JP3372167B2 - Circular dichroic optical element and device therefor - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention is Ru crystal circular dichroism optical element comprising a solidified layer of polymer, and about the liquid crystal display device and a backlight equipment excellent in brightness utilizing the same <br/> .

[0002]

BACKGROUND ART Heretofore, there has been known a circular dichroic optical element in which a liquid cholesteric liquid crystal composed of a low molecular weight substance is sealed between substrates such as glass in an aligned state. This is because the helical axis of the liquid crystal molecule is in a Grandjean orientation perpendicular to the optical element, and about half of the light of a certain wavelength out of natural light that is incident parallel to the helical axis (incident angle 0 degree). Is transmitted as right (or left) circularly polarized light, and the other half is transmitted as left (or right) circularly polarized light.
λ = n · p (where n is the average refractive index of the liquid crystal and p is the spiral pitch of the cholesteric phase). The left and right of the reflected circularly polarized light are determined in the spiral state of the cholesteric phase, and coincide with the spiral turning direction.

In the above-mentioned circular dichroic dichroic optical element, since the reflected light and the transmitted light are separated, there is a possibility that the reflected light can also be used, and a dichroic dye or the like can be used in a stretched film such as polyvinyl alcohol. It is expected as a substitute for the polarizing plate that is adsorbed. However, such a polarizing plate is often used in a liquid crystal display device or the like, but the light transmitted as linearly polarized light is 50% or less of the incident light, and other light is absorbed in the polarizing plate and cannot be used. This is one of the reasons why it is difficult to increase the brightness and reduce the power consumption of the liquid crystal display device.

However, the conventional circular dichroic dichroic optical element is thick and heavy because it is necessary to use a substrate as described above, which impairs the lightness and thinness of the liquid crystal display device. was there. There is also a problem that the alignment state of the cholesteric liquid crystal, for example, the pitch is likely to change with temperature or the like.

Although a cholesteric liquid crystal polymer has been proposed (Japanese Patent Laid-Open No. 55-21479, US Pat. No. 5,332,522), a solidified product such as a film having a good alignment state such as a low molecular weight substance can be obtained. Is difficult, or the alignment process requires a long time such as several hours, or the glass transition temperature is low and the durability is insufficient, resulting in poor practicality.
In either case, it was difficult to obtain a solid-state circularly polarized dichroic optical element such as a film.

[0006]

The present invention technical problem of the invention] is thin, light and made of solid of liquid crystal polymer, it shall be the object that the orientation state of pitch, etc. to obtain a hard circular dichroism optical element changes in a practical temperature.

[0007]

A solution means of the present invention is made to have a solidified layer of a liquid crystal polymer composed of a cholesteric liquid crystal phase was Grandjean orientation, the liquid crystal polymer by the following general formula (a)
The monomer unit represented by the formula (b)
A copolymer containing Nomar unit is intended to provide a circular dichroism optical element, characterized in der Rukoto which the component. General formula (a): (However, R ¹ is hydrogen or a methyl group, m is an integer of 1 to 6, X ¹ is a CO ₂ group or an OCO group, and p and q are 1
Or 2, and p + q = 3 is satisfied. ) General formula (b): (Wherein, ^{R 2} is hydrogen or a methyl group, n represents an integer of 1 to 6, ^{X 2} is CO ₂ group or OCO group, ^{X 3} is ^{-CO-R 3}
Or -R ⁴ , and R ³ thereof is R ⁴ is And R ⁵ is: )

[0008]

EFFECTS OF THE INVENTION With the above configuration, it is possible to obtain a circular dichroic optical element that is made of a thin and lightweight solidified liquid crystal polymer and in which the alignment state such as the pitch does not easily change at a practical temperature. Also in based on the the liquid crystal polymer may depositing of a film of Grandjean orientation of a good mono-domain state can be easily formed, stable the alignment process be achieved in a short time such as several minutes in a glass state can immobilize, Ru can efficiently form a circular dichroism optical element excellent in durability and storage stability
At the same time , the helical pitch of the cholesteric phase can be easily controlled, and an optical element exhibiting circular dichroism in the visible light region can be easily obtained.

[0009]

The optical element of the present invention embodiments of the Invention state, and are not showing a circular dichroism having a solidified layer of a liquid crystal polymer composed of a cholesteric liquid crystal phase was Grandjean orientation, its <br/> liquid crystal polymer containing but a monomer unit represented by the following general formula (a), a monomer unit represented by the general formula (b)
Yes to the copolymer it is an ingredient.

General formula (a): (However, R ¹ is hydrogen or a methyl group, m is an integer of 1 to 6, X ¹ is a CO ₂ group or an OCO group, p and q are 1 or 2, and p + q = 3 is satisfied.)

