MXPA98008066A - Mixes of liqui crystal polymers - Google Patents

Abstract

A mixture of liquid crystalline polymers containing two or more cholesteric liquid crystalline polymers or at least one nematic liquid crystalline polymer and at least one cholesteric liquid crystalline polymer, variations in the components and proportions of the mixture make it possible to obtain all shades of color and produce them reproducibly, polymer blends are suitable as materials or as effective pigments.

Description

MIXES OF LIQUID CRYSTAL POLYMERS flEnQRI? PEs? F PTIVA The invention relates to liquid crystalline mixtures (combinations) of cholesteric polymers with nematic and / or cholesteric polymers. to a process for its preparation, and to its use as polymeric materials and effect pigments. The main chain cholesteric polymers can be prepared analogously to the main chain nematic polymers using an additional chiral comonomer (US 4,412,059, EP 0 196 785 Bl? EP O 608991 Al; EP 0 391 368 Bl) OR reacting chain nematic polymers Main (LCPs) with additional chiral comonomers (EP O 283 273 A2). The cholesteric main chain polymers are distinguished by a propeller superstructure. This results primarily in a material that no longer has the anisotropy of the mechanical properties that are usual in nematic polymers liquid crystal. In addition, the material exhibits pronounced color effects due to selective reflection in the propeller superstructure. The precise reflection of color depends on the angle of view and in particular on the passage of the propeller. For any desired angle of view - for example a planar perpendicular view of a specimen - the reflection color is a color having a wavelength corresponding to the pitch of the helix superstructure. This means that the reflected light has a shorter wavelength the shorter the pitch of the helix. The helix pitch that is formed depends essentially on the proportion of the chiral comonomer. the nature of the incorporation into the polymer, the degree of polymerization and the structure of the chiral comonomer ("helical bending power"). In addition, many systems also exhibit a certain dependence on the temperature of the passage in the cholesteric phase and thus also a variation of the coloristic properties. It is thus possible to prepare a polymer having a green or blue effect simply by varying the proportion of the chiral comonomer. However, it is disadvantageous in these colored polymers that the color can not be reproduced identically directly in the synthesis. Although the repetition of the synthesis of a blue polymer generally gives a blue polymer again, the polymers visibly differ in hue, so that they can not be considered as identical colors in conventional color testing methods, which avoids their use as polymers. gmentos. DE-A-44 16 993 »attempts to solve the problem of precise color modification using the temperature dependence of a cholesteric main chain polymer. However, the described polymers having this temperature dependency have a variety of disadvantages. For example »precise color adjustment. which usually does not take place until they are on the painted surface of the article, for example the automobile, although a precise control of the temperature seems very difficult and not possible at all under conditions of car painting in series, due to the fact that small temperature gradients result in changes in hue. The polymer described in DE-A-44 16 993 is based on sulfur 4-hydroxypheni 1 l- (3-hydroxy-2-methyl) porpi 1 as the chiral component, which must be prepared in a complex synthesis. The liquid crystal polymers are soluble in solvents "so that the problems of swelling occur again with a clear cover, which likewise results in a modification of the pitch and thus in a change in the color properties. Neither are these pigments as usually understood by experts, because they are soluble in many solvents. The use of polymers containing thioether groups is associated with the major disadvantage that thioethers are very easily oxidized. and the structure of liquid crystals is thus destroyed. Such oxidation can take place »for example, even with small amounts of ozone »as it occurs in ambient air in the summer months (DE-A1-43 14 736). The additional step of crosslinking by UV irradiation is also disadvantageous. Complete cross-linking under control conditions is necessary in this system "because otherwise it is cross-linked in an uncontrolled manner over time due to the UV content of the sun's rays. A major disadvantage of this system is that "the color determining substance in the paint body and the essential substance of the paint body itself are identical" (DE-4416 993 al. Page 8 »lines 1-2). This means that the pigments and the binders can not be combined freely »as is usual in the art to optimize the surface properties. (Patents) DE-A1-4240 743 and E.U.A.-A-4, 410 »570 describe applications of cholesteric» cross-linked liquid crystals as pigments. However, these systems also have disadvantages. In the first place »they do not exhibit the temperature stability that is essential under conventional series painting conditions» and in the second they swell in the paint »resulting in a change of color. During the baking of the paint »the shrinkage of the helix and a subsequent associated color change take place again» in such a way that the precise adjustment of color is very difficult. Furthermore, the systems described above in which the color has been adjusted by heat treatment or a specific temperature program do not have the desired properties of refinishing. The object of the present invention is to avoid the disadvantages of the prior art and to provide a material which has reproducible color properties. the stability of temperature that is necessary for automotive finishes in series and has high resistance to chemical compounds (insolubility).

