JP2013105010A - Photosensitive coloring composition for color filter, color filter for liquid crystal display device and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive coloring composition for color filters capable of manufacturing a liquid crystal display device having excellent oblique visibility.SOLUTION: There is provided a photosensitive coloring composition which forms each of colored pixels 3R, 3G and 3B for color filters and contains pigments, a resin, a monomer and solvents, in which two or more pigments are contained as the pigment, 50% or more of solvents of the solvents is a solvent having an evaporation rate of 10 to 35 when the evaporation rate of butyl acetate is 100, the mass ratio (monomer/resin) of the monomer and the resin is in the range of 0.3 to 1.0. And a coating film, which is obtained by applying the photosensitive coloring composition on a glass substrate, followed by drying, exposing, developing and post-baking steps, has a film stress σ of 0 to +30.

Description

  The present invention relates to a liquid crystal display device having excellent visibility in an oblique direction and a front surface, and a material used when manufacturing the liquid crystal display device. That is, the present invention includes, in addition to the liquid crystal display device, a color filter necessary for producing such a liquid crystal display device having excellent visibility and a photosensitive coloring composition necessary for producing the color filter. provide.

  The liquid crystal display device is a display element that utilizes the birefringence of liquid crystal molecules, and includes a liquid crystal cell, a polarizing element, and an optical compensation layer. Such a liquid crystal display device is roughly classified into a transmission type having a light source inside and a reflection type having a structure using an external light source, depending on the type of light source.

  The transmissive liquid crystal display device has a configuration in which two polarizing elements are arranged on both sides of a liquid crystal cell, and one or two optical compensation layers are provided between the liquid crystal cell and the polarizing element. The reflective liquid crystal display device has a configuration in which a reflector, a liquid crystal cell, one optical compensation layer, and one polarizing element are arranged in this order.

  In the liquid crystal cell, rod-like liquid crystal molecules sandwiched between two substrates are aligned and sealed, and a voltage is applied to the electrode layers disposed on both sides or one side of the two substrates, thereby producing a rod-like liquid crystal. This is a mechanism for switching light transmission / light-shielding by changing the orientation state of the active molecule.

  A liquid crystal cell is different in the alignment state of rod-like liquid crystalline molecules, and is composed of TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), OCB (Optically Compensated Bend), N (p. Various display modes such as VA (Vertically Aligned) and HAN (Hybrid Aligned Nematic) have been proposed.

  The polarizing element generally has a configuration in which two transparent protective films made of triacetyl cellulose (hereinafter referred to as TAC) are attached to both sides of a polarizing film obtained by diffusing iodine into polyvinyl alcohol (hereinafter referred to as PVA). Have

  Various optical compensation layers have been proposed. For example, in a VA mode liquid crystal display device having good display characteristics in a range of a high viewing angle, nx with respect to the three-dimensional main refractive indexes nx, ny, and nz. A biaxial retardation film having a refractive index ellipsoid represented by ≧ ny> nz is also used (see Non-Patent Document 1).

  In recent years, liquid crystal display devices have been evaluated for their space-saving, light-weight, and power-saving properties due to their thinness, and they are rapidly expanding as television viewers, as well as brightness, contrast, and visibility in all directions. There is a strong demand to further improve display performance.

  Specifically, for television applications, normally black mode IPS and VA liquid crystal display devices capable of higher contrast and wide viewing angle display are particularly preferred, and the optical compensation layer described above is also used. Colors that are black when viewed from the front and designed to minimize color changes when viewed from the diagonal are used.

  However, the optical compensation layer used in the above-described VA mode liquid crystal display device is generally a biaxial retardation film formed by stretching in the biaxial direction, or is polymerizable liquid crystalline and / or non-polymerized. In most cases, the retardation film is formed by applying a liquid crystalline material, and is controlled at the level of advanced display quality required for the three-dimensional main refractive index nx, ny, nz. It was difficult.

  Specifically, not only the birefringence of the liquid crystal material but also the thickness direction retardation values (hereinafter referred to as Rth (R), Rth (G), Rth) of the red, green and blue colored pixel layers constituting the color filter. (B)), it is necessary to determine and manufacture the three-dimensional main refractive index of the optical compensation layer, and an in-plane retardation value represented by two parameters nx and ny, In addition to simultaneously controlling the retardation value in the thickness direction represented by the three parameters nx, ny, and nz with high accuracy, wavelength dispersion of the birefringence of the liquid crystal material, and red, green, and color constituting the color filter It is difficult to provide the optical compensation layer with wavelength dispersion that compensates for both of the thickness direction retardation values of light in the red region, green region, and blue region of each colored pixel layer of blue. In the liquid crystal display device, it is still the most Not be said to have been designed in such value.

  As a result, the visibility from the front (vertical direction) with respect to the display surface is good, but the optical observation is not optimally compensated for the visibility observed from an oblique angle such as 45 degrees (hereinafter abbreviated as oblique visibility). Only a specific color leaks light, and colors such as reddish, bluedish, greenish, etc. are generated during black display.

  Compared to other members used in liquid crystal display devices, the retardation of the color filter was relatively small. Therefore, in the conventional liquid crystal display device, the retardation of the color filter is hardly taken into account, and the compensation capability of the optical compensation layer is not considered. However, it has become a level that cannot be ignored in liquid crystal televisions and the like that require high contrast and wide viewing angle characteristics.

  In particular, high-contrast liquid crystal display devices having 1000 or 3000 or more have been required to have a high image quality required for black display.

  On the other hand, a polymer having a planar structure group is contained in the side chain of the colored polymer thin film, or birefringence reducing particles having a birefringence opposite to that of the polymer are contained in the colored polymer thin film. Attempts have been made to reduce the amount of retardation of the color filter (see, for example, Patent Documents 1 and 2).

  In addition, the in-plane retardation of the blue region of the color filter is made larger than that of the green and red regions, thereby increasing the amount of blue leakage light and offsetting the yellowing that is complementary to blue overall. There has been disclosed a method for improving that the entire display device is colored yellow when the display device is viewed obliquely (see, for example, Patent Document 3).

  Further, the thickness direction retardation values Rth (R), Rth (G), and Rth (B) of the red, green, and blue pixels of the color filter are set to match the wavelength dispersibility of the liquid crystal material or retardation film. A method for improving oblique visibility by setting> Rth (G)> Rth (B) or Rth (R) <Rth (G) <Rth (B) is disclosed (for example, see Patent Document 4). .

  However, the thickness direction retardation value of the color filter varies greatly depending on the type of pigment used, and the thickness direction retardation value varies depending on the fineness or dispersion of the pigment or matrix resin (for example, acrylic resin or cardo resin). The present inventors have found that the degree becomes large, and a method including these polymer thin film and birefringence reducing particles cannot obtain a sufficient effect, and cannot solve the above problem.

  For color filters based on transparent resins represented by acrylic resins with good dispersibility of organic pigments for high contrast liquid crystal display devices, the required high contrast value (1000 or more, more preferably 3000 or more) is obtained. It was difficult to improve oblique visibility while maintaining. In particular, in recent years when high definition and high contrast are required, it has been difficult to improve oblique visibility while obtaining a high-definition pattern by photolithography.

  In addition, in the prior art, a color filter with a small birefringence is simply an excellent color filter, and even though a means for improving oblique visibility has been studied, as a high-contrast liquid crystal display device, Considering the wavelength dispersion of the birefringence of the liquid crystal material and the optical compensation layer, there has been little investigation on means for adjusting the thickness direction retardation of each color of the color filter to an optimum value to a level that does not cause a problem with black display. .

  The mechanism of the phase difference in the colored layer of the color filter is not clear. In particular, it is difficult to control the phase difference, and it is difficult to achieve both the patterning characteristics and the phase difference.

JP 2000-136253 A JP 2000-187114 A JP 2001-242460 A JP 2007-212603 A

Ishibe et al., The Society for Information Display Digest, 1094.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a liquid crystal display device having excellent oblique visibility. Another object of the present invention is to provide a photosensitive coloring composition for a color filter capable of producing such a liquid crystal display device, and a color filter formed using the photosensitive coloring composition. .

In order to solve the above problems, a first aspect of the present invention is a photosensitive coloring composition for forming a colored pixel of a color filter for a liquid crystal display device, the photosensitive coloring containing a pigment, a resin, a monomer and a solvent. In the composition:
Containing two or more pigments as the pigment,
50% or more of the solvents are solvents having an evaporation rate of 10 to 35 when the evaporation rate of butyl acetate is 100.
The mass ratio of monomer to resin (monomer / resin) is in the range of 0.3 to 1.0;
And, when this photosensitive coloring composition is applied on a glass substrate, and the film stress σ of the coating film obtained through the steps of drying, exposure, development, and post-baking is calculated by the formula (1), the film There is provided a photosensitive coloring composition for a color filter, wherein the stress σ is in the range of 0 to +30.

σ = E · h ² / [6 (1-λ) R · t] Formula (1)
(Wherein, E represents the Young's modulus of the substrate, h represents the substrate thickness (m), λ represents the Poisson's ratio of the substrate, and t represents the coating thickness (m). R represents the effective radius of curvature (m). 1 / R = 1 / R ₂ − where R ₁ is the radius of curvature of the substrate before forming the colored coating film, and R ₂ is the radius of curvature of the substrate after forming the colored coating film.
Is a numerical value to satisfy the ₁ / _R 1. )
According to a second aspect of the present invention, there is provided a photosensitive coloring composition according to claim 1, which comprises a retardation adjusting agent.

  According to a third aspect of the present invention, the retardation adjusting agent is one or more organic compounds selected from an organic compound having a planar structural group having one or more crosslinkable groups, a melamine compound, and a benzylic compound. The photosensitive coloring composition according to claim 2 is provided.