General formula (b): (However, R ² is hydrogen or a methyl group, n is an integer of 1 to 6, X ² is a CO ₂ group or an OCO group, X ³ is —CO—R ³ or —R ⁴ , and R ³ is R ⁴ is And R ⁵ is as follows. )

The acrylic monomer capable of forming the monomer units represented by the above general formulas (a) and (b) can be synthesized by an appropriate method. Incidentally, a synthesis example of the acrylic monomer represented by the formula (a1) is shown below.

[0013]

That is, in the above description, ethylene chlorohydrin and 4-hydroxybenzoic acid are first heated and refluxed in an alkaline aqueous solution using potassium iodide as a catalyst to obtain a hydroxycarboxylic acid, which is then added to acrylic acid or methacrylic acid. By dehydration reaction with (meth) acrylate to esterify the (meth) acrylate with 4-cyano-4′-hydroxybiphenyl in the presence of DCC (dicyclohexylcarbodiimide) and DMAP (dimethylaminopyridine). (A1) can be obtained.

A synthetic example of the acrylic monomer represented by the formula (b1) is shown below.

In the above, first, hydroxyalkyl halide and 4-hydroxybenzoic acid are heated to reflux in an alkaline aqueous solution with potassium iodide as a catalyst to obtain a hydroxycarboxylic acid, which is then dehydrated with acrylic acid or methacrylic acid. The reaction is performed to obtain (meth) acrylate, and the (meth) acrylate is esterified with a phenol having a CO group containing an R ³ group at the 4-position in the presence of DCC and DMAP to obtain the target (b1). You can

The phenol having an R ³ group-containing CO group at the 4-position can be prepared, for example, by first reacting methyl chloroformate and 4-hydroxybenzoic acid in an alkaline aqueous solution to form a carboxylic acid, which is then oxalyl chloride. It can be obtained by reacting with H—R ³ in pyridine / tetrahydrofuran to introduce an R ³ group and then treating it with aqueous ammonia to remove the protecting group.

In the synthesis of the above formula (b1), the following compound added in the final step Can be replaced with the following to obtain the acrylic monomer represented by the formula (b2).

That is, a hydroxycarboxylic acid is dehydrated with (meth) acrylic acid to give a (meth) acrylate, and the (meth) acrylate is a phenol having an asymmetric carbon group at the 4-position in the presence of DCC and DMAP. The desired product (b2) can be obtained by esterification with.

The phenol having an asymmetric carbon group at the 4-position can be obtained by azeotropic dehydration of 4-hydroxybenzaldehyde and (S)-(-)-1-phenylethylamine in toluene as described below. You can

Therefore, other acrylic monomers capable of forming the monomer units represented by the general formulas (a) and (b) should also be synthesized in the same manner as above using appropriate raw materials having a desired introducing group. You can

The liquid crystal polymer used for forming the optical element is
One or more kinds of the monomer units represented by the general formula (a) and one or more kinds of the monomer units represented by the general formula (b) are copolymerized. The copolymerization ratio is such that when the content of the monomer unit represented by the general formula (b) is too large, the liquid crystallinity becomes poor, and when it is too small, the cholesteric liquid crystallinity becomes poor, so that
60 to 95% by weight of the monomer unit represented by, and 40 to 5% by weight of the monomer unit represented by the general formula (b) are preferable.

If the molecular weight of the copolymer is too small, the film-forming property will be poor. If it is too large, the liquid crystal will be poorly aligned and the monodomain will be poor, and it will be difficult to form a uniform alignment state. Based on this, 2,000 to 100,000 is preferable, and 25,000 to 50,000 is particularly preferable.

The copolymer can be prepared in accordance with a usual acrylic monomer polymerization method such as a radical polymerization method, a cationic polymerization method, or an anionic polymerization method. When the radical polymerization method is applied, various polymerization initiators can be used, but above all, the decomposition temperature of azobisisobutyronitrile, benzoyl peroxide, etc. is neither high nor low and decomposes at an intermediate temperature. Those are preferably used.

In the copolymer, the pitch of the cholesteric liquid crystal changes depending on the content of the monomer unit represented by the general formula (b). 3 and 4 exemplify the relationship between the content and the central wavelength showing circular dichroism. Note that the graph in FIG. 3 uses (a2) and (b3) represented by the chemical formulas in Examples described later as the monomer components of the copolymer, and (a2) and (b6) in the case of FIG. Since the wavelength exhibiting circular dichroism is determined by the pitch, the wavelength exhibiting circular dichroism can be adjusted by controlling the content of the monomer unit represented by the general formula (b). Therefore, an optical element exhibiting circular dichroism with respect to light in the visible light range can be easily obtained as in Examples described later.

