxy radical, C₆-C₄₀Arylalkyloxy radical, C₂-C₄₀Heteroaryl group, C₄-C₄₀Cycloalkyl radical, C₄-C₄₀Cycloalkenyl groups, and the like. Particularly preferred is C₁-C₂₂Alkyl radical, C₂-C₂₂Alkenyl radical, C₂-C₂₂Alkynyl, C₃-C₂₂Allyl radical, C₄-C₂₂Alkyldienyl radical, C₆-C₁₂Aryl radical, C₆-C₂₀Arylalkyl and C₂-C₂₀A heteroaryl group.

Other preferred carbyl and hydrocarbyl groups are those having 1 to 40C atoms, preferably 1 to 25C atoms, more preferablyA linear, branched or cyclic alkyl radical selected from 1 to 12C atoms, which is unsubstituted or mono-or polysubstituted by F, Cl, Br, I or CN, and in which one or more non-adjacent CH's are present₂The radicals may each, independently of one another, be substituted by-C (R)^x)＝C(R^x)-、-C≡C-、-N(R^x) -, -O-, -S-, -CO-O-, -O-CO-O-are replaced in such a way that O and/or S atoms are not directly linked to each other.

In the above, R^xPreferably represents H, halogen, a linear, branched or cyclic alkyl chain having 1 to 25C atoms, wherein furthermore one or more non-adjacent C atoms may be replaced by-O-, -S-, -CO-O-, -O-CO-O-, and wherein one or more H atoms may be replaced by fluorine, an optionally substituted aryl or aryloxy group having 6 to 40C atoms or an optionally substituted heteroaryl or heteroaryloxy group having 2 to 40C atoms.

Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, trifluoromethyl, perfluoro-n-butyl, 2,2, 2-trifluoroethyl, perfluorooctyl, perfluorohexyl and the like.

Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, and the like.

Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl and the like.

Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, 2-methylbutoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecoxy, n-dodecoxy and the like.

Preferred amino groups are, for example, dimethylamino, methylamino, methylphenylamino, phenylamino, and the like.

Aryl and heteroaryl groups may be monocyclic or polycyclic, i.e. they may have one ring (such as phenyl) or two or more rings, which may also be fused (such as naphthyl) or covalently linked (such as biphenyl), or contain a combination of fused rings and linked rings. Heteroaryl contains one or more heteroatoms, preferably selected from O, N, S and Se.

Particularly preferred are monocyclic, bicyclic or tricyclic aryl groups having 6 to 25C atoms and monocyclic, bicyclic or tricyclic heteroaryl groups having 2 to 25C atoms, which optionally contain fused rings and which are optionally substituted. Preference is furthermore given to 5-, 6-or 7-membered aryl and heteroaryl, where in addition one or more CH groups may be replaced via N, S or O in such a way that the O atoms and/or S atoms are not directly connected to one another.

Preferred aryl radicals are, for example, phenyl, biphenyl, bitriphenyl, [1,1':3',1 "]-terphenyl-2' -yl, naphthalene, anthracene, binaphthyl, phenanthrene, pyrene, dihydropyrene, perylene,Perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene, spirobifluorene (spirobifluorene), and the like.

Preferred heteroaryl groups are, for example, 5-membered rings, such as pyrrole, pyrazole, imidazole, 1,2, 3-triazole, 1,2, 4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, isoxazole, 1, 2-thiazole, 1, 3-thiazole, 1,2, 3-oxadiazole, 1,2, 4-oxadiazole, 1,2, 5-oxadiazole, 1,3, 4-oxadiazole, 1,2, 3-thiadiazole, 1,2, 4-thiadiazole, 1,2, 5-thiadiazole, 1,3, 4-thiadiazole, 6-membered rings, such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3, 5-triazine, 1,2, 4-triazine, 1,2, 3-triazine, 1,2,4, 5-tetrazine, 1,2,3, 4-tetrazine, 1,2,3, 5-tetrazine or fused radicals, such as indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxaloimidazole, benzoxazole, naphthooxazole, anthraoxazole, phenanthroioxazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5, 6-quinoline, benzo-6, 7-quinoline, benzo-7, 8-quinoline, benzisoquinoline, acridine, phenothiazine, phenoxazine, benzopyridazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacarbazole, benzocarbazine, phenanthridine, phenanthroline, thieno [2,3b ] thiophene, thieno [3,2b ] thiophene, Dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazole thiophene, or combinations of these groups. Heteroaryl groups may also be substituted with alkyl, alkoxy, thioalkyl, fluoro, fluoroalkyl or other aryl or heteroaryl groups.

The (non-aromatic) alicyclic and heterocyclic groups include both saturated rings, i.e. those containing only single bonds, and partially unsaturated rings, i.e. those which may also contain multiple bonds. The heterocycle contains one or more heteroatoms, preferably selected from Si, O, N, S and Se.

The (non-aromatic) alicyclic and heterocyclic groups may be monocyclic, i.e. contain only one ring (e.g. cyclohexane), or polycyclic, i.e. contain multiple rings (e.g. decahydronaphthalene or bicyclooctane). Saturated groups are particularly preferred. Preference is furthermore given to mono-, bi-or tricyclic groups having 3 to 25 atoms, which optionally contain fused rings and which are optionally substituted. Further preferred are 5-, 6-, 7-or 8-membered carbocyclic radicals in which, in addition, one or more C atoms may be replaced by Si and/or one or more CH groups may be replaced by N and/or one or more non-adjacent CH groups₂The groups may be replaced by-O-and/or-S-.

Preferred alicyclic and heterocyclic groups are, for example, 5-membered groups, such as cyclopentane, tetrahydrofuran, tetrahydrothiophene, pyrrolidine; 6-membered groups such as cyclohexane, silacyclohexane (silane), cyclohexene, tetrahydropyran, tetrahydrothiopyran, 1, 3-dioxane, 1, 3-dithiane, piperidine; 7-membered groups, such as cycloheptane; and fused groups such as tetralin, decalin, indane, bicyclo [1.1.1] pentane-1, 3-diyl, bicyclo [2.2.2] octane-1, 4-diyl, spiro [3.3] heptane-2, 6-diyl, octahydro-4, 7-methanoindan-2, 5-diyl.

The aryl, heteroaryl, (non-aromatic) alicyclic and heterocyclic groups optionally bear one or more substituents preferably selected from the group consisting of silyl, sulfonic, sulfonyl, formylRadical, amino radical, imino radical, nitrile radical, mercapto radical, nitro radical, halogen and C_1-12Alkyl radical, C_6-12Aryl radical, C_1-12Alkoxy, hydroxy, or combinations of these groups.

Preferred substituents are, for example, solubility-promoting groups, such as alkyl or alkoxy; electron withdrawing groups such as fluorine, nitro or nitrile; or substituents which serve to raise the glass transition temperature (Tg) of the polymer, especially bulky groups such as tertiary butyl or optionally substituted aryl groups.

Preferred substituents (also referred to below as "L") are, for example, F, Cl, Br, I, OH, -CN, -NO₂、-NCO、-NCS、-OCN、-SCN、-C(＝O)N(R^x)₂、-C(＝O)Y^x、-C(＝O)R^x、-C(＝O)OR^x、-N(R^x)₂Wherein R is^xHaving the meaning mentioned hereinbefore, and Y as defined above^xRepresents halogen; optionally substituted silyl; optionally substituted aryl or heteroaryl having 4 to 40, preferably 4 to 20 ring atoms; and a linear or branched alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group having 1 to 25C atoms, wherein one or more H atoms may optionally be replaced by F or Cl.

"substituted silyl or aryl" preferably means substituted by halogen, -CN, R^y、-OR^y、-CO-R^y、-CO-O-R^y、-O-CO-R^yor-O-CO-O-R^yIs substituted in which R^yRepresents H, a linear, branched or cyclic alkyl chain having 1 to 12C atoms.

In the formulae shown above and below, a substituted phenylene ring

Preferably is

Wherein L, identically or differently on each occurrence, has one of the meanings given above and below, and is preferably F, Cl, CN, NO₂、CH₃、C₂H₅、C(CH₃)₃、CH(CH₃)₂、CH₂CH(CH₃)C₂H₅、OCH₃、OC₂H₅、COCH₃、COC₂H₅、COOCH₃、COOC₂H₅、CF₃、OCF₃、OCHF₂、OC₂F₅Or P-Sp-, very preferably F, Cl, CN, CH₃、C₂H₅、OCH₃、COCH₃、OCF₃Or P-Sp-, most preferably F, Cl, CH₃、OCH₃、COCH₃Or OCF₃。

"halogen" means F, Cl, Br or I, preferably F or Cl, more preferably F.

The term "cycloheteroalkyl ring" or "cycloheteroalkyl" within the meaning of the present invention is indicated to mean a non-aromatic mono-or multicycloalkyl ring comprising at least one heteroatom and may also be referred to as a heterocycloalkyl ring.

The term "alkylaryl" as used in the context of the present invention relates to a group having the structure-alkyl-aryl, which is linked via an alkyl group. Both alkyl and aryl groups comprise substituted groups in this context. With respect to the term "substituted", reference is made to the above comments.

The term "alkylheteroaryl" as used in the context of the present invention relates to a group having an-alkyl-heteroaryl structure, which is linked via an alkyl group. Both alkyl and heteroaryl groups comprise substituted groups in this context. With respect to the term "substituted", reference is made to the above comments.

The "polymerizable group" (P) is preferably selected from groups comprising a C ═ C double bond or a C ≡ C triple bond, and groups suitable for ring-opening polymerization, such as, for example, oxetanyl or epoxy groups.

Preferably, the polymerizable group (P) is selected fromFrom CH₂＝CW¹-COO-、CH₂＝CW¹-CO-、CH₂＝CW²-(O)_k3-、CW¹＝CH-CO-(O)_k3-、CW¹＝CH-CO-NH-、CH₂＝CW¹-CO-NH-、CH₃-CH＝CH-O-、(CH₂＝CH)₂CH-OCO-、(CH₂＝CH-CH₂)₂CH-OCO-、(CH₂＝CH)₂CH-O-、(CH₂＝CH-CH₂)₂N-、(CH₂＝CH-CH₂)₂N-CO-、CH₂＝CW¹-CO-NH-、CH₂＝CH-(COO)_k1-Phe-(O)_k2-、CH₂＝CH-(CO)_k1-Phe-(O)_k2-、Phe-CH＝CH-，

Wherein

W¹Represents H, F, Cl, CN, CF₃Phenyl or alkyl having 1 to 5C atoms, in particular H, F, Cl or CH₃，

W²Represents H or an alkyl group having 1 to 5C atoms, in particular H, methyl, ethyl or n-propyl,

W³and W⁴Each independently of the other represents H, Cl or an alkyl group having 1 to 5C atoms, Phe represents a1, 4-phenylene group which is optionally substituted by one or more groups L as defined above but different from P-Sp, preferably the preferred substituents L are F, Cl, CN, NO₂、CH₃、C₂H₅、OCH₃、OC₂H₅、COCH₃、COC₂H₅、COOCH₃、COOC₂H₅、CF₃、OCF₃、OCHF₂、OC₂F₅And also phenyl, and

k₁、k₂and k₃Each independently of the other represents 0 or 1, k₃Preferably represents 1, and k₄Is an integer from 1 to 10.

Particularly preferred polymerizable groups P are CH₂＝CH-COO-,CH₂＝C(CH₃)-COO-,CH₂＝CF-COO-,CH₂＝CH-,CH₂＝CH-O-,(CH₂＝CH)₂CH-OCO-,(CH₂＝CH)₂CH-O-,Wherein W²Represents H or an alkyl group having 1 to 5C atoms, in particular H, methyl, ethyl or n-propyl.

