JP2002179669A - Optically active compound, photo-reactive chiral agent, liquid crystal composition, method for changing twist structure of liquid crystal, method for fixing spiral structure of liquid crystal, liquid crystal color filter, optical film and recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photo-reactive chiral agent having photo-reactivity and capable of considerably changing the twisting power (twist angle) of a liquid crystal compound generated by light irradiation. SOLUTION: The photo-reactive chiral agent is expressed by formula (2) [R3 is a substituted or unsubstituted alkynyl, C(R4)=CH2, a substituted or unsubstituted aryl or CH=CH-R5; R4 is a substituted or unsubstituted aryl or a substituted or unsubstituted heterocyclic group; R5 is phenyl or phenyl or naphthyl substituted with at least one substituent selected from an acyl, an alkoxycarbonyl and an aryloxycarbonyl; and a binaphthyl group has (R) or (S) axial asymmetryl].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel optically active compound, a photoreactive chiral agent, a liquid crystal composition using the same, a method for changing the twisted structure of a liquid crystal, and a method for fixing a helical structure of a liquid crystal. , A liquid crystal color filter, an optical film, and a recording medium.

[0002]

2. Description of the Related Art In recent years, liquid crystal materials such as cholesteric liquid crystals having a helical structure and exhibiting various selective reflection colors due to the twisting force (twist angle) of the spiral have attracted attention. Because of its excellent color purity of reflected light, it is widely used for optical filters, liquid crystal color filters, recording media, and the like. For example, a color filter used for a color liquid crystal display or the like generally includes red (R), green (G), and blue (B) pixels, and a black matrix for improving display contrast is formed between the pixels. It is composed. Conventionally, such color filters are mainly those in which a pigment is dispersed in a resin or dyes are dyed, and the production method is also such that a colored resin liquid is applied onto a glass substrate by spin coating or the like. In general, a method of forming a color resist layer and performing patterning by a photolithography method to form a color filter pixel or printing a color pixel directly on a substrate has been common.

[0003] However, for example, the manufacturing method by the printing method has a disadvantage that it is difficult to form a high-definition image pattern with a low pixel resolution, and the manufacturing method by the spin coating method causes a large material loss and a large loss. There is a drawback that coating unevenness when coating on a substrate having a large area is large. Further, according to the production method by the electrodeposition method, it is possible to obtain a color filter having relatively high resolution and less unevenness of the colored layer, but has a disadvantage that the production process is complicated and liquid management is difficult. As described above, as a process for manufacturing a color filter, there has been a demand for a manufacturing method capable of easily and easily manufacturing a high-quality color filter with little material loss.

On the other hand, the performance of a color filter is required to be high in transmittance and color purity. In recent years, a method using a dye has been optimizing a type of a dye and a dyeing resin, and a method using a pigment has become more difficult. The use of finely dispersed pigments has improved the above requirements. However, in recent liquid crystal display (LCD) panels, the requirements for the transmittance and color purity of color filters are extremely high. Particularly, in color filters for reflective LCDs, white display of paper white, contrast, and color reproducibility are both compatible. Is difficult, but in the conventional manufacturing method,
Color filters manufactured by dyeing a dye in a resin or dispersing a pigment are all light-absorbing color filters, so the improvement in color purity by further improving transmittance is almost at its limit. Had reached.

Under such circumstances, a polarization type color filter mainly comprising cholesteric liquid crystal has been known. This polarization-based color filter reflects a certain amount of light and transmits the rest to display an image, so it has high light use efficiency and is superior to the light absorption type color filter in terms of transmittance and color purity. It has the performance which it did. On the other hand, in the manufacturing method, from the viewpoint of obtaining a uniform thickness, a method of forming a film on a substrate by using a spin coating method or the like has been generally performed. Was disadvantageous.

A method using a photoreactive chiral compound as a means for solving the above problems and ensuring uniformity of the color purity and the like of the color filter film and reducing the number of manufacturing steps can be realized. Useful. In this method, when a liquid crystal composition containing a photoreactive chiral compound is irradiated with light having a reaction wavelength of the chiral compound in a pattern, the reaction of the chiral compound proceeds according to the intensity of the irradiation energy, and Since the helical pitch (helical twist angle) changes, the principle is used that a selective reflection color is formed for each pixel only by pattern exposure with a light amount difference. That is, there is an advantage that the number of times of patterning at the time of forming the color filter can be completed by one mask exposure using masks having different transmitted light amounts. Therefore, a film functioning as a color filter can be formed by immobilizing the patterned cholesteric liquid crystal compound after patterning by imagewise light irradiation. This can be applied to optical films, image recording, and the like.

In particular, when a color filter is manufactured by a single mask exposure, B (blue), G (green),
It is desired that three primary colors (red) can be formed with high color purity by one exposure. However, when the rate of change of the twist of the liquid crystal is small, sufficient color purity cannot be obtained. Therefore, from the viewpoint of displaying three primary colors having high color purity in one exposure, practically, as a photoreactive chiral compound to be used, a twisting power (HTP: helical twisting power) of a helical structure of a liquid crystal compound is used. It is necessary to use a chiral compound (chiral agent) having a large torsion change rate, which can be greatly changed. In other words, by using a chiral compound having a large twist change rate, the width of the hue selectively reflected by the change in the amount of light is expanded.

[0008] Liquid Crystals, 1996, 21, 327 and Liqu
id Crystals, 1998, 24, 219, states that introducing a substituent at the 6-position and 6'-position of 2,2'-methylenedioxy-1,1'-binaphthol may increase HTP. However, there is no mention as to which substituent is introduced to obtain an optically active compound having photoreactivity and capable of greatly changing HTP of a liquid crystal compound.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems. First, it is possible to control the orientation of a liquid crystal compound when coexisting with the liquid crystal compound. It is another object of the present invention to provide an optically active compound and a photoreactive chiral agent which have photoreactivity and can greatly change the torsional force (twist angle) of a liquid crystal compound by light irradiation. In particular, when coexisting with a nematic liquid crystal compound, the twisted structure of the liquid crystal compound is greatly changed according to the amount of light irradiation, and an optical element capable of selectively reflecting over a wide range including three primary colors (B, G, R). It is an object to provide an active compound and a photoreactive chiral agent. Second, a liquid crystal composition that can easily control the orientation of the liquid crystal compound and can greatly change the torsional force (twist angle) of the liquid crystal compound by light irradiation, particularly, the rate of change in twist of the liquid crystal by light irradiation. It is an object of the present invention to provide a liquid crystal composition which is capable of performing wide-range selective reflection including three primary colors and displaying three primary colors having high color purity when used as a cholesteric liquid crystal phase. Third, it is an object to provide a method that can easily change the twisted structure of the liquid crystal and a method that can easily fix the spiral structure of the liquid crystal.

Fourth, it is an object of the present invention to provide a liquid crystal color filter having high color purity which can be easily produced by light irradiation. Fifth, it is an object to provide an optical film exhibiting optical characteristics that can be easily produced by light irradiation. Sixth, it is an object of the present invention to provide a recording medium that can easily record an image with high color purity by light irradiation.

[0011]

Means for solving the above problems are as follows. That is, <1> an optically active compound represented by the following general formula (1).

[0012]

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[0013] In the general formula (1), R ¹ is a substituted or unsubstituted alkynyl group, or -C (R ²⁾ = represents CH _2, R ²
Represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. In the above formula, the binaphthyl moiety has either (R) or (S) axial asymmetry.

<2> A photoreactive chiral agent represented by the following general formula (2)

[0015]

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In the general formula (2), R^ThreeIs substituted or unsubstituted
Alkynyl group, —C (R^Four) = CH _Two, Replacement or nothing
A substituted aryl group or -CH = CH-R^FiveAnd R^FourIs
Substituted or unsubstituted aryl group or substituted or unsubstituted
Represents a substituted heterocyclic group,^FiveIs a phenyl group or acyl
Group, alkoxycarbonyl group and aryloxycarbo
Substituted with at least one substituent selected from a phenyl group
Represents a phenyl group or a naphthyl group. In the above formula,
The naphthyl moiety has an axial asymmetry of either (R) or (S).
Have.

<3> The photoreactive chiral agent according to <2>, wherein R ³ represents a substituted or unsubstituted alkynyl group or —C (R ⁴ ) ＝ CH ₂ . <4> At least a liquid crystalline compound, and <2> or <3>
And a photoreactive chiral agent described in (1). <5> A liquid crystal composition containing a liquid crystal compound having a polymerizable group, a photopolymerization initiator, and the photoreactive chiral agent described in <2> or <3>. <6> The liquid crystal composition according to <5>, wherein the photopolymerization initiator and the photoreactive chiral agent have different photosensitive wavelength ranges.