  The 4th aspect of this invention is the color filter which formed the colored pixel using the photosensitive coloring composition in any one of Claims 1-3, Comprising: The thickness direction retardation of the said colored pixel Provided is a color filter for a liquid crystal display device, characterized in that, when Rth is calculated by Equation (2), the absolute value of the thickness direction retardation Rth is 2.0 or less.

Rth = {(Nx + Ny) / 2−Nz} × d (2)
(Where Nx is the refractive index in the x direction in the plane of the colored pixel layer, Ny is the refractive index in the y direction in the plane of the colored pixel layer, and Nz is the refractive index in the thickness direction of the colored pixel layer. There is a slow axis where Nx is Nx ≧ Ny, and d is the thickness (nm) of the colored pixel layer.
According to a fifth aspect of the present invention, there is provided a liquid crystal cell comprising the color filter according to claim 4, polarizing plates respectively disposed on both outer surfaces of the liquid crystal cell, and an optical compensation layer provided inside the polarizing plates. In a liquid crystal display device comprising:
The liquid crystal display device is displayed in black, and the chromaticity (u, v) expressed in the CIE 1960 color system is measured, and the chromaticity (u (⊥), v (⊥)) when viewed from the vertical direction, When the chromaticity difference Δuv with respect to the chromaticity (u (θ), v (θ)) viewed from an orientation inclined by θ ° from the normal direction of the display surface is calculated by the following equation (3), 0 <θ Provided is a liquid crystal display device having a chromaticity difference Δuv of 0.02 or less in a range of ≦ 60.

Δuv = [{u (⊥) −u (θ)} ² + {v (⊥) −v (θ)} ² ] ^1/2 Equation (3)
According to a sixth aspect of the present invention, there is provided the liquid crystal display device according to claim 5, which is a VA method or an IPS method.

  When the photosensitive coloring composition contains two or more kinds of pigments as the pigment, the mass ratio of the solvent, the monomer and the resin satisfies the above-mentioned conditions, and the film stress σ is in the range of 0 to +30, the implementation described later As can be seen from the examples, the absolute value of the thickness direction retardation Rth is 2.0 or less. For this reason, a color filter was prepared using this photosensitive coloring composition, and the color filter thus prepared was used. The liquid crystal display device has no difference between the front direction visibility and the oblique direction visibility. Therefore, it is possible to manufacture a liquid crystal display device in which both are excellent.

1 is a schematic sectional view showing a color filter according to an embodiment of the present invention. 1 is a schematic cross-sectional view illustrating an example of a liquid crystal display device including a color filter according to an embodiment of the present invention.

The photosensitive coloring composition according to the present invention contains a pigment, a resin, a monomer and a solvent as essential components. The photosensitive coloring composition which concerns on this invention needs to contain a 2 or more types of pigment as said pigment. In addition, the solvent may be one kind or a mixture of two or more kinds of solvents, either in the case of using one kind of solvent or in the case of using a mixture of two or more kinds of solvents, The solvent occupying 50% or more must be a solvent having an evaporation rate of 10 to 35 when the evaporation rate of butyl acetate is 100. The mass ratio of the monomer to the resin (monomer / resin) needs to be in the range of 0.3 to 1.0. And in addition to satisfying these conditions, after applying this photosensitive coloring composition on a glass substrate, the film stress σ of the coating film obtained through the steps of drying, exposure, development, and post-baking is expressed as an equation When calculated in (1), the film stress σ needs to be in the range of 0 to +30.

σ = E · h ² / [6 (1-λ) R · t] Formula (1)
(Wherein, E represents the Young's modulus of the substrate, h represents the substrate thickness (m), λ represents the Poisson's ratio of the substrate, and t represents the coating thickness (m). R represents the effective radius of curvature (m). This is a numerical value satisfying 1 / R = 1 / R ₂ −1 / R ₁ , where R ₁ is the radius of curvature of the substrate before forming the colored coating film and R ₂ is the radius of curvature of the substrate after forming the colored coating film. is there.)
By the way, the photosensitive coloring composition according to the present invention preferably contains a photopolymerization initiator in addition to the essential components. If necessary, it may contain a sensitizer, a chain transfer agent, a dispersion aid for uniformly dispersing the pigment in the composition, a retardation adjusting agent, a storage stabilizer, an adhesion improver, and the like.

  And the photosensitive coloring composition of this invention which satisfies the said conditions is utilized in order to form the coloring pixel of the color filter of a liquid crystal display device. Thus, a liquid crystal display device provided with a color filter manufactured using this photosensitive coloring composition is excellent in visibility in the oblique direction and the front.

  Therefore, first, the color filter and the liquid crystal display device will be described, and then the principle of the present invention will be described. And the composition of the said photosensitive coloring composition, a manufacturing method, and its usage method (formation method of the colored pixel of a color filter) are demonstrated.

(Description of color filter and liquid crystal display device)
FIG. 1 shows a configuration example of a color filter for a liquid crystal display device in which colored pixels 3 are formed with the photosensitive coloring composition of the present invention. A black matrix 2 is provided on a transparent substrate 1 and is partitioned by the black matrix 2. In this area, three colored pixels of red pixel 3R, green pixel 3G, and blue pixel 3B are formed.

  Next, FIG. 2 is a schematic cross-sectional view of a liquid crystal display device 4 including a color filter according to an embodiment of the present invention. A liquid crystal display device 4 shown in FIG. 2 is a typical example of a TFT drive type liquid crystal display device for a liquid crystal TV, and includes a first substrate 5 and a second substrate which are disposed to be opposed to each other, and these A liquid crystal (LC) is sealed between them.

  As can be seen from the figure, the transparent substrate 1 constituting the color filter is used as the second substrate. In the color filter used in FIG. 2, a transparent protective film (not shown) is formed so as to cover the colored pixels 3, and a transparent electrode 12 made of, for example, ITO is formed on the transparent filter 12. An alignment layer 13 is provided so as to cover the surface.

  As will be described later, a transparent substrate 1 having a transparent electrode can be used. In this case, the transparent electrode 12 on a transparent protective film (not shown) is not required.

  The liquid crystal (LC) is TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), OCB (Optically Compensated Bc). .

  A TFT (thin film transistor) array 7 is formed on the inner surface of the first substrate 5, and a transparent electrode layer 8 made of, for example, ITO is formed thereon. An alignment layer 9 is provided on the transparent electrode layer 8. Further, on the outer surface of the substrate 5, a polarizing plate 10 including a retardation film is formed.

  A polarizing plate 14 is formed on the outer surface of the transparent substrate 1. A backlight unit 16 including a three-wavelength lamp 15 is provided below the polarizing plate 10.

(Description of the principle of the present invention)
In order to improve both the visibility when the display surface of the liquid crystal display device 4 is observed from its normal direction (front direction) and the visibility when viewed from an oblique direction, The thickness direction retardation value Rth (R) of the red pixel 3R, the thickness direction retardation value Rth (G) of the green pixel 3G, and the thickness direction retardation value Rth (B) of the blue pixel 3B are all 2 or less. There must be. In the case of having colored pixels of other colors, the thickness direction retardation value Rth of the colored pixels needs to be 2 or less.

  Here, the thickness direction retardation value Rth is the product of the value obtained by subtracting the thickness direction refractive index from the average of the in-plane refractive indexes of the respective pixels 3R, 3G, and 3B and the thickness (nm) of the pixels 3R, 3G, and 3B. Rth (R) is a thickness direction retardation value for light having a wavelength of 610 nm passing through the red pixel 3R, Rth (G) is a thickness direction retardation value for light having a wavelength of 545 nm passing through the green pixel 3G, and Rth ( B) represents a thickness direction retardation value for light having a wavelength of 450 nm passing through the blue pixel 3B.

  The thickness direction retardation value Rth of each of the colored pixels 3R, 3G, and 3B is obtained by measuring the continuous light including the wavelength of the transmitted light peak region in the visible region (for example, the light wavelength range of 380 nm to 780 nm) and a plurality of inclinations. It is obtained by irradiating the colored pixels 3R, 3G, 3B from the angle and measuring the three-dimensional refractive index using a phase difference measuring device such as a spectroscopic ellipsometer.

  For example, the red pixel 3R uses light having a wavelength of 610 nm, the green pixel 3G has a wavelength of 545 nm, and the blue pixel 3B has a wavelength of 450 nm, and the phase difference is measured with light from at least two directions of the front and the incident angle of 45 degrees, and Nx, Ny, After obtaining the three-dimensional refractive index of Nz, the thickness direction retardation value (Rth) is calculated by the following equation (2).

Rth = {(Nx + Ny) / 2−Nz} × d (2)
In the formula, Nx is a refractive index in the x direction in the plane of each colored pixel 3R, 3G, 3B, Ny is a refractive index in the y direction in the plane of each colored pixel 3R, 3G, 3B, and Nz Is the refractive index in the thickness direction of each of the colored pixels 3R, 3G, 3B, and is a slow axis where Nx is Nx ≧ Ny. d is the thickness (nm) of each colored pixel 3R, 3G, 3B.

  At this time, when the object to be measured is a color filter, the measurement is performed through a mask processed so as to pass through each of the colored pixels 3R, 3G, and 3B, whereby the position of each colored pixel 3R, 3G, and 3B is measured. A phase difference value can be obtained.

  In addition, for example, when light having a wavelength of 610 nm is used as incident light, the phase difference value caused only by the red pixel 3R, when 545 nm, the phase difference value caused only by the green pixel 3G, and when the light is 450 nm, blue As a phase difference value caused only by the pixel 3B, an approximate value of each single colored pixel can be estimated.

By the way, the optical compensation layer used in the VA mode liquid crystal display device is generally nx ≧ ny.
It is almost always a biaxial retardation film having a refractive index ellipsoid represented by> nz, or a retardation film formed by applying a polymerizable liquid crystalline and / or non-polymerizable liquid crystalline material. Thus, when these films are used, the thickness direction retardation value Rth of the retardation film generally has a wavelength dispersion that increases as the wavelength increases or increases as the wavelength decreases. .