Further preferred polymerizable groups (P) are vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxy groups, most preferably acrylate or methacrylate, especially acrylate.

Preferably, all of the multireactive polymerizable compounds and subformulae thereof comprise one or more branched groups comprising two or more polymerizable groups P (multireactive polymerizable groups) instead of one or more groups P-Sp-.

Suitable groups of this type and polymerizable compounds comprising them are described, for example, in US 7,060,200B 1 or US 2006/0172090 a 1.

Particular preference is given to polyreactive polymerizable groups selected from the following formulae:

-X-alkyl-CHP^x-CH₂-CH₂P^y I*a

-X-alkyl-C(CH₂P^x)(CH₂P^y)-CH₂P^z I*b

-X-alkyl-CHP^xCHP^y-CH₂P^z I*c

-X-alkyl-C(CH₂P^x)(CH₂P^y)-C_aaH_2aa+1 I*d

-X-alkyl-CHP^x-CH₂P^y I*e

-X-alkyl-CHP^xP^y I*f

-X-alkyl-CP^xP^y-C_aaH_2aa+1 I*g

-X-alkyl-C(CH₂P^v)(CH₂P^w)-CH₂OCH₂-C(CH₂P^x)(CH₂Py)CH₂P^z I*h

-X-alkyl-CH((CH₂)_aaP^x)((CH₂)_bbP^y) I*i

-X-alkyl-CHP^xCHP^y-C_aaH_2aa+1I*k

wherein

alkyl represents a single bond or a linear or branched alkylene group having 1 to 12C atoms, wherein one or more non-adjacent CH groups₂The radicals may each, independently of one another, be substituted by-C (R)^x)＝C(R^x)-、-C≡C-、-N(R^x) -, -O-, -S-, -CO-O-, -O-CO-O-in such a way that O and/or S atoms are not directly linked to one another, and furthermore wherein one or more H atoms may be replaced by F, Cl or CN, wherein R is^xHas one of the above-mentioned meanings and has,

aa and bb each, independently of one another, denote 0, 1,2,3,4, 5 or 6,

x has one of the meanings indicated for X', and

P^vto P^zEach independently of the other having one of the meanings indicated above for P.

Preferred spacer groups Sp are selected from the formula Sp '-X', such that the group "P-Sp-" corresponds to the formula "P-Sp '-X' -", wherein

Sp' represents an alkylene group having 1 to 20, preferably 1 to 12C atoms, which is optionally mono-or poly-substituted by F, Cl, Br, I or CN, and furthermore wherein one or more non-adjacent CH groups₂The radicals may each, independently of one another, be-O-, -S-, -NH-, -NR-^xx-、-SiR^xxR^yy-、-CO-、-COO-、-OCO-、-OCO-O-、-S-CO-、-CO-S-、-NR^xx-CO-O-、-O-CO-NR^0xx-、-NR^xx-CO-NR^yy-, -CH-or-C.ident.C-in such a way that O and/or S atoms are not directly attached to one another,

x' represents-O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR^xx-、-NR^xx-CO-、-NR^xx-CO-NR^yy-、-OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-CF₂CH₂-、-CH₂CF₂-、-CF₂CF₂-、-CH＝N-、-N＝CH-、-N＝N-、-CH＝CR^xx-、-CY^xx＝CY^xx-, -C.ident.C-, -CH-COO-, -OCO-CH-or a single bond,

R^xxand R^yyEach independently of the other represents H or an alkyl radical having 1 to 12C atoms, and

Y^xxand Y^yyEach representing H, F, Cl or CN independently of the other.

X' is preferably- -O- -, - -S- -CO- -, - -COO- -, - -OCO- -, - -O- -COO- -, - -CO- -NR-^xx-、-NR^xx-CO-、-NR^xx-CO-NR^yy-or a single bond.

Typical spacer groups Sp' are, for example- (CH)₂)_p1-、-(CH₂CH₂O)_q1-CH₂CH₂-、-CH₂CH₂-S-CH₂CH₂-、-CH₂CH₂-NH-CH₂CH₂-or- (SiR)^xxR^yy-O)_p1-, wherein p1 is an integer of 1 to 12, q1 is an integer of 1 to 3, and R^xxAnd R^yyHave the meaning mentioned above.

A particularly preferred group-X '-Sp' -is- (CH)₂)_p1-、-O-(CH₂)_p1-、-OCO-(CH₂)_p1-、-OCOO-(CH₂)_p1-, wherein p1 is an integer of 1 to 12.

Particularly preferred radicals Sp' are, for example, in each case linear methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, ethylene, propylene and butylenyl.

In the context of the present invention, it is,

represents trans-1, 4-cyclohexylene, and

represents a1, 4-phenylene group.

For the purposes of the present invention, the group-COO-or-CO₂Is represented byEster groups of (A), and the radicals-OCO-, -O₂C-or-OOC-is represented by formulaEster group of (a).

A "polymer network" is a network in which all polymer chains are connected to each other by a number of cross-linking points to form individual macroscopic entities. The polymer network may appear in the following types:

the graft polymer molecules are branched polymer molecules in which one or more side chains differ from the main chain in structure or configuration.

Star polymer molecules are branched polymer molecules in which a single branch point creates multiple linear chains or arms. If the arms are identical, the star polymer molecules are said to be regular. Star polymer molecules are said to be diverse if adjacent arms are composed of different repeating subunits.

The comb polymer molecules consist of a main chain with two or more tri-directional branching points and linear side chains. If the arms are identical, the comb polymer molecule is said to be regular.

Brush polymer molecules consist of a main chain with linear, unbranched side chains, and wherein one or more of the branching points have a four-way functionality or greater.

Throughout the description and claims of this specification, the words "comprise" and "contain" and variations of the words, for example "comprising" and "comprises", mean "including but not limited to", and are not intended to (and do not) exclude other components. On the other hand, the word "comprising" also encompasses, but is not limited to, the term "consisting of … …".

Throughout the description and claims of this specification, the words "obtainable" and "obtained" and variations of the words mean "including but not limited to", and are not intended to (and do not) exclude other components. On the other hand, the phrase "obtainable" also encompasses, but is not limited to, the term "obtained".

All concentrations are quoted in weight percent and relate to the whole individual mixture, all temperatures are quoted in degrees celsius and all temperature differences are quoted in degrees difference (differential degree).

Detailed Description

Preferably the compound of formula UVI is selected from the following subformulae:

wherein

R⁶And R⁷Each independently represents a hydrogen atom, a hydroxyl group or a halogen atom,

R⁸to R¹³Each independently is a group selected from the group consisting of H, alkyl, aryl, heteroaryl, alkylaryl, alkylheteroaryl, alkenyl, and alkynyl,

X¹represents O or S, and is represented by,

and R is¹⁴And R¹⁵Selected from the group consisting of H, -C (═ O) R⁸Alkyl, alkenyl, alkynyl, aryl, cycloalkyl, heteroaryl and cycloheteroalkyl.

In a preferred embodiment, the compound of formula UVI is selected from the group of compounds wherein R is¹To R⁵At least one of them represents-OH; preferably at least R¹represents-OH.

Thus, the compound of formula UVI is selected from the group of compounds of the following subformulae:

wherein

R⁶And R⁷Each independently represents a hydrogen atom, a hydroxyl group or a halogen atom,

R⁸to R¹³Each independently is a group selected from the group consisting of H, alkyl, aryl, heteroaryl, alkylaryl, alkylheteroaryl, alkenyl, and alkynyl,

X¹represents O or S, and

R¹⁴and R¹⁵Selected from the group consisting of H, -C (═ O) R⁸Alkyl, alkenyl, alkynyl, aryl, cycloalkyl, heteroaryl and cycloheteroalkyl.

In a preferred embodiment, the compound of formula UVI is selected from the group of compounds wherein R is³Or R⁵At least one of them represents-H; preferably R³And R⁵Both represent-H.

Thus, the compound of formula UVI is selected from the group of compounds of the following subformulae:

wherein

R⁶And R⁷Each independently represents a hydrogen atom, a hydroxyl group or a halogen atom,

R⁸to R¹³Each independently is a group selected from the group consisting of H, alkyl, aryl, heteroaryl, alkylaryl, alkylheteroaryl, alkenyl, and alkynyl,

X¹represents O or S, and

R¹⁴and R¹⁵Selected from the group consisting of H, -C (═ O) R⁸Alkyl, alkenyl, alkynyl, aryl, cycloalkyl, heteroaryl and cycloheteroalkyl.

In a preferred embodiment, the compound of formula UVI is selected from the group of compounds wherein R is⁸To R¹³Represents an alkyl group.

Thus, the compound of formula UVI is selected from the group of compounds of the following subformulae:

wherein

R²And R⁴Each independently selected from the group consisting of H, -alkyl, -OH, -alkylaryl, -alkylheteroaryl-cycloalkyl, cycloheteroalkyl, alkenyl, aryl and-SO₃H, and is selected from the group consisting of

R⁶And R⁷Each independently represents hydrogen or halogen, preferably hydrogen

l, k, m, n, o and p are each independently an integer of 2 to 20, preferably 2 to 10, more preferably 2 to 5,

X¹represents O or S, and

R¹⁴and R¹⁵Selected from the group consisting of H, -C (═ O) alkyl, alkenyl, alkynyl, aryl, cycloalkyl, heteroaryl, and cycloheteroalkyl.

In a preferred embodiment, the compound of formula UVI is selected from the group of compounds wherein R is²And R⁴Preferably each independently represents an alkylaryl group, especially an alkylphenyl group, or an alkyl group, especially a linear or branched alkyl group having from 5 to 15 carbon atoms, of which one or more- (CH)₂) The-group may be substituted with-COO-, -OCO-in such a way that no two oxygen atoms are linked together.

In a preferred embodiment, the compound of formula UVI is selected from the group of compounds of the following subformulae:

preferably, the proportion of the compound of formula UVI in the LC medium is from 0.01 to 5% by weight, very preferably from 0.05 to 3% by weight, in particular from 0.1 to 2% by weight, of the total medium.

Compounds of the formula UVI and its subformulae can be analogous to standard works known to the person skilled in the art and described in Organic Chemistry, such as, for example, Houben-Weyl, Methoden der organischen Chemistry [ Methods of Organic Chemistry ]]Thieme-Verlag, Stuttgart. Some of the compounds may also be under the trademark(BASF, Germany), such as328、384、900、928、970 and1130, commercially available.

Preferably, the one or more di-or multireactive mesogenic compounds are selected from the group of compounds of formula DRM

P¹-Sp¹-MG-Sp²-P² DRM

Wherein

P¹And P²Independently of one another, represent a polymerizable group,

Sp¹and Sp²Independently of one another, are a spacer group or a single bond, and

MG is a rod-like mesogenic group, preferably selected from the group consisting of formula MG,

-(A¹-Z¹)_n-A²- MG

wherein

A¹And A²In each case independently of one another, an aromatic or cycloaliphatic radical, which optionally contains one or more heteroatoms selected from the group consisting of N, O and S and optionally via L¹One or more of mono-substitution or multi-substitution,

L¹is P-Sp-, F, Cl, Br, I, -CN, -NO₂、-NCO、-NCS、-OCN、-SCN、-C(＝O)NR⁰⁰R⁰⁰⁰、-C(＝O)OR⁰⁰、-C(＝O)R⁰⁰、-NR⁰⁰R⁰⁰⁰、-OH、-SF₅Optionally substituted silyl, aryl or heteroaryl having 1 to 12C atoms, preferably 1 to 6C atoms, and straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12C atoms, preferably 1 to 6C atoms, wherein one or more H atoms are optionally replaced by F or Cl,

R⁰⁰and R⁰⁰⁰Independently of one another, H or alkyl having 1 to 12C atoms,

Y¹and Y²H, F, Cl or CN are represented independently of each other,

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.

