JP2002121408A - Pigment complex and layered structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a complex of a liquid crystal pigment and/or a liquid crystal film which keeps the ability of color tone-changing by angle and has stability against heat and solvent. SOLUTION: The complex consisting of a liquid crystal pigment and/or a liquid crystal film, and a dispersing medium. The liquid crystal pigment is obtained through crosslinking by using a mixture (liquid crystal mixture) consisting of a crosslinking liquid crystal substance having a chiral phase and having polymerizable groups whose at least 90% is contained in molecules (crosslinking molecules) having at least two polymerizing groups. In a mixture, the polymerizable group exists in an amount of 3.2-15 mmole based on 1 g of the liquid crystal mixture. Further, a complex has a multilayered structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a composite comprising a liquid crystal pigment having excellent thermal stability and a dispersion medium, and a composite comprising the same.
The present invention relates to a composite having a multilayer structure of two or more layers containing at least one layer and at least one substrate layer, and uses thereof.

[0002]

2. Description of the Related Art A liquid crystal having a chiral phase (Liquid-
Materials having a (Crystal) structure (liquid crystal materials) are known. The preparation of such materials consisting of liquid crystal organosiloxanes is described, for example, in U.S. Pat. No. 5,211,877. Pigments (liquid crystal pigments) containing oriented, three-dimensionally crosslinked substances having a liquid crystal structure with a chiral phase, their production and use are described, for example, in DE 424.
No. 0743 (corresponding to US Pat. No. 5,362,315).

[0003] For example, a problem in processing a liquid crystal material into a coating material is a color of the material that varies depending on the application temperature. Conventional liquid crystal materials (for example US-A 521187) in lacquer systems
Liquid crystal organosiloxane described in No. 7 or DE4
When using a liquid crystal pigment disclosed in US Pat. No. 240,743, a processing temperature of 130 ° C. (normal processing temperature in OME coating of automobile bodies) and a processing temperature of 80 ° C. (normal processing temperature in repair coating). A different color results.

[0004] This different behavior of liquid crystal pigments is usually caused by the swelling of the pigments in the production of lacquers and the shrinkage of the lacquers upon drying, ie the action of solvents on the pigments. The structure of the pigment is changed by the swelling process and any leaching of uncrosslinked components from the pigment. Heating of the dried coating results in significant relaxation of the cholesteric liquid crystal helix, ie, a reduction in the helix pitch. At the same time, the reflection center wavelength (Reflexion) which is directly proportional to the pitch of the helix
smittenwelllenge) changes. The color of the pigment shifts towards shorter wavelengths. A shift to a blue portion that can be visually recognized clearly occurs. Depending on the processing temperature selected, i.e. the baking temperature of the lacquer containing such liquid-crystal pigments, a different relaxation of the helix appears in the pigment. This results in undesirable different shades depending on the processing temperature.

[0005] EP-A0887399 (classification number 09)
US09 / 090025) addresses this problem by using, as a pigment material, a crosslinkable liquid crystal organosiloxane which, after crosslinking, results in a liquid crystal pigment having a glass transition temperature (Tg) of up to 80 ° C. and a low extractable fraction uncrosslinked. Solve by choosing. At the same time, complete and single relaxation of the helix is achieved at each temperature above Tg,
This always produces the same color at these temperatures.
The structural properties of these organosiloxanes include flexible structural components in the liquid crystal monomer that are the basis of the pigment,
This is achieved by selecting the so-called spacers accordingly. These organosiloxanes modified with flexible structural parts can be used as liquid crystal pigments in a crosslinked state.
It has indeed a very good thermal stability in the working range of from 130 ° C to 130 ° C, but independently of the working window (working range of 80 ° C to
It has a strong swelling at 130 ° C. or lower because the crosslinking density is relatively small due to the spacer. E
P-A0887399 (classification number 09/090025)
Liquid crystal pigments consisting of a mixture according to US patent application Ser. Causes a shift to the red part. In addition, the modification of the organosiloxanes disclosed in EP-A-0 877 399 has the problem that a costly additional synthesis step causes a clear increase in costs, ie the steps are lengthened.

[0006] EP0887398 (Category No. 09/1)
(Corresponding to the US application having 00019) shows the possibility of obtaining, for the known liquid-crystal pigments, a system in which no appreciable color difference can be ascertained visually at different processing temperatures by selecting an appropriate matrix. This system has the disadvantage that the user has no freedom in choosing its matrix for the liquid crystal pigment. Users are limited in the choice of lacquer components (binders and solvents).

[0007] EP 0 760 836 (US Pat. No. 5,807,749)
No. 7) is a low molecular weight monofunctional, which is distinguished by higher color gloss, higher crosslink density and better chemical resistance than in conventional lacquers and simpler production than hitherto known liquid crystal pigments Disclosed are interference pigments comprising liquid crystalline side chain polymers from functional or bifunctional acrylates. These liquid crystal pigments are also important for painting at about 80 ° C.
Within the processing temperature range of 現 れ る 130 ° C., it has very poor thermal stability which manifests in a shift of the central reflection wavelength greater than 2 nm.

It is known to use these liquid crystal pigments for various purposes. However, the development of the liquid crystal pigment composite which solved these problems and various uses using the same were not clear.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a composite of a liquid crystal pigment and / or a liquid crystal film which is stable to heat and solvent while maintaining the tunability of the angle color.

In the sense of the present invention, the liquid-crystal pigments and films of component (a) of the composite exhibit a visually noticeable color shift in a lacquer or plastic matrix within a temperature interval of 80 ° C. to 130 ° C. Otherwise thermostable.

[0011]

The object of the present invention is to provide a polymerizable polymer containing at least 90% of the polymerizable groups.
In a liquid crystal mixture having a chiral phase which is a polymerizable group component of a molecule having one polymerizable group (crosslinked molecule), 3.2 to 15 mmol of polymerizable groups are present per 1 g of the liquid crystal mixture. And a composite comprising a liquid crystal pigment and / or a liquid crystal film and a dispersion medium.

That is, the present invention relates to (1) a composite comprising (a) a liquid crystal pigment and / or a liquid crystal film and (b) a dispersion medium, provided that (a) contains a polymerizable group and Is a polymerizable group component of a molecule having at least two polymerizable groups (crosslinked molecules), and a mixture comprising a crosslinkable liquid crystal substance having a chiral phase (liquid crystal mixture)
, Polymerizable groups 3.2 to 15 per gram of liquid crystal mixture
The composite layer according to (2) or (1), which is a liquid crystal pigment and / or a liquid crystal film obtained by cross-linking a mixture of a cross-linkable liquid crystal substance having a chiral phase characterized in that millimoles thereof are present. , Containing at least one substrate layer
(1) The composite or multilayer structure according to (1) or (2), wherein the dispersion medium is a dispersion medium for ink or paint, and (4) the dispersion medium is a resin. ,
The composite or multilayer structure according to (2), (5) the composite or multilayer structure according to (1) or (2), wherein the dispersion medium is a liquid, or (6) the composite according to (1) to (5). Anti-counterfeiting product using the body or the multilayer structure, (7) a cosmetic product using the composite or the multilayer structure according to (1) to (5),
(8) The substance having a chiral phase containing a polymerizable group in (a) is a liquid crystal pigment and / or a liquid crystal film obtained by crosslinking a low molecular weight, oligomer or polymer substance having a chiral phase or a mixture of these substances. The composite or multilayer structure according to any one of (1) to (7),
(9) (a) is a general formula: Y ¹ -A ¹ -M ¹ -A ² -Y ^{2 wherein} Y ¹ and Y ² are the same or different, for example, an acrylate group or a methacrylate group, an epoxy group, an isocyanate group And a polymerizable group such as a hydroxy group, a vinyl ether group or a vinyl ester group, and A ¹ and A ² are represented by the general formula C _n H _2n, wherein n is from 0 to 20.
And one or more methylene groups may be substituted by an oxygen atom) or the same or different groups, and M ¹ has the general formula —R ¹ —X ¹ —R ² —X ² — R ³ -X
³ -R ⁴ - has, wherein R ^1, R ^2, R ³ and R ^4, -
O-, -COO-, -CONH-, -CO-, -S-,
-C≡C-, -CH = CH-, -N = N-, -N = N
(O) - it is the same or selected from the group of means different divalent radicals, R ² -X ² -R ³ or R ² -X ² or R ² -
X ² -R ³ -X ³ may be a CC bond, X ¹ ,
X ² and X ³ are 1,4-phenylene, 1,4-cyclohexylene, arylene substituted with B ¹ and / or B ² and / or B ³ or O, N and S 6 to 6 in the aryl nucleus containing two heteroatoms
Heteroarylene having 10 atoms, B ¹ and / or
Or the same or different groups selected from the group of cycloalkylenes having 3 to 10 carbon atoms substituted by B ² and / or B ³ , wherein B ¹ , B ² and B
^3, -H, C ₁ ~C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₂₀ alkylthio, C ₁ -C ₂₀ alkylcarbonyl, C ₁ -C ₂₀ alkoxycarbonyl, C ₁ -C ₂₀ alkylthiocarbonyl , -OH, -F, -Cl, -Br,
-I, -CN, -NO _2, formyl, acetyl and ether oxygen, 1-20 alkyl group having a carbon atom which is interrupted by a thioether sulfur or ester groups,
Or the same or different substituents selected from the group of an alkoxy group or an alkylthio group], and a general formula: V ¹ -A ¹ -W ¹ -Z-W ² -A ² -V ² [ Wherein V ¹ and V ² are the same or different and include acrylate or methacrylate, epoxy, vinyl ether or vinyl ester, isocyanate,
₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₁ -C
₂₀ alkylthio group, C ₁ -C ₂₀ alkoxycarbonyl group, C ₁ -C ₂₀ alkylthiocarbonyl group, -OH,-
F, -Cl, -Br, -I, -CN, -NO 2, formyl, acetyl and ether oxygen, which is interrupted by a thioether sulfur or ester groups, 1-20 alkyl group having a carbon atom, an alkoxy group, or Represents an alkylthio group, A ¹ and A ² have the meanings described and W ¹ and W ² have the general formula —R ¹ —X ¹ —R ² —X ² —R ³ —
Wherein R ¹ , R ² and R ³ have the meanings described, and R ² or R ² —X ² may be a C—C bond;
And X ¹ and X ² have the meanings described and Z is a divalent chiral group consisting of the group of dianhydrohexite, hexosene, pentosene, binaphthyl derivatives, biphenyl derivatives, tartaric acid derivatives or optically active glycols. A chiral compound), wherein the polymerizable groups in the total mixture (of which at least 90%
Is present in molecules having at least two polymerizable groups), characterized in that the concentration is between 3.2 and 15 mmol / g. (10) 70 to 99% by weight of a compound of the general formula Y ¹ -A ¹ -M ¹ -A ² -Y ² and a general formula V ¹ -A ¹ -W ^1-
Characterized in that it is a liquid crystal pigment obtained by crosslinking the claims 9 mixture, wherein the containing Compound 1 to 30 wt% of ^{Z-W 2 -A 2 -V 2} (1) ~ (7 )).