  In general, for a VA mode liquid crystal display device having both liquid crystal birefringence and wavelength dispersion when viewed from an oblique direction, the wavelength dispersion of the thickness direction retardation value Rth of these retardation films is the wavelength of the liquid crystal. If the dispersibility is not completely compensated, there is a problem that the display characteristics viewed from an oblique direction are deteriorated particularly during black display. That is, when viewed from an oblique direction, the black display adversely affects the yellowish visibility.

  On the other hand, it is desirable that the absolute value of the birefringence of each colored pixel 3R, 3G, 3B of the color filter is 0.01 or less. That is, it is usually desirable that the thickness direction retardation value (Rth) is as close as possible to Rth (R) = Rth (G) = Rth (B) = 0, and in this case, each colored pixel 3R, 3G of the color filter is desirable. , 3B does not affect the visibility in the oblique direction during black display. However, the thickness direction retardation values Rth (R), Rth (G), and Rth (B) of the colored pixels 3R, 3G, and 3B are different from each other. For example, the red pixel 3R has a positive or negative thickness direction retardation value. The blue pixel 3B has a positive thickness direction retardation value, and the green pixel 3G has a negative thickness direction retardation value.

  As a result, the colored pixels 3R, 3G, and 3B of the color filter affect the visibility in the oblique direction during black display, and thus the visibility from the front (vertical direction) with respect to the display surface is good, but 45 degrees, etc. In visibility observed from an oblique direction, only a specific color leaks light, and coloring such as reddish, yellowish, bluish, or greenish occurs when viewed from an oblique direction during black display.

  In the color filter, the most desirable value for the phase difference values Rth (R), Rth (G), and Rth (B) of the colored pixels 3R, 3G, and 3B varies depending on the combination with other members. In the case of biaxial retardation films widely used in VA mode liquid crystal display devices, the thickness direction retardation value of these films has a value smaller than the thickness direction retardation value of the liquid crystal. , 3G, 3B are preferably positive values of phase difference values Rth (R), Rth (G), Rth (B).

  Note that as the contrast of the color filter increases and the depolarization of the color filter decreases, the chromaticity when viewed from the front during black display approaches the chromaticity with a bluish color in crossed Nicols of the polarizing plate. . For this reason, in order to minimize the color change when viewed from the front and when viewed from an oblique direction, the chromaticity when viewed from an oblique direction must be bluish.

  That is, the dichroism of the polarizing plate is also improved, and in recent years, a high-contrast polarizing plate has been used, but most of the hues in crossed Nicols are bluish. That is, since there is much light leakage from the polarizing plate at a wavelength around 400 nm, the hue when viewed from the front during black display is bluish.

  Therefore, it is necessary to select a combination that obtains optimal oblique visibility in a combination of optical members of a liquid crystal display device such as a liquid crystal, a polarizing plate, a retardation plate, and an alignment film. In order to minimize the color change at the time, it is necessary to make the chromaticity when viewed obliquely blue.

As a result of diligent investigations on these, the present inventors formed each colored pixel 3R, 3G, 3B of the color filter using the photosensitive coloring composition satisfying the above-described conditions, and obtained the color filter It was discovered that both the front visibility and the oblique visibility are excellent when a liquid crystal display device is manufactured using the above-mentioned.

  Each of the colored pixels 3R, 3G, 3B formed using the photosensitive coloring composition according to the present invention has its thickness direction retardation Rth (R), Rth (G) calculated by the above formula (2). , Rth (B) is 2.0 or less for any colored pixel. The liquid crystal display device manufactured using the color filter having the colored pixels 3R, 3G, and 3B has a chromaticity (u, v) expressed in the CIE1960 color system by displaying the liquid crystal display device in black. Chromaticity when viewed from the vertical direction (u (⊥), v (⊥)) and chromaticity when viewed from an orientation inclined by θ ° from the normal direction of the display surface (u (θ) , V (θ)) and the chromaticity difference Δuv with the following formula (3), the chromaticity difference Δuv is 0.02 or less in the range of 0 <θ ≦ 60.

Δuv = [{u (⊥) −u (θ)} ² + {v (⊥) −v (θ)} ² ] ^1/2 Equation (3)
Then, the chromaticity difference between the chromaticity (u (、), v (⊥)) when viewed from the front and the chromaticity (u (θ), v (θ)) when viewed from the oblique direction as described above. Since Δuv is small, there is no difference between front visibility and oblique visibility.

  By the way, in order to manufacture a liquid crystal display device excellent in front visibility, the following conditions may be satisfied.

That is, first, each colored pixel 3R, 3G, 3B formed on a transparent substrate is sandwiched between two polarizing plates, a backlight is applied from one polarizing plate side, and light transmitted through the other polarizing plate is luminance. The contrast C calculated from the ratio of the light luminance (Lp) in the parallel state and the light luminance (Lc) in the orthogonal state is calculated from C = Lp / Lc. At this time,
The contrast measured and calculated by sandwiching a transparent substrate on which the colored pixels 3R, 3G, and 3B are not formed between two polarizing plates is defined as CS. Further, when the contrast of the red pixel 3R is CR, the contrast of the yellow pixel 3Y is CY, the contrast of the green pixel 3G is CG, and the contrast of the blue pixel 3B is CB, CR / CS> 0.45, CY / CS> 0. .45, CG / CS> 0.45, and CB / CS> 0.45, the front visibility during black display of the liquid crystal display device is excellent. That is, it is possible to reproduce a tight black display with little light leakage.

  When CR / CS> 0.45, CY / CS> 0.45, CG / CS> 0.45, and CB / CS> 0.45 are not satisfied, that is, CR / CS ≦ 0. 45, or CY / CS> 0.45, or CG / CS ≦ 0.45, or CB / CS ≦ 0.45, light leakage during black display increases, and excellent front view Liquid crystal display device cannot be obtained.

  Therefore, each of the colored pixels 3R, 3G, 3B is formed using the photosensitive coloring composition according to the present invention, and the contrast CR, CG, CB of each of the colored pixels 3R, 3G, 3B and the contrast of the transparent substrate. When the ratios CR / CS, CG / CS, and CB / CS are all greater than 0.45, a liquid crystal display device excellent in both front visibility and oblique visibility can be manufactured.

(Description of composition of photosensitive coloring composition)
As described above, the photosensitive coloring composition of the present invention comprises a pigment, a resin, a monomer, and a solvent as essential components, and if necessary, a photopolymerization initiator, a sensitizer, a chain transfer agent, and a pigment. It contains a dispersion aid, a retardation adjusting agent, a storage stabilizer, an adhesion improver and the like that are uniformly dispersed therein. Therefore, each of these components will be described sequentially.

(Description of pigment)
The photosensitive coloring composition of the present invention is used as a material for forming each colored pixel 3R, 3G, 3B of a color filter. For this reason, it is necessary to use a pigment of an appropriate color according to the color of the target colored pixel.

  And as mentioned above, the photosensitive coloring composition of this invention needs to contain 2 or more types of pigments as a pigment. In the case of containing only one pigment, the process after applying the coloring composition, particularly post-baking, causes the interaction between the pigments to act greatly, and the film stress of each colored pixel 3R, 3G, 3B increases. By including two or more kinds of pigments, the interaction between the same pigments can be relaxed, and the film stress can be reduced.

  For example, in the case of a red composition used as a material for forming the red pixel 3R, a red pigment may be used as a main pigment, and a yellow pigment or an orange pigment may be used in combination. In the case of a green composition used as a material for forming the green pixel 3G, a yellow pigment can be used in combination with the green pigment. In the case of a blue composition used as a material for forming the blue pixel 3B, a purple pigment can be used in combination with a blue pigment.

  It is desirable to use organic pigments as these colored pigments. Inorganic pigments can be used, but in general, inorganic pigments are used in combination with organic pigments to ensure good coatability, sensitivity, developability, etc. while balancing saturation and lightness. .

  For this reason, the organic pigment which can be used for each of these photosensitive coloring compositions will be described below. In addition, examples of inorganic pigments just in case include, for example, metal oxide powders such as yellow lead, zinc yellow, red rose (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, Examples thereof include metal sulfide powder and metal powder.

  Examples of red organic pigments that can be used in the red composition include C.I. I. Pigment Red 7, 14, 41, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 81: 4, 146, 168, 177, 178, 179, 184, 185, Examples thereof include red pigments such as 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, and 279.

Examples of yellow organic pigments that can be used in the red composition include C.I. I. Pigment
Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 147, 151, 152, 153, 154, 155, 156, 161 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 187, 188, 193 194, 199, 198, 213, 214, and the like.

Examples of the orange organic pigment that can be used in the red composition include C.I. I. Pigment
Orange 36, 43, 51, 55, 59, 61, 71, 73 and the like.

When one or more of these diketopyrrolopyrrole red pigments and anthraquinone red pigments are included, the thickness direction retardation Rth (R) can be easily controlled. That is, first, the diketopyrrolopyrrole red pigment can be moved to the positive direction by moving the thickness direction retardation Rth (R) in the positive direction by reducing the average value of the primary particle size by refining. By keeping the average value coarse, it is possible to bring the thickness direction retardation Rth (R) in the negative direction, and the absolute value thereof can be controlled to some extent. In addition, the anthraquinone red pigment easily obtains a thickness direction retardation Rth (R) close to 0 regardless of the miniaturization treatment.

  Examples of the diketopyrrolopyrrole red pigment include C.I. I. Pigment Red 254 and an anthraquinone red pigment include C.I. I. Pigment Red 177 can be preferably used.