Preferred radicals A¹And A²Including but not limited to furan, pyrrole, thiophene,Oxazole, thiazole, thiadiazole, imidazole, phenylene, cyclohexylene, bicyclooctylene, cyclohexenylene, pyridine, pyrimidine, pyrazine, azulene, indane, fluorene, naphthalene, tetrahydronaphthalene, anthracene, phenanthrene and dithienothiazolesThiophenes, which are all unsubstituted or substituted by 1,2,3 or 4 groups L as defined above.

Particularly preferred radicals A¹And A²Selected from 1, 4-phenylene, pyridine-2, 5-diyl, pyrimidine-2, 5-diyl, thiophene-2, 5-diyl, naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydro-naphthalene-2, 6-diyl, indan-2, 5-diyl, bicyclooctylene or 1, 4-cyclohexylene, wherein one or two non-adjacent CH' s₂The groups are optionally replaced by O and/or S, wherein these groups are unsubstituted or substituted by 1,2,3 or 4 groups L as defined above.

Particularly preferred radicals Z¹Preferably selected independently of one another at each occurrence from-COO-, -OCO-, -CH₂CH₂-、-CF₂O-、-OCF₂-, -C.ident.C-, -CH ═ CH-, -OCO-CH ═ CH-, -CH ═ CH-COO-, or a single bond.

Very preferred di-reactive mesogenic compounds of formula DRM are selected from the following formulae:

wherein

P⁰Independently of one another in the case of a plurality of occurrences, is a polymerizable group, preferably an acryloyl group, methacryloyl group, oxetane group, epoxy group, vinyl group, heptadiene, vinyloxy group, propenyl ether or styryl group,

l, the same or different at each occurrence, has L in Targeted DRM¹One of the meanings given, and independently of one another in each case in a plurality of occurrences, is preferably selected from F, Cl, CN or optionally halogenated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 5C atoms,

r is 0, 1,2,3 or 4,

x and y are independently of one another 0 or the same or different integers from 1 to 12,

z is each and independently 0 or 1, wherein if adjacent x or y is 0, then z is 0.

Especially preferred are compounds of formula DRMa1, DRMa2 and DRMa3, in particular those of formula DRMa 1.

Preferably, the polymerisable LC material further comprises at least one mono-reactive mesogenic compound, preferably selected from the formula MRM,

P¹-Sp¹-MG-R MRM

wherein P is¹、Sp¹And MG has the meaning given in formula DRM,

r is F, Cl, Br, I, -CN, -NO₂、-NCO、-NCS、-OCN、-SCN、-C(＝O)NR^xR^y、-C(＝O)X、-C(＝O)OR^x、-C(＝O)R^y、-NR^xR^y、-OH、-SF₅Optionally substituted silyl, straight-chain or branched alkyl having 1 to 12C atoms, preferably 1 to 6C atoms, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, in which one or more H atoms are optionally replaced by F or Cl,

x is halogen, preferably F or Cl, and

R^xand R^yIndependently of one another, H or alkyl having 1 to 12C atoms.

Preferably, the mono-reactive mesogenic compound of formula MRM is selected from the following formulae:

wherein P is⁰L, r, x, y and z are represented by formula DRMa-1 to formula DRMe as defined in formula (I),

R⁰is alkyl, alkoxy, sulfanyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 or more, preferably 1 to 15, C atoms or represents Y⁰，

Y⁰Is F, Cl, CN, NO₂、OCH₃、OCN、SCN、SF₅Or mono-, oligo-or polyfluorinated alkyl or alkoxy having 1 to 4C atoms,

Z⁰is-COO-, -OCO-, -CH₂CH₂-、-CF₂O-、-OCF₂-, -CH-, -OCO-CH-, -CH-COO-or a single bond,

A⁰independently of one another in multiple occurrences, is unsubstituted or substituted by 1,2,3 or 4 radicals L, or trans-1, 4-cyclohexylene,

u and v are independently of one another 0, 1 or 2,

w is 0 or 1, and

wherein the phenyl ring and the naphthyl ring may additionally be substituted by one or more identical or different radicals L.

More preferred are compounds of formula MRM1, MRM2, MRM3, MRM4, MRM5, MRM6, MRM7, MRM9 and MRM10, especially compounds of formula MRM1, MRM4, MRM6 and MRM7, and in particular compounds of formula MRM1 and MRM 7.

Compounds of formula DRM, MRM and their subformulae can be prepared analogously to Methods known to the person skilled in the art and described in standard works of Organic Chemistry, such as Houben-Weyl, Methoden der organischen Chemistry [ Methods of Organic Chemistry ], Thieme-Verlag, Stuttgart.

The proportion of said mono-, di-or multireactive liquid crystal compound in the polymerizable liquid crystal material according to the invention as a whole 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 in the range of 50 to 99.9% by weight.

In a preferred embodiment, the proportion of the bireactive or multireactive polymerisable mesogenic compound in the polymerisable liquid crystal material according to the invention as a whole is preferably in the range of from 5 to 99% by weight, more preferably in the range of from 10 to 97% by weight, and even more preferably in the range of from 15 to 95% by weight.

In another preferred embodiment, the proportion of mono-reactive polymerisable mesogenic compounds in the polymerisable liquid crystal material according to the present invention as a whole, if present, is preferably in the range of from 5 to 80 wt. -%, more preferably in the range of from 10 to 75 wt. -%, and even more preferably in the range of from 15 to 70 wt. -%.

In another preferred embodiment, the proportion of the multireactive polymerisable mesogenic compound, if present, in the polymerisable liquid crystal material according to the invention as a whole is preferably in the range of from 1 to 30 wt. -%, more preferably in the range of from 2 to 20 wt. -%, and even more preferably in the range of from 3 to 10 wt. -%.

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

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

In another preferred embodiment, the polymerisable LC material is achiral, i.e. it does not contain any chiral polymerisable mesogenic or other chiral compounds.

In another preferred embodiment, the polymerisable LC material comprises at least one mono-reactive mesogenic compound, preferably selected from the group consisting of formula MRM-1, at least one di-reactive mesogenic compound, preferably selected from the group consisting of formula DRMa-1, and one or more compounds of formula UVI.

In another preferred embodiment, the polymerisable LC material comprises at least one mono-reactive mesogenic compound, preferably selected from the group consisting of formula MRM-7, at least one di-reactive mesogenic compound, preferably selected from the group consisting of formula DRMa-1, and one or more compounds of formula UVI.

In another preferred embodiment, the polymerisable LC material comprises at least two mono-reactive mesogenic compounds, preferably selected from compounds of formula MRM-1 and/or MRM-7, at least one di-reactive mesogenic compound, preferably selected from compounds of formula DRMa-1, and one or more compounds of formula UVI.

In another preferred embodiment, the polymerisable LC material comprises at least two mono-reactive mesogenic compounds, preferably selected from compounds of formula MRM-1 and/or MRM-7, at least two di-reactive mesogenic compounds, preferably selected from compounds of formula DRMa-1, and one or more compounds of formula UVI.

In another preferred embodiment, the polymerisable LC material comprises at least two di-reactive mesogenic compounds, preferably selected from compounds of formula DRMa-1, and one or more compounds of formula UVI.

In another preferred embodiment, especially for negative optical dispersion applications, the polymerizable LC material as described above additionally comprises one or more compounds of formula ND,

wherein

U^1,2Independently of one another, are selected from

Including their mirror images, in which the ring U is¹And U²Each bonded to the group- (B) through an upright bond_q-, and one or two non-adjacent CH's in these rings₂The radicals being optionally replaced by O and/or S, and a ring U¹And U²Optionally substituted by one or more groups L,

l has L in Targeted DRM, the same or different at each occurrence¹One of the meanings given, and in the case of a plurality of occurrences preferably independently of one another, is selected from F, Cl, CN or optionally halogenated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 5C atoms,

Q^1,2independently of one another, is CH or SiH,

Q³is C or Si, and is characterized in that,

each occurrence of B is independently of the other-C.ident.C-, -CY¹＝CY²-or an optionally substituted aromatic or heteroaromatic group,

Y^1,2independently of one another, H, F, Cl, CN or R⁰，

q is an integer from 1 to 10, preferably 1,2,3,4, 5,6 or 7,

R⁰and R⁰⁰Independently of one another, H or alkyl having 1 to 12C atoms,

m and n are each independently of the other 0, 1,2,3 or 4,

o and p are independently of one another 0, 1,2,3 or 4,

R^1-5independently of one another, are identical or different radicals selected from: H. halogen, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C(＝O)NR⁰R⁰⁰、-C(＝O)R⁰、-NH₂、-NR⁰R⁰⁰、-SH、-SR⁰、-SO₃H、-SO₂R⁰、-OH、-NO₂、-CF₃、-SF₅P-Sp-, optionally substituted silyl, or carbyl or hydrocarbyl radicals having 1 to 40C atoms which are optionally substituted and optionally contain one or more heteroatoms, or represents P or P-Sp-, or is substituted by P or P-Sp-, wherein the compound contains at least one group R^1-5The group represents P or P-Sp-or is substituted by P or P-Sp-,

p is a polymerizable group, and P is a polymerizable group,

sp is a spacer group or a single bond.

Preferably, the child groups forming the bridging group B in formula ND are preferably selected from groups having a bond angle in the range of 120 ° or more, preferably 180 °. Very particular preference is given to a-C.ident.C-group or a divalent aromatic group which is linked in the para-position to its vicinal radical, such as, for example, 1, 4-phenylene, naphthalene-2, 6-diyl, indan-2, 6-diyl or thieno [3,2-b ] thiophene-2, 5-diyl.

Further possible sub-groups include-CH-, -CY ═ CH-¹＝CY²-, -CH ═ N-, -N ═ CH-, -N ═ N-and-CH ═ CR⁰-, in which Y¹、Y²、R⁰Having the meaning given above.

Preferably in formula ND bridging group or- (B)_q-comprises one or more groups selected from-C ≡ C-, optionally substituted 1, 4-phenylene and optionally substituted 9H-fluoren-2, 7-diyl. In formula ND the radicals or B are preferably selected from the group consisting of-C.ident.C-, optionally substituted 1, 4-phenylene and optionally substituted 9H-fluoren-2, 7-diyl, in which the H atom in the fluorenyl group in position 9 is optionally replaced by a carbon radical or a hydrocarbon radical.

Very particular preference is given to bridging groups of the formula ND or- (B)_q-is selected from the group consisting of-C.ident.C-, -C.ident.C-,

wherein r is 0, 1,2,3 or 4, and L has the meaning as described below.

Preferably, the bridging group is attached to a non-aromatic ring of the mesogenic group, such as U in formula ND¹And U²Preferably selected from Wherein R is⁵As defined in formula ND.

Preferably, the aromatic radical A in formula ND^1-4May be monocyclic, i.e. having only one aromatic ring (such as for example phenyl or phenylene), or polycyclic, i.e. having two or more fused rings (such as for example naphthyl or naphthylene). Particular preference is given to mono-, bi-or tricyclic aromatic or heteroaromatic groups having up to 25C atoms, which may also contain fused rings and are optionally substituted.

Preferably, in the compounds of the formula ND, non-aromatic carbocycles and heterocycles A^1-4Included are those that are saturated (also referred to as "fully saturated"), i.e., they contain only C atoms or heteroatoms attached by single bonds, and unsaturated (also referred to as "partially saturated"), i.e., they also contain C atoms or heteroatoms attached by double bonds. The non-aromatic ring may also comprise one or more heteroatoms, preferably selected from Si, O, N and S.