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below.

[0014] One of the objects of the present invention, the color difference,
DIN 5033 and DIN of two lacquer samples customarily produced by the lacquer application at the stated temperature
Color spacing (Farbabstand) ΔE according to 6174
^{When *} is 2 or less, it is recognized as visually unrecognizable (L. Dulog, H. Schweiger,
Farbe & Lack 1997, pp. 30-44). To achieve this object in the green range, in which the eyes are particularly sensitive to color differences in brilliant pigments, according to the invention, when the lacquer samples are produced at 80 ° C. to 130 ° C., the central reflection wavelength is less than 2 nm. It is necessary to become.

The liquid crystal mixture used for obtaining the liquid crystal pigment and / or liquid crystal film of the present invention is preferably a low molecular weight, oligomer or polymer substance having a chiral phase as a substance to which a polymerizable group is bonded. Or it contains a mixture of these substances. These chiral phases may be thermochromic twisted nematic, smectic or discotic phases. The substance may have a thermotropic phase or a lyotropic phase.

Particularly preferably, the liquid-crystal mixtures according to the invention have the general formula Y¹-A¹-M¹-A^Two-Y^Two [Where Y¹And Y^TwoAre the same or different, for example
Acrylate or methacrylate, epoxy,
Socyanate group, hydroxy group, vinyl ether group or
Means a polymerizable group such as a vinyl ester group, and
And A¹And A^TwoIs the general formula C_nH_2n(Where n is 0-2
An integer of 0, wherein one or more methylene groups are
Or the same or different groups)
And M1 has the general formula -R¹-X¹-R^Two-X^Two-R^Three
-X^Three-R^Four-Where R¹, R^Two, R^ThreeAnd R
^FourIs -O-, -COO-, -CONH-, -CO-,
-S-, -C≡C-, -CH = CH-, -N = N-,-
Same or different selected from the group of N = N (O)-
A divalent radical, and R^Two-X^Two-R^ThreeOr R^Two-X
^TwoOr R^Two-X^Two-R^Three-X^ThreeMay be a CC bond
And X ¹, X^Two, X^ThreeIs 1,4-phenylene,
1,4-cyclohexylene, B¹And / or B^TwoAnd
And / or B^ThreeArylene or O, N or
Containing 1 to 3 heteroatoms from the group of
Heteroaryl having 6 to 10 atoms in reel nucleus
N, B¹And / or B^TwoAnd / or B^ThreeReplaced by
Cycloalkylene having 3 to 10 carbon atoms
The same or different groups selected from the group of
And B¹, B^TwoAnd B^ThreeIs -H, C₁~ C₂₀Alkyl, C
₁~ C₂₀Alkoxy, C₁~ C₂₀Alkylthio, C₁~ C
₂₀Alkylcarbonyl, C₁~ C₂₀Alkoxycarboni
Le, C₁~ C₂₀Alkylthiocarbonyl, -OH,-
F, -Cl, -Br, -I, -CN, -NO_Two, Holmi
Acetyl and ether oxygen, thioether sulfur
Or 1 to 20 carbon atoms interrupted by
Alkyl, alkoxy or alkylthio
The same or different substituents selected from the group of
And a compound of the general formula: V¹-A¹-W¹-Z-W^Two-A^Two-V^Two [V¹And V^TwoMay be the same or different
Acrylate or methacrylate, epoxy
Group, vinyl ether group or vinyl ester group, isocyanate group
Anate group, C₁~ C₂₀Alkyl group, C₁~ C₂₀Alkoki
Si, C₁~ C₂₀Alkylthio, C₁~ C₂₀Alkoxycal
Bonil, C₁~ C₂₀Alkylthiocarbonyl, -OH,
-F, -Cl, -Br, -I, -CN, -NO_Two, Hor
Mill, acetyl and ether oxygen, thioether sulfur
Or 1-20 carbons interrupted by an ester group
Alkyl group, alkoxy group or alkyl having atom
A thio group, A¹And A^TwoHas the stated meaning
And W¹And W^TwoIs the general formula -R¹-X¹-R^Two-X^Two-R^Three
-Where R¹, R^TwoAnd R^ThreeMeans the described meaning
And R^TwoOr R^Two-X^TwoIs a CC bond,
Well, and X¹And X^TwoHas the stated meaning and
And Z are dianhydrohexite, hexosene, pen
Tosen, binaphthyl derivatives, biphenyl derivatives, tartar
Divalent key from the group of acid derivatives or optically active glycols
A chiral compound).
In this case, the polymerizable groups in the entire mixture (at least 90
% Is present in molecules having at least two polymerizable groups
Is between 3.2 and 15 mmol / g.
You.

In particular, the liquid-crystal mixtures according to the invention comprise 70-99% by weight of a compound of the general formula Y ¹ -A ¹ -M ¹ -A ² -Y ² as defined above and a compound of the general formula defined above. V
^{1 -A 1 -W 1 -Z-W} 2 -A 2 containing the compound 1 to 30 wt% of -V ^2, this time the polymerizable groups in the total mixture (at least 90% at least two polymerizable Concentration present in molecules with groups) is between 3.2 and 15 mmol / g.

The general formula Y ¹ -A ¹ -M ¹ -A ^2- depends on the color adjustment.
90 to 95% by weight of a compound of Y ^{2 and} a compound of the general formula V ¹ -A ^1-
Particular preference is given to mixtures having from 5 to 10% by weight of compounds of the formula W ¹ -Z-W ² -A ² -V ² , whereby the polymerisable groups in the total mixture (at least 90% of which are at least 2 polymerisable groups) Concentrations of 3.2 and 15)
Between mmol / g.

In a particularly simple embodiment, the liquid-crystal mixtures according to the invention are between 500 and 1,000, in particular 5
450-800, preferably 460-625, in combination with a chiral compound having an average molecular weight between 00-700.
Low molecular weight nematic crosslinkable unsubstituted hydroquinone dibenzoate derivative having an average molecular weight of
A hydroquinone monobenzoate derivative having an average molecular weight of from 00 to 400, preferably from 220 to 300,
The average molecular weight of the whole mixture does not exceed 625.

The unsubstituted hydroquinone dibenzoate derivative and the hydroquinone monobenzoate derivative are preferably at a clear temperature (Tc) of 150 ° C., preferably 80
It has even a large liquid crystal phase width of ° C. Even for the mixture components having non-liquid crystal properties, the liquid crystal phase width of the entire mixture must not be reduced to 30 ° C. or less. The mixture itself is monotropic liquid crystalline (monotropic liquid crystalline).
lin).

Another object of the present invention is to process in a lacquer system and other polymer matrices, such as liquid plastics, in the usual temperature range of 80.degree. C. to 130.degree. A highly crosslinked thermostable liquid crystal film having a chiral phase and a chiral phase having a chirality of less than 2 nm and exhibiting reduced interaction with solvents compared to known liquid crystal pigments even below this processing temperature range, especially at room temperature. It is to provide a composite of a liquid crystal pigment. The reduced interaction is manifested in particular in the form of reduced swelling and, consequently, a shift of the intrinsic color towards the red part.

This problem is solved by using a liquid crystal film and a liquid crystal pigment comprising the crosslinked liquid crystal mixture of the present invention.

Known low molecular weight difunctional monomers having a high molar mass are not suitable for preparing the liquid crystal films and liquid crystal pigments of the present invention having improved thermal stability. Such low molecular weight monofunctional or difunctional monomers for chiral nematic mixtures, as disclosed, for example, in EP 0 479 466 or EP 0 760 836, actually have mainly two polymerizable units, but their molecular weight is Large compared to the number of units, so that, for example, the average molecular weight of the individual components is 650 and 2 per molecule
In the case of individual polymerizable units, only up to 3.08 mmol of polymerizable units per gram of mixture are produced. After polymerization of such a mixture, virtually complete cross-linking is present, but the number of net knots per volume element, the cross-link density, is due to the thermal stability and the color invariance that appears parallel to it. It is too low to prevent solvent interactions of the crosslinked polymer to a guaranteed degree.

The liquid-crystal mixtures according to the invention are, for the first time, 80
Within the processing temperature range of from 0 ° C to 130 ° C, it enables the production of thermally stable liquid crystal pigments having a relaxed central wavelength difference of 2 nm or less in a matrix such as a conventional polymer binder.