  In addition, it can be said that the value of the thickness direction retardation Rth (R) almost satisfies the additive rule depending on the blending ratio of the pigment used. For this reason, the amount of red pigment used is 0 to 100% by weight, preferably 10 to 90% by weight, and 0 to 66% by weight of anthraquinone red pigment based on the total weight of the red pigment. %, Preferably 5 to 70% by weight, from the viewpoint of the hue, brightness, film thickness, contrast, etc. of the red pixel 3R. In particular, when focusing on the contrast CR, 25 diketopyrrolopyrrole red pigment is used. It is more preferable that the amount of the anthraquinone red pigment is 30 to 60% by weight.

  Moreover, as a yellow pigment used together with this red pigment, an azo metal complex yellow pigment is preferable from the viewpoint of high contrast. Examples of the azo metal complex yellow pigment include C.I. I. Pigment Yellow 150 is preferable in terms of excellent light resistance, heat resistance, transparency, coloring power, and the like. The amount of the azo metal complex yellow pigment used is preferably 5 to 25% by weight based on the total weight of the pigments contained in the red composition, and if it is less than 5% by weight, the brightness is sufficiently improved. It is difficult to adjust the hue, and when it exceeds 30% by weight, the hue is excessively shifted to yellow, and the color reproducibility is deteriorated.

  Next, a halogenated metal phthalocyanine green pigment can be used as the green organic pigment that can be used in the green composition. For example, C.I. I. Pigment Green 7, 36, 58. Moreover, as a yellow organic pigment which can be used for a green composition, an azo yellow pigment or a quinophthalone yellow pigment can be used. Examples of the azo yellow pigment include C.I. I. Pigment Yellow 150, and quinophthalone yellow pigments include C.I. I. Pigment Yellow 138 is preferable in terms of excellent light resistance, heat resistance, transparency, coloring power, and the like.

  When the green pixel 3G is formed of a green composition containing at least one of the halogenated metal phthalocyanine green pigment, azo yellow pigment, and quinophthalone yellow pigment, the thickness direction retardation Rth (G) is easily obtained. Can be controlled. That is, the metal halide phthalocyanine green pigment can control the direction phase difference Rth (G) to some extent by selecting the center metal. For example, when the center metal is copper, the direction phase difference Rth (G ) Is a small value, but when the central metal is zinc, the value of the directional phase difference Rth (G) can be made larger than when copper is the central metal. Further, when an azo yellow pigment is used, a positive direction phase difference Rth (G) is obtained regardless of the miniaturization treatment, and when a quinophthalone yellow pigment is used, a negative direction is obtained regardless of the miniaturization treatment. A phase difference Rth (G) is obtained.

The amount of the pigment used is 30 to 90% by weight of the halogenated metal phthalocyanine green pigment, 0 to 60% by weight of the azo yellow pigment or quinophthalone yellow pigment, based on the total weight of the pigments contained in the green composition. It is preferably 5 to 60% by weight from the viewpoint of the hue, brightness, film thickness, etc. of the green pixel 3G. More preferably, the halogenated metal phthalocyanine green pigment is 50 to 85% by weight, the azo yellow pigment is 5 to 45% by weight, and the quinophthalone yellow pigment is 5 to 45% by weight.

  Next, as the blue organic pigment that can be used in the blue composition, a metal phthalocyanine blue pigment can be used. For example, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, and the like. Among these, C.I. is from the viewpoint of excellent light resistance, heat resistance, transparency, coloring power, and the like. I. Pigment Blue 15: 6 is preferred.

  Further, as the purple organic pigment that can be used in the blue composition, a dioxazine-based purple pigment can be used. For example, C.I. I. PigmentViolet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and the like. Among these, C.I. is from the viewpoint of excellent light resistance, heat resistance, transparency, coloring power, and the like. I. Pigment Violet 23 is preferred.

  Among these pigments, when the blue pixel 3B is formed from a blue composition containing at least one of a metal phthalocyanine-based blue pigment and a dioxazine-based purple pigment, the thickness direction retardation Rth (B) close to negative 0. It becomes easy to get.

  The amount used is 40 to 100% by weight of the metal phthalocyanine-based blue pigment, 0 to 50% by weight of the dioxazine-based violet pigment, preferably 1 to 50% by weight, based on the total weight of the pigments contained in the blue composition. It is preferable from the viewpoint of the hue, brightness, and film thickness of the pixel, and more preferably, the metal phthalocyanine blue pigment is 50 to 98% by weight and the dioxazine violet pigment is 2 to 25% by weight.

  Next, it is desirable that the primary particles of the pigment contained in each of the colored pixels 3R, 3G, and 3B be small in order to obtain good front visibility, particularly a tightened color with low black luminance in black display. For this reason, it is desirable that the primary particles of the pigment contained in the photosensitive coloring composition as the material of the colored pixels 3R, 3G, 3B are also small. That is, in the particle size distribution of the primary particles of the pigment contained in the photosensitive coloring composition, the particle diameter d50 (median value) corresponding to 50% of the total amount in the integrated curve of the number particle size distribution is 40 nm or less. Is preferred. An organic pigment having a median particle diameter d50 exceeding 40 nm adversely affects front visibility. On the other hand, when the median value d50 is 40 nm or less, it is possible to obtain a liquid crystal display device with good visibility from the front direction by realizing high luminance and high contrast of the color filter. The median value d50 is desirably 30 or less, and more desirably 20 or less. The particle diameter d50 is desirably 5 nm or more. If it is smaller than this, it will be difficult to disperse the pigment, and it will be difficult to maintain fluidity while maintaining the stability of the colored composition. As a result, the luminance and color characteristics of the color filter are deteriorated. The median value d50 of the pigment particle diameter can be calculated by photographing the pigment with a transmission electron microscope and analyzing the image of the photograph.

  As a means for controlling the median value d50 and thickness direction retardation of the pigment, a method of controlling the median d50 and the particle shape by mechanically grinding the pigment (referred to as grinding method), dissolved in a good solvent A method of depositing a pigment in a poor solvent to precipitate a pigment having a desired median value d50 and particle shape (referred to as a precipitation method), and a method for producing a pigment having a desired median value d50 and particle shape at the time of synthesis (synthetic precipitation method) And so on). Depending on the synthesis method and chemical properties of the pigment to be used, an appropriate method can be selected for each pigment.

Each method will be described below, but any method may be used as a method for controlling the primary particle diameter and particle shape of the pigment contained in the colored pixel layer constituting the color filter according to the embodiment of the present invention. .

  In the grinding method, the pigment is mechanically kneaded using a ball mill, sand mill or kneader together with a grinding agent such as water-soluble inorganic salt such as salt and a water-soluble organic solvent that does not dissolve it. This is a method of obtaining a pigment having a desired primary particle size and particle shape by washing and removing the inorganic salt and the organic solvent, followed by drying.

  However, since the pigment may crystallize by the salt milling treatment, a method of preventing crystal growth by adding a solid resin or a pigment dispersant that is at least partially dissolved in the organic solvent during the treatment is effective.

  As for the ratio of the pigment to the inorganic salt, if the ratio of the inorganic salt is increased, the efficiency of refining the pigment is improved, but the productivity is lowered because the amount of pigment processed is reduced. In general, 1 to 30 parts by weight, preferably 2 to 20 parts by weight of the inorganic salt is used per 1 part by weight of the pigment. The water-soluble organic solvent is added so that the pigment and the inorganic salt are uniformly solidified. Although depending on the blending ratio of the pigment and the inorganic salt, the water-soluble organic solvent is usually added in an amount of 0.1% by weight based on 1 part by weight of the pigment. Used in an amount of 5 to 30 parts by weight.

  More specifically, regarding the grinding method, a small amount of a water-soluble organic solvent is added as a wetting agent to a mixture of a pigment and a water-soluble inorganic salt, and after kneading with a kneader or the like, the mixture is poured into water to achieve high speed. Stir with a mixer or the like to form a slurry. Next, this slurry is filtered, washed with water, and dried to obtain a pigment having a desired primary particle size and particle shape.

  The precipitation method is a method in which a pigment is dissolved in an appropriate good solvent and then mixed with a poor solvent to precipitate a pigment having a desired primary particle size and particle shape. The type and amount of the solvent, the precipitation temperature, the precipitation The primary particle size and particle shape can be controlled by the speed or the like.

  In general, pigments are difficult to dissolve in solvents, so the solvents that can be used are limited. For example, strongly acidic solvents such as concentrated sulfuric acid, polyphosphoric acid and chlorosulfonic acid, or basic substances such as dimethylformamide solution of liquid ammonia and sodium methylate Solvents are known.

  As a typical example of the precipitation method, there is an acid pasting method in which a solution in which a pigment is dissolved in an acidic solvent is poured into another solvent and reprecipitated to obtain fine particles. Industrially, a method of injecting a sulfuric acid solution into water is generally used from the viewpoint of cost. The concentration of sulfuric acid to be used is not particularly limited, but is preferably 95 to 100% by weight. The amount of sulfuric acid used with respect to the pigment is not particularly limited. However, if the amount is too small, the solution viscosity is high and handling becomes poor. On the other hand, if the amount is too large, the processing efficiency of the pigment decreases. Is preferably used.

  The pigment need not be completely dissolved. The temperature at the time of dissolution is preferably from 0 to 50 ° C. Below this temperature, sulfuric acid may freeze and the solubility will be low. If the temperature is too high, side reactions tend to occur.

  The temperature of the water to be injected is preferably 1 to 60 ° C. When the injection is started at a temperature higher than this temperature, boiling occurs due to the heat of dissolution of sulfuric acid, and the operation is dangerous. It will freeze at temperatures below this. The injection time is preferably 0.1 to 30 minutes with respect to 1 part of the pigment. As the time increases, the primary particle size tends to increase.