Preferably in formula ND, non-aromatic and aromatic rings or A^1-4Selected from trans-1, 4-cyclohexylene and 1, 4-phenylene, optionally substituted with one or more groups L.

Very particular preference is given to compounds of the formula ND in which m and p are 1 and n and o are 1 or 2. Further preferred are compounds of formula ND, wherein m and p are 1 or 2, and n and o are 0. Further preferred are compounds wherein m, n, o and p are 2.

In the compounds of the formula ND, the connecting group connecting the aromatic and nonaromatic cyclic groups in the mesogenic group or Z^1-4Preferably selected from-O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR-⁰-、-NR⁰-CO-、-NR⁰-CO-NR⁰-、-OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-CH₂CH₂-、-(CH₂)₃-、-(CH₂)₄-、-CF₂CH₂-、-CH₂CF₂-、-CF₂CF₂-、-CH＝CH-、-CY¹＝CY²-、-CH＝N-、-N＝CH-、-N＝N-、-CH＝CR⁰-、-C≡C-、-CH＝CH-COO-、-OCO-CH＝CH-、CR⁰R⁰⁰Or a single bond, very preferably selected from-COO-, -OCO-and single bonds.

Preferably, in the compound of formula ND, the substituents on the ring, such as L, are preferably selected from the group consisting of P-Sp-, F, Cl, Br, I, -CN, -NO₂、-NCO、-NCS、-OCN、-SCN、-C(＝O)NR⁰R⁰⁰、-C(＝O)X、-C(＝O)OR⁰、-C(＝O)R⁰、-NR⁰R⁰⁰、-OH、-SF₅Optionally substituted silyl, aryl or heteroaryl having 1 to 12C atoms, preferably 1 to 6C atoms, and straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12C atoms, preferably 1 to 6C atoms, wherein one or more H atoms are optionally replaced by F or Cl, wherein R is⁰And R⁰⁰As defined in formula ND, and X is halogen.

Preferably, the compound of formula ND comprises one or more terminal groups such as R substituted with two or more polymerizable groups P or P-Sp-^1-4Or substituents such as R⁵(polyfunctional polymerizable group). Suitable multifunctional polymerizable groups of this type are disclosed, for example, in US 7,060,200B 1 or US 2006/0172090 a 1.

Very preferred compounds of the formula ND are those of the following subformula:

wherein R is^1-5、A^1-4、Z^1-4B, m, n, o, p and q have one of the meanings given above.

Particular preference is given to compounds of the following sub-formulae:

wherein Z has Z as given above¹Has a R other than P-Sp-as given above¹And P, Sp, L and r are as defined above, and in the mesogenic groups the phenyl ring is optionally substituted by one or more groups L as defined above.

Furthermore, preference is given to polymerizable liquid-crystalline media in which the compound of formula ND is selected from compounds of formula ND 25 or ND 26, in particular in which Z represents-COO-, r is 0 at each occurrence, and P, Sp is as defined above.

In these preferred compounds P-Sp-is preferably P-Sp ' -X ', where X ' is preferably-O-, -COO-or-OCOO-.

Compounds of formula ND, subformulae thereof and suitable synthetic methods therefor are disclosed in WO 2008/119427 a 1.

The amount of the compound of formula ND in the polymerisable LC material is preferably 1 to 50%, very preferably 1 to 40%.

Especially the combination of a compound of formula UVI with a compound of formula ND results in a beneficial reduction of light dispersion and in a beneficial thermal durability of light dispersion and/or retardation compared to a polymerisable LC material not utilizing this particular combination.

In another preferred embodiment, the polymerizable LC material optionally comprises one or more additives selected from the group consisting of: further polymerization initiators, antioxidants, surfactants, stabilizers, catalysts, sensitizers, inhibitors, chain transfer agents, co-reactive monomers, reactive visbreaking agents, surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, adhesives, flow improvers, degassing or defoaming agents, deaerators, diluents, reactive diluents, auxiliaries, colorants, dyes, pigments and additives for nanoparticles.

In a further preferred embodiment, the polymerisable LC material optionally comprises one or more additives selected from polymerisable non-mesogenic compounds (reactive detackifiers). The amount of these additives in the polymerisable LC material is preferably 0 to 30%, very preferably 0 to 25%.

The reactive viscosity-reducing agents used are not only what are referred to in the practical sense as reactive viscosity-reducing agents, but also the auxiliary compounds already mentioned above, which comprise one or more complementary reactive units or polymerizable groups P, for example hydroxyl groups, thiol groups or amino groups, by means of which reaction with the polymerizable units of the liquid-crystalline compound can take place.

Generally, the photopolymerizable substances include, for example, mono-, di-or polyfunctional compounds containing at least one olefinic double bond. Examples thereof are vinyl esters of carboxylic acids, such as vinyl esters of lauric acid, myristic acid, palmitic acid and stearic acid, and vinyl esters of dicarboxylic acids, such as vinyl esters of succinic acid, adipic acid, allyl and vinyl ethers of monofunctional alcohols and methacrylic acid and acrylic esters, such as allyl and vinyl ethers and methacrylic acid esters and acrylic esters of lauryl alcohol, myristyl alcohol, palmityl alcohol and stearyl alcohol, and diallyl and divinyl ethers of difunctional alcohols, such as diallyl and divinyl ethers of ethylene glycol and 1, 4-butanediol.

Also suitable are, for example, methacrylates and acrylates of polyfunctional alcohols, in particular those which, in addition to the hydroxyl groups, contain no further functional groups or at most ether groups. Examples of such alcohols are difunctional alcohols, such as ethylene glycol, propylene glycol and their higher condensed representatives, for example diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and the like, butanediol, pentanediol, hexanediol, neopentyl glycol, alkoxylated phenolic compounds, such as ethoxylated and propoxylated bisphenols, cyclohexanedimethanol, trifunctional and polyfunctional alcohols, such as glycerol, trimethylolpropane, butanetriol, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, and also the corresponding alkoxylated, in particular ethoxylated and propoxylated, alcohols.

Other suitable reactive viscosity reducers are polyester (meth) acrylates, which are (meth) acrylates of polyester polyols.

Examples of suitable polyester polyols are those which can be prepared by esterifying polycarboxylic acids, preferably dicarboxylic acids, with polyhydric alcohols, preferably diols. Starting materials for such hydroxyl-containing polyesters are known to those skilled in the art. Dicarboxylic acids which may be used are succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid and isomers and hydrogenation products thereof, and esterifiable or ester-transferable derivatives of the acids, such as anhydrides and dialkyl esters. Suitable polyols are the alcohols mentioned above, preferably ethylene glycol, 1, 2-and 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, cyclohexanedimethanol and polyglycols of the ethylene and propylene glycol type.

Further suitable reactive viscosity reducers are 1, 4-divinylbenzene, triallylcyanurate, the acrylic esters of tricyclodecenyl alcohols of the formula

Also known as dihydrodicyclopentadienyl acrylate, and allyl esters of acrylic acid, methacrylic acid and cyanoacrylate.

Among the reactive visbreaking agents mentioned by way of example, in particular and in view of the preferred compositions mentioned above, those comprising photopolymerizable groups are used.

Such groups include, for example, diols and polyols, such as ethylene glycol, propylene glycol and their higher condensed representatives, for example diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and the like, butanediol, pentanediol, hexanediol, neopentyl glycol, cyclohexanedimethanol, glycerol, trimethylolpropane, butanetriol, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol and also the corresponding alkoxylated, in particular ethoxylated and propoxylated, alcohols.

In addition, the groups also include, for example, alkoxylated phenolic compounds, such as ethoxylated and propoxylated bisphenols.

Furthermore, these reactive viscosity reducers may be, for example, epoxy or urethane (meth) acrylates.

For example, epoxy (meth) acrylates are those obtainable by reacting epoxidized olefins or poly-or diglycidyl ethers, such as bisphenol a diglycidyl ether, with (meth) acrylic acid, as are known to the person skilled in the art.

In particular, urethane (meth) acrylates are likewise known to the person skilled in the art as products of the reaction of hydroxyalkyl (meth) acrylates with poly-or diisocyanates.

Such epoxy and urethane (meth) acrylates are included as "mixed forms" in the compounds listed above.

If reactive viscosity-reducing agents are used, their amounts and properties must be matched to the respective conditions, so that on the one hand a satisfactory desired effect, for example a desired coloration of the composition according to the invention, is achieved, but on the other hand the phase behavior of the liquid-crystalline composition is not excessively impaired. For example, low cross-linked (high cross-linked) liquid crystal compositions can be prepared using corresponding reactive viscosity reducers having relatively low (high) numbers of reactive units per molecule.

For example, the group of diluents includes:

C1-C4-alcohols, such as methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, sec-butanol, and in particular C5-C12-alcohol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol and n-dodecanol and isomers thereof, glycols, such as 1, 2-ethanediol, 1, 2-and 1, 3-propanediol, 1,2-, 2, 3-and 1, 4-butanediol, di-and triethylene glycol and di-and tri-propanediol, ethers, such as methyl tert-butyl ether, 1, 2-ethanediol mono-and di-methyl ether, 1, 2-ethanediol mono-and di-ethyl ether, 3-methoxypropanol, 3-isopropoxypropanol, tetrahydrofuran and dioxane, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), C1-C5-alkyl esters, such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate and amyl acetate, aliphatic and aromatic hydrocarbons, such as pentane, hexane, heptane, octane, isooctane, petroleum ether, toluene, xylene, ethylbenzene, tetrahydronaphthalene, decahydronaphthalene, dimethylnaphthalene, white mineral spirits, and mixtures of these,Andmineral oils, such as gasoline, kerosene, diesel oil and heating oil, and also natural oils, such as olive oil, soybean oil, rapeseed oil, linseed oil and sunflower oil.

It is of course also possible to use mixtures of these diluents in the compositions according to the invention.

These diluents may also be mixed with water as long as there is at least partial miscibility. Examples of suitable diluents here are C1-C4-alcohols, such as methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol and sec-butanol, diols, such as 1, 2-ethanediol, 1, 2-and 1, 3-propanediol, 1,2-, 2, 3-and 1, 4-butanediol, di-and tri-ethanediol and di-and tri-propanediol, ethers, such as tetrahydrofuran and dioxane, ketones, such as acetone, methyl ethyl ketone and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), and C1-C4-alkyl esters, such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate.

The diluent is optionally used in a proportion of about 0 to 10.0 wt%, preferably about 0 to 5.0 wt%, based on the total weight of the polymerizable LC material.

The antifoaming agent and degassing agent (c1)), the lubricant and flow aid (c2)), the thermal curing or radiation curing aid (c3)), the substrate wetting aid (c4)), the wetting and dispersing aid (c5), the water repellent agent (c6)), the adhesion promoter (c7)) and the aid promoting scratch resistance (c8)) cannot be strictly defined from each other in their roles.

For example, lubricants and flow aids are also often used as defoamers and/or deaerators and/or aids to promote scratch resistance. The radiation curing aids may also act as lubricants and flow aids and/or deaerators and/or substrate wetting aids. In each case, some of these auxiliaries can also fulfill the function of adhesion promoter (c 8)).

Corresponding to what has been described above, certain additives can therefore be classified into several groups c1) to c8) described below.

In group c1) the antifoam agent comprises silicon-free and silicon-containing polymers. The silicon-containing polymers are, for example, unmodified or modified polydialkylsiloxanes or branched, comb or block copolymers comprising polydialkylsiloxane and polyether units, the latter being obtainable from ethylene oxide or propylene oxide.