Such liquid crystal films and liquid crystal pigments can be prepared from the liquid crystal mixtures according to the invention by methods known in the prior art, in particular as described in the above-mentioned specification.

In one method for producing a liquid crystal film of the present invention, the liquid crystal mixture of the present invention is applied and oriented in a liquid crystal state on a smooth support, three-dimensionally crosslinked by polymerization of the liquid crystal mixture, and peeled from the support. Is obtained by

The liquid crystal mixture of the present invention has a viscosity of 3 to 15 μm.
m, preferably 3 to 6 μm, on a smooth surface.

The orientation can be effected, for example, by shearing with a doctor or a roller.

The polymerization of the oriented liquid crystal material can be carried out in a manner known per se, for example by means of radicals using commercially available thermal initiators, by electron beams or in combination with commercially available photoinitiators by UV irradiation. It can be performed using light or by an addition or condensation reaction.

Crosslinking of the mixture of the present invention in the chiral structure state is carried out, as radical polymerization, ionic polymerization or metal catalyzed polymerization or as polycondensation reaction, depending on the type of polymerizable group, polycondensable group or polyadditive group. Alternatively, the polymerization is performed using a polymerization reaction that proceeds as a polyaddition reaction.

The initiation of the free-radical polymerization can be effected thermally with the corresponding initiators or with UV rays or with high-energy radiation such as electron beams using commercially available photoinitiators. The advantage of radical polymerization by heat or polymerization by electron beam curing is that UV-absorbers (UVAs) or radical scavengers (UVAs) or radical scavengers (UVAs) can be used in polymerizable mixtures, for example for outdoor applications, in order to stabilize the resulting pigments or films against UV light. A sunscreen such as HALS) can also be added, and the loss of polymerization conversion does not occur because of the blocking of the photoinitiator by UVA, as is the case with UV curing. With it
No reduction in network density occurs.

When the curing of the liquid crystal film is carried out by means of peroxides or by electron beams, the liquid crystal mixtures according to the invention are preferably formulated with commercially available light-blocking agents, such as UV absorbers or radical scavengers, in an amount of from 0.5 to 0.5%. It can be contained at a total concentration of 5% by weight.

In addition to the light stabilizers, the mixtures according to the invention can contain other customary additives for inhibiting oxidation, inhibiting polymerization or for improving rheological properties. In addition, pigments or absorbing fillers such as carbon black and fluorescent dyes or pigments may be included.

Further, a method for producing the liquid crystal pigment of the present invention will be described.

Such a method is characterized in that the liquid crystal film of the present invention is pulverized into platelet-shaped particles.

Particularly, the liquid crystal film has a thickness of 5 to 100 μm,
It is particularly pulverized into platelet-shaped particles having a diameter of 10 to 50 μm.

[0037] Pigments of the stated geometric dimensions are preferred pigments. Pigments can be separated by a particle size selection method. The particle size distribution can also be appropriately selected depending on the application.

The (b) dispersion medium in the present invention is used in combination with a liquid crystal pigment and / or a liquid crystal film. In the case of a liquid crystal pigment, a material having good pigment dispersibility is used. A familiar material is used, and a transparent material in the visible light region is more desirable. Preferred examples of the dispersion medium include a vehicle for ink, a main component for forming a coating film for paint, a solvent for paint, a resin, and a liquid substance.

When the liquid crystal pigment of the present invention is used as a printing ink, for example, a printing ink containing the liquid crystal pigment can be directly produced by mixing with a varnish for a printing ink or a solvent for a printing ink. As the solvent for the printing ink or the solvent in the varnish in that case, a solvent containing no aromatic as long as it is a solvent suitable for the printing ink, such as a high-boiling petroleum solvent, an aliphatic hydrocarbon solvent, or a higher alcohol solvent. Can be used alone or in combination of two or more.

Similarly, as a resin for a printing ink varnish when producing a printing ink, a resin suitable for a printing ink such as a rosin-modified phenol resin, a rosin-modified maleic resin, a petroleum resin, an alkyd resin; A drying oil or polymerization drying oil suitable for printing inks such as linseed oil can be used singly or in combination of two or more with other additives for printing inks.

The ink containing a liquid crystal pigment or a liquid crystal film of the present invention may be an ultraviolet-curable type, an infrared-curable type, or an OCR (Opti).
cal character recognition) It can be suitably used as an ink.

The composite containing the liquid crystal pigment and / or the liquid crystal film of the present invention can be suitably used as a solvent, a water-based, or a powder-based known paint film forming element, a solvent, and the like.

As a coating film forming main element, a main substance for forming a coating film generally used for a coating material can be used. When liquid crystal pigments are used, they can be mixed and dispersed in a fluid state using a stirrer or the like without requiring a particularly high temperature. When a liquid crystal film is used, a composite can be produced by applying a substance that forms a coating film to the liquid crystal film. As an example of the main element for forming a coating film for paint, boil oil (boil oil A,
Boil oil B, boil oil C, boil oil D), stand oil,
Shellac, rosin, ester gum, Gilsonite, coal tar, acrylic resin (thermoplastic acrylic resin, thermosetting acrylic resin), alkyd resin, epoxy resin, chlorinated rubber, vinyl chloride vinyl acetate copolymer, xylene resin, cumarone resin, Synthetic resin emulsion (vinyl acetate, acrylic, styrene / butadiene, ethylene-
Vinyl acetate, vinyl propionate, epoxy, etc.), water-soluble resin (alkyd resin, phenol resin, amino resin, acrylic resin, etc.), silicone resin (alkyd resin, acrylic resin, polyester resin, etc.) Including modified products such as epoxy resin), petroleum resin, phenolic resin, butyral resin, polyamide resin, polyurethane,
Polyester, urea and melamine resins, nitrocellulose, acetylbutylcellulose, and the like.

The coating solvent is a solvent used for thinning the coating. These solvents may be contained in the above-mentioned coating film, or may be used alone as a liquid substance described below. Examples of coating solvents include mineral spirits, rubber volatile oil, petroleum-based mixed solvents, hydrocarbons such as toluene, xylene, solvent naphtha, and turpentine oil;
Chlorinated hydrocarbons such as trichlorethylene and ethylene tetrachloride; alcohols such as methanol, ethanol, isopropanol and butanol; ethylene glycol monoethyl ether and ethylene glycol monobutyl ether;
Ether alcohols and ethers such as; ethyl acetate,
Esters and ether esters such as butyl acetate, ethylene glycol monoethyl ether acetate, etc .; acetone,
Ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone;

As the resin, both a thermoplastic resin and a thermosetting resin can be used.

As the thermoplastic resin, styrene resins (rubber-reinforced styrene resin, GPPS, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-
Styrene copolymer, etc.), olefin resin (high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, etc.), methacrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyamide resin, Polyester resin, polycarbonate resin,
Examples include polyacetal resin, polyphenylene ether resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyarylate resin, polymethylpentene, and the like.

Other resins include thermosetting resins such as polytetrafluoroethylene, epoxy resin, petroleum resin, alkyd resin, and furan resin.

Further, natural rubber, butadiene rubber, silicone rubber, polyisoprene rubber, chloroprene rubber,
Synthetic rubber such as ethylene propylene rubber, butyl rubber, isobutylene rubber, styrene / butadiene rubber, styrene / isoprene / styrene block copolymer rubber, acrylic rubber, acrylonitrile / butadiene rubber, hydrochloric acid rubber, chlorosulfonated polyethylene rubber, and polysulfide rubber Etc. are also included in this category.

As the resin of the paint, a resin for powder paint composed of an epoxy resin, an epoxy ester resin, a polyester urethane resin, an acrylic resin, etc .; Resins for water-based paints, such as urethane and the like, are also included in the category of the above-mentioned paint resins.

As the liquid substance, a substance which is liquid at room temperature and transparent is used. For example, silicone oil, mineral oil, glycerin, water, and the like can be used in addition to the substances listed above as examples of the coating solvent. Liquid substances are mainly combined with liquid crystal pigments, and are used by confining them in a certain space and by creating a flow. As the liquid substance, those having a specific gravity close to that of the liquid crystal pigment of the present invention are more preferably used.

The composite of the present invention comprises (a) a liquid crystal pigment and / or a liquid crystal film and (b) a dispersion medium. The composition ratio with the medium is (a) / (b) =
It is 0.01 / 99.99 to 99.99 / 0.01. When (a) is a liquid crystal pigment, preferably (a) /
(B) = 0.05 / 99.95 to 50/50,
More preferably, (a) / (b) = 0.1 / 99.9 to 25/75. When (a) is a liquid crystal pigment, the most preferable range differs depending on the application, and for paints, (a) / (b) = 1/99 to 15/85,
In the case of ink use, (a) / (b) = 3/97 to 25
/ 75, and when the dispersion medium is a resin, (a) /
(B) = 0.1 / 99.9 to 5/95. Although the method for producing the composite of the present invention is not particularly limited, the composite with a relatively low-viscosity dispersion medium such as a vehicle for ink, a main component for forming a coating film for coating, a solvent for coating, a liquid substance, some resins, and the like. When forming, it can be appropriately prepared by stirring, shaking, mixing, etc. without heating. A highly viscous material such as a thermoplastic resin can be easily formed into a composite by mixing the resin with a liquid crystal pigment and / or a liquid crystal film and heating. Examples of specific methods include known methods generally used for molding thermoplastic resins, such as injection molding, extrusion molding, blow molding, inflation molding, vacuum molding, Banbury mixer, roll, extrusion kneader, After being mixed by such methods as above, it is molded into various molded articles. Further, after being formed into a film, a biaxially stretched film, a sheet, a foamed sheet, a foamed bead, or the like, it can be further molded into a desired molded body. Further, lamination of a liquid crystal film is also included in the present invention.