Next, the primary particle diameter and particle shape of the pigment can be controlled by combining the precipitation method and the grinding method. For example, a combination of salt milling and acid pasting. According to this method, it can be carried out while taking into account the sized particle size of the pigment, and furthermore, fluidity as a dispersion can be secured at this time.

  During salt milling or acid pasting, in order to prevent aggregation of pigments accompanying primary particle size and particle shape control, the following pigment derivatives, resin type pigment dispersants, surfactants and other dispersing aids may be used in combination. it can.

  Further, by controlling the primary particle size and particle shape in the form of coexistence of two or more pigments, even a pigment that is difficult to disperse alone can be finished as a stable dispersion.

  There is a leuco method as a special precipitation method. When vat dyes such as flavantron, perinone, perylene, and indanthrone are reduced with alkaline hydrosulfite, the quinone group becomes a hydroquinone sodium salt (leuco compound) and becomes water-soluble. A pigment having a small primary particle size insoluble in water can be precipitated by adding an appropriate oxidizing agent to the aqueous solution for oxidation.

  The synthetic precipitation method is a method in which a pigment having a desired primary particle size and particle shape is precipitated simultaneously with the synthesis of the pigment. However, when the produced fine pigment is taken out of the solvent, if the pigment particles are not aggregated into large secondary particles, filtration, which is a general separation method, becomes difficult. It is applied to azo pigments synthesized in water.

  Furthermore, as a means for controlling the primary particle size and particle shape of the pigment, the primary particle size of the pigment is reduced by dispersing the pigment for a long time with a high-speed sand mill or the like (so-called dry milling method in which the pigment is dry pulverized). It is also possible to disperse at the same time.

  In addition, it is preferable that a pigment is contained in the ratio of 5-70 weight% on the basis (100 weight%) of the total solid content of the photosensitive coloring composition concerning this invention. More preferably, it is 20 to 50% by weight.

(Description of solvent)
As described above, the solvent contained in the photosensitive coloring composition of the present invention may be one kind of solvent or a mixture of two or more kinds of solvents. However, when one kind of solvent is used or two or more kinds of solvents. In any case of using the mixture, the solvent occupying 50% or more must be a solvent having an evaporation rate of 10 to 35 when the evaporation rate of butyl acetate is 100. Examples of such a solvent include ethyl-3-ethoxypropionate (EEP, evaporation rate 12), cyclohexanone (evaporation rate 23), propylene glycol monomethyl ether acetate (PgMAc, evaporation rate 34), and the like. Further, if the evaporation rate is in the range of 10 to 35, other solvents can be selected.

  A solvent occupying less than 50% can be used regardless of its evaporation rate. For example, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether, toluene, methyl ethyl ketone, ethyl acetate, Methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like.

  The solvent can be used in an amount of 800 to 4000 parts by weight, preferably 1000 to 2500 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.

(Description of resin)
The resin contained in the photosensitive coloring composition of the present invention is preferably a transparent resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. The transparent resin may be a thermoplastic resin, a thermosetting resin, or a photosensitive resin. As described above, the mass ratio of monomer to resin (monomer / resin) needs to be in the range of 0.3 to 1.0.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. And acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, polyethylene, polypropylene, polyimide resins, and the like.

  Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, and a phenol resin.

  Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group, A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used.

  Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A half-esterified product can also be used.

  The resin can be used in an amount of 20 to 400 parts by weight, preferably 50 to 250 parts by weight, with respect to 100 parts by weight of the pigment in the coloring composition.

(Explanation of monomer)
The monomer is cured by irradiation with radiation such as ultraviolet rays to produce a transparent resin.

  Monomers that are precursors of transparent resins include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, and pentaerythritol tri (meth) acrylate. , Various acrylic and methacrylic esters such as trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, melamine (meth) acrylate, epoxy (meth) acrylate, (Meth) acrylic acid, styrene, vinyl acetate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, acrylonitrile and the like. These can be used alone or in admixture of two or more.

  As described above, the amount of the monomer is such that the mass ratio of the monomer to the resin (monomer / resin) is in the range of 0.3 to 1.0.

(Description of photopolymerization initiator)
As described above, it is desirable to add a photopolymerization initiator to the photosensitive coloring composition of the present invention. By irradiating the coating film of the photosensitive coloring composition containing this photopolymerization initiator with radiation such as ultraviolet rays, the monomer contained in the coating film at the irradiation position is polymerized or crosslinked to form a coating film at this position. Is cured. Then, by developing with a developer, it is possible to remove the uncured coating film and selectively leave the cured coating film to form the colored pixels 3R, 3G, and 3B. It is.

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1 Acetophenone photopolymerization initiators such as -one, benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4- F Benzophenone photopolymerization initiators such as nylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Thioxanthone photopolymerization initiators such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s- Triazine, 2,4-bis (trichloro Methyl) -6-styryl s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -striazine, 2- (4-methoxy-naphth-1-yl) -4,6 Initiation of triazine photopolymerization such as -bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine Agents, borate photopolymerization initiators, carbazole photopolymerization initiators, imidazole photopolymerization initiators, and the like are used.

  The photopolymerization initiator can be used in an amount of 5 to 200 parts by weight, preferably 10 to 150 parts by weight, with respect to 100 parts by weight of the pigment in the photosensitive coloring composition.

(Explanation of sensitizer)
Although the said photoinitiator is used individually or in mixture of 2 or more types, in addition to this, a sensitizer can be added to a photosensitive coloring composition.

  As sensitizers, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, and the like.

  The sensitizer can be contained in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

(Description of chain transfer agent)
As described above, a chain transfer agent can be added to the photosensitive coloring composition as necessary. A polyfunctional thiol can be illustrated as a typical chain transfer agent. The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercap -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto -s- triazine. These polyfunctional thiols can be used alone or in combination.

  The polyfunctional thiol can be used in an amount of 0.2 to 150 parts by weight, preferably 0.2 to 100 parts by weight, with respect to 100 parts by weight of the pigment in the coloring composition.

(Description of dispersion aid)
The dispersion aid is added for the purpose of uniformly dispersing the pigment in the photosensitive coloring composition. Examples of such a dispersion aid include a resin-type pigment dispersion aid, a surfactant, and a pigment derivative.

  Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion, a coloring composition comprising a pigment dispersed in a pigment carrier and an organic solvent using a dispersion aid is used. If so, a color filter excellent in transparency can be obtained. The dispersion aid can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.

  As a resin-type pigment dispersion aid, it has a pigment affinity part that has the property of adsorbing to the pigment and a part that is compatible with the pigment carrier, and adsorbs to the pigment to stabilize the dispersion of the pigment into the pigment carrier. It works to do.

  Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more.

  The dye derivative is a compound in which a substituent is introduced into an organic dye, and is preferably close to the hue of the pigment to be used. However, if the addition amount is small, those having different hues may be used.

  Organic dyes also include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone that are not generally called dyes.

  Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. You can use what you have. In particular, a pigment derivative having a basic group is preferably used because it has a large pigment dispersion effect. These can be used alone or in admixture of two or more.

(Description of retardation adjusting agent)
The retardation adjusting agent is added for the purpose of improving the oblique visibility of the liquid crystal display device. The retardation adjusting agent is an additive capable of adjusting the thickness direction retardation Rth (R), Rth (G), Rth (B) of each of the colored pixels 3R, 3G, 3B formed using the photosensitive coloring composition.

  The compound that can be used as a retardation adjusting agent is preferably an organic compound with good dispersibility in order to ensure a high contrast of 1000 or 3000 or more.

  Specifically, particles in the form of particles such as inorganic substances can be used, but it is desirable to avoid them from the viewpoints of light scattering and depolarization.

  Specific retardation adjusting agents are selected from organic compounds having a planar structure group having one or more crosslinkable groups, melamine resins, porphyrin compounds, benzylic compounds, styrenic compounds, and polymerizable liquid crystal compounds. More than species can be selected.

  Examples of the planar structural group include a substituent having at least one aromatic ring. For example, in the case of monocyclic hydrocarbons, phenyl group, cumenyl group, mesityl group, tolyl group, xylyl group, benzyl group, phenethyl group, styryl group, cinnamyl group, trityl group, etc. A known compound having a group, naphthyl group, biphenylene group, acenaphthylene group, fluorene group, phenanthryl group, anthracene group, triphenylene group, pyrene group, naphthacene group, pentaphen group, pentacene group, tetraphenylene group, trinaphthylene group, etc. It can be used as an organic compound having a structural group. Among heteromonocyclic compounds, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, triazine group, etc.For heteropolycyclic compounds, indolizinyl group, isoindolyl group, indolyl group, purinyl group, quinolyl group, isoquinolyl group , Phthalazinyl group, naphthyridinyl group, quinoxalinyl group, cinolinyl group, carbazolyl group, carbolinyl group, acridinyl group, porphyrin group, and the like, and examples thereof include those having substituents such as hydrocarbon groups and halogen groups It may be.

  As the at least one crosslinkable group attached to the planar structure group, an unsaturated polymerizable group (A, B, C, D, E, F) represented by the following formulas (A to U) or a functional group (I, J, K, L, M, N, O) or a thermally polymerizable group (G, H, P, Q, R, S, T, U) is preferable, and an epoxy group (G, H) is more preferable. A crosslinkable group represented by P to U is most preferably used.

Further, the unsaturated polymerizable group is more preferably an ethylenically unsaturated polymerizable group (A, B, C, D), and —CH ₂ NHCOCH═CH ₂ , —CH ₂ NHCO (CH ₂ ) ₇ CH═ CH (CH ₂ ) ₇ CH ₃ , —OCO (C ₆ H ₄ ) O (CH ₂ ) ₆ CH═CH _{2 and the} like are also preferably used.