It has been discovered that the disadvantages of the prior art can be avoided "surprisingly" by using mixtures of cholesteric polymers with cholesteric and / or nematic polymers and that materials can be provided that can be reproduced reproducively in their coloristic properties. The present invention therefore relates to mixtures of liquid crystalline polymers consisting of at least two liquid crystalline cholesteric polymers or at least one liquid crystalline nematic polymer and at least one sterile non-liquid crystal steric polymer. If, for example, a cholesteric main chain polymer (CLCP) having a dark violet color is mixed in the foundry with a nematic main chain polymer (LCP) having the pale beige color typical of LCPs (this pale beige color) of the LCPs will be referred to hereinafter as "colorless") »it is observed that the mixture has very bright color properties. Depending on the percentage of the mixture, very bright blue colors are obtained »green or even yellow gold. This is very surprising »as it is known by experts in the field that the pigment mixture is generally associated with a decrease in brilliance and opaque hue. The color change in the mixture of CLCP and LCP is presumably attributable to the fact that the LCP is mixed with the CLCP in such a way that the helix pitch is specifically increased. Such an increase in the step size of ice is associated with a change in the wavelength of the light selectively reflected »which is evident from the color change. Surprisingly, a precise setting of the mixing ratio of CLCP-LCP allows any desired color reflection to be established specifically and reproducibly. However, the hue resulting from a certain percentage of mix is not predictable and must be determined by an appropriate experiment. However, the new mixtures are not restricted only to pale beige LCPs and to dark violet CLCPs. The following possibilities exist for the preparation of new LCP mixtures having pronounced selective reflection: a) Mixtures of colorless LCPs with CLCPs whose helix pitch is highly twisted towards the end of the short wave (close to 400 nm) of the visible spectrum or even beyond the visible spectrum: Such CLCPs generally have a dark brown to dark violet color which appears very dirty and not very bright. The LCP affects the propeller of the CLCP in the mix thereof in such a way that it changes from the short wave tip of the visible spectrum into the visible spectrum which is evident from the bright reflection colors. With an increase in the proportion of LCP »the color reflection of the mixture changes towards colors of longer wavelength» this is »a mixture with a CLCP that itself has a violet coloristic property exhibits blue» green coloristic properties and finally yellow gold with an increase in the proportion of LCP b) Mixtures of colorless CLCPs with CLCPs as described under a): the term CLCPs without color is taken to mean CLCPs that form a steric colloidal phase »but that they have only one very weak twisting »this is» the helix pitch is larger than the long wave limit of visible light. Such a polymer exhibits the same beige impression as an LCP. The aforementioned mixtures also exhibit bright reflections of color "attributable to the specific increase in the helix pitch of the highly twisted CLCP through the incorporation of the softly bent CLCPs. c) Mixtures of colorless CLCPs or LCPs with colored CLCPs: The coloristic properties of colored CLCPs. eßto is »polymers that already exhibit colors of coleßteric reflection» can be modified in an objective way by incorporating colorless CLCPs or colorless LCPs. Non-twisted LCP or weakly twisted CLCP may increase the helix pitch in the mix with the colored CLCP and thus result in a change in the color properties. Anyway, the color change is limited to relatively long wave colors, because the pitch of the helix is increased. This means that it is possible »for example» to change a CLCP having green color properties to yellow gold color properties by incorporating LCP or CLCP without color. However, it is not possible to change a CLCP having green coloristic properties to blue color properties by incorporating a colorless LCP or CLCP because this would correspond to a greater helix twist. d) Mixtures of a plurality of colored CLCPs: The blending of a plurality of colored CLCPs also allows establishing a helix pitch and establishing the corresponding coloristic properties in an objective manner. For example, the helix of a blue CLCP can be increased in the step by mixing with a gold yellow CLCP in such a way that a mixture with green coloristic properties is obtained. e) Mixtures of a plurality of colored CLCPs having different directions of rotation of the propeller: The helix pitch of a sample having a highly twisted propeller may also be increased by incorporating a mixture also having a highly twisted propeller, but opposite direction of rotation »which is evident from relatively long-wave colors. Samples that have helices of different directions of rotation are obtained simply by using the corresponding enantiomers. For example »it is possible to prepare a sample with <; R) - (-) - 2-methypiperazine as the chiral monomer and a corresponding sample of opposite passage with (S) - (+) - 2-methylpiperazine as the chiral comonomer. The mixtures described above are not restricted to two mixing components in each case. It is also possible to prepare mixtures of a plurality of »for example 2 to 10» advantageously 2 to 5 components, not all of which need to be under the categories of a) to e). For example, it is possible to prepare a mixture of two LCPs. different a colorless CLCP »a plurality of colored CLCPs and a highly twisted CLCP. In general »the passage of a mixture is given by the meaning of the steps of the individual components. It is advisable to select the individual components of the mixture in such a way that the resulting coloristic properties are within the desired range. The fine adjustment of the hue is then carried out by means of the percentage of mixing of the components. However, new LCP mixes can also make it possible to cover the entire color spectrum using only two different mixing components. It is then unnecessary to look for another mix component for each nuance; instead a "highly bent polymer is sufficient" which can then be mixed with polymer having only a weak bend, or none at all »to give any desired coloristic property. The blends also allow for differences in the color properties of several batches of polymers to be compensated. For example, the color differences that appear in the preparation of a green product from the preparation conditions that have not been reproduced optimally can be compensated by means of appropriate mixing. For the purpose of the present invention preference is given to mixtures of polymers consisting of one or more liquid crystalline cholesteric polymers having selective reflection in the visible wavelength region of the light and one or more liquid crystalline cholesteric polymers having having Selective reflection in the invisible wavelength region of light. For the purposes of the present invention, preference is given even more to polymer blends consisting of at least two different liquid cholesteric crißtalinoß polymers, each of which has selective reflection in the visible wavelength region of the light. For the purposes of the present invention, it gives greater preference to mixtures of polymers consisting of at least two different polymeric cholesteric crystalline fluids, each of which has selective reflection in the invisible wavelength region of the light. but on different sides of the visible spectrum. The mixing ratios of LCP: CLCP or CLCP: CLCP in the new mixtures of liquid crystalline polymers can be as desired and are determined by the hue to which it is aspirated in each case. Relationships extend, for example. from 1 to 99:99 to 1% by weight, preferably from 10 to 90:90 to 1054 by weight in the respective components.