In the composite of the present invention, various additives such as a plasticizer, a lubricant, a stabilizer, an antioxidant, an ultraviolet absorber, and a release agent may be added to the composite of the present invention, if necessary, without departing from the spirit of the present invention. , Other pigments, dyes, carbon black, titanium oxide,
Inorganic fillers, fragrances, oils and fats, dispersing aids, flame retardants, release agents, rust preventives, fungicides, bactericides, and the like can also be added. The order and amount of these additions are appropriately selected.

The multilayer structure of the present invention comprises a metal, an organic material,
It is composed of a substrate layer made of any of inorganic materials and a layer of the above-mentioned composite. The substrate layer is in contact with the layer of the composite according to claim 1 (layer 1) and forms at least two layers. The present invention also includes a multilayer structure having two or more layers, wherein layer 1 is sandwiched between substrate layers.
A more complex color effect can be obtained by adopting a layer structure, a three-layer structure in which the substrate layer is sandwiched between the layers 1, or a structure of four or more layers. As an example of the substrate layer, iron is iron,
Examples thereof include stainless steel, aluminum, copper, brass, titanium, nickel, and lead. These metals may be plated on the surface, coated with glass or the like, or painted. Organic materials include various thermoplastic resins, thermosetting resins, elastomers, wood, paper, nuts, grass nuts, lacquerware, woven fabrics, nonwoven fabrics,
Knitted fabrics, yarns, sheets, artificial leather, natural leather, and the like can be given. These organic materials may be plated on the surface or coated with paint or the like. Examples of the inorganic material include glass, pottery, porcelain, cement, gypsum board, natural stone, slag, mortar, and the like. These surfaces may be coated with glass.

These composites having a multilayer structure are prepared as appropriate. For example, a mixture which can be the layer 1 is applied to the substrate layer, or conversely, the substrate layer is first prepared and then the substrate layer is applied. Alternatively, it can be produced by separately producing and bonding the layer 1 and the substrate layer.

Forgery prevention products in the present invention include paper money, money, various kinds of cash vouchers, securities, credit cards, cash cards, prepaid cards, debit cards,
Gift certificate card, JR card (orange card, Io card, etc.), IC card, personal medical record card, national information card, brand logo, brand mark, PC software, music software, video software box and CD-ROM
A product using the composite of the present invention for preventing forgery of a main body or a case of a DVD / floppy (registered trademark) disk / tape. These are supplied in the form of, for example, an anti-counterfeit ink, an anti-counterfeit paint, a composite in which a liquid crystal pigment is dispersed in a sheet, a laminated composite, and the like.

With the recent development of color copiers and electronic equipment, precise copying can be easily performed. By using the composite of the present invention, forgery by means such as a color copier, a scanner, or a digital camera can be prevented. Forgery can be prevented by applying circularly polarized light to the liquid crystal pigment of the present invention.

The composite of the present invention is expected to have a wide range of applications. Specific examples include the following examples. The composite of the present invention is effective in adding identification, marking, design, decoration, and the like to products for various uses as exemplified.

As geography-related applications, globes, celestial globes,
Moon globe, various planet models, maps, weather observation equipment (thermometer,
Examples include a barometer, a hundred-leaf box, an anemometer, an anemometer, a hygrometer, a cloud meter, a cloud gauge, a rain gauge, and the like.

Plant-related applications include trees (eg, trunks,
Paint and decorate leaves, branches, stumps, etc.), cones (for example, decorations for wreaths, pine cones and other cones for decoration, decoration for lease), fruits, nuts, vegetables (eg, watermelon, Surface decorations such as pumpkins), flowerpots, planters, watering cans, and the like.

[0060] Animal-related applications include crustaceans (shrimp, crab, and decoration of these), shells, turtle shells, horns, teeth, bones, eggs, harnesses, collars, bells, baskets, breeding boxes of various animals. ,
And the like.

Examples of human body-related applications include cosmetic applications (hair pieces, artificial hair, artificial eyelashes, eye shadow, blusher, lipstick, foundation, face paint, body make-up supplies, makeup, nail color (nail paint), skin Patches or disks adhering to lips, etc., sunscreen, body lotion, etc.).

[0062] Agriculture-related applications include tractors, silos, cowsheds, piggeries, poultry houses, sheep huts, fences, naya, greenhouses, ridged plows, compost spreaders, tandem disk crushers, weeders, sowing machines, mowers, Examples include a grass collector, a hay baling machine, a harvesting machine, and a storage machine.

Examples of construction-related applications include various tents, huts, houses, buildings, theaters, karaoke facilities, dance facilities (discos, dance halls, etc.), churches, temples, various religious facilities, stations, halls, hotels, restaurants, parking lots, etc. For interior and exterior of car parks, meeting halls, etc. Exterior walls, roofs, columns, windows, rooftops, tiles, glass,
Examples include walls, streetlights, roads, railways, manholes, sidewalks, traffic lights, bus stops, curtains, curtains, acoustic ceilings, chairs, borders, and the like.

House-related applications include interior and exterior of houses,
Walls, stairs, handrails, ceilings, doors, windows, fireplaces, chimneys, stoves, ducts, electric furnaces, air conditioners, heating appliances, heating and cooling appliances, and their accessories, fans, and the like.

As home-related applications, tables, service wagons, chairs, sofas, benches, beds, chests,
TEST, dresser, costume dance, cupboard, sideboard, cocktail cabinet, glass window, curtain, curtain pole, roll screen, blind, indoor shutter, light bulb, fluorescent light, lighting equipment cover and lantern, lantern, chandelier, mirror ball, Ceiling light, floor stand, glass, decanter, mug,
Cups, spice holders, various dishes, teapots, vegetable bowls, salad bowls, jugs, knives, forks, spoons, kitchen knives, funnels, drainers, tea strainers, walnut splits, lemon squeezers, cheese graters, pasta machines, jadeies,
Fly return, bottle opener, corkscrew, kitchen timer,
Cooking scale, whisk, rolling pin, squeezing, various types, coffee maker, siphon, pan, frying pan, mixer,
Juicer, kettle, toaster, microwave, hot plate, refrigerator, range, range hood, iron,
Examples include a coffee mill, a dishwasher, a washing machine, a dryer, a vacuum cleaner, and the like.

Gardening-related applications include flowerpots, fences, stone slabs, hand sprays, sprinklers, hoses, hose reels, watering cans, tank sprays, excavators, scoops, plows, kettles, hooks, rakes, rakes, hoes, pickaxes, and transplants. Irons, trimmers, pruning shears, pruning shears, saws, wheelbarrows, rollers, lawnmowers, chain saws, and the like.

Do-it-yourself-related applications include hammer, chisel, mallet, sword, nail, screwdriver, screw, canna, file, saw, pliers, spanners, bolts,
Drills, clamps, vise, drill presses, circular saws, bricks,
Steel, chair, concrete, block, tile, wood, various boards, locks, various trowels, bathtubs, toilet bowls, basins, sinks, various stoppers and handles, various wrench, bow saw, rubber cup, piping, stepladder, ladder , Soldering iron, welding machine, cylinder, goggles, face shield, pliers, wiring, and the like.

The clothing-related applications include coats, vests,
Kimono, obi, dress, hat, shoes, windbreaker, jumper, blouson, jacket, belt, buckle,
Suspenders, pants, shirts, ties, bowties,
Ascot tie, underwear, socks, sweater, polo shirt,
Cardigans, gloves, T-shirts, skirts, pants, blouses, collars, stockings, pajamas, nightgowns, swaddling, diapers, bibs, shoelaces, sweatshirts,
Trainers, swimwear, leotards, spats, anoraks, leg warmers, tank tops, slippers, sneakers, boots, hooks, sandals, sleighs, straws, geese, shoes, shoe brushes, shoe racks, furoshiki, kimono, kimono accessories, etc. As accessories for jewelry, earrings, earrings, pendants, rockets, necklaces, rings, bracelets, pins, tie pins, name plates, nail polish, nail clippers, cosmetics, cosmetic containers (e.g., compact, lotion bottles, etc.), Examples include a headstock, a hairbrush, a comb, a hair clip, a curler, a hair clip, a hair ornament, a hairpin, a hair dryer, and the like.

The daily necessities related applications include toothbrush, toothpaste tube, shaving, razor, shaving brush,
Umbrella, walking stick, glasses, opera glasses, luggage (travel luggage, attache case, briefcase, etc.), eyeglass cases, wallets, key cases, pouches, passport cases, second bags, memo cases, shoulder bags,
Tote bag, duffel bag, hobo bag, sea bag box bag, clutch bag, duffle bag, drawstring bag, muff, shopping bag, carry bag, makeup bag, costume bag, makeup bag, carrier, suitcase, cigar, cigarette , Cigarette holder, cigarette package, carton, pipe, pipe rack, cigarette pouch, match, match box, book match, lighter, ashtray, etc. , Camera, film, film can, lens (exterior), filter (exterior), strobe (exterior), tripod, pan head, lens attached film, underwater camera waterproof cover, still video camera, disk camera, digital camera, Various storage media and Case (floppy disk, cassette tape, hard disk, records, compact discs, CD-ROM, DVD, etc.), exposure meter, slide projector, screen, cutter, TV,
Various remote control devices (remote control), portable television, radio, portable radio, video, speakers, stereo, compact disc player, portable compact disc player, cassette tape deck, portable cassette tape deck, portable radio cassette player , MD deck, portable MD deck, portable CD cassette player with radio, video camera, digital video camera, tuner, amplifier, record player, micro horn, headphone, turntable, parabolic antenna (for receiving BS broadcast, etc.), telephone ,
Examples include a mobile phone, a videophone, a public phone, a facsimile, a telex, a keyboard, and the like.