  These crosslinkable groups are glycidyl (meth) acrylate, 2- (meth) acryloyloxyisocyanate, tolylene-2, 4-, when the planar structural group has at least one reactive functional group such as a hydroxyl group. It can be easily obtained by reacting a functional group that reacts with the reactive functional group such as diisocyanate and a compound having an ethylenically unsaturated group by a known method.

メラミン化合物としては、下記一般式（２）で表される市販のものを好ましく用いることができるが、上述の平面構造基を有する化合物であれば何でもよく公知のものを使用できる。以下にメラミン化合物を例示する。

As the melamine compound, a commercially available compound represented by the following general formula (2) can be preferably used, but any compound having the above-mentioned planar structure group may be used, and a known compound can be used. Examples of melamine compounds are given below.

（式中、Ｒ_１、Ｒ_２、Ｒ_３はそれぞれ水素原子、メチロール基、アルコキシメチル基、アルコキシｎ−ブチル基、Ｒ_４、Ｒ_５、Ｒ_６はそれぞれメチロール基、アルコキシメチル基、アルコキシｎ−ブチル基である。）
また、上記以外に１，３，５−トリアジン環を有する化合物で、例えば特開２００１−１６６１４４号公報に記載のものを使用することができる。また下記一般式（３）に示す化合物も好ましく用いられる。

(In the formula, R ₁ , R ₂ and R ₃ are each a hydrogen atom, a methylol group, an alkoxymethyl group, an alkoxy n-butyl group, R ₄ , R ₅ and R ₆ are a methylol group, an alkoxymethyl group and an alkoxy n- (It is a butyl group.)
In addition to the above, compounds having a 1,3,5-triazine ring, for example, those described in JP-A No. 2001-166144 can be used. In addition, compounds represented by the following general formula (3) are also preferably used.

（Ｒ_７〜Ｒ_１４はそれぞれ独立に、水素原子、アルキル基、アルケニル基、アリール基または複素環基であり、水素原子であることが特に好ましい。）
または下記一般式（４）で表されるポルフィリン骨格を有する化合物を好ましく用いることができる。ｎは１〜２０の整数であり、２であるものが好ましく用いられる。

(R _{7 to} R ₁₄ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and particularly preferably a hydrogen atom.)
Alternatively, a compound having a porphyrin skeleton represented by the following general formula (4) can be preferably used. n is an integer of 1 to 20, and 2 is preferably used.

（式中、Ｒ_１５〜Ｒ_２２はそれぞれ独立に水素原子、ハロゲン原子、アルコキシ基、アルキルチオ基、置換もしくは未置換のフェノキシ基、置換もしくは未置換のナフトキシ基、置換もしくは未置換のフェニルチオ基、または置換もしくは未置換のナフチルチオ基を表す。）
式（４）のＲ_１５〜Ｒ_２２におけるハロゲン原子としては、フッ素、塩素、臭素、ヨウ素などがあげられる。アルコキシ基およびチオアルキル基としては、特に限定されるものではないが、置換基中のアルキル基が炭素数１〜１２の直鎖、分岐或いは環状のアルキル基が好ましく、炭素数１〜８の直鎖、分岐或いは環状のアルキル基が特に好ましい。−Ｚは−ＣＨ−、−Ｎ−を表す。

(Wherein R _{15 to} R ₂₂ are each independently a hydrogen atom, a halogen atom, an alkoxy group, an alkylthio group, a substituted or unsubstituted phenoxy group, a substituted or unsubstituted naphthoxy group, a substituted or unsubstituted phenylthio group, or Represents a substituted or unsubstituted naphthylthio group.)
Examples of the halogen atom in R _{15 to} R ₂₂ in the formula (4) include fluorine, chlorine, bromine and iodine. The alkoxy group and thioalkyl group are not particularly limited, but the alkyl group in the substituent is preferably a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and a linear chain having 1 to 8 carbon atoms. Particularly preferred are branched or cyclic alkyl groups. -Z represents -CH- or -N-.

Specific examples of the alkyl group in the alkoxy group and the thioalkyl group in the formula (4) include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, sec -Butyl group, t-butyl group, n-pentyl group, iso-pentyl group, 2-methylbutyl group, 1-methylbutyl group, neo-pentyl group, 1,2-dimethylpropyl group, 1,1 dimethylpropyl group, cyclopentyl Group, n-hexyl group, 4-methylpentyl group, 3methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3
-Dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutyl group, 1,1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,2,2-trimethylbutyl group, 1,1,2-trimethylbutyl group, 1-ethyl-2-methylpropyl group, cyclohexyl group, n-heptyl group, 2- Methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5methylhexyl group, 2,4-dimethylpentyl group, n-octyl group, 2-ethylhexyl group, 2,5-dimethylhexyl group, 2,5 , 5-trimethylpentyl group, 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, n-octyl group, 3,5,5-trimethylhexyl group n-nonyl group, n-decyl group, 4-ethyloctyl group, 4-ethyl 4,5-dimethylhexyl group, n-undecyl group, n-dodecyl group, 1,3,5,7-tetraethyloctyl group, 4 -Butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group, 6-methyl-4-butyloctyl group, n-tetradecyl group, n-pentadecyl group, 3,5-dimethylheptyl group, 2,6- Dimethylheptyl group, 2,4-dimethylheptyl group, 2,2,5,5-tetramethylhexyl group, 1-cyclopentyl-2,2-dimethylpropyl group, 1-cyclohexyl-2,2-dimethylpropyl group, etc. Can be mentioned.

  Specific examples of the substituted or unsubstituted phenoxy group of the formula (4) include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2-ethylphenoxy group, 3- Ethylphenoxy group, 4-ethylphenoxy group, 2,4-dimethylphenoxy group, 3,4-dimethylphenoxy group, 4-t-butylphenoxy group, 4-aminophenoxy group, 4-dimethylaminophenoxy group, 4-diethylamino A phenoxy group etc. are mentioned.

  Specific examples of the substituted or unsubstituted naphthoxy group of the formula (4) include 1-naphthoxy group, 2-naphthoxy group, nitronaphthoxy group, cyanonaphthoxy group, hydroxynaphthoxy group, methylnaphthoxy group, trifluoromethyl. A naphthoxy group etc. are mentioned.

  Specific examples of the substituted or unsubstituted phenylthio group of the formula (4) include phenylthio group, 2-methylphenylthio group, 3-methylphenylthio group, 4-methylphenylthio group, 2-ethylphenylthio group. Group, 3-ethylphenylthio group, 4-ethylphenylthio group, 2,4-dimethylphenylthio group, 3,4-dimethylphenylthio group, 4-t-butylphenylthio group, 4-aminophenylthio group, 4-dimethylaminophenylthio group, 4-diethylaminophenylthio group, etc. are mentioned.

  Specific examples of the substituted or unsubstituted naphthylthio group of the formula (4) include 1-naphthylthio group, 2-naphthylthio group, nitronaphthylthio group, cyanonaphthylthio group, hydroxynaphthylthio group, and methylnaphthylthio group. And a trifluoromethylnaphthylthio group.

  Further, X in the formula (4) may be used in combination of two or more kinds of substituents. For example, a compound having a 1,3,5-triazine ring and a substituent having a porphyrin skeleton can be used in combination.

  Specific examples of the plane-containing structural group epoxy compound include, for example, bisphenol type epoxy compounds such as bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol AD type epoxy compounds, hydrogenated bisphenol A type epoxy compounds; Type epoxy compounds, novolak type epoxy compounds such as cresol novolak type epoxy compounds; for example, glycidyl amines such as tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, tetraglycidyl-mxylenediamine Epoxy compounds; for example, glycidyl esters such as diglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate Epoxy compounds; for example, triglycidyl isocyanurate, etc. complex Kaeshiki epoxy compounds such as glycidyl glycidoxy Arch setup in can be exemplified. An example is shown in the following general formula (5).

重合性液晶化合物としては、棒状液晶性分子またはディスコティック液晶性分子を適用することが可能であるが、特にディスコティック液晶性分子が好ましい。棒状液晶性分子としては、特開２００６−１６５９９公報に記載の液晶性分子が採用可能で、他、例えばアゾメチン類、アゾキシ類、シアノビフェニル類、シアノフェニルエステル類、安息香酸エステル類、シクロヘキサンカルボン酸フェニルエステル類、シアノフェニルシクロヘキサン類、シアノ置換フェニルピリミジン類、アルコキシ置換フェニルピリミジン類、フェニルジオキサン類、トラン類およびアルケニルシクロヘキシルベンゾニトリル類なども用いられる。ディスコティック液晶性分子としては、例えば特開平８−２７２８４号公報に記載のものを使用できる。以下にその例を示す。

As the polymerizable liquid crystal compound, a rod-like liquid crystal molecule or a discotic liquid crystal molecule can be applied, and a discotic liquid crystal molecule is particularly preferable. As the rod-like liquid crystalline molecules, liquid crystalline molecules described in JP-A-2006-16599 can be adopted, and for example, azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoates, cyclohexanecarboxylic acid Phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are also used. As the discotic liquid crystalline molecules, for example, those described in JP-A-8-27284 can be used. An example is shown below.

上記式において、Ｙは、アルキレン基、アルケニレン基、アリーレン基、−ＣＯ−、−ＮＨ−、−Ｏ−、−Ｓ−およびそれらの組み合わせからなる群より選ばれる二価の連結基、および該二価の基を少なくとも二つ組み合わせた基であることが最も好ましい。

In the above formula, Y represents a divalent linking group selected from the group consisting of an alkylene group, an alkenylene group, an arylene group, —CO—, —NH—, —O—, —S—, and combinations thereof; Most preferably, the group is a combination of at least two valent groups.

  The alkylene group preferably has 1 to 12 carbon atoms, the alkenylene group preferably has 2 to 12 carbon atoms, and the arylene group preferably has 6 to 10 carbon atoms. . The alkylene group, alkenylene group and arylene group may have a substituent (eg, alkyl group, halogen atom, cyano, alkoxy group, acyloxy group).