The main group nematic polymers (LCPs) can be all LCPs known to the person skilled in the art, as listed in G.W. Becker. D. Braun. "Kunstßtoff-Handbuch". Volume 3/3. page 219-258. Cari Hanßer Verlag. Munich 1994. Preferred LCPs are those containing monomers of the group consisting of aromatic hydroxycarboxylic acids and / or aromatic dicarboxylic acids and aromatic diols. In those groups. Hydroxydrocarboxylic aromatic acids can be replaced by hydrocarboxylic cycloaliphatic acids or amy nocarboxylic aromatic acids, aromatic dicarboxylic acids can be replaced by cycloalphatic dicarboxylic acids. and the aromatic diols can be replaced by aromatic diamines, inophenols and / or cycloaliphatic diols. Considering the stoichiometric ratios of said monomers from one to another, it must be ensured that the stoichiometry of the functional groups by polycondensation with ester formation and / or amino bonds which are known to the experts in the medium are ensured. In addition, the polymers can also contain components having more than two functional groups, for example dihy drox benzoic acids, trihydroxy benzenes acids or triitic acids. These components act as branching points in the polymer and can only be added in low concentrations, for example from 0 to 5 Y. molar, in order to avoid crosslinking of the material. Particularly preferred LCPs are nematic β-polymers of the main group constructed from the following units of individual groups of monomers: aromatic hydroxycarboxylic acids and aminocarboxylic acids: "O-C) > - f)) - COOH IfeN -0- COOH Aromatic dicarboxylic acids and aliphatic dicarboxylic acids: Aromatic diols, aminophenols and aromatic diamines H * N \ 0 / ~ 0H H, N 2N_ "NH2 ~ NH2 Loe LCPs used are very particularly preferably compounds in which the aromatic hydroxy carboxylic acid is p-hydroxybenzoic acid and / or 2-hydroxy-6-naphthoic acid , the aromatic dicarboxylic acid is 2,6-naphthalenedicarboxylic acid, terephthalic acid and / or isophthalic acid, and the aromatic diol is hydroquinone, resorcinol and / or 4,4'-dihydroxy bifen.The CLCPs that can be used in accordance with the invention are all cholesteric polymers Eßtoß include both the main chain coleßteric β-polymer and the side-group cholesteric polymers Examples of side group ßon pol ißi loxane polymers, cyclic ßiloxanes, polyacrylates and polymethacrylates containing mesogens in a side group. Meßenoßß in the side group may contain all the structures β known to the person skilled in the art, for example substituted phenyl β-benzoate or biphenols. The main chain β -ßßßßßßßßerßß polymers are generally prepared from a chiral component and from hydroxycarboxylic acids and / or a combination of dicarboxylic acids and diols. In general, said polymers consist essentially of aromatic constituents, but it is also possible to use cycloaliphatic and aliphatic components, for example, cyclohexane dicarboxylic acid. For the purposes of the present invention, preference is given to chain-linker polymers containing: a) from 0 to 99.9 mol% of at least one compound from the group consisting of aromatic acids hydroxycarboxylic acidic acid, cycloaliphatic hydroxycarboxylic acids and aromatic acids amine. carboxyl; b) from 0 to 49.95 *? molar of at least one compound from the group consisting of aromatic dicarboxylic acids and cycloal phatic acid dicarboxylic acid; c) from 0 to 49.95 mol% of at least one compound of the group consisting of aromatic diols, cycloaliphatic diols and aromatic d amiñas; d) from 0.1 to 40 molar, preferably from 1 to 25 molar, of chiral, bifunctional comonomers, and e) from 0 to 5 molar% of a branching component containing more than two functional groups (OH or COOH), where the sum is 100% molar. In consideration of the percentages given, it must be ascertained that the stoichiometry known to the person skilled in the art of the functional groups so that the polycondensation is ensured. In addition, the polymers can also contain components having more than two functional groups, for example »dihydroxybenzoic acid» trihydroxy encene acid or trimellitic acid. These components act as branching points in the polymer and can be added only at low concentrations, for example from 0 to 5 mol%, in order to avoid crosslinking of the material. Particular preference is given to the cholesteric group-core polymers constructed from the following individual group-monomers: a) hydroxycarboxylic aromatic acids and aminocarboxylic acids: , - ^ - ^ COOH ^ HlN - @ - -C OH HO- CO b) aromatic dicarboxylic acids and aliphatic d carboxylic acids: HOOC - ^^ - COOH H0OC- < ^ -H; ^ - COOH c) aromatic diols, aminophenols and aromatic diamines: H2N < ) -NH 'd) monomeroß qu ralee »b trabaleß: H00C-CH2-CH-CH, -CH2-C00H CH, CH ~ C IH-CH, CH OH OH where R and R 'are each. independently of each other.