<7> A method in which the liquid crystal composition according to any one of <4> to <6> is irradiated with light to change the structure of the photoreactive chiral agent, thereby changing the twisted structure of the liquid crystal. is there. <8> After the liquid crystal composition according to <5> or <6> is imagewise irradiated with light in the photosensitive wavelength range of the photoreactive chiral agent, the liquid crystal composition is in the photosensitive wavelength range of the photopolymerization initiator. This is a method for fixing a helical structure of a liquid crystal, comprising a step of performing photopolymerization by irradiating light. <9> A liquid crystal color filter containing at least a liquid crystalline compound and the photoreactive chiral agent described in <2> or <3>. <10> At least a liquid crystal compound and <2> or <3>
And an optical film containing the photoreactive chiral agent described in (1). <11> At least a liquid crystal compound and <2> or <3>
And a photoreactive chiral agent.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION [Optically Active Compound] The optically active compound of the present invention is represented by the following general formula (1). The optically active compound has a site that undergoes a structural change upon irradiation with light. In the following formula, the binaphthyl moiety has either (R) or (S) axial asymmetry.

[0020]

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In the general formula (1), R ¹ represents a substituted or unsubstituted alkynyl group or —C (R ² ) ＝ CH ₂ ;
R ² represents a substituted or unsubstituted aryl group. In the above formula, the binaphthyl moiety has either (R) or (S) axial asymmetry.

The substituted or unsubstituted alkynyl group represented by R ¹ preferably has 2 to 30 carbon atoms, particularly preferably 2 to 20 carbon atoms. Examples of the substituent of the substituted alkynyl group include a halogen atom, an aryl group, an alkenyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group,
A cyano group is preferred, and an aryl group and an acyloxy group are particularly preferred. Examples of the substituted or unsubstituted alkynyl group represented by R ¹ include an ethynyl group, a phenylethynyl group,
-Acetyloxyphenylethynyl group and the like.

R ² represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. The substituted or unsubstituted aryl group represented by R ² has a total carbon number of 6 to
It is preferably 40, and particularly preferably 6 to 30. As the substituent of the substituted aryl group, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and a cyano group are preferable. An electron donating group such as an alkenyl group and an alkoxy group is preferable. Examples of the substituted or unsubstituted aryl group include a β-naphthyl group, a 4-methylphenyl group, a 4-vinylphenyl group, a 4-butyloxyphenyl group, and a 4-benzoyloxyphenyl group.

The substituted or unsubstituted heterocyclic group represented by R ² preferably has 4 to 40 carbon atoms, particularly preferably 4 to 30 carbon atoms. As the heterocyclic group,
A pyridine ring, a pyrimidine ring, a furan ring, and a benzofuran ring are preferred, and a pyridine ring and a pyrimidine ring are particularly preferred. Examples of the substituent of the substituted heterocyclic group include the same substituents as those of the above-mentioned substituted aryl group, and preferred substituents are also the same.

The substituted or unsubstituted alkynyl group represented by R ¹ and / or the substituted or unsubstituted aryl group or substituted or unsubstituted heterocyclic group represented by R ² are any of the following groups: May be substituted.

[0026]

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In the above formula, W represents a hydrogen atom or a methyl group, and k represents 0 or 1.

The optically active compound represented by the general formula (1), when used in combination with a liquid crystal, has excellent performance as a photoreactive chiral agent described later. Naturally, it can be used as an ordinary optically active compound, and can be applied to a helical structure inducing agent in an STN element or a TN element.

[Photoreactive Chiral Agent] The optically active compound represented by the following general formula (2) is a compound that can function as a photoreactive chiral agent. The photoreactive chiral agent of the present invention,
It is characterized by comprising an optically active compound represented by the following general formula (2). When coexisting with a liquid crystal compound, the orientation of the liquid crystal compound can be controlled and the helical pitch of the liquid crystal compound can be controlled by light irradiation. Can be changed. In particular, the optically active compound represented by the general formula (2) has a twisting power (HT) of a helical structure of the liquid crystal compound.
(P: helical twisting power), the photoreactive chiral agent of the present invention using the compound can greatly change the HTP of the liquid crystal compound.

The optically active compound represented by the following general formula (2) has an axial asymmetry of either (R) or (S).
The binaphthyl moiety is characterized by being racemized to a mixture of the (R) form and the (S) form by light irradiation.

[0031]

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In the general formula (2), R ³ is a substituted or unsubstituted alkynyl group, —C (R ⁴ ) ＝ CH ₂ , a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or CH = represents a CH-R ^5. Among them, R ³ is preferably a substituted or unsubstituted alkynyl group or —C (R ⁴ ) ＝ CH ₂ .

Examples of the substituted or unsubstituted alkynyl group R ³ represents the same meaning as the substituted or unsubstituted alkynyl group R ³ represents the general formula (1), and preferred ranges are also the same. R ⁴ has the same meaning as R ² in formula (1), and the preferred range is also the same.

The substituted or unsubstituted aryl group represented by R ³ preferably has 6 to 40 carbon atoms, particularly preferably 6 to 30 carbon atoms. Examples of the substituent of the substituted aryl group include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an acyl group,
An alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and a cyano group are preferable, and in particular, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group,
Acyloxy groups are preferred. Examples of the substituted or unsubstituted aryl group include a phenyl group, a β-naphthyl group,
-Methylphenyl group, 4-vinylphenyl group, 4-butyloxyphenyl group, and 4-benzoyloxyphenyl group.

The substituted or unsubstituted heterocyclic group represented by R ³ preferably has 4 to 40 carbon atoms, particularly preferably 4 to 30 carbon atoms. As the heterocyclic group,
A pyridine ring, a pyrimidine ring, a furan ring, and a benzofuran ring are preferred, and a pyridine ring and a pyrimidine ring are particularly preferred. Examples of the substituent of the substituted heterocyclic group include the same substituents as those of the above-mentioned substituted aryl group, and preferred substituents are also the same. Examples of the substituted or unsubstituted heterocyclic group include a pyrimidin-2-yl group.

In the general formula (2), R ⁵ is a phenyl group,
Or a phenyl or naphthyl group substituted with at least one substituent selected from an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group. The total number of carbon atoms of the acyl group as a substituent of the phenyl group or the naphthyl group is preferably 2 to 30,
More preferably, it is 20. The total number of carbon atoms of the alkoxycarbonyl group which is a substituent of the phenyl group or the naphthyl group is preferably 2 to 30, more preferably 2 to 20. The total number of carbon atoms of the aryloxycarbonyl group as a substituent of the phenyl group or the naphthyl group is preferably from 7 to 40, and more preferably from 7 to 30. Further, substitution positions of these substituents, -CH ethenyl group ^{(-CH = CH-R 5 =} CH-
On the other hand, in the case of a phenyl group, the position is preferably 4 and in the case of a naphthyl group, the position is preferably 5. The R ^5, phenyl group, 4-butoxycarbonylphenyl group, 4-benzoylphenyl group, a 4-naphthyloxycarbonyl phenyl group, a 6-methoxycarbonyl-2-yl group.

A substituted or unsubstituted alkynyl group represented by R ³ , a substituted or unsubstituted aryl group,
^The substituted or unsubstituted aryl group represented by ⁴ and the phenyl group or naphthyl group substituted by the substituent represented by R ⁵ may be substituted by any of the following groups.

[0038]

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In the above formula, W represents a hydrogen atom or a methyl group, and k represents 0 or 1.

Hereinafter, specific examples of the optically active compound (optically active compound represented by formula (1) or (2)) usable in the photoreactive chiral agent of the present invention (exemplified compound 1) -1 to 11: Specific examples of the compound represented by the general formula (1), Exemplified compounds 2-1 to 14: the general formula (2)
Are shown below, but the present invention is not limited to the following specific examples.

[0041]

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[0042]

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[0043]

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The optically active compound represented by the general formula (1) or (2) can be produced using the following compound A as a starting material. That is, it can be produced by a coupling reaction between compound A and monosubstituted acetylene under a palladium catalyst or a coupling reaction between compound A and an organic boronic acid under a palladium catalyst. For details of these reactions, see the Chemical Society of Japan, 4th edition, Experimental Chemistry Lecture 19 (Maruzen), pp. 27-36, 121-129.
348-352.