The copolymer may be used alone or in combination of two or more thereof to form an optical element. The wavelength range showing circular dichroism can also be adjusted by mixing two or more kinds of copolymers having different wavelength ranges showing circular dichroism. In the present invention, a liquid crystal polymer having a glass transition temperature of 80 ° C. or higher is used in view of durability of the obtained optical element, stability of orientation characteristics such as pitch with respect to temperature change during practical use, and invariability. What is preferable can be used for formation of an optical element.

In the present invention, one of the monomer units represented by the above general formula (a) or general formula (b) is used.
Use of a homopolymer consisting of two or more species based on the general formula as a liquid crystal polymer of a mixed system of a polymer of the general formula (a) and a polymer of the general formula (b) for forming an optical element. You can also The mixing ratio, molecular weight and the like can be based on those of the above-mentioned copolymer.

The optical element exhibiting circular dichroism can be formed by a method similar to the conventional alignment treatment. By the way, as an example, after forming an alignment film made of polyimide, polyvinyl alcohol, etc. on a substrate and rubbing it with a rayon cloth or the like, a liquid crystal polymer is spread on it to have a glass transition temperature or higher, isotropic phase. Examples include a method of heating below the transition temperature and cooling to below the glass transition temperature in the state where the liquid crystal polymer molecules are in the Grandjean orientation to bring them into a glass state to form a solidified layer in which the orientation is fixed.

As the above-mentioned substrate, for example, triacetyl cellulose, polyvinyl alcohol, polyimide, polyarylate, polyester, polycarbonate, polysulfone, polyether sulfone, a film made of a plastic such as an epoxy resin, or a glass plate is used. Can be used. The solidified layer of the liquid crystal polymer formed on the substrate can be used as it is for an optical element as an integrated body with the substrate, or can be peeled from the substrate and used as an optical element made of a film or the like.

The liquid crystal polymer may be spread by a heating and melting method or as a solution with a solvent. As the solvent, for example, methylene chloride, cyclohexanone, trichloroethylene, tetrachloroethane, N-methylpyrrolidone, tetrahydrofuran or the like can be appropriately used. The development can be performed with an appropriate coating machine such as a bar coater, a spinner, or a roll coater.

The thickness of the solidified layer of the liquid crystal polymer to be formed is
If it is too thin, it becomes difficult to exhibit circular dichroism, and if it is too thick, it is inferior in uniform alignment and does not exhibit circular dichroism, or it takes a long time for the alignment treatment.
m, especially 1 to 10 μm is preferable. When forming the optical element, various additives such as polymers other than the copolymer, stabilizers, plasticizers and other inorganic or organic materials, or metals can be blended as necessary.

The optical element of the present invention exhibits circular dichroism, but a single layer of a solidified liquid crystal polymer layer is usually limited to a wavelength range exhibiting circular dichroism. The limitation is generally as wide as a wavelength range of about 100 nm, but when applied to a liquid crystal display device or the like, it is desired to exhibit circular dichroism in the entire visible light range.

In the present invention, by laminating a solidified layer of a liquid crystal polymer showing circular dichroism with respect to light having different wavelengths, the wavelength range showing circular dichroism can be expanded. Such layering is advantageous not only in expanding the wavelength range but also in coping with the wavelength shift of obliquely incident light.
Two or more layers can be laminated in a combination in which the central wavelengths of reflected circularly polarized light are different. When laminating, it is preferable to reduce the surface reflection loss at each interface by using an adhesive or the like.

By the way, the central wavelength of the reflected circularly polarized light is 300.
A combination of liquid crystal polymer solidified layers of ~ 900 nm that reflect circularly polarized light in the same direction, and different central wavelengths of selective reflection,
Especially, by using different combinations of 50 nm or more, 2
It is possible to form an optical element that exhibits circular dichroism in a wide wavelength range by laminating 6 to 6 kinds. In addition, the point that the combination of those that reflect circularly polarized light in the same direction is that the phase states of the circularly polarized light reflected in each layer are aligned to prevent different polarization states in each wavelength range, and are reflected through a reflective layer, etc. The purpose is to improve the efficiency when reusing circularly polarized light.

The optical element of the present invention separates incident light into left and right circularly polarized light on the basis of its circular dichroism and supplies it as transmitted light and reflected light, but has a wide viewing angle. The present invention can be preferably applied to various devices such as a direct-view type liquid crystal display device which has a small change in optical characteristics with respect to a change in viewing angle and can be directly observed even from an oblique direction. In particular, it is possible to improve the utilization efficiency of light by reusing the reflected circularly polarized light through a reflection layer and the like, and it is preferable to use it as a backlight system in a liquid crystal display device or the like because it is easy to increase the area. sell.