H. C x -Cß alkyl or phenyl "preferably H or CH 3. CLCPs are particularly preferable polymers containing camphoric and / or isosorbide acid as a chiral component and p-hydroxybenzoic acid and / or 2-hydroxy-6-naphthoic acid and / or terephthalic acid and / or isophthalic acid and / or hydroquinone. and / or resorcinol and / or 4,4'-dihydroxybiphenyl and / or 2,6-naphthalide carboxylic acid. The chimeric comonomers β are preferably used in an enantiomerically pure form. If mixtures of enantiomers of a type are used, it must be ensured that one of a form of enantiomer is present in an effective excess. The monomers used according to the invention can be used either directly or precursor expedients can be used which are converted into the desired monomers under the subsequent reaction conditions. For example, aminophenol and trimellitic anhydride can be used in place of M- (4-h-droxifeni 1) -trimel itimide. The polycondensation can be carried out by any polycondensation process known to the person skilled in the art, for example, "fused condensation with acetic anhydride" which is described in EP-A-0 391368. The monomers are preferably chained through cross-linkages. ester (polyester) and / or by means of amide bonds (polyester ether / pol ida) but can also be chained by other types of chaining known to the person skilled in the art, for example polyester. When the monomer units are selected, it must be ensured that the stoichiometry known to the person skilled in the art of the functional groups is ensured, that is, that functional groups that react with each other in the polycondensation reaction are used in suitable percentages. For example, when dicarboxylic acids and diols are used, a number of hydroxyl groups that coincide with the number of carboxyl groups must be present. Instead of carboxylic acids, it is also possible to use carboxylic acid derivatives, for example, acid chlorides or carboxylic acid esters. Instead of hydroxyl components, it is also possible to use the corresponding hydroxyl derivatives, for example, acetylated hydroxyl compounds. The polymer units described may also contain more advanced substi-ters, for example methyl, methoxy or halogen. When cholesteric polymers of the side group are used, it is also advantageous to use side-glass liquids as a component of the mixture. The polymers to be mixed may also contain interlacing groups, so that it is possible to fix the mixture of non-liquid crystal polymers by, for example, photoentrelation. In a preferred embodiment both the CLCPs and the LCPs have very low solubility "so their molecular peptides can not be determined by the methods otherwise usualeß (GPC or light diffusion). The intrinsic viscosity of the polymers in a solution of pentafluorophenol / hexafluoro-isopropanol can be used as a measure of molecular weight. For the purposes of the present invention, the particularly suitable polymers are those having an intrinsic viscosity of 0.1 to 10 dl / g. The intrinsic viscosity and therefore the molecular weight of the CLCP and the LCP may differ, but it is advantageous if both are in a comparable order of magnitude. The mixing of CLCPs and LCPs can be carried out in the casting in conventional equipment »eg mixers» extruders »mixer reactors and high shear mixer casters or roller mills. The use of an extruder is preferred here. , because the desired color can be established directly by varying the proportions of the polymer. For example, sufficient LCP may be equalized within a continuous blue CLCP extrusion until the mixture has the desired color, for example, a green color. The precise shade can be determined directly on the extruded material. However, the polymers can also be premixed as powders or pellets and then extruded. In addition »it is possible to precipitate and further process the mixture from a common solution. For example »side-effect cholesteric pol isi loxane» as described in DE-A1-4416 191 or US-A-4 »410.570, can be made from a solution containing an achiral (nematic) polysiloxane of side group or a cholesteric polysiloxane of side group of a different color to give a film that can be crosslinked by photo-crosslinking, as for example by UV irradiation, and further processed, and which is distinguished by the fact that its color can be established precisely to through the mixing ratio. The mixture behaves like a new polymer, which may be further processed in a manner similar to the starting polymer, for example, as a material. A material is a formed structure, for example an injection molding, extruded profile or pipe, tape, film or fiber. The resulting mixture is particularly suitable as a basic material for the preparation of platelet-shaped effect pigments, which are distinguished, in particular, by their hue reproducibility. The new polymer mixtures are even more suitable as starting material for the production of cover effects or powder coating effects. In the examples below, the parts are by default.