The traffic-related applications include automobile interior and exterior (bonnet, roof, fender, door, door mirror, bumper, bucket seat, seat belt, rear seat, buckle, door inner handle, door pocket, armrest, door inner panel, window, Sunroof, rearview mirror, sunshade, instrument panel, center console, shift lever, pedal, turn signal, steering wheel, instrument panel, wiper switch, wiper, tire, wheel, disk, wheel cover, spoiler,
Etc.), truck interior and exterior parts (air horn, current plate, radiator grille, exhaust stack, various decorations, trailer, bulkhead, etc.), motorcycle parts (fuel tank, front fender, spoiler, tandem seat, muffler, hand grip, Mirror, instrument panel, fuel tank cap, throttle grip, etc.), helmet, snowmobile various parts, bicycle various parts (front fork, head tube, top tube, seat tube, seat stay, chain stay, down tube,
Handlebar stem, saddle, bed, mudguard, water bottle, inflator, gear lever, handlebar, headlight, etc.), mountain bike, lock, bicycle helmet, side back, trailer house, bridge, guardrail, road marking, railcar interior and exterior (Passenger cars, freight cars, locomotives, tank cars, hopper cars, refrigerated cars, container car exterior, seats, tables, armrests, etc.)
Gates, barriers, alarms, ships, leisure boats, yachts (hulls, sails, etc.), buoys, lighthouses, airplanes, gliders, helicopters, various vehicles in airports, rockets, etc.

As office equipment-related applications, ballpoint pens,
Pencil, eraser holder, marker, stick glue, paper knife, stapler, pencil sharpener, clip, various stamps, punch, tape holder, letter scale, index card and drawer, bookend, desk tray, arch board, clipboard, various holders,
Various files, desk, chair, desk mat, sideboard, filing cabinet, partition, computer and auxiliary equipment (display, keyboard, mouse, mouse pad, printer, main unit, modem, etc.), magazine rack, coat hook, coat rack, Lockers, calculators, typewriters, copy machines, and the like.

The music-related applications include accordion,
Bagpipe, harmonica, panpipe, sheet music, metronome, piano, organ, violin, double bass,
Cello, viola, harp, guitar, electric guitar, saxophone, piccolo, clarinet, flute, bassoon, oboe, English horn, trumpet,
Cornet, bugle, trombone, tuba, euphonium, french horn, drum, timpani,
Triangles, cymbals, castanets, tambourines, chimes, xylophones, dora, synthesizers, electronic pianos, drums, and the like.

[0073] Handicraft related applications include sewing machines, roulettes, tape measures, thimbles, needle sticks, threading, scissors, buttons, buckles, fasteners, knitting sticks, knitting machines, loom stands, embroidery, looms, thread winding, books, pottery, woodworking Goods, paints, felt pens, colored pencils, crayons, brushes, airbrushes, easels, and the like.

Sports-related applications include baseball supplies (bats, helmets, uniforms, stockings, pants, masks, frames, mitt, gloves, balls, protectors, leggings, batting gloves, spike shoes, dugouts, baseball fields, etc.), Cricket supplies (bats, wickets, balls, legs, shoes, etc.), soccer supplies (uniforms, pants, shining, soccer shoes, balls, goals, flags,
Stadium, etc.), American football equipment (helmets, jerseys, wristbands, face masks, pants, socks, football, elbow pats, serpats, rib pats, protective cups, knee pads, flags, stadiums, cheerleader supplies, marching band supplies,
Etc.), rugby supplies, hockey supplies, ice hockey supplies, sticks, basketball supplies, netball supplies, handball supplies, volleyball supplies, tennis supplies (racquets, racket cases, headbands, polo shirts, wristbands, pants, squats, vibration prevention Rubber, tennis shoes, socks, tennis balls, nets, etc.), squash supplies, racket ball supplies, badminton supplies, table tennis supplies (racquets, table tennis tables, nets, etc.)
Wears, etc.), curling goods, swimming goods (swimming caps, swimming wear, ropes, pools, stadiums, swimming goggles, beach umbrellas, etc.), diving goods, water polo goods, scuba diving goods (snorkels, wet suits, etc.) Masks, buoyancy adjusters, cylinders, mouthpieces, harnesses, console gauges, fins, boots, spearguns, etc.), sailing supplies, surfing supplies, windsurfing supplies (boards, masts, windows, suits, etc.), boat supplies, Water skiing equipment, balloon supplies, skydiving supplies, paragliding supplies, hang gliding supplies, gliding supplies, skiing equipment (skis, poles, skiwear, goggles, ski caps, gloves, ski shoes,
Etc.), cross-country skiing equipment, jumping equipment, luge equipment, bobsledding equipment, skating equipment, inline skating equipment, kanji, riding equipment, horse racing equipment, athletics (marathon, sprinting, middle distance running, long distance running, hurdles) , Relays, pole vaults, high jumps, shot puts, hammer throws, long jumps, disability sports, etc.) supplies, gymnastics supplies, weightlifting supplies, training supplies (strength training machines, barbells, cycling machines, climbers, boat rowers, dumbbells, hand grips, Jump ropes, ankle and wrist weights, twist bars, expanders, training suits, etc.), fencing supplies, judo supplies, karate supplies, kendo supplies, boxing supplies, fishing supplies (fly, fly rod, spinning reel, fishing hook, Poon, pseudo bait, boots, in-process,
Fishing clothes, fishing tackle boxes, jumpers, cooler boxes, tie nets,
Etc.), billiard supplies, golf supplies (golf clubs, golf balls, tees, golf gloves, head covers,
Golf shoes, golf bags, golf carts, electric carts, etc.), mountaineering equipment, bowls and petting equipment, bowling equipment, archery equipment, camping equipment (tents, tarps, air mats, sleeping bags, cooking utensils, tableware, lanterns, heaters, stoves , Water bottle, water tank, thermos, cooler box, hatchet, knife, shovel, bow saw, rope, etc.), synchronized swimming, running, walking, rhythmic gymnastics, dance, aerobics, various sports Supplies (stadium jumpers, binoculars, megaphones, balloons, flags, drums, caps, sun visors, etc.), and the like.

Game-related applications include playing cards, dominoes, chess, backgammon, go, shogi, darts, video games, dice, roulette, slot machines,
Carta, Sugoroku, top, kite, various game center game machines, pachinko, mahjong, and the like.

Examples of applications related to measuring instruments include a thermometer, a thermometer, an indoor thermostat, a wristwatch, a clock, a floor clock,
A balance, an electronic scale, a weight scale, a pressure gauge, a tape measure, a sphygmomanometer, a protractor, and the like are included.

Examples of applications related to optical equipment include magnifying glasses, glasses, telescopes, and the like.

Health and safety related applications include first aid boxes, wheelchairs, walking sticks, crutches, earplugs, safety earmuffs,
Safety helmets, safety vests, safety shoes, and the like.

Examples of energy-related applications include oil and gas storage tanks, tank trailers, tank cars, tankers, floodgates, dams, power transmission towers, electric poles, solar panels, windmills, and the like.

The symbol-related applications include flags, streamers, bunting, flagpoles, pole heads, emblems, safety signs, general signs, road signs, product handling signs, and the like.

Other uses include various packaging materials, packaging containers, bottles, bottle labels, calendars, posters,
Art printing, and the like.

[0082]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described based on embodiments. Comparative examples 1, 2, and 3 are comparative examples of the reference example. A comparison of the liquid crystal pigments from the liquid crystal mixtures according to Reference Examples 6 to 10 with the liquid crystal pigments from the liquid crystal mixtures according to Comparative Examples 1, 2 and 3 shows that the liquid crystal mixture according to the invention has a total processing temperature range of 80 to 130 ° C.
It shows that a thermally stable liquid crystal film and a liquid crystal pigment having a reflection central wavelength difference of 2 nm or less can be obtained. Reference Example 1
As is evident from FIG. 1, the pigments according to the invention show only a slight interaction with the solvent even at room temperature.

Reference Example 1: a) 249 g (1.5 mol) of ethyl 4-hydroxybenzoate in 3 liters of DMF, 3 g of potassium iodide
(0.018 mol) and 248 g of potassium carbonate (1.
(8 mol) was added to 276.6 g (1.8 mol) of 4-chlorobutyl acetate, and the mixture was stirred at 90 ° C for 11 hours. The reaction mixture was added to 5 l of ice water, and the deposited precipitate was filtered by suction and washed with 4 l of ice water. The crude product was dissolved in 3 l of ethanol, potassium hydroxide (400 g) was added, and the mixture was heated under reflux for 3 hours. The reaction mixture was added to 6 l of ice water, adjusted to be acidic with concentrated hydrochloric acid, and the precipitate was collected by filtration. The precipitate was washed neutral with water and subsequently dried. 4- (4 '
-Hydroxybutoxy) -benzoic acid (282.1 g, 89% yield) was obtained.

B) 1,1,1-Trichloroethane 1.1
4- (4'-hydroxybutoxy) -benzoic acid 2 in 1
82 g (1.34 mol) of freshly distilled acrylic acid 2
30 ml (3.35 mol), 2,6-di-tert. −
Butyl-4- (dimethylaminomethylene) phenol (Ethanox ^(R) 703) consisting of 0.3g and p- toluenesulfonic acid 23.7g was heated under reflux for 10 hours in a water separator. The reaction mixture was cooled to 60 ° C-70.
C., stirred into 2.5 l of petroleum ether and the precipitate was filtered off. After washing with petroleum ether, the precipitate was dried in vacuo at room temperature for 24 hours. 223.7 g of 4- (4'-acryloxybutoxy) benzoic acid (yield 60
%)was gotten.