Deaerators in group c1) include, for example, organic polymers, such as polyethers and polyacrylates, dialkyl polysiloxanes, in particular dimethyl polysiloxanes, organically modified polysiloxanes, such as arylalkyl-modified polysiloxanes, and fluorosilicones.

The action of the antifoam is essentially based on preventing the formation of foam or destroying foam which has already formed. In the medium to be degassed, for example in the composition according to the invention, the antifoam acts essentially by promoting the coalescence of finely divided gas or air bubbles to give larger bubbles and thus accelerating the evolution of gas (or air). Since defoamers are often also used as deaerators and vice versa, these additives have been included together in group c 1).

For example, such an adjuvant may be available from Tego toFoamex 800、Foamex 805、Foamex 810、Foamex 815、Foamex 825、Foamex 835、Foamex 840、Foamex 842、Foamex 1435、Foamex 1488、Foamex 1495、Foamex 3062、Foamex 7447、Foamex 8020、Foamex N、Foamex K 3、Antifoam 2-18、Antifoam 2-18、Antifoam 2-57、Antifoam 2-80、Antifoam 2-82、Antifoam 2-89、Antifoam 2-92、Antifoam 14、Antifoam 28、Antifoam 81、Antifoam D 90、Antifoam 93、Antifoam 200、Antifoam 201、Antifoam 202、Antifoam 793、Antifoam 1488、Antifoam 3062、5803、5852、5863、7008、Antifoam 1-60、Antifoam 1-62、Antifoam 1-85、Antifoam 2-67、Antifoam WM 20、Antifoam 50、Antifoam 105、Antifoam 730、Antifoam MR 1015、Antifoam MR 1016、Antifoam 1435、Antifoam N、Antifoam KS 6、Antifoam KS 10、Antifoam KS 53、Antifoam KS 95、Antifoam KS 100、Antifoam KE 600、Antifoam KS 911、Antifoam MR 1000、Antifoam KS 1100、Airex 900、Airex 910、Airex 931、Airex 935、Airex 936、Airex 960、Airex 970、Airex 980 andairex 985 is commercially available and available from BYK to Andare commercially available.

The auxiliaries in group c1) are optionally used in a proportion of about 0 to 3.0% by weight, preferably about 0 to 2.0% by weight, based on the total weight of the polymerizable LC material.

In group c2), lubricants and flow aids generally include silicon-free and silicon-containing polymers, such as polyacrylates or modifiers, low molecular weight polydialkylsiloxanes. The modification is that some of the alkyl groups have been replaced by a wide variety of organic groups. These organic groups are for example polyether, polyester or even long chain (fluorinated) alkyl groups, the former being most commonly used.

In the correspondingly modified polysiloxanes the polyether groups are generally composed of ethylene oxide and/or propylene oxide units. In general, the higher the proportion of these alkylene oxide units in the modified polysiloxane, the more hydrophilic the resulting product is.

For example, such an adjuvant may be available from Tego toGlide 100、Glide ZG 400、Glide 406、Glide 410、Glide 411、Glide 415、Glide 420、Glide 435、Glide 440、Glide 450、Glide A 115、Glide B1484 (which may also be used as defoamer and deaerator),Flow ATF、Flow 300、Flow 460、Flow 425 andflow ZFS 460 is commercially available. Suitable radiation-curable lubricants and flow assistants, which can also be used for improving scratch resistance, are productsRad 2100、Rad 2200、Rad 2500、Rad 2600 andrad 2700, also available from TEGO.

For example, such auxiliaries may also be obtained from BYK or BYK Thus obtaining the product.

Such auxiliaries are also available, for example, from 3M, e.g.

Such auxiliaries are also available, for example, from Cytonix, e.g.Or

Such auxiliaries are also available, for example, from Merck KGaA, e.g.2300 and2500。

the auxiliaries in group c2) are optionally used in an amount of about 0 to 3.0 wt. -%, preferably about 0 to 2.0 wt. -%, based on the total weight of the polymerizable LC material.

In group c3), the radiation-curing auxiliaries include, in particular, polysiloxanes having terminal double bonds, for example components in which the terminal double bonds are acrylate groups. Such auxiliaries can be crosslinked by actinic or, for example, electron radiation. These adjuvants usually combine several properties. In the uncrosslinked state they can be used as defoamers, deaerators, lubricants and flow aids and/or substrate wetting aids, whereas in the crosslinked state they improve in particular the scratch resistance of, for example, coatings or films which can be produced using the compositions according to the invention. The improvement in the gloss properties of precisely for example those coatings or films is basically considered to be the result of these auxiliary actions as defoamers, deaerators and/or lubricants and flow aids (in the uncrosslinked state).

Examples of suitable radiation curing auxiliaries are products obtainable from TEGORad 2100、Rad 2200、Rad 2500、Rad 2600 andrad 2700 and product available from BYK

In group c3), the thermal curing auxiliaries contain, for example, primary OH groups which are capable of reacting with, for example, isocyanate groups of the adhesive.

Examples of useful thermal curing aids are the products available from BYK And

the auxiliaries in group c3) are optionally used in a proportion of about 0 to 5.0% by weight, preferably about 0 to 3.0% by weight, based on the total weight of the polymerizable LC material.

The substrate wetting aids in group c4) are used in particular for improving the wettability of a substrate to be printed or coated, for example, by a printing ink or coating composition (e.g. a composition according to the invention). The often accompanying improvement in the lubricating and flow behaviour of such printing ink or coating compositions has an effect on the appearance of the finished (e.g. crosslinked) print or coating.

A wide variety of such adjuvants are available, for example, from Tego andWet KL 245、Wet 250、wet 260 andwet ZFS 453 and from BYK to Andare commercially available.

The auxiliaries in group c4) are optionally used in a proportion of about 0 to 3.0% by weight, preferably about 0 to 1.5% by weight, based on the total weight of the liquid-crystal composition.

The wetting and dispersing assistants from group c5) are used in particular to prevent flooding and blooming and sedimentation of the pigments and are therefore, if necessary, particularly suitable for use in pigmented compositions.

These auxiliaries stabilize the pigment dispersion essentially by electrostatic repulsion and/or steric hindrance of the pigment particles comprising these additives, wherein in the latter case the interaction of the auxiliaries with the surrounding medium (e.g. the binder) plays an important role.

Since the use of such wetting and dispersing aids is a common practice, for example, in the field of printing inks and paint technology, the selection of suitable aids of this type generally does not bring any difficulty to the person skilled in the art (if they are used).

Such wetting and dispersing aids may be, for example, available from Tego andDispers 610、Dispers 610S、Dispers 630、Dispers 700、Dispers 705、Dispers 710、Dispers 720 W、Dispers 725 W、Dispers 730 W、dispers 735W anddispers 740W and slave BYK to Andare commercially available.

The amount of auxiliaries in group c5) is used as the average molecular weight of the auxiliaries. In any case, therefore, preliminary experiments are advisable, but this can be done simply by the person skilled in the art.

The hydrophobizing agents in group c6) can be used to impart hydrophobic properties to, for example, prints or coatings produced using the compositions according to the invention. This prevents or at least greatly inhibits swelling due to water absorption and thus changes in the optical properties of, for example, such prints or coatings. Furthermore, when the composition is used as a printing ink, for example in offset printing, water absorption can thereby be prevented or at least greatly reduced.

Such hydrophobing agents may be for example from Tego to TegoPhobe WF、Phobe 1000、Phobe 1000 S、Phobe 1010、Phobe 1030、Phobe 1010、Phobe 1010、Phobe 1030、Phobe 1040、Phobe 1050、Phobe 1200、Phobe 1300、Phobe 1310 andphobe 1400 is commercially available.

The auxiliaries in group c6) are optionally used in a proportion of about 0 to 5.0% by weight, preferably about 0 to 3.0% by weight, based on the total weight of the polymerizable LC material.

Additional adhesion promoters from group c7) were used to improve the adhesion of the two interfaces in contact. It is thus immediately apparent that essentially the only portion of the effective adhesion promoter is that at one or the other interface or both interfaces. If, for example, it is desired to apply liquid or paste-like printing inks, coating compositions or paints to a solid substrate, this usually means that adhesion promoters have to be added directly to the latter or that the substrate (also referred to as primed) has to be pretreated with adhesion promoters, i.e. to impart altered chemical and/or physical surface properties to the substrate.

If the substrate has been primed beforehand with a primer, this means that the interface in contact is the interface of the primer on the one hand and the interface of the printing ink or coating composition or paint on the other hand. In this case, not only the adhesion properties between the substrate and the primer but also the adhesion properties between the substrate and the printing ink or coating composition or lacquer play a role in the adhesion of the entire multilayer structure on the substrate.

Adhesion promoters which may be mentioned in a broader sense are also substrate wetting aids which have already been listed under group c4), but these generally do not have the same adhesion promoting ability.

The diversity of the adhesion promoter systems is not surprising in view of the widely varying physical and chemical properties of the substrates and of the printing inks, coating compositions and paints intended for their printing or coating, for example.

Silane-based adhesion promoters are, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane and vinyltrimethoxysilane. These and other silanes are available from Huls exampleSuch as under the trade nameAre commercially available.

Corresponding technical information from the manufacturer of such additives should generally be used or can be obtained in a simple manner by a person skilled in the art by corresponding preliminary experiments.

However, if these additives are to be added to the polymerizable LC material according to the invention as an aid from group c7), their proportion optionally corresponds to about 0 to 5.0 wt. -%, based on the total weight of the polymerizable LC material. These concentration data are only used as a guide, as the amount and identity (identity) of the additives is determined in each individual case by the nature of the substrate and the printing/coating composition. For this case, corresponding technical information is generally available from the manufacturer of such additives or can be determined in a simple manner by a person skilled in the art by corresponding preliminary experiments.

Adjuvants for improving scratch resistance in group c8) include, for example, the products available from Tego mentioned aboveRad 2100,Rad 2200,Rad 2500,Rad 2600 andRad 2700。

the data given for the amounts of group c3) also apply to these auxiliaries, i.e. these additives are optionally used in a proportion of about 0 to 5.0% by weight, preferably about 0 to 3.0% by weight, based on the total weight of the liquid-crystal composition.