EXAMPLE I SYNTHESIS OF UW LCP 28.218 parts of 2-h-hydroxyl-6-naphthoic acid, 20.718 parts of 4-h-hydroxybenzoic acid, 16.614 parts of terephthalic acid, 9.310 parts of 4.4"-dihydroxybiphenyl and 5.505 partse of resorcinol are mixed in a reactor with 5,268 parts of acetic anhydride »and a mild nitrogen vapor is passed through the reactor.The mixture is heated at 140 ° C for 15 minutes and then maintained at this temperature for 20 minutes.The temperature is then raised to 320 ° C During 150 minutes, the acetic acid begins to distill from approximately 220 ° C. After the temperature has reached 320 ° C, the mixture is moved at this temperature for another 15 minutes.The flowing nitrogen is then finished, and a vacuum The mixture is evacuated in vacuo (approximately 5 mbar) for an additional 30 minutes.The polymer is then aerated with nitrogen, cooled and set aside.The polymer has the beige color which is typical of cadmium nematic polymers. main ena.

E ET.PLQ S NTESIS OF A CLCP 16,931 parts of 2-hydro? I-6-naphthoic acid. 20,718 parts of 4-hydroxy-benzoic acid, 7.267 parts of b-phenyl-4,4 * -d? Carboxylic acid and 4.384 parts of l, 4: 3-6-dinhydro-D-borditol (ißoßorbido) mixed ions of a reactor with 31,457 parts of acetic anhydride, and a soft nitrogen vapor eε passed through the reactor. The mixture is heated at 140 ° C for 15 minutes and then maintained at this temperature for 30 minutes. The temperature is then raised to 335 ° C for 165 minutes. The acetic acid begins to distill from almost 220 ° C. After the temperature has reached 335 ° C, the mixture is moved at this temperature for 30 minutes more. The flowing nitrogen is then finished, and a vacuum is applied. The mixture is moved in vacuum (almost 5 mbar) for 30 more minutes. The polymer is then aerated with nitrogen, cooled and set aside. The polymer has a dark violet color, dirty. The color appears even during vacuum condensation and is only retained after rapid cooling; If the mixture is slowly cooled, the color appears and a gray beige polymer is obtained which readapts the dark violet color upon heating.

SYNTHESIS PE MN g? P 22.582 parts of 2-hydroxy-6-naphthoic acid, 49.723 parts of 4-hydroxy-benzoic acid, 9.968 parts of terephthalic acid and 8.714 parts of 4: 3,6-dianhydro-D-borditol (isosorbide) are mixed in a reactor with 63,283 parts of acetic anhydride, and a mild nitrogen vapor is passed through the reactor. The mixture is heated at 140 ° C for 15 minutes and then maintained at that temperature for 30 minutes. The temperature is then raised to 335 ° C for 165 minutes. The acetic acid begins to distill from almost 220 ° C. After the temperature has reached 335 ° C, the mixture is moved at this temperature for 30 min. The nitrogen flowing then is finished, and a vacuum is applied. The mixture is moved in vacuum (almost 5 mbar) for 30 more minutes. After aeration with nitrogen, the polymer is extruded and pelletized. The polymer has a dirty dark violet color. The color appears even during vacuum condensation.

EEI IQ 4 SYNTHESIS OF A CLCP 45.163 parts of 2-hydroxy-6-naphthoic acid »38.121 parts of 4-h acid drox-benzo co. 6,977 parts of terephthalic acid and 6,138 parts of 1.4: 3.6-dianhydride-D-sorbitol (isoesorbide) ßon mixed in a reactor with 63,283 parts of acetic anhydride, and a mild nitrogen vapor is passed through the reactor. The mixture is heated at 140 ° C for 15 minutes and then maintained at this temperature for 30 minutes. The temperature is then raised to 335 ° C for 165 minutes. The acetic acid begins to distill from almost 220 ° C. After the temperature has reached 335 ° C the mixture is moved at this temperature for 30 more minutes. The flowing nitrogen is then finished, and a vacuum is applied. The mixture is moved in vacuum (almost 5 mbar) for 30 more minutes. After aeration with nitrogen, the polymer is extruded and pelletized. The polymer has a beige color, slightly faded. The color appears even during vacuum condensation and is retained after cooling.

EXAMPLE 5 S NTESIS PE A GWCP 28.218 parts of 2-hydroxy-6-naphthoic acid, 34.530 parts of 4-hydroxy-benzoic acid »8609 parts of cyclohexane-1,4-dicarboxylic acid co. 2.793 parts of 4.4'-dihydroxybifeni and 5.115 parts of l, 4: 3-6-dianhydro-D-ßorbitol (isosorbide) are mixed in a reactor with 52.580 parts of acetic anhydride, and a mild nitrogen vapor is passed through of the reactor. The mixture is heated at 140 ° C for 15 minutes and then maintained at this temperature for 20 minutes. The temperature is then raised to 320 ° C for 150 minutes. The acetic acid begins to distill from almost 220 ° C. After the temperature has reached 320 ° C the mixture is moved at that temperature for 60 more minutes. The flowing nitrogen is then finished and a vacuum is applied. The mixture eß moved in vacuum (almost 5 mbar) for 30 more minutes. The polymer is then aerated with nitrogen, cooled and set aside. The polymer exhibits a bright green gold color when viewed perpendicularly. The color appears even during vacuum condensation and is retained even after cooling.

