News Column

Patent Issued for Polymer Comprising Cyclohexylene Groups and Its Use in Films with Negative Optical Dispersion

August 29, 2014



By a News Reporter-Staff News Editor at Science Letter -- According to news reporting originating from Alexandria, Virginia, by NewsRx journalists, a patent by the inventors Adlem, Kevin (Dorset, GB); Parri, Owain Llyr (Hampshire, GB); Wilkes, David (Southampton, GB); Topping, Claire (Southampton, GB), filed on June 17, 2010, was published online on August 12, 2014 (see also Merck Patent Gesellschaft Mit Beschrankter Haftung).

The assignee for this patent, patent number 8802813, is Merck Patent Gesellschaft Mit Beschrankter Haftung (Darmstadt, DE).

Reporters obtained the following quote from the background information supplied by the inventors: "There is a need for anisotropic optical films that demonstrate negative optical retardation dispersion. For example, a quarter wave film made with negative dispersion birefringent materials will be largely achromatic. Devices such as reflective LCDs that utilise such a quarter wave film will have a dark state that is not coloured. Currently such devices have to use two retarder films to achieve this effect.

"The dispersive power of such a negative dispersion birefringent film can be defined in many ways, however one common way is to measure the optical retardation at 450 nm and divide this by the optical retardation measured at 550 nm (R.sub.450/R.sub.550). If the on-axis retardation of a negative retardation dispersion film at 550 nm is 137.5 nm and the R.sub.450/R.sub.550 value is 0.82, then such a film will be largely a quarter wave film for all wavelengths of visible light and a liquid crystal display device (LCD) using this film as, for example, a circular polarizer would have a substantially black appearance. On the other hand, a film made with an on axis of 137.5 nm which had normal positive dispersion (typically R.sub.450/R.sub.550=1.13) would only be a quarter wave film for one wavelength (550 nm), and an LCD device using this film as, for example, a circular polarizer would have a purple appearance. Another way of representing this information is to plot the change in birefringence as a function of wavelength. FIG. 1 shows a typical birefringence against wavelength plot for a polymerized film made from the commercially available reactive mesogen RM257 (Merck KgaA, Darmstadt, Germany). The R.sub.450/R.sub.550 for this compound is around 1.115.

"In an anisotropic optical film formed by rod-shaped, optically anisotropic molecules, the origin of the retardation dispersion is due to the fact that the two refractive indices n.sub.e, n.sub.o, of the anisotropic molecules (wherein n.sub.e is the 'extraordinary refractive index' in the direction parallel to the long molecular axis, and n.sub.o is the 'ordinary refractive index' in the directions perpendicular to the long molecular axis) are changing with wavelength at different rates, with n.sub.e changing more rapidly than n.sub.o towards the blue end of the visible wavelength spectrum. One way of preparing material with low or negative retardation dispersion is to design molecules with increased n.sub.o dispersion and decreased n.sub.e dispersion. This is schematically shown in FIG. 2. Such an approach has been demonstrated in prior art to give LC's with negative birefringence and positive dispersion as well as compounds with positive birefringence and negative dispersion.

"If the compounds are polymerizable, or are mixed with a polymerizable host material comprising for example polymerizable mesogenic compounds (also known as 'reactive mesogens' or 'RMs'), it is possible to prepare anisotropic optical polymer films with negative dispersion. This can easily be carried out by in situ polymerization, e.g. by exposure to heat or UV radiation, of the polymerizable material when being uniformly oriented in its mesophase, thereby permanently fixing the macroscopically uniform orientation. Suitable polymerization methods are well-known to the person skilled in the art, and are described in the literature.

"Prior art describes the use of coatable materials having negative dispersion for the preparation of optical films. For example, JP 2005-208146 A1 and WO 2006/052001 A1 disclose polymerisable materials largely based on compounds with a 'cardo' core group for the preparation of polymer films with negative dispersion.

"Prior art also reports that optical films with negative dispersion can be obtained by stretching solvent cast or extruded polymer films. For example, A. Uchiyama and T. Yatabe in Journal of Polymer Science, Part B: Polymer Physics, Vol. 41, 1554-1562 (2003), and Jpn. J. Appl. Phys., 42, 5665-5669 (2003), and WO 00/26705 A1 disclose stretched optical polymer films with negative dispersion. These documents report the use of a 'cardo' group to introduce some high refractive index component in a direction orthogonal to the stretched direction of the polymer.