  R is the above-described crosslinkable groups (A) to (U), or an alkyl group, alkenyl group, aryl group or heterocyclic group substituted with the crosslinkable group.

As the unsaturated polymerizable group, an ethylenically unsaturated polymerizable group (A, B, C, D) is more preferable, and —CH ₂ NHCOCH═CH ₂ , —CH ₂ NHCO (CH ₂ ) ₇ CH═CH ( CH ₂ ) ₇ CH ₃ , —OCO (C ₆ H ₄ ) O (CH ₂ ) ₆ CH═CH _{2 and the} like are also preferably used.

(Description of storage stabilizer)
A storage stabilizer is contained in order to stabilize the viscosity with time of the composition. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite. The storage stabilizer can be contained in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.

(Description of adhesion improver)
The adhesion improver is added as necessary for the purpose of improving the adhesion between the coating film of the photosensitive coloring composition of the present invention and the substrate. A silane coupling agent can be illustrated as an adhesion improving agent.

Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopro Lutriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N Examples include aminosilanes such as -phenyl-γ-aminopropyltriethoxysilane, thiosilanes such as γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane.

  The adhesion improver can be contained in an amount of 0.01 to 100 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.

(Description of production method of photosensitive coloring composition)
The photosensitive coloring composition according to the present invention is a three-roll mill in which one or more pigments are mixed with the solvent together with a resin, a monomer and other necessary components (for example, a photopolymerization initiator). It can be produced using various dispersing means such as a two-roll mill, a sand mill, a kneader, and an attritor.

  Moreover, after mixing each pigment separately with a resin, a monomer, etc. in a solvent and manufacturing each composition, these compositions can be mixed and the photosensitive coloring composition concerning this invention can also be manufactured.

  In addition, immediately before the color pixel forming step described later, coarse particles formed by aggregation of pigments, resins, and the like and dust mixed therein are collected from the colored composition by means of centrifugation, sintered filter, membrane filter, or the like. It is desirable to remove. The coarse particles have a diameter of 5 μm or more. In addition, Preferably it is 1 micrometer or more, More preferably, it is 0.5 micrometer or more.

(Description of forming method of colored pixels of color filter)
As a method for forming the colored pixels 3R, 3G, and 3B on the transparent substrate 1 using the photosensitive coloring composition according to the present invention, a known method can be used. For example, a photolithography method, a printing method, an electrodeposition method, or the like. Since the coloring composition according to the present invention has photosensitivity, among these methods, the photolithography method can be suitably used. It is also possible to use a transfer method in which the colored pixels 3R, 3G, and 3B are formed on the peelable transfer base sheet, and then the colored pixels 3R, 3G, and 3B are transferred onto the transparent substrate 1.

  In the photolithography method, a photosensitive coloring composition is applied on the transparent substrate 1 to form a coating film, and the coating film is partially exposed and developed to selectively leave the coating film at the exposed position. In this way, the colored pixels 3 are formed. Heat treatment can also be applied after exposure and development. By this heat treatment, polymerization of the monomer remaining in the colored pixel 3 is promoted. Then, the color filter 1 can be manufactured by repeating this process for each of the colored pixels 3R, 3G, 3B.

Here, as the transparent substrate 1, a glass plate such as soda lime glass, low alkali borosilicate glass, non-alkali alumino borosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate can be used. A transparent electrode may be formed on the surface of the glass plate or the resin plate. This transparent electrode can be used for driving a liquid crystal. As a transparent electrode, a metal oxide such as indium oxide, tin oxide, zinc oxide, antimony oxide, or a combination thereof can be used.

  As a coating method, methods such as spray coating, spin coating, slit coating, and roll coating can be used. What is necessary is just to apply | coat the coating film of a photosensitive coloring composition so that the dry film thickness may be set to 0.2-10 micrometers. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like can be used.

  And, by placing an exposure mask in contact or non-contact with the coating film thus dried, by exposing through the transmission pattern of this exposure mask, the coating film is exposed to the shape of the target colored pixel 3, It can be cured.

  In addition, in order to raise an ultraviolet exposure sensitivity, after forming an oxygen barrier film | membrane on the said coating film, an ultraviolet exposure can also be performed. Examples of the oxygen barrier film include polyvinyl alcohol and water-soluble acrylic resin.

  As a developer for developing the exposed coating film, an aqueous solution of sodium carbonate, sodium hydroxide, or the like can be used. An organic alkali developer such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. Then, by this development, the unexposed coating film is dissolved and removed in a developer, and the coating film in the exposed and cured portion selectively remains to form the colored pixel 3.

  Among the printing methods, there are a method using a printing plate having the same pixel pattern as the colored pixels 3 and an ink jet printing method which does not require a printing plate.

  In the method of using a printing plate, a method in which a photosensitive coloring composition embedded in the pixel pattern of the printing plate is directly transferred onto the transparent substrate 1 for printing, and a photosensitive coloring composition embedded in the printing plate is used. There is a method of transferring to a blanket and transferring the blanket onto the transparent substrate 1 for printing. In addition, a coating film of the photosensitive coloring composition is formed on the blanket, and the printing plate is pressed against the coating film to remove the non-image area coating film from the blanket. Thus, the coating film remaining on the blanket is removed. There is also a method of printing by transferring. In addition, it can harden | cure by exposing the colored pixel 3 formed by printing on the transparent substrate 1 in this way with an ultraviolet-ray. And the photosensitive coloring composition of this invention can apply any method among these methods.

  In addition, according to the printing method, patterning can be performed simply by repeating the printing and drying of the photosensitive coloring composition, so that the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of the fluidity of the ink on the printing machine is also important, and the ink viscosity can be adjusted with a dispersion aid or extender pigment.

Next, the inkjet method is a method in which the colored pixels 3 are directly printed and formed on the transparent substrate 1 by an inkjet apparatus in which a plurality of fine discharge ports (inkjet heads) are arranged for each color. The electrodeposition method uses a transparent conductive film formed on the transparent substrate 1 and produces a color filter by electrodepositing the colored pixels 3 on the transparent conductive film by electrophoresis of colloidal particles. It is.

  The transfer method is a method of transferring the colored pixels 3R, 3G, 3B formed on the peelable transfer base sheet onto the transparent substrate 1 as described above. As a method for forming the colored pixels 3 on the peelable transfer base sheet, a photolithography method, a printing method, an electrodeposition method, or the like can be used.

  Specific examples of the present invention will be described below, but the present invention is not limited to these examples. In addition, since materials used in this embodiment are extremely sensitive to light, it is necessary to prevent exposure to unnecessary light such as natural light, and it goes without saying that all operations are performed under a yellow or red light. Yes. In the examples and comparative examples, “parts” means “parts by weight”.

  The symbol of the pigment indicates a color index number. For example, “PR254” represents “CI Pigment Red 254” and “PY150” represents “CI Pigment Yellow 150”.

  The dye derivatives used in the following examples are shown in Table 1 below.

ａ）微細化顔料の製造
実施例および比較例で用いた微細化顔料を以下の方法により製造した。そして、得られた顔料の平均一次粒子径を、電子顕微鏡写真から一次粒子の大きさを直接計測する一般的な方法で測定した。

a) Production of refined pigments The refined pigments used in Examples and Comparative Examples were produced by the following method. And the average primary particle diameter of the obtained pigment was measured by the general method which measures the magnitude | size of a primary particle directly from an electron micrograph.

  Specifically, the particles in the field of view are photographed with a transmission electron microscope JEM-2010 (manufactured by JEOL Ltd.), and the minor axis diameters of the primary particles of the individual pigments constituting the aggregate on the two-dimensional image The major axis diameter was measured, and the average was taken as the particle diameter of the pigment particles.

  Next, for 100 or more pigment particles, the volume (weight) of each particle is approximated to a rectangular parallelepiped of the obtained particle size to obtain a volume average particle size, and this volume average particle size in an integrated curve of the number particle size distribution. The particle diameter (equivalent circle diameter) corresponding to 50% of the total amount was set to the median value d50. At this time, the colored composition as a sample is ultrasonically dispersed in a solvent, and then the particles are photographed with the microscope. The same result can be obtained by using either a transmission type (TEM) or a scanning type (SEM).

[Production Example 1]
The flask was charged with 170 parts of tert-amyl alcohol under a nitrogen atmosphere. Then 11.04 parts of sodium were added and the mixture was heated to 92-102 ° C. The molten sodium was then held overnight at 100-107 ° C. with vigorous stirring.

  A solution of 44.2 parts of 4-chlorobenzonitrile and 37.2 parts of diisopropyl succinate in 50 parts of tert-amyl alcohol at 80 ° C. is added to the resulting solution at 80-98 ° C. Introduced over 2 hours. After the introduction, the reaction mixture was stirred at 80 ° C. for a further 3 hours and at the same time 4.88 parts of diisopropyl succinate were added dropwise.

The reaction mixture was cooled to room temperature and added to a 20 ° C. mixture of 270 parts of methanol, 200 parts of water, and 48.1 parts of concentrated sulfuric acid and stirring was continued at 20 ° C. for 6 hours. The red mixture was filtered, and the residue was washed with methanol and water, and then dried at 80 ° C. to obtain 46.7 parts of a diketopyrrolopyrrole red pigment (R-1).

[Production Example 2]
Diketopyrrolopyrrole red pigment PR254 (“Irgafoa Red B-CF” manufactured by Ciba Specialty Chemicals; (R-2) 100 parts, dye derivative (D-1) 18 parts, ground salt 1000 parts, and diethylene glycol 120 The parts were placed in a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours.