Reference Example 2: Chiral compound (2- [4'-
(4'-acryloylbutyloxy) benzoyl] -5
Preparation of 2-Anisoyl Isosorbide 902.6 g (4.8 mol) of 2-acetylisosorbide (prepared according to EP 0 578 847, Example 1) are dissolved in 1.7 l of xylene and 900 g (5.3 of anisoyl chloride) in 200 ml of xylene. Mol) was added. The mixture was heated under reflux for 5 hours. After complete conversion, it was cooled to room temperature, during which the product precipitated. The crystal cake was filtered off with suction, washed with 600 ml of petroleum ether and dried in air. 2-acetyl-5-anisoyl isosorbide 127
8.8 g (83% yield) were obtained.

B) 639 g (1.98 mol) of 2-acetyl-5-anisoylisosorbide was added to 2.5 l of methanol.
269 ml of 25% aqueous ammonia solution
(3.96 mol) was added. The solution was stirred at 55 ° C. for 3 hours. The solvent and excess ammonia were evaporated in vacuo and the residue was dried in vacuum. The reaction of 5-anisoyl isosorbide was performed without further purification.

C) 232.35 g (0.83 mol) of 5-anisoylisosorbide thus obtained, 230.0 g (0.87 mol) of 4- (4'acryloylbutyloxy) benzoic acid (prepared according to Reference Example 1) , 2,6-Gee
rt-butyl-4 (dimethylaminomethyl) phenol (Ethanox® 703, Ethyl Cor ⁾
p. , Baton Rouge, LA 70801) and 5.5 g of dimethylaminopyridine.
and cooled to 6 ° C. At this temperature, DC
196.7 g (0.95 mol) of C were added, stirred for 1 hour and subsequently heated to room temperature. The precipitated dicyclohexylurea was filtered off, the solvent was distilled off in vacuo and the residue was recrystallized from 1.5 l of isopropanol. The crystals were washed once more with 1 l of isopropanol. 357 g (82% yield) of 2- [4 '-(4'-acryloylbutyloxy) benzoyl] -5-anisoylisosorbide having a melting point of 82 ° C were obtained.

Reference Example 3 Preparation of Chiral Compound 2- [4- (acryloyloxy) benzoyl] -5- (4-methoxybenzoyl) isosorbide 5-Anisoylisosorbide (prepared according to Reference Example 1b)
13.3 g (47.5 mmol) and 10.6 g (104.5 mmol) of triethylamine were added to 70 m of toluene.
l. At 80 ° C., 4-
(Acryloyloxy) benzoyl chloride (Lork)
owski, H .; J. Reuter, F .; Acta
Chim. Acad. Sci. Hung. 1977
Year, 95 volumes, manufactured on page 423-34) 10g
(47.5 mmol) was added dropwise. The mixture is stirred for 2 hours at 80 ° C., then at room temperature 70 ml of 1N hydrochloric acid are added, the organic phase is washed with water (2 × 50 ml) and saturated sodium hydrogen carbonate solution (50 ml), dried over sodium sulfate and the solvent is eliminated. Removed in vacuo. The resulting syrup was stirred with 75 ml of isopropanol. After filtration, 11.7 g (54% of theory) of 2- [4- (acryloyloxy) benzoyl] -5- (4-methoxybenzoyl) isosorbide having a melting point of 111 ° C. was obtained.

Reference Example 4: Chiral compound di-2,5- [4
Preparation of-(acryloyloxy) benzoyl] isosorbide 20.0 g (137 mmol) of isosorbide and 73.2 g (723 mmol) of triethylamine were dissolved in 120 ml of toluene. At 80 ° C., 60 ml of toluene
4- (acryloyloxy) benzoyl chloride (Lorkowski, HJ; Reuter,
F. Acta Chim. Acad. Sci. Hun
g. (1977, 95, page 423-34) 60.5 g (287 mmol) of a solution were added dropwise.
The mixture is stirred for 2 hours at 80 ° C. and then at room temperature for 10%
80 ml of hydrochloric acid are added, the organic phase is washed with water (2 × 80 ml) and 10% sodium hydrogen carbonate solution (80 ml), dried over sodium sulphate and the solvent is reduced in vacuo to approx.
It was removed to a toluene content of% by weight. To the obtained syrup, 220 ml of ethanol and 200 ml of cyclohexane were added, and the mixture was heated to 80 ° C. with stirring. After cooling and filtration, di-2,5- [4- (acryloyloxy) benzoyl] having a melting point of 115 [deg.] C.
Isosorbide was obtained in a yield of 45.9 g (68% of theory).

Reference Example 5 Preparation of bifunctional component 4- (4-acryloyloxybutoxy) benzoic acid- (4-acryloyloxyphenyl) ester 4- (4-acryloyloxybutoxy) benzoic acid chloride (84.4 g) 0.3 mol) in toluene, and stirring the solution at room temperature, 49.2 g (0.3 mol) of acrylic acid- (4-hydroxyphenyl) ester, 40.0 g (0.4 mol) of triethylamine, toluene 300m
1 and 2 g of 2,6-di-tert-butyl-4-methylphenol were added dropwise within 45 minutes. Thereafter, the mixture was heated to 50 ° C. in the course of 30 minutes, the still warm amine hydrochloride was filtered off, and 800 ml of petroleum ether were stirred into the filtrate. At that time, the target product precipitated. After cooling to 5 ° C., the product was filtered off at 40 ° C. in ethyl acetate and extracted three times with water. The organic phase is dried, concentrated,
The residue was recrystallized from 200 ml of isopropanol.
100 g (yield 82%) of the target substance was obtained. The melting range is between 103 ° C and 105 ° C.

The required acrylic acid (4-hydroxyphenyl) ester is disclosed in DE 4442831 (US565).
Selective monolysis of hydroquinone bisacrylate with sodium methylate (equivalent to
espartung) in a yield of 91%. Monoacrylates are liquid at room temperature. The acid component of the above ester, 4- (4-acryloyloxybutoxy) benzoic acid, is obtained by reacting acetic acid- (4-chlorobutyl) ester with 4-hydroxybenzoic acid methyl ester, and obtaining the free 4- (4) -alkylated methyl ester. -Hydroxybutoxy) obtained by saponification to benzoic acid and esterification with acrylic acid at the hydroxybutoxy group. The acid melts at 124 ° C. (70% yield),
It can be converted to the acid chloride by the usual reaction with thionyl chloride.

Reference Example 6 Three-component green liquid crystal mixture according to the present invention, hydroquinone-bis- [4- (4-acryloylbutoxy) -benzoate] (Broer, DJ; Mo.
1, G. N. Challa, G .; Makromol.
Chem. 1991, Vol. 192, p. 59) 23.93 g, 4- (4-acryloyloxybutoxy) benzoic acid- (4-acryloyloxyphenyl) ester according to Reference Example 5 6.6 g and Reference Example 2 (2- 2.81 g of [4 '-(4'-acryloylbutyloxy) benzoyl] -5-anisoylisosorbide
With 10 mg of triethylamine and 2,6-di-te
rt- butyl-4- (dimethylaminomethylene) - phenol ^{(Ethanox (R) 703, Ethyl} Co
rp. , Baton Rouge, LA70801) 0.09 g
And photoinitiator Irgacure (Rgacure® ⁾
819) (Ciba Spezialitaetenc)
hemie GmbH, Lampertheim)
Weighed together with 0.33 g and dissolved in toluene at 70 ° C. to make an approximately 25% solution. Continue to Celite (Celi
te ^(R) (Manville Corp., Denver,
(USA) / Tonsil ( ^R ) (Suedch)
emie AG, München) (95/5) thickness 5
Filtered through a cm layer. The solvent was removed in a high vacuum (residual content less than 0.1% by weight). The liquid crystal mixture thus obtained has a clear temperature from cholesteric to isotropic of 1
Has 25 ° C. The viscosity is about 200 mPas at 90 ° C. The concentration of the polymerizable groups in this mixture is 3.50 mmol / g without regard to the photoinitiator. The liquid crystal film manufactured according to Reference Example 15 at 93 ° C.
Has a central reflection wavelength of

Reference Example 7: Red liquid crystal mixture of the present invention composed of three components In the same manner as in Reference Example 6, hydroquinone-bis- [4- (4-
Acryloylbutoxy) -benzoate] (Broe
r, D.R. J. Mol, G .; N. Challa, G .;
Makromol. Chem. 1991, Volume 192,
24.09 g, 4- (4-acryloyloxybutoxy) benzoic acid according to Reference Example 5
6.6 g of (4-acryloyloxyphenyl) ester
And 2.32 g of (2- [4 '-(4'-acryloylbutyloxy) benzoyl] -5-anisoylisosorbide and 10 mg of triethylamine according to Reference Example 2.
And 2,6-di-tert-butyl-4- (dimethylaminomethylene) -phenol (Ethanox® 7 ⁾
03, Ethyl Corp. , Baton Rouge, LA
From 0.0801 g of 70801) and 0.33 g of the photoinitiator Irgacure® 819, a red liquid crystal mixture having a clear temperature from cholesteric to isotropic of 130 ° C. was prepared. The viscosity of this mixture is 90
It is about 108 mPas at ° C. The concentration of polymerizable groups in this mixture is 3.52 mmol / g, without regard to the photoinitiator.
It is. From this, the liquid crystal film produced according to Reference Example 15 at 93 ° C. has a reflection central wavelength of 639 nm.