[0045]

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The coordination of the photoreactive chiral agent of the present invention with a liquid crystal compound (preferably a nematic liquid crystal compound) can control the orientation of the liquid crystal compound. In addition, when irradiated with light in the sensitive wavelength range,
Along with the light reaction, the twisting power (HTP: helical twisting power) of the helical structure of the liquid crystal compound can be changed. In addition, when the photoreactive chiral agent represented by the general formula (2) is used, particularly, the HT
The rate of change of P becomes large. In particular, when the liquid crystal phase is a cholesteric liquid crystal phase, B (blue), G (green), and R (red)
Selective reflection over a wide wavelength range including the primary colors can be obtained. The selective reflection characteristic of the light wavelength is determined by the twist angle of the helical structure of the liquid crystalline compound, and the greater the angle, the wider the color width of the selective reflection, which is useful.

The HTP represents the twisting force of the helical structure of the liquid crystal, that is, HTP = 1 / (pitch × concentration of chiral agent [weight fraction]). For example, the helical pitch of liquid crystal molecules at a certain temperature ( One cycle of the helical structure; μm) is measured, and this value can be obtained by converting [μm ⁻¹ ] from the concentration of the chiral agent (chiral agent). When a selective reflection color is formed by light illuminance using a photoreactive chiral agent, the change rate of HTP (= HTP before irradiation / HTP after irradiation) is as follows. 5 or more is preferable, and 2.5 or more is more preferable.
Is preferably 0.7 or less, more preferably 0.4 or less.

Further, as the photoreactive chiral agent of the present invention,
When using an optically active compound having a structure in which one or more polymerizable bonding groups are introduced in the molecule, a liquid crystal prepared using a liquid crystal composition containing the photoreactive chiral agent and a liquid crystal compound is used. It is preferable because the heat resistance of a color filter, an optical film, a recording medium and the like is improved. In addition, the photoreactive chiral agent of the present invention can be used in combination with a known chiral agent having no photoreactivity, such as a chiral compound having a large temperature dependence of torsional force. Examples of the chiral agent having no photoreactivity include JP-A-2000-44451 and JP-T-10-509726.
No., WO98 / 00428, Special Table 2000-5068
No. 73 and JP-A-9-506088 can be used.

[Liquid Crystal Composition] The liquid crystal composition of the present invention comprises at least the photoreactive chiral agent of the present invention and a liquid crystal compound. The liquid crystal compound is preferably a nematic liquid crystal compound. The liquid crystal compound of the present invention, if necessary, a polymerizable monomer, a polymerization initiator, a binder resin, a solvent, a surfactant, a polymerization inhibitor, a thickener,
Other components such as dyes, pigments, ultraviolet absorbers, and gelling agents may be included. It is particularly preferable that the liquid crystal composition of the present invention contains a surfactant. For example, in the case of applying a liquid crystal composition in the form of a coating liquid to form a layer, the alignment state at the air interface of the layer surface can be controlled three-dimensionally, and in particular, in the case of a cholesteric liquid crystal, a selective reflection wavelength having higher color purity can be obtained. Obtainable.

The content of the photoreactive chiral agent in the liquid crystal composition is not particularly limited and can be appropriately selected, but is preferably about 0.1 to 30% by mass.

The liquid crystal compound contained in the liquid crystal composition is preferably a liquid crystal compound having a refractive index anisotropy Δn of 0.10 to 0.40. The structure is not particularly limited, and a low-molecular liquid crystal compound, a high-molecular liquid crystal compound, a polymerizable liquid crystal compound, or the like can be used. Among them, a nematic liquid crystal compound is preferable. As the liquid crystalline compound, for example, an alignment substrate that has been subjected to an alignment treatment such as a rubbing treatment can be used, and a liquid crystal compound in a liquid crystal state at the time of melting can be applied on the substrate to be aligned. In order to fix the liquid crystal state, means such as cooling and polymerization can be used.

Specific examples of the liquid crystalline compound include the following compounds. However, the present invention is not limited to these.

[0053]

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[0054]

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[0055]

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In the above formula, n represents an integer of 1 to 1000. In each of the above exemplified compounds, those in which the connecting group of the aromatic ring is changed to the following structure can also be mentioned as suitable compounds.

[0057]

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Among the above, the liquid crystalline compound is preferably a liquid crystalline compound having a polymerizable group or a crosslinkable group in the molecule from the viewpoint of securing sufficient curability and heat resistance of the layer.

The content of the liquid crystal compound in the liquid crystal composition of the present invention is based on the mass of the solid content of the liquid crystal composition.
30-99.9 mass% is preferred, and 50-95 mass% is more preferred. It is preferable that the content is in the above range because the liquid crystal compound can be easily controlled to a desired orientation.

The liquid crystal composition of the present invention may contain a polymerizable monomer. When the polymerizable monomer is contained, a desired orientation is obtained by changing the torsional force of the liquid crystal by light irradiation (for example, in the case of producing a color filter, the distribution of the selective reflection wavelength is formed, that is, after patterning). The helical structure (selective reflectivity) can be fixed, and the strength of the liquid crystal composition after the fixing can be further improved. However, when the liquid crystal compound has an unsaturated bond in the same molecule, the same effect can be obtained without adding the polymerizable monomer.

The polymerizable monomer includes, for example, a monomer having an ethylenically unsaturated bond, and specifically, a polyfunctional monomer such as pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate. Specific examples of the monomer having an ethylenically unsaturated bond include the following compounds, but are not limited to these in the present invention.

[0062]

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The amount of the polymerizable monomer to be added is preferably 0.5 to 50% by mass based on the mass of the solid content of the liquid crystal composition. It is preferable that the addition amount be in the above range, since sufficient curability can be obtained and the alignment of liquid crystal molecules is not hindered.

In order to fix the helical structure of the liquid crystal of the liquid crystal composition of the present invention, when a polymerization reaction of a polymerizable compound (a liquid crystal compound having a liquid crystal compound having an unsaturated bond) is used, the liquid crystal composition is It is preferable to add a photopolymerization initiator to the product.

The photopolymerization initiator can be appropriately selected from known ones, for example, p-methoxyphenyl-2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxy) Styryl) -5-trichloromethyl 1,3,4-oxadiazole, 9-phenylacridine, 9,10-dimethylbenzphenazine,
Benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, benzyldimethyl ketal, thioxanthone / amine, triarylsulfonium hexafluorophosphate and the like. In addition, Japanese Unexamined Patent Application Publication No.
Examples thereof include bisacylphosphine oxides described in JP-A-29997 and the like, and acylphosphine oxides described in DE4230555 such as Lucirin TPO.

The photopolymerization initiator preferably has a photosensitive wavelength range different from the photosensitive wavelength range of the optically active compound represented by the general formula (2). Here, having different photosensitive wavelengths means that the photosensitive central wavelengths of the two do not overlap and, for example, the liquid crystals are not mutually exposed at the time of image exposure or polymerization curing so as not to cause a decrease in hue purity due to image display characteristics and selective reflection. This means that the orientation is not changed. In order not to overlap the photosensitive center wavelength,
In addition to relying on the molecular structures of the two, it can also be performed by controlling the wavelength of light irradiated through a band-pass filter or the like.

The amount of the photopolymerization initiator to be added is preferably 0.1 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the liquid crystal composition. It is preferable that the addition amount be in the above range because the curing efficiency at the time of light irradiation can be increased and the time required for curing can be shortened, and the light transmittance from the ultraviolet region to the visible light region can be maintained high.

The liquid crystal composition of the present invention further contains, as other components, a binder resin, a solvent, a surfactant, a polymerization inhibitor, a thickener, a dye, a pigment, an ultraviolet absorber, a gelling agent, and the like. You can also. As the binder resin,
For example, polystyrene, polystyrene compounds such as poly-α-methylstyrene, cellulose resins such as methyl cellulose, ethyl cellulose, acetyl cellulose, acidic cellulose derivatives having a carboxyl group in the side chain, polyvinyl formal, acetal resins such as polyvinyl butyral, JP No. 59-44615, Japanese Patent Publication No. 54-34
No. 327, JP-B-58-12577, JP-B-54-2
No. 5957, JP-A-59-53836, JP-A-59-53836.
Methacrylic acid copolymers described in the respective publications of 71048,
Acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like can be mentioned.

The homopolymer of an alkyl acrylate and the homopolymer of an alkyl methacrylate are also mentioned. In these, the alkyl group is a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an iso-butyl group.
-Butyl group, n-hexyl group, cyclohexyl group, 2-
Examples thereof include an ethylhexyl group. In addition, a polymer having a hydroxyl group to which an acid anhydride is added, a benzyl (meth) acrylate / (homopolymer of methacrylic acid) acrylic acid copolymer or benzyl (meth) acrylate / (meth) acrylic acid / other monomer And the like.