FIGS. 1 and 2 exemplify a liquid crystal display device using the optical element of the present invention in a backlight system. Reference numeral 4 is a backlight system, 1 is an optical element thereof, 2 is a retardation layer for converting circularly polarized light into linearly polarized light, and 3 is a light source. Further, 5 is a polarizing plate and 6 is a liquid crystal cell. 1
1, 12 and 13 are liquid crystal polymer solidified layers forming a laminated optical element, 31 is a light source holder, 41 and 44 are light diffusion plates, 42 is a light emitting layer, 43 and 46 are reflective layers, 45 is a housing space, 7 Is a retardation plate for compensation.

A liquid crystal display device is generally formed by appropriately assembling components such as a polarizing plate, a liquid crystal cell, a backlight, and a retardation plate for compensation, if necessary, and incorporating a drive circuit. In the present invention, as shown in the figure,
Optical element 1 and retardation layer 2 for converting circularly polarized light into linearly polarized light
There is no particular limitation except that the light is incident on the liquid crystal cell 6 via, and it can be formed in a conventional manner.

Therefore, any liquid crystal display device is required as long as it is necessary to make the polarized light enter the liquid crystal cell. Although it can be preferably used for those using twisted nematic liquid crystals or super twisted nematic liquid crystals, non-twisted liquid crystals, guest-host liquid crystals in which a dichroic dye is dispersed in liquid crystals, or ferroelectric liquid crystals are used. It can also be used for things. The liquid crystal driving method is not particularly limited.

Although the liquid crystal cell 6 has polarizing plates 5 on both sides in the illustrated example, the polarizing plate on the backlight side can supply light having excellent linear polarization through an optical element or the like. Can be omitted. The linear polarization, that is, the circular polarization of the circularly polarized light that has passed through the optical element is performed via the retardation layer 2 disposed on the optical element 1. Therefore, the liquid crystal cell is arranged on the retardation layer 2 in the backlight system.

The phase difference layer for converting the circularly polarized light transmitted through the optical element into linearly polarized light changes the phase of the circularly polarized light emitted from the optical element to convert the circularly polarized light into a state having a large amount of linearly polarized light and transmits it through a polarizing plate or the like. The purpose is to make the light easy. Therefore, as the phase difference layer, the circularly polarized light emitted from the optical element is
A large amount of linearly polarized light can be formed corresponding to a phase difference of 4 wavelengths, and light of other wavelengths has a major axis in a direction as parallel as possible with the linearly polarized light and is as linearly polarized as possible. A material that can be converted into a nearly flat elliptically polarized light can be preferably used.

By arranging the retardation layer as described above, the linear polarization direction of the emitted light and the major axis direction of the elliptically polarized light are arranged as parallel as possible to the transmission axis of the polarizing plate.
It is possible to obtain light having a large amount of linearly polarized light components that can be transmitted through the polarizing plate.

The retardation layer can be formed of an appropriate material and is preferably transparent and gives a uniform retardation. Generally, a retardation plate made of a stretched film of a plastic such as polycarbonate, a unidirectionally oriented product of a nematic liquid crystal polymer, or a twisted orientation product is used. The retardation of the retardation layer can be appropriately determined according to the wavelength range of circularly polarized light emitted from the optical element. By the way, in view of wavelength characteristics and practicality in the visible light region, taking into consideration that most retardation plates exhibit positive birefringence wavelength dispersion than their material characteristics, the phase difference is small, In particular, a material which gives a phase difference of 100 to 200 nm can be preferably used in many cases.

The retardation layer can be formed as one layer or two or more layers. In the case of a retardation layer consisting of one layer, it is preferable that the wavelength dispersion of birefringence is smaller because the polarization state can be made uniform for each wavelength. On the other hand, the superposition of the retardation layers is effective for improving the wavelength characteristics in the wavelength range, and the combination thereof may be appropriately determined depending on the wavelength range and the like.

When two or more retardation layers for the visible light region are used, it is often the case that one or more odd-numbered layers are included as the layer that gives a retardation of 100 to 200 nm, as described above, because of the linear polarization component. It is preferable in terms of obtaining light. 100-200
The layers other than the layer that gives the phase difference of nm are usually 200 to 400.
It is preferable to form a layer that gives a phase difference of nm from the viewpoint of improving wavelength characteristics and the like, but it is not limited to this.

In the liquid crystal display device exemplified above, the reflection layers 43 and 46 are provided on the bottom surface of the backlight system, and the circularly polarized light reflected by the optical element 1 is reflected through the reflection layer, and the optical element is again returned as the returned light. It is intended to improve the light utilization efficiency by making the light incident on. That is, the circularly polarized light reflected by the optical element is confined between the reflective layer and the reflective layer, and repeated reflection between the reflective layer and the optical element is converted into a circularly polarized state that can be transmitted through the optical element. The unused portion is reduced.