EXAMPLE 6 SYNTHESIS E U Gt P 4,703 parts of 2-hydroxy-6-naphthoic acid. 3,453 parts of 4-hydroxy-benzoic acid, 4,153 parts of terephthalic acid, 270 parts of p-pheni-lenediamine, 1,590 parts of d-methyl-1-benzidine and 2,192 parts of l-4: 3,6-dianhydro-D-bordbitol (isosorbide ) are mixed in a reactor with 10,460 parts of acetic anhydride, and a mild nitrogen vapor is passed through the reactor. The mixture is heated at 140 ° C for 15 minutes and then maintained at this temperature for 20 minutes. The temperature is then raised to 325 ° C for 150 minutes. In acetic acid it begins to distill from 220 ° C. After the temperature has reached 325 ° C. the mixture is moved at this temperature for 60 more minutes. The flowing nitrogen is then finished, and a vacuum is applied. The mixture is moved in vacuum (almost 5 mbar) for 30 more minutes. The polymer is then aerated with nitrogen, cooled and set aside. The polymer has a violet color. The color appears even during vacuum condensation and is retained even after cooling.

E EttP Q 7 SYNTHESIS OF A CLCP 11. 287 parts of 2-hydroxy-6-naphthoic acid. 13,812 parte of 4-hydroxy-benzoic acid. 4,323 parts of naphthalene-2,6-d carboxylic acid. 1,396 parts of 4.4'd hydroxy-feni lo. and 1826 parts of 1.4: 3 »6-d? 'anhydro-D-ororbit1 (isosorbide) are mixed in a reactor with 20.971 parts of acetic anhydride» and a mild nitrogen vapor is passed through the reactor. The mixture is heated at 140 ° C for 15 minutes and then maintained at this temperature for 20 minutes. The temperature is then raised to 330 ° C for 150 minutes. The acetic acid begins to distill from almost 220 ° C. After the temperature has reached 330 ° C the mixture is moved at this temperature for 20 min. The flowing nitrogen is then finished »and a vacuum is applied. The mixture is moved in vacuum (7 mbar) for 40 more minutes. The polymer is then aerated with nitrogen, cooled and set aside. The polymer has a yellowish greenish-gold color, very bright, when viewed perpendicularly. The color appears even during vacuum condensation and is retained even after cooling.

EXAM Q 9 SYNTHESIS OF A CLCP ,317 parts of 2-hydroxy-6-naphthoic acid. 39,778 parts of 4-hydroxybenzoic acid »18» 993 parts of 4 »4-dihydroxybiphenyl and 20,444 parts of camphoric acid (lR.3S) - (+) are mixed in a reactor with 62.914 parts of acetic anhydride, and a mild steam of nitrogen is passed through the reactor. The mixture is heated at 140 ° C for 15 minutes and then maintained at this temperature for 30 minutes. The temperature is then raised to 335 ° C for 165 minutes. The acetic acid begins to distill from 220 ° C. After the temperature has reached 335 ° C, the mixture is moved at this temperature for 30 more minutes. The flowing nitrogen is then finished, and a vacuum is applied. The mixture is moved in vacuum (almost 5 mbar) for 30 more minutes. The polymer is then aerated with nitrogen »cooled and removed. The polymer has a bright gold-red color. The color appears even during vacuum condensation.

SYNTHESIS PE A CLC 4,703 parts of 2-idroxy-6-naphthoic acid; 3,453 parts of 4-hydroxybenzoic acid. 4,153 parts of terephthalic acid, 216 parts of p-phenyl-enediamine, 1,272 parts of dimeti Ibencidin, 451 parts of diaminophen-1-benzimidazole and 2,192 parts of l »4: 3» 6-dianhydro-D-sorbitan (isobiso) ßon ezcladaß in a reactor with 10,460 parts of acetic anhydride. and a gentle nitrogen vapor is passed through the reactor. The mixture is heated at 14 ° C for 15 minutes and then maintained at this temperature for 20 minutes. The temperature is then raised to 320 ° C for 150 minutes. The acetic acid begins to distill from 220 ° C. After the temperature has reached 320 ° C. the mixture is moved at this temperature for 60 minutes more. The flowing nitrogen is then finished, and a vacuum is applied. The mixture is moved in vacuum (almost 5 mbar) for 30 minutes more. The polymer is then aerated with nitrogen, cooled and set aside. The polymer has a blue-green color. The color appears even during condensation in vacuum and retained even after cooling. The material is very brittle.

AXIS? PLQ IQ S NTESIS PE A CLCP 1,411 parts of 2-hydroxy-6-naphthoic acid, 1,727 parts of 4-hydroxybenzoic acid, 415 parts of terephthalic acid and 250 parts of (R) - (-) - 2-methylpiperazine are mixed in a reactor with 2,619 parts of acetic anhydride, and a mild nitrogen vapor is passed through the reactor. The mixture is heated at 140 ° C for 15 minutes and then maintained at this temperature for 30 minutes. The temperature is then raised to 330 ° C for 165 minutes. The acetic acid begins to distill from almost 220 ° C. After the temperature has reached 330 ° C. the mixture is moved at this temperature for 30 more minutes. The flowing nitrogen is then finished, and a vacuum is applied. The mixture is moved in vacuum (almost 5 mbar) for 30 minutes more. The polymer is then aerated with nitrogen, cooled and set aside. The polymer has a slightly faded beige color. The color appears even during vacuum condensation and is retained even after cooling.