The content of the binder resin in the liquid crystal composition is preferably from 0 to 50% by mass, more preferably from 0 to 30% by mass. When the content is within the range,
It is preferable because it does not hinder the alignment of the liquid crystal compound.

In the liquid crystal composition of the present invention, it is preferable to use a surfactant together with the photoreactive chiral agent and the liquid crystal compound. As the surfactant, a surfactant having an excluded volume effect is preferable. Here, exerting the excluded volume effect means, for example, when a layer containing a liquid crystal composition is formed by coating, three-dimensionally controlling the spatial alignment state at the air interface on the surface of the layer. Specifically, a nonionic surfactant is preferable, and a nonionic surfactant can be appropriately selected from known nonionic surfactants.

In the present invention, the liquid crystal composition may contain a polymerization inhibitor. The polymerization inhibitor is added for the purpose of improving storage stability. Examples include hydroquinone, hydroquinone monomethyl ether, phenothiazine, benzoquinone, and derivatives thereof. The amount of the polymerization inhibitor to be added is 0 to the polymerizable monomer.
It is preferably from 10 to 10% by mass, more preferably from 0 to 5% by mass.

The liquid crystal composition of the present invention can be prepared by dissolving and dispersing each of the above-mentioned components in an appropriate solvent, and can be used by molding it into an arbitrary shape or forming it on a support or the like. . Here, examples of the solvent include 2-butanone, cyclohexanone, methylene chloride, chloroform and the like.

The liquid crystal composition of the present invention can be used for producing color filters, optical films and recording media. For example, when irradiating the liquid crystal composition of the present invention with light in the sensitive wavelength range of the photoreactive chiral agent while changing the amount of light,
The twisting force of the liquid crystal can be changed according to the amount of light irradiation, and a twisted structure of the liquid crystal, that is, regions having different degrees of spiral twist can be formed. For example, in the case of producing a color filter, the liquid crystal composition is irradiated with light in a desired pattern at a desired amount of light to arbitrarily change the selective reflection color indicated by the liquid crystal in accordance with the twisting force, thereby obtaining RGB.
Layers can be formed.

In particular, when the liquid crystal phase formed by the molecular orientation of the liquid crystalline compound is a cholesteric liquid crystal phase, the color width of the selective reflection color indicated by the liquid crystal increases in accordance with the twisting force.
It is possible to obtain selective reflection in a wide wavelength range including the primary colors (B, G, R), which is particularly important in that the three primary colors of BGR can be displayed with high color purity. In this respect, in particular, the optically active compound represented by the general formula (2) can greatly change the twisting power of the helical structure of the liquid crystal. Therefore, the liquid crystal composition containing the compound (chiral agent) can be used. By using, blue (B), green (G), red (R)
A wide range of hues including the three primary colors can be displayed, and three primary colors having excellent color purity can be obtained.

Specifically, a color filter can be manufactured as follows. That is, when the liquid crystal composition is irradiated with light of a certain wavelength, the co-existing photoreactive chiral agent (photoreactive optically active compound represented by the general formula (2)) responds according to the irradiation intensity, and the liquid crystal composition reacts. The helical structure (twist angle) is changed, and a different selective reflection color is shown by this structural change, and an image-like pattern is formed (patterning). Therefore, if light irradiation is performed while changing the irradiation intensity for each desired region, a plurality of colors are presented in accordance with the irradiation intensity, for example, exposure is performed through an exposure mask created by changing the light transmittance like an image. Thus, an image, that is, a colored region having different selective reflection can be simultaneously formed by one light irradiation. In addition, since it depends on the compound represented by the general formula (2), the formed colored region shows a wide range of selective reflection colors and can form three primary colors of BGR having excellent color purity. This light irradiation can be performed without any particular limitation as long as the irradiation intensity can be changed for each desired region, in addition to the method using an exposure mask.

In the case of forming a liquid crystal color filter, an optical film or the like to be described later, light of a certain wavelength is imagewise exposed and patterned as described above, and further irradiated with light to polymerize the liquid crystal composition. The helical structure of the liquid crystal can be fixed to a desired selective reflection color by photopolymerizing and curing the reactive group. Details of these forming methods will be described later.

The light source used for light irradiation is preferably a light source that emits ultraviolet light because it has a high energy and can rapidly change the structure of the liquid crystal compound and perform the polymerization reaction.
High-pressure mercury lamps, metal halide lamps, Hg-Xe lamps and the like are mentioned. Further, it is preferable to have a light quantity variable function.

As described above, when a color filter is manufactured using the liquid crystal composition containing the photoreactive chiral agent of the present invention, the rate of change of the twisting force of the helical structure of the liquid crystal with respect to the amount of light is large. In the case of a cholesteric liquid crystal phase, the color width of the selective reflection color that can be exhibited by the liquid crystal phase is expanded, and three primary colors of blue (B), green (G), and red (R) having excellent color purity can be obtained.

As described above, by using the liquid crystal composition of the present invention to change the twisting force of the helical structure in the liquid crystal phase by light irradiation, a color filter, a circularly polarized light separating film, and a stereoscopic image can be easily obtained. Optical films such as spectacles, polarizing masks, and optical compensation films can be formed. Further, application to a broadband switchable mirror, an optical writing type recording medium, or the like is also possible. Ferroelectric liquid crystal, antiferroelectric liquid crystal, T
By doping the GB phase, patterning of the polarization state and patterning of the helical pitch can be performed. Further, the liquid crystal composition of the present invention may contain a non-chiral azo or styrene-based compound which isomerized by light, thereby further increasing the rate of change of the helical pitch during light irradiation. There is.

As described above, by irradiating the optically active compound (photoreactive chiral agent) represented by the general formula (2) with light having a specific wavelength, the twisting force of the coexisting liquid crystal is changed to change the helical structure. Can be done. According to one embodiment, the liquid crystal composition of the present invention comprises at least one liquid crystal compound having a polymerizable group, a photopolymerization initiator, and an optically active compound represented by the general formula (2). In the method for fixing a helical structure of a liquid crystal according to the present invention, the changed helical structure can be fixed by polymerizing the liquid crystalline compound, and the strength of the liquid crystal composition after the fixing is improved. Can be further improved. It is preferable that the photopolymerization initiator and the optically active compound have different sensitive wavelength ranges.

Specifically, it can be performed as follows. That is, first, similarly to the above, light in the photosensitive wavelength region of the optically active compound in the liquid crystal composition is irradiated imagewise. By this light irradiation, the optically active compound responds and changes the helical structure of the liquid crystal to form an image-like pattern (patterning). After this patterning, light in the sensitive wavelength region of the photopolymerization initiator in the liquid crystal composition is irradiated. Then, the liquid crystal compound is polymerized by the photopolymerization initiator, and is fixed while maintaining the changed helical structure.
Before this step, for example, a step such as nitrogen substitution may be provided.

When the photosensitive wavelength region of the optically active compound is different from the photosensitive wavelength region of the photopolymerization initiator, the irradiation of light for changing HTP and the irradiation of light for photopolymerization do not affect each other. . Therefore, when imagewise exposed to change the HTP, photopolymerization does not proceed, so that patterning with the HTP change rate as set becomes possible, while photopolymerization to fix the helical structure is performed. The optically active compound does not react to light, and the formed HTP change pattern can be reliably immobilized.

In the case of forming a liquid crystal color filter, an optical film or the like to be described later, after light is imagewise exposed to light having a wavelength to which the optically active compound is sensitive as described above, a photopolymerization initiator is further added. The polymerizable group in the liquid crystal composition is photopolymerized and cured by irradiation with light having a sensitive wavelength, and the helical structure of the liquid crystal is fixed to a desired selective reflection color. Details of these forming methods will be described later.

Light sources used for light irradiation are the same as those described above.

Hereinafter, the liquid crystal color filter, optical filter and recording medium of the present invention will be described in detail. [Liquid Crystal Color Filter] The liquid crystal color filter of the present invention contains at least the liquid crystal composition of the present invention, that is, at least contains the nematic liquid crystal compound and the photoreactive chiral agent of the present invention. In addition, if necessary, a polymerizable monomer, a photopolymerization initiator, other components listed in the liquid crystal composition of the present invention, a surfactant having an excluded volume effect, and the like can be contained.

Hereinafter, the liquid crystal color filter of the present invention will be described in detail through the description of the method of manufacturing the liquid crystal color filter. The liquid crystal color filter of the present invention may be in the form of a sheet composed only of the liquid crystal composition, or may be provided with a layer (liquid crystal layer) containing the liquid crystal composition on a desired support or temporary support. In this case, another layer (film) such as an alignment film or a protective film may be provided. In the latter case, two or more liquid crystal layers can be laminated, and in this case, the exposure step described later is provided a plurality of times.