Reference Example 8: Three-component green liquid crystal mixture according to the present invention As in Reference Example 6, hydroquinone-bis- [4- (4-
Acryloylbutoxy) -benzoate] (Broe
r, D.R. J. Mol, G .; N. Challa, G .;
Makromol. Chem. 1991, Volume 192,
15.84 g, obtained from page 59), 4.4 g of 4- (acryloyloxy) benzoic acid- (4-acryloyloxyphenyl) ester (obtained according to EP 0 357 074, Example 1) and 4.4 g according to Reference Example 2
1.76 g of [4 '-(4'-acryloylbutyloxy) benzoyl] -5-anisoylisosorbide) and 10 mg of triethylamine and 2,6-di-ter
t-butyl-4- (dimethylaminomethylene) -phenol (Ethanox ^(R) 703, Ethyl Cor
p. , Baton Rouge, LA70801) 0.09g and a photoinitiator IRGACURE CURE ^{(Irgacure (R)} 8
19) From 0.22 g, a green liquid-crystal mixture having a clear temperature from cholesteric to isotropic of 140 ° C. was produced. The viscosity of this mixture at 90 ° C. is about 112 mPas. The concentration of the polymerizable groups in this mixture is 3.78 mmol / g without regard to the photoinitiator. From now on 95 ° C
The liquid crystal film manufactured according to Reference Example 15 was 530 n
It has a central reflection wavelength of m.

REFERENCE EXAMPLE 9 Two-component blue-green liquid crystal mixture according to the present invention, hydroquinone-bis- [4- (4-acryloylbutoxy) -benzoate] (Broer, DJ; Mo.
1, G. N. Challa, G .; Makromol.
Chem. 50.55 g, obtained from 1991, Vol. 192, p. 59), photoinitiator Irgacur (Ir
gacure ^(R) 819) 0.55g, triethylamine 17mg and 2,6-di-tert.. -Butyl-4
-(Dimethylaminomethylene) -phenol (Etha
nox ^(R) 703, Ethyl Corp. Baton Rouge, LA70801) 0.09 g and 2- [4-
29.81 g of a 14.93% toluene solution of (acryloyloxy) benzoyl] -5- (4-methoxybenzoyl) isosorbide (obtained by Reference Example 3) was weighed. The mixture was brought to an oil bath temperature of 150 using a KPG stirrer.
Homogenized at 0 ° C. until a clear solution resulted. Careful application of a vacuum removes the toluene-lean fraction.
The mixture was stirred under a vacuum of 1 mbar until the mixture melted isotropically (about 10 minutes).

The material was cooled immediately until the material temperature was about 80-90 ° C. The mixture has a cholesteric to isotropic clear temperature of 142 ° C. and about 200 mPas at 80 ° C.
Having a viscosity of The concentration of the polymerizable groups in this mixture is 3.21 mmol / g without regard to the photoinitiator. From now on, the liquid crystal film produced according to Reference Example 15 at 95 ° C. has a reflection central wavelength of 515 nm.

Reference Example 10 Two-component blue-green liquid crystal mixture according to the present invention, hydroquinone-bis- [4- (4-acryloylbutoxy) -benzoate] (Broer, DJ; Mo.
1, G. N. Challa, G .; Makromol.
Chem. 92.3 g, 2,5-bis- [4- (acryloyloxy) benzoyl] -isosorbide (obtained according to Reference Example 4), 7.7 g, photoinitiator Irgacur. (I
rgacure® 819) 1.00 g and 2,6
- di -tert- butyl-4- (dimethylaminomethylene) - phenol (Ethanox ^(R) 703, Eth
ylCorp. , Baton Rouge, LA70801)
0.20 g was weighed. Using a KPG stirrer, the mixture was homogenized at an oil bath temperature of 150 ° C. until a clear solution resulted. The mixture has a clear point of 146 ° C. and a viscosity at 100 ° C. of about 200 mPas. The concentration of polymerizable groups in this mixture is 3.37 mmol / mol without regard to the photoinitiator.
g. From this, the liquid crystal film produced according to Reference Example 15 at 100 ° C. has a reflection wavelength of 476 nm.

Comparative Example 1: DE 4240743, Example 4A
A green liquid crystal mixture according to Example 4A of DE 4240743 was prepared. This liquid crystal mixture contains 1.67 mmol / g of polymerizable groups, without regard to the photoinitiator. From now on, the liquid crystal film manufactured by Reference Example 15 at 90 ° C.
It has a central reflection wavelength of 516 nm.

Comparative Example 2: EP 0 479 466 (WO 9
Green liquid-crystal mixture corresponding to 5/24454) The green liquid-crystal mixture was prepared in a manner analogous to the general process for preparing cholesteric mixtures of EP 0 479 466 by 11.25% by weight of components K6, K from Example 88 in each case 11.25% by weight.
7, K10 and K11 (mixture 36), and Example 92
Components K1, K2, K4 and K5 from (mixture 40)
And 10% by weight of the chiral component K10 from Example 78
(Mixture 26) from the photoinitiator Irgacure (Irg
acure ^{(R )} 907) (Ciba Speziali)
taetenchemie GmbH, Lampertsheim). The mixture has a clear temperature from cholesteric to isotropic of 92 ° C. and contains 3.04 mmol / g of polymerizable groups, without regard to the photoinitiator. From this, the liquid crystal film produced according to Reference Example 15 at 50 ° C. has a reflection central wavelength of 545 nm.

Comparative Example 3: Green liquid-crystal mixture corresponding to EP 0 760 836 A green liquid-crystal mixture was converted to di- [4- (6-) as a nematic component in the same manner as in the general method for producing a cholesteric mixture of EP 0 760 836. Acryloyloxy) -hexyloxy] -benzoic acid-1,4- (2-methyl) -phenyl diester 58% by weight and cholesteryl-3,5-di- (4-acryloyloxybutoxy) -benzoate 42% by weight as a chiral component Manufactured from. Add the photoinitiator Irgacure (Irgac) to the mixture.
ure ^(R) 819) (CibaSpezialitae)
tenchemie GmbH, Lampertsheim) 1
% And 2,6-di-tert-butyl-4- (dimethylaminomethylene) -phenol (E
thanox ^(R) 703, Ethyl Corp. , Baton Rouge, LA70801) 2000 ppm. The mixture has a clear temperature of 61 ° C. from cholesteric to isotropic. It contains 2.79 mmol / g of polymerizable groups, without regard to the photoinitiator. From now on 42
The liquid crystal film produced according to Reference Example 15 at
It has a central reflection wavelength of nm.

Reference Example 11 Interaction of Pigment with Toluene at Room Temperature The bottom of a 1 cm cuvette was coated with a pigment having a chiral structure, and the cuvette was filled with toluene. After 1 hour, the pigment was shaken in a cuvette, after which the pigment was again settled to the bottom. Using a reflection mount, a UV / VIS spectrometer (Pe
The mid-reflection wavelength of the swollen pigment was measured with a model lambda 19) from rkin-Elmer and compared with the mid-reflection wavelength of the corresponding liquid crystal film from which the pigment was produced, measured with the same measuring device.

[0102]

[Table 1]

Reference Example 12: Production of Colored Liquid Crystal Film A monomer mixture comprising a crosslinkable nematic component and a chiral polymerizable component described in Reference Examples 6 to 10 and Comparative Example was prepared in accordance with US Pat. No. 5,362,315 (EP 0686677).
In a cholesteric phase by doctor application on a PET support sheet at the temperatures described in each case by means of the procedure described in paragraphs (1) to (3) -10 μm, and about 300 to 600 mJcm by UV light. ^-2 UV
Cured at A dose. At that time, a liquid crystal film of the color described in each case in a vertical bird's-eye view was obtained. These liquid crystal films exhibit a color shifted toward shorter wavelengths each time at an observation angle that varies from vertical.

Reference Example 13 Production of Liquid Crystal Pigment The photo-crosslinked colored liquid crystal film was peeled off from the support sheet, and a coarse liquid crystal mass was obtained. This coarse mass was subsequently pulverized with an air jet mill (Retsch). The ground product obtained was sieved and the sieve particles having an average particle size of about 30 μm were used for further processing.

Reference Example 14 Production of Lacquer According to the Invention The liquid crystal pigment obtained in Reference Example 13 was mixed with clear lacquer in a ratio of 1: 9 parts by mass. As clear lacquer, Herberts (Firm Herberts)
Topcoat varnish "Standox (Stand
ox) "(the curing agent was added to this immediately before processing)
Or a custom acrylate-melamine resin binder system from Herberts for automotive refinishing. The viscosity was adjusted with a diluent to a drain time of 80 seconds from the DIN-4-flow cup.

Reference Example 15: Thermostable liquid crystal effect paint on glossy cardboard The mixture comprising the pigment and the binder according to Reference Example 14 was used.
Leave it overnight, and pull out the film (Filmziehg
eraet; Erichsen, D-58675He
mer) on black glossy cardboard, the slit height was 180 μm and the drawing speed was 10 mm / sec. After a ventilation time of 10 minutes at room temperature, the samples were heat treated at 80 ° C. for 1 hour or at 130 ° C. for 1 hour. The reflection spectra of the enamel patterns baked at different temperatures were measured using a color meter CM508 / d from Minolta (D-22923 Ahrensburg). As a comparative material,
Pigments were prepared from the liquid-crystal mixtures according to Comparative Examples 1 to 3, applied accordingly and evaluated (concentration of polymerizable groups less than 3.2 mmol / g).

[0107]

[Table 2]

An example was carried out based on these results. In Examples, the liquid crystal pigments of Reference Examples 5, 7, 9, and 10 were used.