"Other documents disclose that the optical properties of stretched polymer films can be controlled by combining polymer components with intrinsically positive and negative birefringence. This optical effect can be achieved either by combining two miscible polymer to make a polymer blend (see for example H. Saito and T. Inoue in Journal of Polymer Science, Part B: Polymer Physics, Vol. 25, 1629-1636 (1987); or K. Kuboyama, T. Kuroda and T. Ougizawa in Macromol. Symp. 249-250, 641-646, (2007)), or by combining two polymer parts or segments; one segment intrinsically positive and the other segment intrinsically negative birefringence into one homopolymer (see for example A. Uchiyama and T. Yatabe in Jpn. J. Appl. Phys. Vol 42, 6941-6945 (2003)).

"The terms 'intrinsically positive' and 'intrinsically negative' birefringence are used to describe the optical properties of polymer films. Examples of stretched polymer films with intrinsically positive birefringence include the following: polycarbonates, polyarylates, polyethylene teraphthalate, polyether sulphone, polyphenylene sulphide, polyphenylene oxide, polyallyl sulphone, polyamide-imides, polyimides, polyolefins, polyvinyl chloride, cellulose. Examples of stretched polymer films with intrinsically negative birefringence include the following: styrene, acrylic ester polymers, methacrylic ester polymers, acrylonitrile polymers.

"The intrinsic birefringence is defined as follows: (.DELTA.n.sub.int)=(n.sub.e-n.sub.o) wherein n.sub.e and n.sub.o are the extraordinary and ordinary index of the polymer molecular chain, respectively.

"The birefringence of the polymer film depends on two basic factors: firstly the various processes used to prepare the film, like for example casting, annealing and stretching, which determine the state of the polymer backbone, and secondly, the intrinsic birefringence of the polymeric material. The magnitude and sign of the latter depends on the polarisability of functional groups and the arrangement of these groups relative to the main chain. For example, polystyrene has an aliphatic backbone with more polarisable phenyl groups orientated largely orthogonal to it. Similarly, polyacrylonitrile has an aliphatic backbone and highly polarisable nitrile group oriented largely orthogonal to the backbone. Both the later polymers demonstrate negative intrinsic birefringence. In other words, the sign of the intrinsic birefringence is determined by the orientation of the chromophore relative to the aligned polymer backbone. For intrinsically negative birefringent polymers, the transition moment of the polarisable groups or chromophores should be oriented away from the polymer backbone. This is further discussed in WO 2007/075264 A1.

"Methods of measuring the birefringence of a cast polymer film are described by J. S. Machell, J. Greener, and B. A. Contestable in Macromolecules, Vol. 23, No. 1, (1990).

"However, many of the materials disclosed in the literature have drawbacks, like for example, the difference between the polarisability of the groups orientated parallel and perpendicular to the stretch axis of the polymer is not sufficiently large, so the polymeric material has to contain a relatively high concentration of units that lower the birefringence dispersion, which are normally the expensive component of the total pre-polymer mixture.

"Therefore, there is a still a need for materials that are suitable for the preparation of polymer films with negative optical dispersion, which are easy to synthesize and available at reduced cost, have good proccessability and have improved properties such as solubility and thermal properties.

"It is therefore an aim of the present invention to provide novel and improved materials for use in polymer films with negative optical dispersion, which show the above-mentioned advantageous properties and do not have the drawbacks of the prior art materials. Another aim of the invention is to extend the pool of materials and polymer films having negative dispersion that are available to the expert. Other aims are immediately evident to the expert from the following description.

"It has been found that these aims can be achieved by providing compounds, materials and films as claimed in the present invention.

"In particular, it was found that this can be achieved by using axially substituted cyclohexane diols to prepare efficient segments in copolymers that can be processed into optical films showing negative dispersion.