As the nematic liquid crystal compound, polymerizable monomer, photopolymerization initiator and other components, the same compounds as those usable in the liquid crystal composition of the present invention can be used. The same applies to the case of the liquid crystal composition. It is preferable to use a surfactant having an excluded volume effect in combination. Further, the content of the photoreactive optically active compound represented by the general formula (2) in the liquid crystal composition constituting the liquid crystal color filter is the same as that of the liquid crystal composition of the present invention described above.

The liquid crystal color filter of the present invention is, for example,
After patterning by imagewise exposure with the first light,
It can be produced by a production method including at least one step of photopolymerizing and curing by the second light (hereinafter, may be referred to as “exposure step”). Further, depending on the manufacturing mode selected, a step of appropriately subjecting the liquid crystal composition to a contact surface with an alignment treatment (alignment treatment step), a step of transferring and forming a liquid crystal layer by adhesion and separation (transfer step), It may be formed through a step of applying and forming a liquid crystal layer (coating step).

Hereinafter, a specific embodiment will be described as an example of a manufacturing method including the above-described exposure step. -Exposure Step- In the exposure step, both patterning and fixing (polymerization curing) of the liquid crystalline compound are performed by light irradiation. That is, after the photoreactive chiral agent is imagewise exposed and patterned by the first light having a wavelength sensitive to the high sensitivity, the polymerization initiator is photopolymerized by the second light sensitive to the high sensitivity. After curing, the helical structure of the liquid crystal compound is fixed to a desired selective reflection color.

When the liquid crystal composition is irradiated with the first light, the co-existing photoreactive chiral agent responds to the illuminance to change the helical structure of the liquid crystal compound, which varies depending on the structural change. An image-like pattern is formed indicating the selective reflection color. Therefore, if light irradiation is performed while changing the irradiation intensity for each desired region, a plurality of colors are presented in accordance with the irradiation intensity, for example, exposure is performed through an exposure mask created by changing the light transmittance like an image. Thus, an image, that is, a colored region having different selective reflection can be simultaneously formed by one light irradiation. Further, a liquid crystal color filter can be manufactured by irradiating second light and curing (fixing) the second light.

The wavelength of the first light is preferably set in the light-sensitive wavelength range of the photoreactive chiral agent, in particular, a wavelength close to the light-sensitive peak wavelength, in that sufficient patterning sensitivity can be obtained. Also, as the wavelength of the second light,
It is preferable to set the polymerization initiator to a light-sensitive wavelength range, particularly to a wavelength close to the light-sensitive peak wavelength, in that sufficient photopolymerization sensitivity can be obtained. The illuminance (irradiation intensity) of the first and second lights is not particularly limited, and can be appropriately selected depending on the material to be used so that sufficient photosensitivity can be obtained during patterning and polymerization curing. As the light source used for the irradiation of the first and second lights, the same light sources as those usable for the light irradiation of the liquid crystal composition can be used.

More specifically, the manufacturing method according to the following first and second embodiments may be used, and the manufacturing method can be more suitably performed according to these two embodiments. [First Embodiment] (1) A step of providing a liquid crystal composition in a coating liquid state on a temporary support to form a transfer material having at least a liquid crystal layer. The liquid crystal composition in the coating liquid can be prepared by dissolving and dispersing each component in an appropriate solvent. Here, as the solvent,
For example, 2-butanone, cyclohexanone, methylene chloride, chloroform and the like can be mentioned. Between the liquid crystal layer and the temporary support, a cushion layer containing a thermoplastic resin or the like may be provided from the viewpoint of ensuring adhesion during transfer, such as when there is a foreign substance or the like on the transfer target. It is also preferable that the surface of the cushion layer or the like is subjected to an orientation treatment (orientation treatment step) such as a rubbing treatment. (2) a step of laminating the transfer material on a light transmissive substrate; In addition to the light transmitting substrate, an image receiving material having an image receiving layer on a base may be used. Further, the liquid crystal composition may be applied directly on the substrate without using the transfer material (application step). Coating can be appropriately selected from known coating methods using a bar coater, a spin coater, or the like. However, the transfer method is preferable in terms of material loss and cost.

(3) A step of removing the transfer material from the light-transmitting substrate to form a cholesteric liquid crystal layer on the substrate (transfer step). The liquid crystal layer may be formed of a plurality of layers by further laminating after the following (4). (4) the cholesteric liquid crystal layer via the exposure mask is irradiated with ultraviolet illuminance [nu ¹ imagewise to form a pixel pattern illustrating the selectively reflected color, this further curing the layer by irradiation with ultraviolet illuminance [nu ² Step (exposure step).

[Second Aspect] (1) A step of forming a liquid crystal layer by directly providing a liquid crystal composition on a support constituting a color filter. Here, the liquid crystal layer can be formed by applying a liquid crystal composition prepared as a coating liquid in the same manner as described above by a known coating method using a bar coater, a spin coater, or the like. Further, an alignment film similar to the above may be formed between the cholesteric liquid crystal layer and the temporary support. The surface of the alignment film or the like is preferably subjected to an alignment treatment (alignment treatment step) such as a rubbing treatment. (2) An exposure step similar to step (4) of the first embodiment.

The thickness of the liquid crystal layer (sheet-like liquid crystal composition) functioning as a liquid crystal color filter is 1.5 to 4
μm is preferred.

Further, a description will be given below with reference to FIGS. 1 to 3 are schematic views showing one embodiment of a process for manufacturing a liquid crystal color filter of the present invention. First, each of the above-described components is dissolved in an appropriate solvent to prepare a liquid crystal composition in a coating liquid (preferably containing a nematic liquid crystal compound). Here, each component and solvent are as described above.

As shown in FIG. 1- (A), a support 10 (hereinafter, also referred to as a “temporary support”) is prepared, and an acrylic resin, polyester, polyurethane, or the like is applied and formed on the support 10. Cushion layer (thermoplastic resin layer) 12
And an alignment film 1 made of polyvinyl alcohol or the like.
4 is laminated. A rubbing process is performed on this alignment film as shown in FIG. This rubbing treatment is not always necessary, but the rubbing treatment can further improve the orientation. Next, FIG.
As shown in (C), a liquid crystal composition in the form of a coating liquid is applied on the alignment film 14 and dried to form a cholesteric liquid crystal layer 16, and then a cover film 18 is provided on the cholesteric liquid crystal layer 16 and transferred. Prepare the material. Hereinafter, the transfer material is referred to as a transfer sheet 20.

On the other hand, as shown in FIG. 1- (D), another support 22 is prepared, an alignment film 24 is formed on the support in the same manner as described above, and the surface is subjected to a rubbing treatment. Hereinafter, this is referred to as a color filter substrate 26.

Next, after the cover film 18 of the transfer sheet 20 was peeled off, the surface of the cholesteric liquid crystal layer 16 of the transfer sheet 20 and the alignment film 24 of the color filter substrate 26 were formed as shown in FIG. Are laminated so that they come into contact with the surface of each other, and laminated through a roll rotating in the direction of the arrow in the figure. Thereafter, as shown in FIG. 1- (F), the alignment film 14 of the transfer sheet 20 and the cushion layer 1 are formed.
2 and the cholesteric liquid crystal layer is transferred together with the alignment film 14 on the color filter substrate. In this case, the cushion layer 12 does not necessarily have to be peeled off together with the temporary support 10.

After the transfer, as shown in FIG. 3G, an exposure mask 28 having a plurality of regions having different light transmittances is arranged above the alignment film 14, and the first mask 28 is provided through the mask 28. The cholesteric liquid crystal layer 16 is irradiated with light in a pattern. The cholesteric liquid crystal layer 16 contains a liquid crystal compound, a chiral compound, or the like so that the helical pitch varies depending on the amount of light irradiation, and a structure having a different helical pitch reflects, for example, green (G) for each pattern. An area that transmits blue (B) and red (R), reflects blue (B),
It is formed to form a region that transmits green (G) and red (R) and a region that reflects red (R) and transmits green (G) and blue (B).

Next, as shown in FIG. 3H, the cholesteric liquid crystal layer 16 is further irradiated with ultraviolet rays at an irradiation intensity different from the light irradiation in the step (G) to fix the pattern. Thereafter, unnecessary portions (for example, remaining portions of the cholesteric liquid crystal layer 16 such as a remaining portion such as a cushion layer and an intermediate layer and unexposed portions) are removed by using 2-butanone, chloroform, or the like, so that the structure shown in FIG. As shown, a cholesteric liquid crystal layer having a BGR reflection region can be formed.