Example 1: Application to ink and application to prevention of forgery 12% by weight of the liquid crystal pigment prepared in Reference Example 10, 80% by weight of linseed oil as a solvent for printing ink, and rosin-modified phenol resin as a resin for printing ink varnish To 8% of each component to prepare a printing ink. Using the prepared ink, screen printing was performed on black paper to prepare a composite. Two such printed materials were left at the same time in an atmosphere of room temperature and 60 ° C. for 1 hour, assuming that the printed matter was in a midsummer automobile. The change in color tone was ΔE ^* = 2, demonstrating practicality.

The printed matter was color-copied, but the copy did not show any change in color tone due to the angle. This shows that there is a forgery prevention effect.

Example 2 Application to Paint 5% by weight of liquid crystal pigment prepared in Reference Example 9 and alkyd resin 1
A coating liquid was prepared with 0% by weight and 85% by weight of isopropanol, and a composite was prepared by coating a metal black panel by spraying. Assuming repair painting and OEM painting of automobiles, one of the painted sheets is
Dry for 0 minutes and the other at 130 ° C. for 30 minutes. The change in color tone was ΔE ^* = 1.2, demonstrating practicality.

Example 3 Application to Artificial Leather 5 parts by weight of the liquid crystal pigment prepared in Reference Example 9 was replaced with S-PVC 1
00 parts by weight, 60 parts by weight of DOP (di-octyl-phthalate) and Irgastab (registered trademark) TK 2
Mixed with 62GV. A layer of 100 μm of this mixture is applied by spatula to a leather-grained paper substrate and
Gelled at 50 ° C. for 3 minutes. After that, black P
A 250 μm layer of the VC mixture was applied in a similar manner on the liquid crystal pigment with the layer and gelled at 160 ° C. for 3 minutes. Finally, the foam layer of the black PVC mixture (fo
am layer) Apply 500 μm on top and 190 ° C
For 2.5 minutes. After removal of the paper substrate, an artificial leather having a green to blue discoloration effect was obtained.

Example 4 Application to Resin 1 98.98 parts by weight of polypropylene PP-V, 1 part by weight of the liquid crystal pigment prepared in Reference Example 7, and 0.02 parts by weight of carbon black were mixed. The mixture was extruded at 230 ° C. to obtain pellets. The pellets were applied during the co-extrusion process to obtain a two-layer blow molded bottle. This bottle is made of PP containing an inner layer of black PP-A 500 μm and a liquid crystal pigment.
-V had an outer layer of 100 μm. This bottle showed a distinct color change with angle.

Example 5 Application to Resin 2 98.98 parts by weight of polycarbonate pellets, 1 part by weight of the liquid crystal pigment prepared in Reference Example 10 and 0.02 parts by weight of carbon black were mixed. The mixture was kneaded at 330 ° C. in a single screw extruder. Injection molded size 50mm x 1
The 00 mm × 3 mm polycarbonate plate showed a clear change in color tone depending on the angle.

Example 6 Application to Cosmetic Applications Reference Example 6 was applied to 99% by weight of a commercially available clear nail paint.
1% by weight of the liquid crystal pigment prepared in the above was dispersed. Next, a black nail paint was applied to the base, and then applied thereon, and then a clear nail paint was applied to obtain a composite having a layer structure. The effect of changing the color tone depending on the angle was observed.

Example 7 Application to Cosmetic Use 1% by weight of the liquid crystal pigment prepared in Reference Example 9 was dispersed in 99% by weight of brown nail paint. This liquid crystal pigment nail paint was applied to a nail. Good hiding power was observed in addition to good color change with angle.

[0117]

The effect of the present invention is to provide a composite of a liquid crystal pigment and / or a liquid crystal film which is stable to heat and solvent while maintaining the variability of the angle color tone.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/29 C09D 5/29 11/00 11/00 201/00 201/00 (71) Applicant 390009003 Zielstattstraβe 20, D-81379 Munchen, F .; R. Germany (72) Inventor Jürgen Kupfer Germany Federal Republic of Munich Schede Röstrasse 10 (72) Inventor Franz-Heinrich Kreuzer Germany Federal Martinsried Josef-Gelstoner-Strasse 14 F-term (reference) 4C083 AD152 BB24 CC28A02F01 AS00A AT00B CA13A CC00 EH46 GB90 JB01 JB12A JJ03 JL00 YY00A 4J002 AA00W AA00X BB12X BG07W CG00X GB00 GH01 4J038 EA011 KA08 4J039 BE01 CA05

Claims (10)

[Claims] 1. A composite comprising (a) a liquid crystal pigment and / or a liquid crystal film and (b) a dispersion medium, wherein (a) contains a polymerizable group and at least 90% of the polymerizable group has at least 2%. Is a polymerizable group component of a molecule having a number of polymerizable groups (crosslinked molecules), and in a mixture (liquid crystal mixture) composed of a crosslinkable liquid crystal substance having a chiral phase, 3.2 to 15 mmol of polymerizable groups per 1 g of the liquid crystal mixture And a liquid crystal pigment and / or a liquid crystal film obtained by crosslinking a mixture comprising a crosslinkable liquid crystal material having a chiral phase. 2. A multilayer structure comprising at least one layer comprising the composite according to claim 1 and at least two layers comprising at least one substrate layer. 3. The composite according to claim 1, wherein the dispersion medium is a dispersion medium for ink or paint, and the multilayer structure according to claim 2. 4. The composite according to claim 1, wherein the dispersion medium is a resin, and the multilayer structure according to claim 2. 5. The composite according to claim 1, wherein the dispersion medium is a liquid substance, and the multilayer structure according to claim 2. 6. A forgery prevention product using the composite or multilayer structure according to claim 1. 7. A cosmetic product using the composite or multilayer structure according to claim 1. 8. A liquid crystal pigment and / or a liquid crystal in which (a) the substance having a chiral phase containing a polymerizable group is a crosslinked substance of a low molecular weight, oligomer or polymer having a chiral phase or a mixture of these substances. The composite or multilayer structure according to claim 1, which is a film. 9. (a) is a compound represented by the general formula: Y ¹ -A ¹ -M ¹ -A ^2-
Y ^{2 wherein} Y ¹ and Y ² are the same or different and represent a polymerizable group such as, for example, an acrylate or methacrylate group, an epoxy group, an isocyanate group, a hydroxy group, a vinyl ether group or a vinyl ester group; ¹ and A ² are represented by the general formula C _n H _2n (where n is 0 to 20)
And one or more methylene groups may be substituted by an oxygen atom) or the same or different groups, and M ¹ has the general formula —R ¹ —X ¹ —R ² —X ² — R ³ -X
³ -R ⁴ - has, wherein R ^1, R ^2, R ³ and R ^4, -
O-, -COO-, -CONH-, -CO-, -S-,
-C≡C-, -CH = CH-, -N = N-, -N = N
(O) - it is the same or selected from the group of means different divalent radicals, R ² -X ² -R ³ or R ² -X ² or R ² -
X ² -R ³ -X ³ may be a CC bond, X ¹ ,
X ² and X ³ are 1,4-phenylene, 1,4-cyclohexylene, arylene substituted with B ¹ and / or B ² and / or B ³ or O, N and S 6 to 6 in the aryl nucleus containing two heteroatoms
Heteroarylene having 10 atoms, B ¹ and / or
Or the same or different groups selected from the group of cycloalkylenes having 3 to 10 carbon atoms substituted by B ² and / or B ³ , wherein B ¹ , B ² and B
^3, -H, C ₁ ~C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₂₀ alkylthio, C ₁ -C ₂₀ alkylcarbonyl, C ₁ -C ₂₀ alkoxycarbonyl, C ₁ -C ₂₀ alkylthiocarbonyl , -OH, -F, -Cl, -Br,
-I, -CN, -NO _2, formyl, acetyl and ether oxygen, 1-20 alkyl group having a carbon atom which is interrupted by a thioether sulfur or ester groups,
Or the same or different substituents selected from the group of an alkoxy group or an alkylthio group], and a general formula: V ¹ -A ¹ -W ¹ -Z-W ² -A ² -V ² [ Wherein V ¹ and V ² are the same or different and include acrylate or methacrylate, epoxy, vinyl ether or vinyl ester, isocyanate,
₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₁ -C
₂₀ alkylthio group, C ₁ -C ₂₀ alkoxycarbonyl group, C ₁ -C ₂₀ alkylthiocarbonyl group, -OH,-
F, -Cl, -Br, -I, -CN, -NO 2, formyl, acetyl and ether oxygen, which is interrupted by a thioether sulfur or ester groups, alkyl groups having 1-20 carbon atoms, an alkoxy group, or A ¹ and A ² have the meanings described and W ¹ and W ²
Has the general formula -R ¹ -X ¹ -R ² -X ² -R ^3- , wherein R ¹ , R ² and R ³ have the meanings described and R ² or R ^2
2 -X ² may be C-C in binding, and X ¹ and X ² means described, and Z is dianhydrohexitol, Hekisosen, pen Tohsang, binaphthyl derivatives, biphenyl derivatives, tartaric acid derivatives or optically A divalent chiral group from the group of active glycols], wherein the polymerizable groups in the total mixture (at least 90% of which are molecules having at least two polymerizable groups) At a concentration of 3.2
The composite or multilayer structure according to any one of claims 1 to 7, wherein the mixture is a liquid crystal pigment obtained by crosslinking a mixture characterized by being between 15 and 15 mmol / g. 10. A compound of the general formula Y ¹ -A ¹ -M ¹ -A ² -Y ² of 70 to 99% by weight and a compound of the general formula V ¹ -A ¹ -W ¹ -Z
Of claims 1-7, wherein it is a liquid crystal pigment obtained by crosslinking the mixture of claim 9, wherein the containing Compound 1 to 30 wt% of the -W ² -A ² -V ² Composite or multilayer structure.