EXAMPLE MIXING A LCP WITH A CLCP The polymers of Examples 1 and 2 are melted at 330 ° C in a flask in an LCP: CLCP ratio of 1: 2 and moved for 15 minutes to give a homogeneous mixture. The mixture has a blue, bright color.

EXAMPLE AZ MIX PE A LCP WITH A CLCP The β-polymer of Example 1 and 2 ßon were melted at 330 ° C in a flask in a LCP: CLCP ratio of 1: 1 and moved for 15 minutes to give a homogeneous mixture. The mixture has a green, bright color.

EXAMPLE 13 PE LCP MIX WITH A CLCP The polymers of Examples 1 and 2 are fused to 330 ° C in a flask in a LCP: CLCP ratio of 2: 1 and moved for almost 15 minutes to give a homogeneous mixture. The mixture has a golden yellow color, bright.

EXAMPLE 14 MIXING A CLCP WITH A CLCP parts of the CLCP prepared in Example 3 are molded to a particle fineness of < 5 mm in a cutting mill, and mixed with 10 parts of the CLCP prepared in Example 4 which has been ground in the same manner. The mixture is then extruded in a single screw extruder at temperatures of 250 ° C to 350 ° C, cooled using air and granulated, giving a mixture that has a bright, blue color, from a perpendicular angle of view and a reddish blue color. , bright, at an oblique angle of view. If this mixture is applied by means of a spatula to a sheet of pre-heated, black-sizing metal, a film is obtained which is bright blue from a perpendicular angle of view and exhibits selective bright red-blue reflection from an oblique angle of view. .

EXAMPLE 15 MIXING A CLCP WITH A CLCP Example 14 is repeated with the mixture of 15 parts of the CLCP prepared in Example 3 and 15 parts of CLCP prepared in Example 4. An obtained mixture having a bright, greenish-blue color at a perpendicular angle of view and a reddish blue color, bright at an oblique angle of view. If this mixture is applied by means of a spatula to a sheet of preheated metal, of black sizing »a film is obtained which is bright» blue-green from a perpendicular angle of view and has a selective »blue» bright reflection from an angle of Oblique view.

EXAMPLE 16 MIX PE A CLCP WITH A CLCP Example 14 is repeated with the mixture of 10 parts of the CLCP prepared in Example 3 and 20 parts of the CLCP prepared in Example 4. A mixture is obtained having a gold-green, bright color, from a perpendicular angle of view and a bluish green, bright from an oblique angle of view. If this mixture is applied by means of a spatula to a sheet of preheated, black-sizing metal, it has obtained a film that is gold-green, shining from a perpendicular angle and has a selective reflection of bluish-green, shiny »from an angle of oblique vißta.

EXAMPLE 17 MIXED PE CLCPLCP WITH A CLCP The mixture of Example 11 is compounded for 10 minutes with the CLCP of Example 5 in a weight ratio of 1: 2 in a mixer at temperatures of 300 ° C to 350 ° C. A mixture is obtained which has a pale blue, bright turquoise color, from a perpendicular angle of view and a dark blue, bright color, from an oblique angle of view. If this mixture is applied by means of a spatula to a sheet of preheated, black-sizing metal, a peel is obtained which is bright, pale turquoise blue, from a perpendicular angle of view and has a bright selective reflection, blue bluish, from an oblique angle of view.

EXAMPLE 19 MIX PE A CLCP WITH A CLCP The CLCP of Example 6 is mixed for 10 minutes with the CLCP of Example 7 in a weight ratio of 1: 2 in a mixer at temperatures of 300 ° C to 350 ° C. A mixture having a turquoise color is obtained, bright, from a perpendicular angle of view and a bluish blue color, bright, from an oblique angle of view. If this mixture is applied by means of a spatula to a sheet of preheated, black-sizing metal, a film is obtained which is bright, turquoise from a perpendicular angle of view and has a selective reflection of bluish blue, bright, from an angle of oblique sight.

EXAMPLE 19 MIX PE A CLCP WITH A CLCP The CLCP of Example B is extruded with the CLCP of Example 9 in a weight ratio of 1: 1 in a twin screw extruder at temperatures of 250C to 350 ° C. A mixture is obtained having a yellowish green color, bright, from a perpendicular angle of view and a greenish blue color, bright, from an oblique angle of view. If this mixture is applied by means of a spatula to a sheet of preheated, black-sizing metal, a peel is obtained which is yellowish-green »bright, from a perpendicular angle and has a selective green-blue, bright reflection» from An oblique angle of view.

EXAMPLE ZO MIX PE A CLCP WITH A CLCP The CLCP of Example 9 is extruded with the CLCP of Example 10 in a weight ratio of 3: 2 in a twin screw extruder at temperatures of 2B5C to 350 ° C. A mixture having a greenish-yellow »bright» color is obtained from a vertical perpendicular angle and has a greenish-turquoise »bright» color from an oblique angle of view. If this mixture is applied by means of a spatula to a sheet of preheated "black sizing" metal, a film is obtained which is greenish yellow, bright, from a perpendicular angle of view and has a selective greenish, bright turquoise reflection from a oblique angle of view.