The method shown in FIGS. 1 to 3 is an embodiment of a method for manufacturing a color filter by a lamination method, but may be a method by a coating method in which a liquid crystal layer is directly formed on a color filter substrate. . In this case, when applied to the above embodiment, a cholesteric liquid crystal layer is applied on the alignment film 24 of the color filter substrate 26 shown in FIG. 1- (D), dried, and then similar to FIGS. The steps shown in ()) are sequentially performed.

These steps and materials to be used, such as a transfer material and a support, are described in Japanese Patent Application Nos. 11-342896 and 11-343665 filed by the present inventors.
The details are described in each specification of the item.

As described above, when the liquid crystal composition containing the optically active compound represented by the general formula (2) is used, the rate of change of the twisting force of the helical structure of the liquid crystal with respect to the amount of light is large.
The color width of the selective reflection color that can be exhibited by the liquid crystal is expanded, and a liquid crystal color filter having three primary colors of blue (B), green (G), and red (R) excellent in color purity can be obtained.

[Optical Film] The optical film of the present invention contains at least the liquid crystal composition of the present invention, that is, at least contains the liquid crystalline compound and the photoreactive chiral agent of the present invention. In addition, if necessary, a polymerizable monomer, a photopolymerization initiator, other components listed in the liquid crystal composition of the present invention, a surfactant having an excluded volume effect, and the like can be contained.

The form of the optical film of the present invention is not particularly limited, and may be a sheet composed only of the liquid crystal composition, or a layer (liquid crystal layer) containing the liquid crystal composition on a desired support or temporary support. It may be in any of the forms provided, and may be further provided with another layer (film) such as an alignment film or a protective film.

As the liquid crystal compound (preferably a nematic liquid crystal compound), a polymerizable monomer, a photopolymerization initiator and other components, the same compounds as those usable in the liquid crystal composition of the present invention can be used. The content, preferred range, and the like are the same as in the case of the liquid crystal composition. Further, the content of the optically active compound represented by the general formula (2) in the liquid crystal composition constituting the optical film is the same as that of the liquid crystal composition of the present invention described above.

The optical film of the present invention can be manufactured by a method substantially similar to that of the liquid crystal color filter, and can be manufactured by a method including at least one exposure step. Further, depending on the manufacturing mode to be selected, it may be formed through steps such as the alignment treatment step, the transfer step, and the coating step. More specifically, the first aspect, the second aspect,
It can also be manufactured in substantially the same manner as the manufacturing method of the embodiment.

As described above, when the liquid crystal composition containing the optically active compound represented by the general formula (2) is used, the rate of change of the twisting force of the helical structure of the liquid crystal with respect to the amount of light is large. By doing so, the liquid crystalline compound can be easily oriented to an arrangement showing desired optical characteristics. For example, in the case of manufacturing an optical filter, an optical filter having a variety of selective reflection colors in which the color width of selective reflection of liquid crystal is widened, and an optical filter of primary colors (B, G, R) having excellent color purity are obtained. be able to.

[Recording Medium] The recording medium of the present invention contains at least the liquid crystal composition of the present invention, that is, contains at least the liquid crystalline compound and the photoreactive chiral agent of the present invention. In addition, if necessary, a polymerizable monomer, a photopolymerization initiator, other components listed in the liquid crystal composition of the present invention, a surfactant having an excluded volume effect, and the like can be contained.

The recording medium of the present invention is not limited in its form, and may be in the form of a sheet comprising only a liquid crystal composition, or may have a desired support or temporary support (hereinafter referred to as “support etc.”). ) May be provided with a layer (liquid crystal layer) containing a liquid crystal composition containing a photoreactive chiral agent. Further, another layer (film) such as an alignment film or a protective film may be provided.

As the liquid crystal compound (preferably a nematic liquid crystal compound), a polymerizable monomer and a photopolymerization initiator, and other components, the same compounds as those usable in the liquid crystal composition can be used. The content, the preferable range, and the like are the same as those of the liquid crystal composition. Further, the content of the optically active compound represented by the general formula (2) in the liquid crystal composition constituting the recording medium is the same as that of the liquid crystal composition of the present invention described above.

The recording medium of the present invention can be suitably prepared, for example, by providing the above-described liquid crystal composition of the present invention on a support or the like. The method of providing the liquid crystal composition on a support or the like includes (1) using a transfer material in which a liquid crystal layer containing the liquid crystal composition of the present invention is provided on a temporary support, and then forming the liquid crystal layer on the support. Transfer method, (2) on a support,
A method of directly applying a liquid crystal composition prepared in a coating liquid state,
And the like. In the methods (1) and (2),
With respect to the transfer material and the method of coating, the embodiments exemplified in the liquid crystal composition of the present invention (first and second embodiments)
It can be applied according to the description of FIGS.

The recording medium of the present invention prepared as described above is irradiated with light in a desired pattern and light amount appropriately selected, so that an image, particularly a cholesteric liquid crystal, can be formed in accordance with the change rate of the twisting force of the liquid crystal. In the case of (1), a colored image composed of selective reflection colors determined by the change rate of the helical pitch can be formed. The image may be formed based on, for example, the above-described “method of changing the helical structure of liquid crystal” and “method of fixing the helical structure of liquid crystal”. Moreover, when the optically active compound represented by the general formula (2) is used as a chiral agent for changing the liquid crystal structure, an image having a wide color reproduction range can be formed because the rate of change of the twisting force of the helical structure of the liquid crystal with respect to the amount of light is large. In particular, in the case of a cholesteric liquid crystal, the hue width at which the liquid crystal selectively reflects can be widened, and a multicolor image with high color purity can be formed. Further, a large change rate of the torsional force greatly contributes to higher sensitivity (higher speed) during image formation. Further, for example, by using a polymerizable liquid crystal compound or a polymerizable monomer, the liquid crystal after patterning can be fixed, and an image having sufficient image stability can be formed. As the light source for light irradiation, the same light source as that usable in the liquid crystal composition of the present invention can be suitably used for optical recording. The same applies to the case of light irradiation for fixing the liquid crystal.

As described above, by using the optically active compound represented by the general formula (2) as a chiral agent that changes the helical structure of a liquid crystal compound (preferably a nematic liquid crystal compound), Torsion force (torsion angle)
Can be greatly changed, so that a color filter, an optical film, and a recording medium can be easily manufactured. For example, when producing a color filter, the selective reflection wavelength range obtained by light irradiation is expanded, and as a result, the color purity of the three primary colors of BGR can be further increased. When an optical film is produced, the liquid crystal compound can be easily oriented in an array having desired optical characteristics by controlling the amount of light irradiation. In particular, when an optical filter is produced, a color filter is used. An optical filter with excellent purity can be manufactured. In a recording medium, the hue of an image to be formed can be diversified.

[0117]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. still,
“Parts” and “%” in the examples all represent “parts by mass” and “% by mass”. Example 1-Production Example of Exemplified Compound 1-1-1 g of (R) -2,2'-methylenedioxy-6,6'-dibromo-1,1'-binaphthol (2.2 mmol
l), 0.02 g (0.028 mmol) of dichlorobis (triphenylphosphine) palladium (II), 0.04 g (0.02 mmol) of copper iodide, 1.2 ml (8.8 mmol) of triethylamine and DM
After mixing 10 ml of F, 0.47 g (4.6 mmol) of phenylacetylene was added, and the mixture was stirred at 70 ° C. for 8 hours. The reaction mixture was subjected to liquid separation using ethyl acetate and water, the ethyl acetate layer was distilled off, and the residue was purified by column chromatography. As a result, 11 mg (0.022 mmol,
(1% yield).

The identification data of the obtained product is shown below. Optical rotation: [α] _D ²⁵ −924.1 ° (c 0.10, Ac
OEt) ¹ H-NMR (CDCl ₃ ): δ (in ppm from tetrame)
thylsilane) 8.15 (2H, s), 7.98 (2H,
d), 7.62-7.52 (4H, m), 7.50 (2
H, d), 7.47-7.30 (10H, m), 5.7.
2 (2H, s)

Example 2-Production Example of Exemplified Compound 1-11-(S) -2,2'-Methylenedioxy-6,6'-dibromo-1,1'-binaphthol 1.5 g (3.3 mm
ol), 46 mg (0.066 mmol) of dichlorobis (triphenylphosphine) palladium (II), 1.8 ml of triethylamine, 2.1 g (6.6 mmol) of tetrabutylammonium bromide, 0.9 g (6.6 mmol) of potassium carbonate, 1.1 g (7.3 mmol) of 2-vinylnaphthalene and 15 ml of DMF were mixed and heated at an external temperature of 100 ° C. for 8 hours.
The reaction mixture was subjected to liquid separation using ethyl acetate and water, the ethyl acetate layer was distilled off, and the residue was purified by column chromatography to give Exemplified Compound 1 as a pale yellow solid
90 mg (0.15 mmol, 5% yield) of -11 was obtained.