Examples of other light, heat and/or oxidation stabilizers which may be mentioned are the following:

alkylated monophenols, for example 2, 6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4, 6-dimethylphenol, 2, 6-di-tert-butyl-4-ethylphenol, 2, 6-di-tert-butyl-4-n-butylphenol, 2, 6-di-tert-butyl-4-isobutylphenol, 2, 6-dicyclopentyl-4-methylphenol, 2- (. alpha. -methylcyclohexyl) -4, 6-dimethylphenol, 2, 6-dioctadecyl-4-methylphenol, 2,4, 6-tricyclohexylphenol, 2, 6-di-tert-butyl-4-methoxymethylphenol, nonylphenols having linear or branched side chains, for example 2, 6-dinonyl-4-methylphenol, 2, 4-dimethyl-6- (1 '-methylundec-1' -yl) phenol, 2, 4-dimethyl-6- (1 '-methylheptadec-1' -yl) phenol, 2, 4-dimethyl-6- (1 '-methyltridec-1' -yl) phenol and mixtures of these compounds, alkylthiomethylphenols, such as 2, 4-dioctylthiomethyl-6-tert-butylphenol, 2, 4-dioctylthiomethyl-6-methylphenol, 2, 4-dioctylthiomethyl-6-ethylphenol and 2, 6-di-dodecyl-thiomethyl-4-nonylphenol,

hydroquinones and alkylated hydroquinones, for example 2, 6-di-tert-butyl-4-methoxyphenol, 2, 5-di-tert-butylhydroquinone, 2, 5-di-tert-amylhydroquinone (2, 5-di-tert-amylhydroquinone), 2, 6-diphenyl-4-octadecyloxyphenol, 2, 6-di-tert-butylhydroquinone, 2, 5-di-tert-butyl-4-hydroxyanisole, 3, 5-di-tert-butyl-4-hydroxyphenyl stearate and bis (3, 5-di-tert-butyl-4-hydroxyphenyl) adipate,

tocopherols, such as alpha-tocopherol, beta-tocopherol, gamma-tocopherol, delta-tocopherol and mixtures of these compounds, and tocopherol derivatives, such as tocopheryl acetate, succinate, nicotinate and polyoxyethylene succinate ("tocoferlate"),

hydroxylated thiodiphenyl ethers, such as 2,2 '-thiobis (6-tert-butyl-4-methylphenol), 2' -thiobis (4-octylphenol), 4 '-thiobis (6-tert-butyl-3-methylphenol), 4' -thiobis (6-tert-butyl-2-methylphenol), 4 '-thiobis (3, 6-di-sec-amylphenol) and 4, 4' -bis (2, 6-dimethyl-4-hydroxyphenyl) disulfide,

alkylidenebisphenols, for example 2, 2' -methylenebis (6-tert-butyl-4-methylphenol), 2' -methylenebis (6-tert-butyl-4-ethylphenol), 2' -methylenebis [ 4-methyl-6- (. alpha. -methylcyclohexyl) phenol ], 2' -methylenebis (4-methyl-6-cyclohexylphenol), 2' -methylenebis (6-nonyl-4-methylphenol), 2' -methylenebis (4, 6-di-tert-butylphenol), 2-ethylenebis (4, 6-di-tert-butylphenol), 2' -ethylenebis (6-tert-butyl-4-isobutylphenol), 2,2 '-methylenebis [6- (. alpha. -methylbenzyl) -4-nonylphenol ], 2' -methylenebis [6- (. alpha.,. alpha. -dimethylbenzyl) -4-nonylphenol ], 4 '-methylenebis (2, 6-di-tert-butylphenol), 4' -methylenebis (6-tert-butyl-2-methylphenol), 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2, 6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1, 3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2, 6-bis (3-tert-butyl-5-methyl-2-hydroxyphenyl) butane, 2 '-methylenebis [6- (. alpha.,. alpha. -dimethylbenzyl) -4-nonylphenol ], 2' -methylenebis [6- (. alpha.,. alpha. -dimethylbenzyl) -4-nonylphenol ], 4-methylenebis [ 5-hydroxy-2-methylphenyl ] butane, 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 4-methyl-2, 4-methyl-phenol, 4-methyl-phenyl, 4, and, 1, 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl-mercaptobutane, ethylene glycol bis [3, 3-bis (3 '-tert-butyl-4' -hydroxyphenyl) butyrate ], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3 '-tert-butyl-2' -hydroxy-5 '-methylbenzyl) -6-tert-butyl-4-methylphenyl ] terephthalate, 1-bis (3, 5-dimethyl-2-hydroxyphenyl) butane, 2-bis (3, 5-di-tert-butyl-4-hydroxyphenyl) propane, ethylene glycol bis [3, 3' -di (3 '-tert-butyl-4' -hydroxyphenyl) butyrate ], bis (3-tert-butyl-4-methylphenyl) dicyclopentadiene, ethylene glycol bis [2- (3,5 '-tert-butyl-4' -methyl-phenyl) butyrate ], bis (3, 5-dimethyl-2-hydroxyphenyl) butane, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenyl) propane, 2-butyl-methyl-4-butyl-methyl-hydroxy-phenyl) propane, 2-butyl-propane, 2-hydroxy-butyl-methyl-ethyl-butyl-1, 2-butyl-hydroxy-ethyl-methyl-ethyl-butyl-methyl-ethyl-4-phenyl-butyl-ethyl-methyl-4-butyl-4-ethyl-methyl-ethyl-butyl-ethyl-butyl-methyl-4-phenyl-butyl-4-ethyl-4-butyl-4-butyl-ethyl-benzene, 2, 2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecyl-mercaptobutane and 1,1,5, 5-tetrakis (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane,

o-, N-and S-benzyl compounds, for example 3,5, 3', 5 ' -tetra-tert-butyl-4, 4 ' -dihydroxydibenzyl ether, octadecyl-4-hydroxy-3, 5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3, 5-di-tert-butylbenzylmercaptoacetate, tris (3, 5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) dithioterephthalate, bis (3, 5-di-tert-butyl-4-hydroxybenzyl) sulfide and isooctyl-3, 5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,

aromatic hydroxybenzyl compounds, such as 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -2,4, 6-trimethyl-benzene, 1, 4-bis (3, 5-di-tert-butyl-4-hydroxybenzyl) -2,3,5, 6-tetramethyl-benzene and 2,4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) phenol,

triazine Compounds, for example 2, 4-bis (octylmercapto) -6- (3, 5-di-tert-butyl-4-hydroxyanilino) -1,3, 5-triazine, 2-octylmercapto-4, 6-bis (3, 5-di-tert-butyl-4-hydroxyphenoxy) -1,3, 5-triazine, 2,4, 6-tris (3, 5-di-tert-butyl-4-hydroxyphenoxy) -1,2, 3-triazine, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanurate, 2,4, 6-tris (3, 5-di-tert-butyl-4-hydroxyphenylethyl) -1,3, 5-triazine, 1,3, 5-tris- (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1, 3, 5-triazine, 1,3, 5-tris (3, 5-dicyclohexyl-4-hydroxybenzyl) isocyanurate and 1,3, 5-tris (2-hydroxyethyl) isocyanurate,

benzylphosphonates, for example dimethyl-2, 5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate and dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate,

acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide and octyl N- (3, 5-di-tert-butyl-4-hydroxyphenyl) carbamate,

for example propionic acid esters and acetic acid esters of monohydric or polyhydric alcohols, such as methanol, ethanol, N-octanol, isooctanol, octadecanol, 1, 6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N' -bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] -octane,

propionamides based on amine derivatives, such as N, N ' -bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N ' -bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine and N, N ' -bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine,

ascorbic acid (vitamin C) and ascorbic acid derivatives, such as ascorbyl palmitate, ascorbyl laurate and ascorbyl stearate, and ascorbyl sulfate and ascorbyl phosphate,

antioxidants based on amine compounds, e.g. N, N '-diisopropyl-p-phenylenediamine, N' -di-sec-butyl-p-phenylenediamine, N '-bis (1, 4-dimethylpentyl) -p-phenylenediamine, N' -bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N '-bis (1-methylheptyl) -p-phenylenediamine, N' -dicyclohexyl-p-phenylenediamine, N '-diphenyl-p-phenylenediamine, N' -bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N '-phenyl-p-phenylenediamine, N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine, N '-dimethyl-pentyl-phenylenediamine, N' -dimethyl-hexyl-p-phenylenediamine, N '-dimethyl-pentyl-p-phenylenediamine, N' -dimethyl-pentyl-phenylenediamine, N '-dimethyl-pentyl-p-phenylenediamine, N' -diphenyl-pentyl-p-phenylenediamine, N '-diphenyl-phenyl-p-phenylenediamine, N' -diphenyl-phenylenediamine, N '-diphenyl, N' -diphenyl, N, N- (1-methylheptyl) -N ' -phenyl-p-phenylenediamine, N-cyclohexyl-N ' -phenyl-p-phenylenediamine, 4- (p-toluenesulfonylamido) diphenylamine, N ' -dimethyl-N, N ' -di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octyl-substituted diphenylamines such as p, p ' -di-tert-octyldiphenylamine, 4-N-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, N ' -dimethyl-N, N ' -di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octyl-substituted diphenylamine, 4-butyrylaminophenol, 4-nonanoylaminophenol, N-2-naphthylamine, N-octylaniline, N-butylaminophenol, N-phenylamine, N-1-naphthylamine, N, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2, 6-di-tert-butyl-4-dimethylaminomethylphenol, 2, 4-diaminodiphenylmethane, 4 '-diaminodiphenylmethane, N, N, N', N '-tetramethyl-4, 4' -diaminodiphenylmethane, 1, 2-bis [ (2-methylphenyl) amino ] ethane, 1, 2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3' -dimethylbutyl) phenyl ] amine, tert-octyl-substituted N-phenyl-1-naphthylamine, a mixture of mono-and di-alkylated tert-butyl/tert-octyldiphenylamines, mixtures of these, and their use, A mixture of mono-and di-alkylated nonyldiphenylamines, a mixture of mono-and di-alkylated dodecyldiphenylamines, a mixture of mono-and di-alkylated isopropyl/isohexyldiphenylamines, a mixture of mono-and di-alkylated tert-butyldiphenylamines, 2, 3-dihydro-3, 3-dimethyl-4H-1, 4-benzothiazine, phenothiazine, a mixture of mono-and di-alkylated tert-butyl/tert-octylphenothiazines, a mixture of mono-and di-alkylated tert-octylphenothiazines, N-allylphenothiazine, N, N, N ', N' -tetraphenyl-1, 4-diaminobut-2-ene, N, N-bis (2,2,6, 6-tetramethylpiperidin-4-yl) hexamethylenediamine, a mixture of mono-and di-alkylated dodecyldiphenylamines, a mixture of mono-and di-alkylated isopropyl/isohexyldiphenylamines, a mixture of mono-and di-alkylated tert-butyl/tert-octylphenothiazines, a mixture of mono-and di-alkylated tert-octylphenothiazines, N, N ', N' -tetraphenyl-1, 4-diaminobutan-2-hexamethylenediamine, a mixture of mono-and a mixture of mono-alkylated diphenylamines, Bis (2,2,6, 6-tetramethylpiperidin-4-yl) sebacate, 2,6, 6-tetramethylpiperidin-4-one and 2,2,6, 6-tetramethylpiperidin-4-ol,

phosphines, phosphites and phosphonites, such as triphenylphosphine, triphenyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2, 4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyl oxypentaerythritol diphosphite, bis (2, 4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4, 6-tri (tert-butylphenyl)) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2, 4-di-tert-butylphenyl) 4, 4' -diphenylene diphosphonite, 6-isooctyloxy-2, 4,8, 10-tetra-tert-butyl-12H-dibenzo [ d, g ] -1,3, 2-dioxaphosphacyclooctene (dioxaphosph cine), 6-fluoro-2, 4,8, 10-tetra-tert-butyl-12-methyl-dibenzo [ d, g ] -1,3, 2-dioxaphosphacyclooctene, bis (2, 4-di-tert-butyl-6-methylphenyl) methyl phosphite and bis (2, 4-di-tert-butyl-6-methylphenyl) ethyl phosphite,