According to the above, along with the measure for reducing the content rate of the light component absorbed in the polarizing plate by the linear polarization of the circularly polarized light through the retardation layer, the light which has been the reflection loss or the absorption loss in the past can be effectively used. Therefore, the light utilization efficiency is improved, and a liquid crystal display device which is bright and has excellent visibility can be formed.

The above-mentioned reflective layer is preferably a layer which causes reflection inversion, such as a metal surface made of aluminum or silver. As a result, the left and right of the reflected circularly polarized light can be reversed to be in the same state as the circularly polarized light on the transmitting side, the transmission efficiency can be improved, and the light utilization efficiency can be efficiently increased. Even in a diffuse reflection layer represented by, for example, an uneven surface, polarization states are randomly mixed based on the diffusion, the polarization states are eliminated, and light utilization efficiency can be improved.

As the light emitting layer, an appropriate layer that emits light to one surface side can be used. Preferably, a material that efficiently emits light without absorption is used. (cold,
A linear light source such as a cathode ray tube or a light source 3 such as a light emitting diode is arranged on the side surface of the light guide plate (42), and the light transmitted through the light guide plate is diffused, reflected, diffracted or interfered with by the light guide plate. Examples thereof include a side-light type backlight (FIG. 1), an EL lamp, a direct type (FIG. 2), and the like, which are known in liquid crystal display devices and emit light to one side of the plate. The optical element is
It is arranged on the light emitting side of the light emitting layer.

The above-mentioned light guide plate, which is adapted to emit the transmitted light to one side, is a transparent or semi-transparent resin plate provided with a diffuser in a dot shape or a stripe shape on the light emitting surface or the back surface thereof. Alternatively, it can be obtained as a resin plate having an uneven structure on its back surface.

When forming the light emitting layer, the light diffusion plates 41 and 44 for obtaining uniform light emission, the prism sheet for controlling the emitting direction of the light, the reflecting means for returning the leaked light,
An auxiliary means such as a light source holder 31 for guiding the light emitted from the linear light source to the side surface of the light guide plate can be arranged at a predetermined position as necessary to form an appropriate combination.

From the viewpoint of obtaining a display with a good contrast ratio by the incidence of highly linearly polarized light, an optical element arranged as a polarizing plate, particularly as a polarizing plate on the backlight side, that is, on the incident side of visible light in a liquid crystal cell. As the polarizing plate on the side closer to, it is preferable to use a polarizing plate having a high degree of polarization such as an iodine-based or dye-based absorption type linear polarizer.

The forming components such as the liquid crystal display device and the backlight system may be laminated and integrated, or may be separated. When forming a liquid crystal display device,
For example, appropriate optical elements such as a diffusion plate, an anti-glare layer, an antireflection film, a protective layer or a protective plate provided on the polarizing plate on the viewing side, and a retardation plate for compensation provided between the liquid crystal cell and the polarizing plate are appropriately arranged. be able to. When the optical element and the retardation layer are used in combination, they may be laminated and integrated, or may be in a separated state. The arrangement position is such that the optical element is interposed between the light emitting side of the light emitting layer and the retardation layer.

The above-mentioned retardation plate for compensation is for the purpose of compensating for the wavelength dependence of birefringence and improving the visibility. Reference numeral 7 in FIGS. is there. In the present invention, it is arranged between the liquid crystal cell on the viewing side and / or the backlight side and the polarizing plate as necessary. As the retardation plate for compensation, an appropriate one may be used depending on the wavelength range and the like, and may be formed as one layer or a superposed layer of two or more layers.

As described above, in the liquid crystal display device according to the present invention, the reflected circularly polarized light by the optical element is reused as the emitted light by the polarization conversion through the reflection layer or the like to prevent the reflection loss and to position the emitted light. By controlling the phase through the phase difference layer and converting the linearly polarized light component of the polarizing plate into a rich optical state, the absorption loss due to the polarizing plate is prevented and the light utilization efficiency can be improved. .

From the point of utilizing the light emitted from the retardation layer as a light source, 65% or more, and especially 70% or more, of linearly polarized light components that can pass through the polarizing plate as long-axis direction components of linearly polarized light or elliptically polarized light are included. It is preferable. In addition, in order to prevent the color change of the display, in the combination of the optical element and the retardation layer, the incident light composed of natural light is emitted as polarized light having a color change Δab of 10 or less based on the NBS method. preferable. The lamination of the liquid crystal polymer solidified layer is more advantageous than the reduction of the color change.