"To achieve negative birefringence dispersion in a stretched polymer film, the wavelength dispersion of the ordinary refractive index should be greater than the wavelength dispersion of the extraordinary refractive index. Intrinsically negative birefringent polymers or segment of polymers enable the wavelength dispersion of the ordinary refractive indices of the polymer to increase. Therefore, a polymer film that demonstrates negative birefringence dispersion should be composed of a suitable molecular ratio of intrinsically negative and intrinsically positive birefringent segments. It is advantageous to minimise the amount of intrinsically negative birefringent segments in the polymer because it decreases the birefringence of the stretched film. It is reasonable to assume that to maximise the 'efficiency' of the polymer segment that contributes to lowering the dispersion of the film, a segment should possess highly polarisable groups and that the polarisable groups should be oriented largely orthogonal to the main chain, and furthermore, its orientation should be constrained so that it remained in this preferred orientation."

In addition to obtaining background information on this patent, NewsRx editors also obtained the inventors' summary information for this patent: "The invention relates to compounds of formula I

"##STR00001##

"wherein k is, in each occurrence independently of one another, 0 or 1, with k in at least one repeating unit being 1, m is, in each occurrence independently of one another, 0 or 1, n is an integer >1, R.sup.1, R.sup.2 are independently of each other straight-chain, branched or cyclic alkylene with 1 to 20, preferably 1 to 12 C-atoms, which is unsubstituted, mono- or polysubstituted by F, Cl, Br, I or CN, and wherein one or more non-adjacent CH.sub.2 groups are optionally replaced, in each case independently from one another, by --O--, --S--, --NH--, --NR.sup.0--, --SiR.sup.0R.sup.00--, --CO--, --CO--O--, --O--CO--, --O--CO--O--, --S--CO--, --CO--S--, --SO.sub.2--, --CO--NR.sup.0--, --NR.sup.0--CO--, --NR.sup.0--CO--NR.sup.00--, --CY.sup.1.dbd.CY.sup.2-- or --C.ident.C-- in such a manner that O and/or S atoms are not linked directly to one another, or a single bond, Y.sup.1, Y.sup.2 are independently of each other H, F, Cl, CN or R.sup.0, R.sup.0, R.sup.00 are independently of each other H or alkyl with 1 to 12 C-atoms, X.sup.1, X.sup.2 are independently of each other a linkage group, preferably selected from the group consisting of --O--, --S--, --CO--, --CO--O--, --O--CO--, --O--CO--O--, --CO--NR.sup.0--, --NR.sup.0--CO--, --NR.sup.0--CO--NR.sup.0--, --OCH.sub.2--, --CH.sub.2O--, --SCH.sub.2--, --CH.sub.2S--, --CF.sub.2O--, --OCF.sub.2--, --CF.sub.2S--, --SCF.sub.2--, --CH.sub.2CH.sub.2--, --(CH.sub.2).sub.n1--, --(CF.sub.2).sub.n1--, --CF.sub.2CH.sub.2--, --CH.sub.2CF.sub.2--, --CF.sub.2CF.sub.2--, --CH.dbd.CH--, --CY.sup.1.dbd.CY.sup.2--, --CH.dbd.N--, --N.dbd.CH--, --N.dbd.N--, --CH.dbd.CR.sup.0--, --C.ident.C--, --CH.dbd.CH--CO--O--, --O--CO--CH.dbd.CH--, --CR.sup.0R.sup.00-- and a single bond, n1 is 1, 2, 3, 4, 5 or 6, B.sup.1, B.sup.2 are independently of each other a bivalent group having high polarisability, preferably selected from the group consisting of --C.ident.C--, --CY.sup.1.dbd.CY.sup.2--, optionally substituted aromatic or heteroaromatic groups, and combinations of the aforementioned, U.sup.1, U.sup.2 are independently of each other, H or a monovalent group of formula II, wherein the asterisk denotes the linkage to the adjacent group B.sup.1 or B.sup.2, respectively