2- (2 '-hydroxyphenyl) benzotriazoles, e.g. 2- (2' -hydroxy-5 '-methylphenyl) benzotriazole, 2- (3', 5 '-di-tert-butyl-2' -hydroxyphenyl) benzotriazole, 2- (5 '-tert-butyl-2' -hydroxyphenyl) benzotriazole, 2- (2 '-hydroxy-5' - (1,1,3, 3-tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5' -di-tert-butyl-2 '-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3' -tert-butyl-2 '-hydroxy-5' -methylphenyl) -5-chlorobenzotriazole, 2- (3 '-sec-butyl-5' -tert-butyl-2 '-hydroxyphenyl) benzotriazole, 2- (2' -hydroxy-4 '-octyloxyphenyl) benzotriazole, 2- (3', 5 '-di-tert-amyl-2' -hydroxyphenyl) benzotriazole, 2- (3,5 '-bis- (. alpha.,. alpha. -dimethylbenzyl) -2' -hydroxyphenyl) benzotriazole, mixtures of the following: 2- (3 '-tert-butyl-2' -hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3' -tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl ] -2' -hydroxyphenyl) -5-chlorobenzotriazole, 2- (3 '-tert-butyl-2' -hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3' -tert-butyl-2 '-hydroxy-5' - (2-octyloxycarbonylethyl) phenyl) benzotriazole Triazole, 2- (3 '-tert-butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl ] -2 '-hydroxyphenyl) benzotriazole, 2- (3' -dodecyl-2 '-hydroxy-5' -methylphenyl) benzotriazole and 2- (3 '-tert-butyl-2' -hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2' -methylenebis [4- (1,1,3, 3-tetramethylbutyl) -6-benzotriazol-2-ylphenol ]; the product of the complete esterification of 2- [ 3' -tert-butyl-5 ' - (2-methoxycarbonylethyl) -2' -hydroxyphenyl ] -2H-benzotriazole with polyethylene glycol 300;

sulfur-containing peroxide scavengers and sulfur-containing antioxidants, such as esters of 3, 3' -thiodipropionic acid, for example lauryl, stearyl, myristyl and tridecyl esters, zinc salts of mercaptobenzimidazole and 2-mercaptobenzimidazole, dibutyl zinc dithiocarbamate, dioctadecyl disulfide and pentaerythritol tetrakis (. beta. -dodecylmercapto) propionate,

esters of unsubstituted and substituted benzoic acids, such as 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3, 5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3, 5-di-tert-butyl-4-hydroxybenzoate and 2-methyl-4, 6-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate,

acrylic esters, such as ethyl alpha-cyano-beta, beta-diphenylacrylate, isooctyl alpha-cyano-beta, beta-diphenylacrylate, methyl alpha-methoxycarbonylcinnamate, methyl alpha-cyano-beta-methyl-p-methoxycinnamate, butyl-alpha-cyano-beta-methyl-p-methoxycinnamate and methyl-alpha-methoxycarbonyl-p-methoxycinnamate, sterically hindered amines, such as bis (2,2,6, 6-tetramethylpiperidin-4-yl) sebacate, bis (2,2,6, 6-tetramethylpiperidin-4-yl) succinate, bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) sebacate, mixtures thereof, Bis (1-octyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) -N-butyl-3, 5-di-tert-butyl-4-hydroxybenzylmalonate, condensation product of 1- (2-hydroxyethyl) -2,2,6, 6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N, N' -bis (2,2,6, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-tert-octylamino-2, 6-dichloro-1, 3, 5-triazine, tris (2,2,6, 6-tetramethylpiperidin-4-yl) nitrilotriacetate, bis (1,2,2,6, 6-tetramethylpiperidin-4-yl) nitrilotriacetate, Tetrakis (2,2,6, 6-tetramethylpiperidin-4-yl) 1,2,3, 4-butanetetracarboxylate, 1' - (1, 2-ethylidene) bis (3,3,5, 5-tetramethylpiperazinone), 4-benzoyl-2, 2,6, 6-tetramethylpiperidine, 4-stearyloxy-2, 2,6, 6-tetramethylpiperidine, bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) 2-n-butyl-2- (2-hydroxy-3, 5-di-tert-butylbenzyl) malonate, 3-n-octyl-7, 7,9, 9-tetramethyl-1, 3, 8-triazaspiro [4.5] decane-2, 4-dione, bis (1-octyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) sebacate, bis (1-octyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) succinate, a condensation product of N, N ' -bis (2,2,6, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-morpholino-2, 6-dichloro-1, 3, 5-triazine, a condensation product of 2-chloro-4, 6-bis (4-N-butylamino-2, 2,6, 6-tetramethylpiperidin-4-yl) -1,3, 5-triazine and 1, 2-bis (3-aminopropylamino) ethane, a condensation product of N, N ' -bis (2,2,6, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and N, N ' -bis (2, 6-tetramethylpiperidin-4-yl) ethane, a condensation product of N-chloro-4, 6-bis (4-butylamino-2, 2,6, 6-tetramethylpiperidin-4-yl) ethane, a condensation product of N, N ' -butylpiperazinone, N ' -bis (4-methyl-piperazinone, N, 2-chloro-4, 6-bis (4-n-butylamino-1, 2,2,6, 6-pentamethylpiperidin-4-yl) -1,3, 5-triazine and 1, 2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7, 7,9, 9-tetramethyl-1, 3, 8-triazaspiro [4.5] -decane-2, 4-dione, 3-dodecyl-1- (2,2,6, 6-tetramethylpiperidin-4-yl) pyrrolidine-2, 5-dione, 3-dodecyl-1- (1,2,2,6, 6-pentamethylpiperidin-4-yl) pyrrolidine-2, 5-diketones, a mixture of 4-hexadecyloxy-and 4-stearyloxy-2, 2,6, 6-tetramethylpiperidine, the condensation product of N, N' -bis (2,2,6, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-cyclohexylamino-2, 6-dichloro-1, 3, 5-triazine, the condensation product of 1, 2-bis (3-aminopropylamino) ethane and 2,4, 6-trichloro-1, 3, 5-triazine, 4-butylamino-2, 2,6, 6-tetramethylpiperidine, N- (2,2,6, 6-tetramethylpiperidin-4-yl) -N-dodecylsuccinimide, N- (1,2,2,6, 6-pentamethylpiperidin-4-yl) -n-dodecylsuccinimide, 2-undecyl-7, 7,9, 9-tetramethyl-1-oxa-3, 8-diaza-4-oxo-spiro [4.5] -decane, a condensation product of 7,7,9, 9-tetramethyl-2-cycloundecyl-1-oxa-3, 8-diaza-4-oxospiro- [4.5] decane and epichlorohydrin, a condensation product of 4-amino-2, 2,6, 6-tetramethylpiperidine with tetramethylolethynyldiurea and poly (methoxypropyl-3-oxy) - [4(2,2,6, 6-tetramethyl) piperidinyl ] -siloxane,

oxamides, for example 4,4 ' -dioctyloxyoxanilide, 2' -diethoxyoxanilide, 2' -dioctyloxy-5, 5 ' -di-tert-butoxanilide, 2' -didodecyloxy-5, 5 ' -di-tert-butoxanilide, 2-ethoxy-2 ' -ethyloxanilide, N ' -bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2 ' -ethoxanilide and its mixture with 2-ethoxy-2 ' -ethyl-5, 4 ' -di-tert-butoxanilide, and mixtures of o-, p-methoxy-disubstituted oxanilides and mixtures of o-and p-ethoxy-disubstituted oxanilides, and

2- (2-hydroxyphenyl) -1,3, 5-triazines, for example 2,4, 6-tris- (2-hydroxy-4-octyloxyphenyl) -1,3, 5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2, 4-bis (2-hydroxy-4-propoxyphenyl) -6- (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (4-methylphenyl) -1,3, 5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- [ 2-hydroxy-4- (2-hydroxy-3-butoxypropoxy) phenyl ] -4, 6-bis (2, 4-dimethyl) -1,3, 5-triazine, 2- [ 2-hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl ] -4, 6-bis (2, 4-dimethyl) -1,3, 5-triazine, 2- [4- (dodecyloxy/tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- [ 2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl ] -4, 6-bis- (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4, 6-diphenyl-1, 3, 5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4, 6-diphenyl-1, 3, 5-triazine, 2,4, 6-tris [ 2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl ] -1,3, 5-triazine and 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1, 3, 5-triazine.

In another preferred embodiment, the polymerisable LC material comprises a material preferably selected fromA series of one or more specific antioxidant additives, for example antioxidants available from Ciba, Switzerland1076 and1010。

in another preferred embodiment, the polymerisable LC material comprises one or more, more preferably a combination of one or two photoinitiators, e.g. selected from commercially available photoinitiatorsOr(Ciba AG) series, in particular Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 817, Irgacure 907, Irgacure 1300, Irgacure 2022, Irgacure 2100, Irgacure 2959 or Darcure TPO, additionally selected from the commercially available OXE02(Ciba AG), NCI 930, N1919T (Adeka), SPI-03 or SPI-04(Samyang), or preferably combinations thereof, such as SPI-03 and NCI-930.

The concentration of the polymerization initiator as a whole in the polymerizable LC material is preferably 0.5 to 5%, very preferably 0.5 to 3%, more preferably 1 to 2%.

Preferably, the polymerisable LC material comprises in addition to one or more compounds of formula UVI

a) One or more di-or multireactive polymerisable mesogenic compounds,

b) optionally one or more mono-reactive polymerizable mesogenic compounds,

c) optionally one or more antioxidant additives,

d) optionally one or more adhesion promoters,

e) optionally one or more surfactants, optionally in combination with one or more surfactants,

f) optionally one or more mono-, di-or multireactive polymerizable non-mesogenic compounds,

g) optionally one or more dyes that exhibit an absorption maximum at the wavelength used to initiate photopolymerization,

h) optionally one or more chain transfer agents,

i) optionally one or more stabilizers, and (c) optionally,

j) optionally one or more lubricants and flow aids, and

k) optionally one or more diluents, and optionally one or more diluents,

l) an optional non-polymerizable nematic component.

More preferably, the polymerisable LC material comprises,

a) one or more compounds of the formula UVI,

b) one or more, preferably two or more, bireactive polymerisable mesogenic compounds, if present, preferably in an amount of from 10 to 90 wt. -%, very preferably from 15 to 75 wt. -%, preferably selected from compounds of formula DRMa-1,

c) optionally one or more, preferably two or more, mono-reactive polymerizable mesogenic compounds, preferably in an amount of from 10 to 95% by weight, very preferably from 25 to 85%, preferably selected from compounds of formula MRM-1 and/or MRM-7,

d) optionally one or more compounds of formula ND, preferably in an amount of 1 to 50%, very preferably 1 to 40%,

e) optionally one or more antioxidant additives, preferably selected from esters of unsubstituted and substituted benzoic acids, in particular1076, and if presentIn an amount of preferably from 0.01 to 2% by weight, very preferably from 0.05 to 1% by weight,

f) optionally one or more lubricants and flow aids, preferably selected from388. FC 4430, Fluor N561 and/or Fluor N562, and if present, preferably in an amount of from 0.1 to 5% by weight, very preferably from 0.2 to 3% by weight, and

g) optionally one or more photoinitiators.

The invention further relates to a method for producing a polymer film by

Providing a layer of a polymerisable LC material as described above and below onto a substrate,

-polymerizing the polymerizable component of the polymerizable LC material by photopolymerization, and

-optionally removing the polymerized LC material from the substrate, and/or optionally providing the polymerized LC material onto another substrate.

The polymerisable LC material may also be dissolved in a suitable solvent.

In a further preferred embodiment, the polymerisable LC material comprises one or more solvents, preferably selected from organic solvents. The solvent is preferably selected from ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone or cyclohexanone; acetates such as methyl, ethyl or butyl acetate or methyl acetoacetate; alcohols such as methanol, ethanol or isopropanol; aromatic solvents such as toluene or xylene; alicyclic hydrocarbons such as cyclopentane or cyclohexane; halogenated hydrocarbons such as di-or tri-chloromethane; glycols or esters thereof such as PGMEA (propylene glycol monomethyl ether acetate), γ -butyrolactone. Binary, ternary or higher mixtures of the above solvents may also be used.

In case the polymerisable LC material comprises one or more solvents, the total concentration of all solids including RM in said one or more solvents is preferably 10 to 60%.

The solution is then coated or printed onto a substrate by spin coating, printing or other known techniques, and the solvent is evaporated prior to polymerization. In most cases, it is suitable to heat the mixture to promote evaporation of the solvent.