In this case, the arrangement angle between the polarization axis of the polarizing plate on the backlight side and the fast axis or the slow axis of the retardation plate depends on the retardation characteristics of the retardation layer, the characteristics of circularly polarized light incident on the retardation layer, and the like. Can be appropriately determined according to By the way, in the case of the retardation plate which gives the retardation of 100 to 200 nm, when the left circularly polarized light is incident, the arrangement angle of the fast axis of the retardation plate is set to 0 with the polarization axis of the polarizing plate as a reference (0 degree). ~ 9
The light transmitted through the polarizing plate can be improved by setting the angle to 0 degree, preferably 35 to 55 degrees, and particularly 45 degrees.

On the other hand, when the right-handed circularly polarized light is incident, the light transmitted through the polarizing plate can be improved by setting the angle based on the slow axis of the retardation plate. When it is composed of two or more layers of retardation film, the outer surface layer is 10
When a layer that gives a retardation of 0 to 200 nm is occupied, it is preferable to set the arrangement angle based on the layer.

[0058]

【Example】

Example 1

33.9 parts by weight (82 mmol) of the monomer represented by the chemical formula (a2) and 9.16 parts by weight (18 mmol) of the monomer represented by the chemical formula (b3) are dissolved by heating in 430 ml of tetrahydrofuran to give 55 to 55 60 ° C
After stabilizing the inside of the reactor and replacing the inside of the reactor with nitrogen gas, 5 ml of a tetrahydrofuran solution containing 0.5 part by weight of azobisisobutyronitrile dissolved in the absence of oxygen was added dropwise to carry out a polymerization treatment for 6 hours. The precipitate was gradually poured into 3000 ml of diethyl ether with stirring to obtain a white polymer precipitate, which was centrifuged, dried and reprecipitated and purified twice more to obtain a copolymer having a weight average molecular weight of 7,000. This copolymer had a glass transition temperature of 88 ° C. and an isotropic phase transition temperature of 225 ° C., and exhibited a cholesteric structure at temperatures in between.

A polyvinyl alcohol layer having a thickness of about 0.1 μm was provided on a triacetyl cellulose film having a thickness of 50 μm, and the polyvinyl alcohol layer was rubbed with a rayon cloth, and a 10 wt% methylene chloride solution of the copolymer was applied to the treated surface. After coating with a bar coater, after drying, it was heated and oriented at 140 ° C. for 15 minutes, and allowed to cool at room temperature to fix the orientation of the liquid crystal polymer in a glass state. The liquid crystal polymer has a thickness of 2 μm, and the film-shaped optical element formed integrally with the triacetyl cellulose film exhibits circular dichroism that reflects blue light specularly. ~ 48
It was left circularly polarized light of 5 nm. The transmission characteristics of the optical element are shown in FIG.

Example 2 36.3 parts by weight (88 mmol) of the monomer of the chemical formula (a2) and 6.11 parts by weight (12) of the monomer of the chemical formula (b3).
A copolymer having a weight average molecular weight of 7500 was obtained in the same manner as in Example 1 except that the copolymer was used in the proportion of 1) to obtain an optical element.
This copolymer had a glass transition temperature of 92 ° C. and an isotropic phase transition temperature of 240 ° C., and exhibited a cholesteric structure at temperatures in between. Moreover, the optical element showed circularly polarized dichroism which reflects red light specularly, and this reflected light was left circularly polarized light having a wavelength of 580 to 695 nm. The transmission characteristics of the optical element are shown in FIG.

Example 3 0.47 of the copolymer obtained according to Example 1 and Example 2 was used.
/0.53 (Example 1 / Example 2) were mixed, and an optical element was obtained according to Example 1. This optical element showed circularly polarized dichroism that reflects green light specularly, and this reflected light was left circularly polarized light having a wavelength of 480 to 585 nm. The transmission characteristics of the optical element are shown in FIG.

Example 4

16.5 parts by weight (40 mmol) of the monomer of the formula (a2), the monomer 1 of the above formula (a3)
A copolymer having a weight average molecular weight of 11,500 was obtained in the same manner as in Example 1 except that 7.1 parts by weight (40 mmol) and 9.18 parts by weight (20 mmol) of the monomer of (b4) were used. This copolymer has a glass transition temperature of 105 ° C.
The isotropic phase transition temperature was 238 ° C., and a cholesteric structure was exhibited at temperatures in between.

On the other hand, an optical element was obtained by using the above-mentioned copolymer to form a liquid crystal polymer solidified layer having a thickness of 3 μm under the alignment treatment conditions of 150 ° C. and 15 minutes according to Example 1. This optical element exhibited circularly polarized dichroism that reflects red-yellow light specularly, and this reflected light was right circularly polarized light having a wavelength of 565 to 675 nm. The transmission characteristics of the optical element are shown in FIG.