"##STR00002## R.sup.3, R.sup.4 are independently of each other straight-chain, branched or cyclic alkyl with 1 to 20, preferably 1 to 12 C-atoms, which is unsubstituted, mono- or polysubstituted by F, Cl, Br, I or CN, and wherein one or more non-adjacent CH.sub.2 groups are optionally replaced, in each case independently from one another, by --O--, --S--, --NH--, --NR.sup.0--, --SiR.sup.0R.sup.00--, --CO--, --CO--O--, --O--CO--, --O--CO--O--, --S--CO--, --CO--S--, --SO.sub.2--, --CO--NR.sup.0--, --NR.sup.0--CO--, --NR.sup.0--CO--NR.sup.00--, --CY.sup.1.dbd.CY.sup.2-- or --C.ident.C-- in such a manner that O and/or S atoms are not linked directly to one another, or a single bond, X.sup.3, X.sup.4 independently of each other have one of the meanings of X.sup.1, Z.sup.1 has in each occurrence independently of one another one of the meanings of X.sup.1, o is 0, 1, 2, 3, 4 or 5, G has one of the meanings of R.sup.1 or is a bivalent group of formula III --X.sup.5-A.sup.1-(Z.sup.2-A.sup.2).sub.p-X.sup.6-- III X.sup.5, X.sup.6 independently of each other have one of the meanings of X.sup.1, A.sup.1, A.sup.2 are independently of each other a carbocylic, heterocyclic, aromatic or heteroaromatic group, which is optionally substituted, Z.sup.2 has in each occurrence independently of one another one of the meanings of X.sup.1, and p is 0, 1, 2 or 3,

"The invention further relates to a formulation comprising one or more compounds as described above and below.

"The invention further relates to a birefringent polymer film obtainable from compound or formulation as described above and below.

"The invention further relates to a birefringent polymer film with R.sub.450/R.sub.550

"The invention further relates to the use of compounds, formulations and polymer films as described above and below in optical, electronic and electrooptical components and devices, preferably in optical films, retarders or compensators having negative optical dispersion.

"The invention further relates to an optical, electronic or electrooptical component or device, comprising a compound, formulation or polymer film as described above and below.

"Said devices and components include, without limitation, electrooptical displays, LCDs, optical films, polarizers, compensators, beam splitters, reflective films, alignment layers, colour filters, holographic elements, hot stamping foils, coloured images, decorative or security markings, LC pigments, adhesives, non-linear optic (NLO) devices, optical information storage devices, electronic devices, organic semiconductors, organic field effect transistors (OFET), integrated circuits (IC), thin film transistors (TFT), Radio Frequency Identification (RFID) tags, organic light emitting diodes (OLED), organic light emitting transistors (OLET), electroluminescent displays, organic photovoltaic (OPV) devices, organic solar cells (O-SC), organic laser diodes (O-laser), organic integrated circuits (O-IC), lighting devices, sensor devices, electrode materials, photoconductors, photodetectors, electrophotographic recording devices, capacitors, charge injection layers, Schottky diodes, planarising layers, antistatic films, conducting substrates, conducting patterns, photoconductors, electrophotographic applications, electrophotographic recording, organic memory devices, biosensors, biochips, optoelectronic devices requiring similar phase shift at multiple wavelengths, combined CD/DVD/HD-DVD/Blu-Rays, reading, writing re-writing data storage systems, or cameras."

For more information, see this patent: Adlem, Kevin; Parri, Owain Llyr; Wilkes, David; Topping, Claire. Polymer Comprising Cyclohexylene Groups and Its Use in Films with Negative Optical Dispersion. U.S. Patent Number 8802813, filed June 17, 2010, and published online on August 12, 2014. Patent URL: http://patft.uspto.gov/netacgi/nph-Parser?Sect1=PTO1&Sect2=HITOFF&d=PALL&p=1&u=%2Fnetahtml%2FPTO%2Fsrchnum.htm&r=1&f=G&l=50&s1=8802813.PN.&OS=PN/8802813RS=PN/8802813

Keywords for this news article include: Polymer Physics, Polymer Science, Merck Patent Gesellschaft Mit Beschrankter Haftung.

Our reports deliver fact-based news of research and discoveries from around the world. Copyright 2014, NewsRx LLC


For more stories covering the world of technology, please see HispanicBusiness' Tech Channel



Source: Science Letter


Story Tools






HispanicBusiness.com Facebook Linkedin Twitter RSS Feed Email Alerts & Newsletters