The identification data of the obtained product is shown below. Optical rotation: [α] _D ²⁵ + 1.258 ° (c0.10, Ac
OEt) ¹ H-NMR (CDCl ₃ ): δ (in ppm from tetrame)
thylsilane) 8.08-7.42 (24H, m), 7.
40 (4H, s), 5.72 (2H, s)

Example 3-Preparation Example of Exemplified Compound 1-8 (R) -2,2'-Methylenedioxy-6,6'-dibromo-1,1'-binaphthol 1 g (2.2 mmol)
l), dichlorobis (triphenylphosphine) palladium (II) 0.07 g (0.1 mmol), triethylamine 1.2 ml (8.8 mmol), tetrabutylammonium iodide 2 g (5.4 mmol)
l), potassium carbonate 1.2 g (7.0 mmol), 4
-0.61 g (4.5 mmol) of methoxystyrene and 15 ml of DMF were mixed,
Heated for hours. The reaction mixture was subjected to liquid separation using ethyl acetate and water, the ethyl acetate layer was distilled off, and the residue was purified by column chromatography. As a result, 0.25 g of Compound 1-8 (0. .44 mmol,
(20% yield).

The identification data of the obtained product is shown below. Optical rotation: [α] _D ²⁵ -1153 ° (c0.10, CHC
l ₃ ) ¹ H-NMR (CDCl ₃ ): δ (in ppm from tetrame)
thylsilane) 8.00-7.87 (4H, m), 7.6
0-7.42 (10H, m), 7.15 (4H, s),
6.95-6.87 (4H, m), 5.70 (2H,
s), 3.82 (6H, s)

Example 4-Production Example of Exemplified Compound 2-2-(S) -2,2'-Methylenedioxy-6,6'-dibromo-1,1'-binaphthol 2.0 g (4.4 mm
ol), 0.2 g (0.17 mmol) of tetrakis (triphenylphosphine) palladium (0), 1.9 g (18 mmol) of sodium carbonate, 1.5 g (9.9 mmol) of 4-methoxyphenylboronic acid and DMF
Twenty milliliters were mixed and heated at an external temperature of 100 ° C. for 8 hours. The reaction mixture was subjected to liquid separation using ethyl acetate and water, the ethyl acetate layer was distilled off, and the residue was purified by column chromatography. As a result, 0.25 g of Exemplified Compound 2-2 as a white solid (0.2 g) was obtained. 49 mmol, yield 11
%) Obtained.

The identification data of the obtained product is shown below. Optical rotation: [α] _D ²⁵ + 877 ° (c0.10, AcOE
t) ¹ H-NMR (CDCl ₃ ): δ (in ppm from tetrame)
thylsilane) 8.10 (2H, s), 8.05-8.0
0 (2H, m), 7.72-7.45 (10H, m),
7.05-6.98 (4H, m), 5.71 (2H,
s), 3.88 (6H, s)

Example 5-Production Example of Exemplified Compound 2-11-(S) -2,2'-Methylenedioxy-6,6'-dibromo-1,1'-binaphthol 1.5 g (3.3 mm
ol), 46 mg (0.066 mmol) of dichlorobis (triphenylphosphine) palladium (II), 1.8 ml (13 mmol) of triethylamine, 2.5 g (6.6 m) of tetraamyl ammonium bromide
mol), potassium carbonate 0.9 g (6.6 mmol)
l), methyl 4-vinylbenzoate 1.1 g (7.3 m
mol.) and 15 ml of DMF were mixed and heated at an external temperature of 100 ° C. for 8 hours. The reaction mixture was subjected to liquid separation using ethyl acetate and water, the ethyl acetate layer was distilled off, and the residue was purified by column chromatography. As a result, 80 mg (0.1 mg) of Exemplified Compound 2-11 as a pale yellow solid was obtained.
3 mmol, 4% yield).

The identification data of the obtained product is shown below. Optical rotation: [α] _D ²⁵ + 1150 ° (c0.10, AcO
Et) ¹ H-NMR (CDCl ₃ ): δ (in ppm from tetrame)
thylsilane) 8.10-7.95 (8H, m), 7.6
8-7.47 (10H, m), 7.40 (2H, d),
7.24 (2H, d), 5.72 (2H, s), 3.9
5 (6H, s)

Example 6: Measurement of change in helical pitch due to light irradiation Each of the exemplified compounds shown in Table 1 was mixed with a liquid crystal compound (ZLI-1132, manufactured by Merck) in the composition shown in Table 1 to form a cholesteric liquid crystal. Compositions 1-4 were prepared. Each of the compositions was injected into a wedge-type cell (glass thickness: 1.1 mm, blue plate) which had been subjected to a uniaxial orientation treatment with a polyimide orientation film, and the helical pitch at room temperature was measured using a polarizing microscope. Table 1 shows the helical pitch measured for the cholesteric liquid crystal compositions 1 to 4 before light irradiation, and the helical twisting power (HTP) calculated based on the helical pitch.

Next, each of the wedge cells was irradiated with ultraviolet light from a high-pressure mercury lamp at an irradiation intensity of 300 mW / cm ² for 3 minutes. After irradiation, the helical pitch at room temperature was measured in the same manner as above. Spiral pitch measured for cholesteric liquid crystal compositions 1 to 4 after light irradiation,
Table 1 shows the helical twisting power (HTP) calculated based on this and the HTP change rate defined above.

[0129]

[Table 1]

From the results shown in Table 1, it was found that the optically active compound represented by the general formula (1) or (2) can greatly change the helical twisting power (HTP) by irradiation with ultraviolet rays. . In addition, when the direction of the twist before and after the irradiation of the ultraviolet ray was confirmed by the contact method, the direction of the twist did not change before and after the irradiation in any of the cells.

Example 7: Fabrication of Broadband Circularly Polarized Reflector (1) Preparation of Substrate A polyimide alignment film (LX-1400,
After applying a coating solution by a spin coater and drying in an oven at 100 ° C. for 5 minutes,
The alignment film was formed by firing in an oven at 250 ° C. for 1 hour. Further, the surface of the film was subjected to an orientation treatment by a rubbing treatment to produce a glass substrate with an orientation film.

(2) Production A coating solution prepared according to the following formulation was applied on the alignment film of the glass substrate provided with the alignment film obtained above using a bar coater.
After holding on a hot plate at 110 ° C. for 5 minutes, light irradiation was performed for 10 minutes with an ultrahigh pressure mercury lamp at this temperature through a band-pass filter having a light source central wavelength of 365 nm.

Then, the sample was kept at 110 ° C. in a dark place for 5 minutes, and then the band pass filter was removed.
The entire surface was further exposed to light at an irradiation energy of 500 mJ / cm ² by the same ultra-high pressure mercury lamp as described above while blowing nitrogen gas, and polymerized and cured. As described above, a circularly polarized light reflecting plate was produced.

[0134]

Embedded image

The circularly-polarized light reflecting plate obtained from the above was 450 to 6
It exhibited selective reflection in a wide wavelength range over 50 nm, and had sufficient band characteristics as a broadband circularly polarized light reflector. In addition, the left circularly polarized light reflectance at a selective reflection wavelength of 550 nm was 95%.

Example 8: Fabrication of liquid crystal color filter (1) Preparation of filter substrate A polyimide alignment film (LX-1400, manufactured by Hitachi Chemical DuPont) was applied on a glass substrate by a spin coater, and 100 ° C. After drying in the oven for 5 minutes, 2
It was baked in an oven at 50 ° C. for 1 hour to form an alignment film.
Further, the surface of the film was subjected to an orientation treatment by a rubbing treatment to produce a glass substrate with an orientation film.

(2) Formation of Filter Layer On the alignment film of the glass substrate provided with the alignment film obtained above, a coating solution for a photosensitive resin layer prepared according to the following formulation was applied by a spin coater, and this was applied at 100 ° C. For 2 minutes to form a photosensitive resin layer.