The polymerisable LC material may be applied to the substrate by conventional coating techniques such as spin coating, bar coating or knife coating. The polymerizable LC material can also be applied to the substrate by conventional printing techniques known to the skilled person, such as, for example, screen printing, offset printing, roll-to-roll printing, letterpress printing, intaglio printing, rotogravure printing, flexographic printing, engraved intaglio printing, pad printing, heat seal printing, ink jet printing or printing by means of a stamp (stamp) or printing plate.

Suitable substrate materials and substrates are known to the expert and are described in the literature, as are conventional substrates, for example glass or plastic, for example, for use in the optical film industry. Particularly suitable and preferred substrates for the polymerization are polyesters such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), polyvinyl alcohol (PVA), Polycarbonate (PC), Triacetylcellulose (TAC), or cyclo-olefin polymer (COP), or known color filter materials, in particular Triacetylcellulose (TAC), cyclo-olefin polymer (COP), or known color filter materials.

The polymerisable LC material preferably shows a uniform alignment throughout the layer. Preferably the polymerisable LC material exhibits a uniform planar or a uniform homeotropic alignment.

The Friedel-Creagh-Kmetz rule can be used to predict whether a mixture will adopt planar or homeotropic alignment by comparing the surface energies of the RM layer and the substrate:

if gamma is_RM>γ_sThe reactive mesogenic compound will show homeotropic alignment if gamma_RM<γ_sThe reactive mesogenic compound will show a planar alignment.

When the surface energy of the substrate is relatively low, the intermolecular forces between the reactive mesogens are stronger than the forces across the RM-substrate surface. Thus, the reactive mesogens are aligned perpendicular to the substrate (homeotropic alignment) to maximize the intermolecular forces.

Homeotropic alignment can also be achieved by using amphiphilic materials; they may be added directly to the polymerisable LC material or the substrate may be treated with these materials in the form of homeotropic alignment layers. The polar head of the amphiphilic material is chemically bonded to the substrate, and the hydrocarbon tail is directed perpendicularly to the substrate. The intermolecular interaction between the amphiphilic material and the RMs promotes homeotropic alignment. Commonly used amphiphilic surfactants are described above.

Another method for promoting homeotropic alignment is to apply corona discharge treatment to the plastic substrate, thereby creating alcohol or ketone functional groups on the substrate surface. These polar groups may interact with polar groups present in the RM or surfactant to promote homeotropic alignment.

When the surface tension of the substrate is greater than that of RM, the force across the interface dominates. The interfacial energy is minimized if the reactive mesogens are aligned parallel to the substrate, so the long axis of the RM can interact with the substrate. Unidirectional planar alignment may be promoted by coating the substrate with a polyimide layer and then rubbing the alignment layer with velvet cloth.

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

In general, an overview of alignment technology is given by i.sage in "Thermotropic Liquid Crystals", edited by g.w.gray, John Wiley & Sons,1987, pages 75-77; and given by T.Uchida and H.seki in "Liquid Crystals-Applications and Uses Vol.3", B.Bahadur, edited by World Scientific Publishing, Singapore 1992, pages 1-63. Further reviews of alignment materials and techniques are given by j.cognard, mol.crystal.liq.crystal.78, Supplement 1(1981), pages 1 to 77.

To prepare the polymer film according to the present invention, the polymerisable compounds in the polymerisable LC material are polymerised or crosslinked (if one compound comprises two or more polymerisable groups) by in situ photopolymerisation.

The photopolymerization can be carried out in one step. It is also possible to photopolymerize or crosslink in a second step the compounds which have not reacted in the first step ("end cure").

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

The photopolymerisation of the LC material is preferably effected by exposing it to actinic radiation. Actinic radiation means irradiation with light, such as 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 irradiation, in particular with UV light. As a source for actinic radiation, for example a single UV lamp or a set of UV lamps may be used. When high lamp power is used, the curing time can be reduced. Another possible source for optical radiation is a laser, such as, for example, a UV laser, an IR laser or a visible laser.

The curing time depends inter alia on the reactivity of the polymerizable LC material, the thickness of the coating layer, the type of polymerization initiator and the power of the UV lamp. The curing time is preferably 5 minutes or less, very preferably 3 minutes or less, most preferably 1 minute or less. For mass production, short curing times of ≦ 30 seconds are preferred.

Suitable UV radiation powers are preferably in the range from 5 to 200mWcm^-2More preferably in the range of 50 to 175mWcm^-2And most preferably in the range of 100 to 150mWcm^-2Within the range of (1).

Suitable UV doses, in relation to the applied UV radiation and as a function of time, are preferably in the range of 25 to 7200mJcm^-2More preferably in the range of 500 to 7200mJcm^-2And most preferably in the range of 3000 to 7200mJcm^-2Within the range of (1).

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 from 1 to 70 ℃, preferably from 5 to 50 ℃, even more preferably from 15 to 30 ℃.

The polymerized LC film according to the present invention has good adhesion to plastic substrates, particularly TAC, COP and color filters. It can therefore be used as an adhesive or base coat for subsequent LC layers which would otherwise not adhere well to the substrate.

The preferred thickness of the polymerized LC film according to the present invention is determined by the desired optical properties of the film or the final article. For example, if the polymerized LC film is not used primarily as an optical film, but for example as an adhesive, alignment or protective layer, its thickness is preferably not more than 1 μm, in particular not more than 0.5 μm, very preferably not more than 0.2 μm.

For example, the uniformly homeotropic or planar aligned polymer films of the present invention can be used as retardation or compensation films, for example in LCDs, to improve contrast and brightness at large viewing angles and to reduce chroma. They can be used outside the switchable liquid crystal cells in LCDs, or between substrates (usually glass substrates), forming switchable liquid crystal cells and accommodating switchable liquid crystal media (in-cell applications).

For optical applications of the polymer film, it preferably has a thickness of from 0.5 to 10 μm, preferably from 0.5 to 5 μm, in particular from 0.5 to 3 μm.

The optical retardation of the polymer film (δ (λ)) as a function of the wavelength (λ) of the incident light beam is given by the following equation (7):

δ(λ)＝(2πΔn·d)/λ (7)

where (Δ n) is the birefringence of the film, (d) is the thickness of the film and λ is the wavelength of the incident beam.

According to Snellius' law, birefringence as a function of the direction of an incident beam of light is defined as

Δn＝sinΘ/sinΨ (8)

Where sin Θ is the angle of incidence or the tilt of the optical axis in the membrane and sin Ψ is the corresponding angle of reflection.

Based on these laws, the birefringence and hence the optical retardation depend on the thickness of the film and the tilt angle of the optical axis in the film (see Berek compensator). Thus, the skilled person realizes that different optical retardations or different birefringence can be induced by adjusting the orientation of the liquid crystal molecules in the polymer film.

The birefringence (Δ n) 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 invention is less than 200nm, preferably less than 180nm and even more preferably less than 150 nm.

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

In summary, the polymerized LC films and polymerizable LC materials according to the invention can be used in optical elements such as polarizers, compensators, alignment layers, circular polarizers or color filters (in liquid crystal displays or projection systems), for decorating images, for producing liquid crystals or effect pigments, and in particular in reflective films having a spatially varying reflective color, for example in decorative multicolor images, information storage or security applications, such as non-counterfeitable documents such as identification or credit cards, banknotes and the like.

The polymerized LC film according to the invention can be used in transmissive or reflective type displays. They can be used in conventional OLED displays or LCDs, in particular in DAP (aligned phase deformation) or VA (vertical alignment) mode LCDs, such as for example ECB (electrically controlled birefringence), CSH (color homeotropic), VAN or VAC (vertically aligned nematic or cholesteric) displays, MVA (multi-domain vertical alignment) or PVA (patterned vertical alignment) displays, in bend mode displays or in hybrid displays, such as for example OCB (optically compensated bend box or optically compensated birefringence), R-OCB (reflective OCB), HAN (hybrid aligned nematic) or pi-cell (pi-cell) displays, furthermore in displays of TN (twisted nematic), HTN (highly twisted nematic) or STN (super twisted nematic) mode, in AMD-TN (active matrix driven TN) displays, or in IPS (in-plane switching) mode displays, which are also referred to as "super TFT" displays. VA, MVA, PVA, OCB and pi-cell displays are particularly preferred.

The polymerisable LC materials and polymer films according to the invention are particularly useful as in EP 0829744, EP 0887666A 2, EP 0887692, US 6,046,849, US 6,437,915 and in "Proceedings o the SID 20^th3D Display as described in International Display Research Conference,2000", page 280. A 3D display of this type comprising a polymer film according to the invention is another object of the invention.

The invention has been described above and below with particular reference to preferred embodiments. It is to be understood that various changes and modifications may be made herein without departing from the spirit and scope of the invention.

Many of the compounds mentioned above and below or mixtures thereof are commercially available. All these compounds are known or can be prepared by processes known per se, as described in the literature (for example in standard works such as Houben-Weyl, Methoden der Organischen Chemie [ Methods of Organic Chemistry ], Georg-Thieme-Verlag, Stuttgart), precisely under reaction conditions which are known and suitable for the reaction in question. Variants which are known per se and are not mentioned here can also be used here.

It will be appreciated that variations may be made to the foregoing embodiments of the invention while still falling within the scope of the invention. Unless otherwise stated, alternative features serving the same, equivalent or similar purpose may be substituted for each feature disclosed in this specification. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.

All of the features disclosed in this specification may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive. In particular, the preferred features of the invention are applicable to all aspects of the invention and may be combined in any combination. Likewise, features described in non-essential combinations may be used separately (not in combination).

It will be appreciated that many of the features described above, particularly those of the preferred embodiments, are inventive in their own right and not just as part of an embodiment of the invention. Independent protection for these features may also be sought in addition to or in place of any presently claimed invention.

The invention will now be described in more detail with reference to the following working examples, which are illustrative only and do not limit the scope of the invention.

Examples

General procedure

The mixture was dissolved in toluene/cyclohexanone (7/3) at 33.3% solids. The solution was spin coated on a green glass substrate, coated with rubbed PI, at 2000 rpm. Annealing the film at 68 ℃ for 120 seconds and in N₂The atmosphere was transferred using a Fusion conveyer, H bulb (95% power, 10m/min, about 300 mJ/cm)²UV B) curing.

The films were laminated to the pressure sensitive adhesive and left open surface, so the total film was stacked as glass/polymer film/pressure sensitive adhesive and the films were subjected to durability testing.

To measure the difference in retardation and dispersion of the cured film depending on the thermal stress, the initial retardation and dispersion were measured using an Axoscan ellipsometer. The membrane was then treated with Suntest XLS + (350W/m)²) Stressed for up to 120 hours. After the test, the delay characteristics and dispersion were measured again. By retardation (Δ R) before and after UV testing_in) And/or dispersion (R)₄₅₀/₅₅₀) The difference in (a) quantifies durability.

Use of compounds of formula UVI

Example 1

The following mixture M1 RMM was prepared according to the following table:

the mixture M1 was divided into 2 portions and one portion was mixed with 1.5% w/w UVI-a, while one portion remained unchanged.

Each mixture was dissolved, coated and cured as described above and the changes in retardation and dispersion were determined before and after stress testing. The results are summarized in the following table:

stress for 24 hours:

host mixture	Stabilizer	Measurement of	ΔR_in[％]	Δ(R₄₅₀/₅₅₀)[％]
					M1	-	-	3.3	3.5
M1	UVI-a	1.5％w/w	0.4	1.1

Stressed for 120 hours:

Host mixture	Stabilizer	Measurement of	ΔR_in[％]	Δ(R₄₅₀/₅₅₀)[％]
					M1	-	-	9.2	7.5
M1	UVI-a	1.5％w/w	2.6	2.8

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Polymerizable liquid crystal material and polymerized liquid crystal film

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