Example 5 36.3 parts by weight of a monomer of the following chemical formula (a4) (85
A copolymer having a weight average molecular weight of 21,000 was obtained in the same manner as in Example 1 except that the monomers (9 mmol) and (b5) were used in an amount of 9.09 parts by weight (15 mmol). This copolymer had a glass transition temperature of 95 ° C. and an isotropic phase transition temperature of 215 ° C., and exhibited a cholesteric structure at temperatures in between.

[0067]

On the other hand, a liquid crystal polymer solidified layer having a thickness of 5 μm was formed according to Example 1 by using the above copolymer to obtain an optical element. This optical element exhibits circularly polarized dichroism that reflects red light specularly, and this reflected light has a wavelength of 590 to 695.
It was right circularly polarized light of nm. The transmission characteristics of the optical element are shown in FIG.

Example 6 The optical elements obtained according to Examples 1, 2 and 3 were laminated with an acrylic adhesive layer interposed therebetween to obtain an optical element exhibiting circular dichroism in the wavelength range of 410 to 690 nm. . The transmission characteristics of this optical element are shown in FIG.

When a 1/4 wavelength plate made of a laminate of two stretched films made of polycarbonate was laminated on the above optical element via an acrylic adhesive layer, and natural light was made incident thereon, a color based on the NBS system was obtained. Change Δab is 3
And it was a very small one. In addition, the optical element equipped with this quarter wavelength plate was subjected to a heating test at 80 ° C. for 1000 hours,
Alternatively, when subjected to a wet heat test at 60 ° C., 90% RH, for 1000 hours, almost no change in optical properties or appearance was observed in any of the tests, and the durability was excellent.

Further, when a liquid crystal display device having a structure according to FIG. 1 was formed by using the above-mentioned optical element provided with a quarter-wave plate, a brightness of 90 cd / m ² was exhibited. 50 compared to the case without (60 cd / m ² ).
% Improvement in brightness.

Example 7

Monomer 3 represented by the above chemical formula (a2)
1.8 parts by weight (77 mmol) and the above chemical formula (b6)
According to the same manner as in Example 1 except that 10.2 parts by weight (23 mmol) of the monomer represented by the above was dissolved in 415 ml of tetrahydrofuran with a weight average molecular weight of 7300, a glass transition temperature of 85 ° C and an isotropic phase transition temperature of 215 ° C. A copolymer showing a cholesteric structure was obtained at a temperature in the meantime, and the same method as in Example 1 was followed by heating and orientation treatment at 150 ° C. for 5 minutes to obtain circular dichroism for specularly reflecting blue light. As shown, an optical element having left-handed circularly polarized light having a reflected light wavelength of 410 to 485 nm was obtained. The transmission characteristics of the optical element are shown in FIG.

Example 8 35.5 parts by weight of a monomer of the chemical formula (a2) (86 mmol), 6.20 parts by weight of a monomer of the chemical formula (b6) (14)
A copolymer having a weight average molecular weight of 7100 was obtained in the same manner as in Example 7 except that the copolymer was used in the proportion of 1) to obtain an optical element.
This copolymer had a glass transition temperature of 89 ° C. and an isotropic phase transition temperature of 230 ° C., and exhibited a cholesteric structure at temperatures in between. Moreover, the optical element showed circularly polarized dichroism which reflects red light specularly, and this reflected light was left circularly polarized light having a wavelength of 580 to 695 nm. The transmission characteristics of the optical element are shown in FIG.

Example 9 0.47 of the copolymer obtained according to Example 7 and Example 8 was used.
/0.53 (Example 7 / Example 8) were mixed, and an optical element was obtained according to Example 7. This optical element showed circularly polarized dichroism that reflects green light specularly, and this reflected light was left circularly polarized light having a wavelength of 480 to 585 nm. The transmission characteristics of the optical element are shown in FIG.

Example 10 The optical elements obtained according to Examples 7, 8 and 9 were laminated with an acrylic adhesive layer interposed therebetween to obtain an optical element exhibiting circular dichroism in the wavelength range of 410 to 690 nm. . The transmission characteristics of this optical element are shown in FIG.

When a 1/4 wavelength plate made of a laminate of two stretched films made of polycarbonate was laminated on the above-mentioned optical element via an acrylic adhesive layer and natural light was made incident thereon, a color based on the NBS system was obtained. Change Δab is 3
And it was a very small one. In addition, the optical element equipped with this quarter wavelength plate was subjected to a heating test at 80 ° C. for 1000 hours,
Alternatively, when subjected to a wet heat test at 60 ° C., 90% RH, for 1000 hours, almost no change in optical properties or appearance was observed in any of the tests, and the durability was excellent.

Further, when a liquid crystal display device having a structure according to FIG. 1 was formed by using the optical element provided with the quarter wavelength plate, a brightness of 90 cd / m ² was exhibited. 50 compared to the case without (60 cd / m ² ).
% Improvement in brightness.