[0138]

Embedded image

Next, the photosensitive resin layer was colored by holding on a hot plate at 100 ° C. for 5 minutes so as to make contact with the surface of the glass substrate. Further, on the photosensitive resin layer, the transmittance is different in three stages (0%, 46%, 92%), and the respective regions are arranged corresponding to blue pixels, green pixels, and red pixels. An ultra-high pressure mercury lamp is arranged via a photomask and a bandpass filter centered at 365 nm,
Irradiation was performed with an ultra-high pressure mercury lamp through this photomask and bandpass filter to perform patterning. The irradiation energy at this time was 900 mJ / cm ² for the red pixel.
And the irradiation intensity was 30 mW / cm ² .

Next, the photomask and the band-pass filter were removed, and the irradiation energy was 500 mJ / cm ² by the same ultra-high pressure mercury lamp while blowing nitrogen gas.
The entire surface was further exposed and polymerized and cured. Furthermore, in order to promote the degree of curing of the filter portion (photosensitive resin layer), the
For 20 minutes to obtain a color filter on which red, green, and blue pixel patterns were formed. At the time of the patterning, the helical pitch of the liquid crystal (twisting force of the liquid crystal) can be largely changed by irradiation,
A pixel pattern composed of red, green, and blue with high color purity could be formed.

Example 9 Preparation of Optical Compensation Film for STN Element A polyethylene vinyl alcohol (PVA) film having a saponification degree of 99.5% was formed on triacetyl cellulose (TAC) having a thickness of 80 μm by a bar coating method. 110 ° C
Heated under for 3 minutes. A rubbing treatment was performed on the PVA film, and a coating solution prepared according to the following formulation was further heated and applied by a bar coater, and dried in an oven at 120 ° C. for 3 minutes to form a film.

[0142]

Embedded image

Next, at a temperature of 100 ° C., ultraviolet irradiation was performed from above the film using a high-pressure mercury lamp (irradiation energy 3).
00mJ / cm ² ) to polymerize and cure the film.
An optical compensation film for an element was manufactured (hereinafter referred to as “STN compensation film”).
Called. ). When the film thickness of the STN compensation film at this time was measured, it was 5.0 μm. Further, from the polarization transmission spectrum profile of the STN compensation film, it was found that the orientation (spiral structure) of the liquid crystal molecules was twisted in the film thickness direction at 240 degrees, and the twist angle (rotation angle) of the spiral was 240 degrees. Also, an STN compensation film having a twist angle (-240 degrees) opposite to that of the film is prepared, and these films are overlapped so that the liquid crystal molecules in the matched portion are orthogonal to each other, and the absorption axes are orthogonal to each other. It was inserted between two polarizing plates and visually observed, and showed a good black color. Therefore, it was confirmed that the film (STN compensation film) formed as described above functions as an optical compensation film for an STN element.

Example 10: Prevention of generation of reverse twist domain for TN element A polyimide alignment film (LX-1400, Hitachi Chemical DuPont, Ltd.) was formed on an ITO film of a glass substrate having an ITO film.
Coating solution was applied by a spin coater, dried in an oven at 100 ° C for 5 minutes, and then dried in an oven at 250 ° C.
After firing for an hour, an alignment film was formed. Further, a rubbing treatment was performed on the surface of the film to perform an orientation treatment so that the rubbing angle was 90 degrees, thereby producing two glass substrates with an orientation film. The glass substrates with the alignment films were arranged so that the alignment films faced each other, and bonded with a two-liquid epoxy resin adhesive mixed with spacer beads having a diameter of 6 μm to form driving cells. When the thickness of the cell was measured by an optical interference method, it was 5.4 μm.

A composition having the following composition was injected into the cell. [Composition] Cholesteric liquid crystal composition (ZLI-1132, manufactured by Merck) 99.9% Photoreactive chiral agent of the present invention (exemplified compound 1-11 described above) 0.1%

Next, when the driving cell after injection was inserted between two polarizing plates whose absorption axes were orthogonal to each other and observed visually, no generation of a reverse twist domain was observed. Therefore, there is no reduction in contrast due to the occurrence of reverse twist, and an image display excellent in contrast and color purity can be expected.

[0147]

According to the present invention, first, when coexisting with a liquid crystal compound, the orientation of the liquid crystal compound can be controlled, and the compound has photoreactivity and exhibits liquid crystal properties by light irradiation. The present invention can provide an optically active compound and a photoreactive chiral agent that can greatly change the twisting power (twisting angle) of a compound. In particular, when coexisting with a nematic liquid crystal compound, the twisted structure of the liquid crystal compound is greatly changed according to the amount of light irradiation, thereby enabling a wide range of selective reflection including three primary colors (B, G, R). An active compound and a photoreactive chiral agent can be provided. Second, a liquid crystal composition that can easily control the alignment of the liquid crystal compound and can greatly change the torsional force (torsion angle) of the liquid crystal compound by light irradiation, particularly, the rate of change in twist of the liquid crystal by light irradiation. When used as a cholesteric liquid crystal phase, it is possible to provide a liquid crystal composition that can perform selective reflection over a wide range including three primary colors and can display three primary colors with high color purity. Third, it is possible to provide a method for easily changing the twisted structure of the liquid crystal and a method for easily fixing the spiral structure of the liquid crystal.

Fourth, it is possible to provide a liquid crystal color filter having high color purity which can be easily produced by light irradiation. Fifth, it is possible to provide an optical film exhibiting optical characteristics that can be easily produced by light irradiation. Sixth, it is possible to provide a recording medium that can easily record an image with high color purity by light irradiation.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a part of a process of manufacturing a liquid crystal color filter of the present invention.

FIG. 2 is a schematic view showing a part of a process of manufacturing a liquid crystal color filter of the present invention.

FIG. 3 is a schematic view showing a part of a process of manufacturing a liquid crystal color filter of the present invention.

[Explanation of symbols]

 Reference Signs List 10 support (temporary support) 12 cushion layer (thermoplastic resin layer) 14, 24 alignment film 16 liquid crystal layer (liquid crystal composition) 18 cover film 20 transfer sheet 22 substrate 26 substrate for color filter 28 exposure mask

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02F 1/1334 G02F 1/1334 1/1335 505 1/1335 505 // C07M 7:00 C07M 7:00 ( 72) Inventor Mitsuyoshi Ichihashi 200, Onakazato, Fujinomiya City, Shizuoka Prefecture F-Film Co., Ltd. TA04 TA12 2H091 FA02Y FA11X FA11Z FB04 FB12 FC01 FC12 FC23 FD04 GA06 HA07 HA10 JA02 KA03 LA15 LA19 LA20 4H027 BA01 BD12 BD14 DH01 DH03 DH04

Claims (11)

[Claims] 1. An optically active compound represented by the following general formula (1). Embedded image (In the general formula (1), R ¹ represents a substituted or unsubstituted alkynyl group or —C (R ² ) ＝ CH ₂ , and R ² represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group Wherein the binaphthyl moiety has an axial asymmetry of either (R) or (S).) 2. A photoreactive chiral agent represented by the following general formula (2). Embedded image In (formula (2), R ³ is a substituted or unsubstituted alkynyl ^{group, -C (R 4) = CH} 2, an aryl group or a -CH = CH-R ⁵ substituted or unsubstituted, R ⁴ is Represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, wherein R ⁵ is substituted with a phenyl group or at least one substituent selected from an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group Represents a phenyl group or a naphthyl group, wherein the binaphthyl moiety has an axial asymmetry of either (R) or (S). 3. The photoreactive chiral agent according to claim 2, wherein R ³ represents a substituted or unsubstituted alkynyl group or —C (R ⁴ ) ＝ CH ₂ . 4. A liquid crystal composition containing at least a liquid crystalline compound and the photoreactive chiral agent according to claim 2 or 3. 5. A liquid crystal composition comprising a liquid crystal compound having a polymerizable group, a photopolymerization initiator, and the photoreactive chiral agent according to claim 2 or 3. 6. The liquid crystal composition according to claim 5, wherein the photopolymerization initiator and the photoreactive chiral agent have different photosensitive wavelength regions. 7. A method for irradiating the liquid crystal composition according to claim 4 with light to change the structure of the photoreactive chiral agent, thereby changing the twisted structure of the liquid crystal. 8. The liquid crystal composition according to claim 5, wherein
After irradiating light in the photosensitive wavelength region of the photoreactive chiral agent in an imagewise manner, and irradiating light in the photosensitive wavelength region of the photopolymerization initiator to perform photopolymerization, the helical structure of the liquid crystal How to immobilize. 9. A liquid crystal color filter containing at least a liquid crystalline compound and the photoreactive chiral agent according to claim 2 or 3. 10. An optical film containing at least a liquid crystalline compound and the photoreactive chiral agent according to claim 2 or 3. 11. A recording medium containing at least a liquid crystalline compound and the photoreactive chiral agent according to claim 2 or 3.