Claims (15)

NOVELTY OF THE INVENTION CLAIMS

1. - A method for adjusting the color of liquid crystalline polymers »comprising mixing at least one liquid crystalline cholesteric polymer having selective reflection in the visible wavelength region of light waves and at least one liquid crystalline cholesteric polymer having a selective reflection in the region of invisible wavelength of light; or at least two different liquid crystalline cholesteric polymers each of which has selective reflection in the visible wavelength region of the light; or at least two different liquid crystalline cholesteric polymers each of which has selective reflection in the invisible wavelength region of the light, but on different sides of the visible spectrum; or at least one liquid crystalline nematic polymer and at least one liquid crystalline cholesteric polymer with one or the other in the mixture, and, if desired, extruding the mixture.

2. The process according to claim 1 »further characterized in that the crystalline liquid cholesteric polymers are cholesteric main chain polymers.

3. The process according to claim 1 or 2. further characterized in that the liquid crystalline cholesteric polymers are polyesters.

4. The process according to claim 2 or 3 »further characterized in that the main chain cholesteric polymer comprises from 0 to 99.9 mol% of at least one compound from the group consisting of aromatic hydrocarboxylic acids. cycloalicyclic hydroxycarboxylic acids and ammonium carboxylic aromatic acids; from 0 to 49.95 mol% of at least one compound from the group consisting of aromatic dicarboxylic acids and cycloaliphatic dicarboxylic acids; from 0 to 49.95 mol% of at least one compound from the group consisting of aromatic diols, cycloalpha diols. and aromatic diamines; 0.1 to 40 X molar, preferably 1 to 25 Y. molar, of chiral comonomers. bifunctional and from 0 to 5 mol% of a branching component containing more than two functional groups, wherein the sum is 10054 molar.

5. The process as claimed in claim 4 further characterized in that the bifunctional comonomer qu? Ral contains at least one compound of the formula CT H H00C-CH2 -CH-CH2 -CH, C00H CH3 -CH-CH-CH, I I I CH, OH OH HOCH2. -CH - 0H HOOC -. COO H O O O O R R 'R X R' in which R and R 'are each. independently of one another. H »C ^ -C alkyl. or phenyl »preferably H or CHa.

6. The process according to claim 4 or 5. further characterized in that the main chain cholesteric polymer comprises p-hydroxy benzoic acid »2-hydroxy acid? i-6-naphthoic; terephthalic acid »isophthalic acid» 2,6-naphthal endi carboxylic acid. hydroquinone. resorcinol »4» 4-dihydroxybifeni or a combination thereof.

7. The process according to claim 1, further characterized in that the cholesteric crißtalino polymer liquid eß cholesteric polymer side group.

8. The process according to claim 7, further characterized in that the side group polymers contain polysiloxanes, cyclic siloxanes, polyacrylates and / or polymethacrylates in the main chain and mesogenic groups in the side chains.

9. The process according to at least one of claims 1 to 8, further characterized in that the liquid crystalline nematic polymer comprises hydroxycarboxylic aromatic acids and / or aromatic dicarboxylic acids and aromatic diols.

10. A mixture of non-liquid crystal polymers consisting of at least two crystalcrystalline cholesteric polymers or at least one liquid crystalline nematic polymer and at least one liquid crystalline cholesteric polymer in which the liquid crystalline cholesteric polymer is a polymer of main chain which consists of from 0 to 99.9 mol% of at least one compound of the group consisting of aromatic hydroxycarboxylic acids, cycloaliphatic acids hydro? carboxylic acids and aromatic acids amcarcarboxylic acids; from O to 49.95 mol% of at least one compound from the group consisting of aromatic dicarboxylic acids and cycloaliphatic dicarboxylic acids; from O to 49.955 molar of at least one compound from the group consisting of aromatic diols, cycloaliphatic diols, and aromatic diamines; from 0.1 to 40 mol%, preferably from 1 to 25 V. molar of chiral, bifunctional comonomers of the group consisting of H where R and Rt »each» independently of each other »ßon Cx-Cß alkyl or phenyl» preferably H or CH3 »and from 0 to 5 mol% of a branching component containing more than two functional groups» in where the sum is 100% molar.

11. A polymer mixture according to claim 10, comprising p-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, terephthalic acid. isothalic acid. 2,6-naphthalenedicarboxylic acid. hydroquinone, resorcinol. 4.4'-dihydroxybiphenyl. or a combination thereof.

12. A polymer mixture according to any of claims 10 or 11. further characterized in that the non-liquid crystal nematic polymer comprises hydroxycarboxylic aromatic acids and / or aromatic dicarboxylic acids and aromatic diols.

13. A mixture of polymers according to one or more of claims 10 to 12 further characterized in that said mixture is used as a material.

14. A mixture of polymers according to one or more of claims 10 to 12 further characterized in that said mixture is used as a starting material for the preparation of effect pigments.

15. A mixture of polymers according to one or more of claims 10 to 12 further characterized in that said mixture is used as a starting material for the production of effect coatings or effect coating powders.