Comparative Example 39.0 parts by weight (80 mmol) of the monomer of the following chemical formula (C), and 9.14 parts by weight (20) of the monomer of (D).
A copolymer having a weight average molecular weight of 18,000 was obtained in the same manner as in Example 1 except that the copolymer was used in the proportion of 1 mmol. This copolymer has a glass transition temperature of 71 ° C. and an isotropic phase transition temperature of 20.
The temperature was 5 ° C., and a cholesteric structure was exhibited at a temperature in between.

On the other hand, an attempt was made to form a solidified layer of a liquid crystal polymer using the above-mentioned copolymer according to Example 1. However, a uniform alignment product could not be obtained, and the liquid crystal polymer layer having a thickness of 3 μm was also specular. Circular dichroism was inadequate with no reflection and diffuse reflection. Figure 1 shows the transmission characteristics of this optical element.
5 shows. It is considered that the diffuse reflection is because a uniform Grandjean orientation is not formed.

[Brief description of drawings]

FIG. 1 is a sectional view of an example of a liquid crystal display device.

FIG. 2 is a cross-sectional view of another liquid crystal display device example.

FIG. 3 is a graph showing the relationship between the content of the monomer unit of general formula (b) and the central wavelength showing circular dichroism.

FIG. 4 is another graph showing the relationship between the content of the monomer unit of the general formula (b) and the center wavelength showing circular dichroism.

FIG. 5 is a graph showing transmission characteristics

FIG. 6 is a graph showing other transmission characteristics.

FIG. 7 is a graph showing another transmission characteristic.

FIG. 8 is a graph showing another transmission characteristic.

FIG. 9 is a graph showing another transmission characteristic.

FIG. 10 is a graph showing another transmission characteristic.

FIG. 11 is a graph showing another transmission characteristic.

FIG. 12 is a graph showing another transmission characteristic.

FIG. 13 is a graph showing another transmission characteristic.

FIG. 14 is a graph showing another transmission characteristic.

FIG. 15 is a graph showing another transmission characteristic.

[Explanation of symbols]

1: Optical element (11, 12, 13: solidified layer of liquid crystal polymer) 2: Phase difference layer 3: Light source 4: Backlight system 5: Polarizing plate
6: Liquid crystal cell

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shu Mochizuki, 1-2, Shimohozumi, Ibaraki City, Osaka Prefecture Nitto Denko Corporation (56) Reference JP-A-7-35925 (JP, A) JP 1-308487 (JP, A) JP-A-3-45906 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C02B 5/30 C09K 19/54 G02F 1/1335 510 C08F 220/30 C08F 220/36

Claims (9)

(57) [Claims] 1. A becomes to have a solidified layer of a liquid crystal polymer composed Grandjean oriented cholesteric liquid crystal phase, the
The liquid crystal polymer is a monomer represented by the following general formula (a):
Unit and a monomer unit represented by the general formula (b)
Circular dichroism optical element which includes an der Rukoto which the copolymer and the component, characterized. General formula (a): (However, R ¹ is hydrogen or a methyl group, m is an integer of 1 to 6, X ¹ is a CO ₂ group or an OCO group, and p and q are 1
Or 2, and p + q = 3 is satisfied. ) General formula (b): (Wherein, ^{R 2} is hydrogen or a methyl group, n represents an integer of 1 to 6, ^{X 2} is CO ₂ group or OCO group, ^{X 3} is ^{-CO-R 3}
Or -R ⁴ , and R ³ thereof is R ⁴ is And R ⁵ is: ) 2. The liquid crystal polymer according to claim 1, wherein the liquid crystal polymer is 80
Optical element is a shall of Yusuke ℃ glass transition temperature above. 3. The optical element according to claim 1, which exhibits circular dichroism with respect to light in the visible light region. 4. The liquid crystal polymer according to claim 1,
The copolymer to be formed is a monomer represented by the general formula (a)
A unit represented by the general formula (b) is 60 to 95% by weight.
Optical element containing 40 to 5% by weight of nomer unit
Child. 5. The method of Claim 1-4, an optical element comprising a stack of solidified layer of a liquid crystal polymer showing a circular dichroism to light of different wavelengths. 6. The method of claim 1 to 5, an optical element having a phase difference layer to linearly polarized light of circularly polarized light. 7. The optical element according to claim 6, wherein the incident light composed of natural light is emitted as polarized light having a color change Δab based on the NBS method of 10 or less. 8. A liquid crystal display device comprising the optical element according to any one of claims 1 to 7 on an incident side of visible light in a liquid crystal cell. 9. The backlight apparatus characterized by comprising an optical element according to claim 1 to 7 on the light emitting side.