  The mixture was poured into 2000 parts of warm water and stirred for about 1 hour with a high-speed mixer while heating to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. Dried to obtain 115 parts of a salt milled pigment (R-3). The primary particle diameter of the obtained pigment is shown in Table 2 below.

[Production Example 3]
100 parts of anthraquinone red pigment PR177 (“Chromophthal Red A2B” manufactured by Ciba Specialty Chemicals), 8 parts of a dye derivative (D-2), 700 parts of crushed salt, and 180 parts of diethylene glycol are made of 1 gallon kneader made of stainless steel (Inoue Seisakusho) And kneaded at 70 ° C. for 4 hours.

  The mixture was put into 4000 parts of warm water, heated to about 80 ° C., stirred with a high speed mixer for about 1 hour to form a slurry, filtered and washed with water to remove salt and solvent, and then at 80 ° C. for 24 hours. Dried to obtain 102 parts of a salt milled pigment (R-4). The primary particle diameter of the obtained pigment is shown in Table 2 below.

[Production Example 4]
A separable flask was charged with 150 parts of water, and further stirred with 63 parts of 35% hydrochloric acid to prepare a hydrochloric acid solution. While paying attention to foaming, 38.7 parts of benzenesulfonyl hydrazide was charged, and ice was added until the liquid temperature became 0 ° C. or lower. After cooling, 19 parts of sodium nitrite was charged over 30 minutes, stirred for 30 minutes at 0 to 15 ° C., and then sulfamic acid was charged until no coloration was observed on the potassium iodide starch paper.

  Next, after adding 25.6 parts of barbituric acid, it heated up to 55 degreeC and stirred as it was for 2 hours. Next, 25.6 parts of barbituric acid was added, and after raising the temperature to 80 ° C., sodium hydroxide was added until the pH reached 5. After further stirring for 3 hours at 80 ° C., the temperature was lowered to 70 ° C., followed by filtration and washing with warm water.

  The obtained press cake was reslurried in 1200 parts of warm water, and then stirred at 80 ° C. for 2 hours. Thereafter, filtration was performed at the same temperature, and washing with 2000 parts of water at 80 ° C. was performed with warm water, and it was confirmed that benzenephonamide was transferred to the filtrate side. The obtained press cake was dried at 80 ° C. to obtain 61.0 parts of disodium azobarbituric acid.

  Next, 200 parts of water was charged into a separable flask, and 8.1 parts of the obtained disodium azobarbituric acid powder was added and dispersed while stirring. After uniformly dispersing, the solution was heated to 95 ° C., and 5.7 parts of melamine and 1.0 part of diallylaminomelamine were added.

  Further, a green solution obtained by dissolving 6.3 parts of cobalt (II) chloride hexahydrate in 30 parts of water was added dropwise over 30 minutes. After completion of the dropwise addition, complexation was performed at 90 ° C. for 1.5 hours.

  Thereafter, the pH was adjusted to 5.5, 20.4 parts of xylene, 0.4 part of sodium oleate, and 16 parts of water were previously stirred to add 20.4 parts of an emulsion, and further heated for 4 hours. Stir. After cooling to 70 ° C., it was quickly filtered, and washing with warm water at 70 ° C. was repeated until the inorganic salt could be washed.

  Thereafter, 14 parts of an azo yellow pigment (Y-1) was obtained through drying and grinding processes. The primary particle diameter of the obtained pigment is shown in Table 2 below.

[Production Example 5]
160 parts of yellow pigment (CI Pigment Yellow 138, “PALIOTOL YELLOW K0961HD” manufactured by BASF), 1600 parts of sodium chloride, and 270 parts of diethylene glycol (manufactured by Tokyo Chemical Industry) 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) And kneaded at 60 ° C. for 15 hours. Next, this mixture is poured into about 5 liters of warm water, heated to about 70 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, then filtered and washed to remove sodium chloride and diethylene glycol, After drying at 80 ° C. for 24 hours, 157 parts of a salt milled pigment (Y-2) was obtained.

[Production Example 6]
120 parts of halogenated copper phthalocyanine-based green pigment PG36 (“Rionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1600 parts of crushed sodium chloride, and 270 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 70 ° C. And kneaded for 12 hours.

  The mixture was poured into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 117 parts of salt milling pigment (G-1).

  The primary particle diameter of the obtained pigment is shown in Table 2 below.

[Production Example 7]
In a molten salt of 200 ° C. of 356 parts of aluminum chloride and 6 parts of sodium chloride, 46 parts of zinc phthalocyanine was dissolved, cooled to 130 ° C., and stirred for 1 hour. The reaction temperature was raised to 180 ° C., and bromine was added dropwise at 10 parts per hour for 10 hours. Thereafter, chlorine was introduced at 0.8 parts per hour for 5 hours.

  The reaction solution was gradually poured into 3200 parts of water, then filtered and washed with water to obtain 107.8 parts of a crude zinc halide phthalocyanine pigment. The average number of bromine contained in one molecule of the crude zinc halide phthalocyanine pigment was 14.1 and the average number of chlorine was 1.9.

  120 parts of the obtained crude zinc halide phthalocyanine pigment, 1600 parts of crushed salt and 270 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 12 hours.

  The mixture was poured into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 117 parts of salt milling process pigments (G-2). The primary particle diameter of the obtained pigment is shown in Table 2 below.

[Production Example 8]
Copper phthalocyanine-based blue pigment PB15: 6 (Toyo Ink Mfg. Co., Ltd. “Lionol Blue E
S "), 100 parts of crushed salt, and 100 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 70 ° C for 12 hours.

  The mixture was poured into 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 98 parts of salt milling pigment (B-1). The primary particle diameter of the obtained pigment is shown in Table 2 below.

ｂ）アクリル樹脂溶液の調製
反応容器にシクロヘキサノン８００部を入れ、容器に窒素ガスを注入しながら１００℃に加熱して、同温度で下記のモノマーおよび熱重合開始剤の混合物を１時間かけて滴下して重合反応を行った。

b) Preparation of acrylic resin solution Put 800 parts of cyclohexanone in a reaction vessel, heat to 100 ° C. while injecting nitrogen gas into the vessel, and drop the mixture of the following monomer and thermal polymerization initiator at the same temperature over 1 hour. Then, a polymerization reaction was performed.

Styrene 60.0 parts Methacrylic acid 60.0 parts Methyl methacrylate 65.0 parts Butyl methacrylate 65.0 parts Azobisisobutyronitrile 10.0 parts After dropwise addition, the mixture is further reacted at 100 ° C for 3 hours, and then azo A solution in which 2.0 parts of bisisobutyronitrile was dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour to synthesize a resin solution.

  After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. An acrylic resin solution was prepared.

c) Retardation adjuster A melamine compound (trade name: Nicalac MX-750; manufactured by Nippon Carbide Industries) was used as a retardation adjuster.

d) Preparation of colored composition A mixture having the composition shown in Table 3 below was uniformly stirred and mixed, and then filtered through a 1 µm filter to obtain each color resist.

  In the table, when the evaporation rate of butyl acetate is 100, the evaporation rate of cyclohexanone is 23, the evaporation rate of propylene glycol monomethyl ether acetate (PgMAc) is 34, and the evaporation rate of ethyl-3-ethoxypropionate (EEP). The speed is 12.

ｅ）各色塗膜の作製
上記表３に示した各着色組成物をスピンコート法によりガラス基板に塗工した後、クリーンオーブン中で、７０℃で２０分間プリベークした。次いで、この基板を室温に冷却後、超高圧水銀ランプを用い、紫外線を露光した。

e) Preparation of each color coating film Each colored composition shown in Table 3 was applied to a glass substrate by a spin coating method, and then pre-baked at 70 ° C. for 20 minutes in a clean oven. Next, the substrate was cooled to room temperature and then exposed to ultraviolet rays using an ultrahigh pressure mercury lamp.

  Next, this substrate was spray-developed using an aqueous sodium carbonate solution at 23 ° C., then washed with ion-exchanged water and air-dried. Thereafter, post-baking was performed at 230 ° C. for 30 minutes in a clean oven to obtain each color coating film. The film thickness of the dried coating film was 2.0 μm in all cases.

f) Measurement of film stress σ, thickness direction retardation value, contrast, etc. [film stress σ]
Table 4 below shows the value of the film stress σ calculated by the following equation (1). However, the thickness h of the glass substrate is 0.5 mm.

σ = E · h ² / [6 (1-λ) R · t] Formula (1)
(Wherein, E represents the Young's modulus of the glass substrate, h represents the glass substrate thickness (m), λ represents the Poisson's ratio of the glass substrate, and t represents the coating thickness (m). R represents the effective radius of curvature ( m), where R ₁ is the radius of curvature of the glass substrate before forming the colored coating film, and R ₂ is the radius of curvature of the glass substrate after forming the colored coating film, 1 / R = 1 / R ₂ -1 / R ₁ Is a numerical value that satisfies
[Thickness direction retardation value Rth]
The thickness direction retardation value can be obtained as follows. Using a transmission spectroscopic ellipsometer (“M-220” manufactured by JASCO Corporation), measurement is performed at a wavelength of every 5 nm in the range of 400 nm to 700 nm from the direction inclined 45 ° from the normal direction of the substrate on which the coating film is formed. Then, the ellipso parameter δ was obtained.

  The retardation value Δ (λ) at each wavelength can be obtained from Δ = δ / 360 × λ, and the three-dimensional refractive index is calculated using this value, and the thickness direction retardation value (Rth) is calculated from the following equation 2. Asked.

  Although Rth of each wavelength can be obtained from the above measurement, in this evaluation, the red pixel was calculated as 610 nm, the green pixel as 545 nm, and the blue pixel as 450 nm.

Rth = {(Nx + Ny) / 2−Nz} × d (2)
(Where Nx is the refractive index in the x direction in the plane of the colored pixel layer, Ny is the refractive index in the y direction in the plane of the colored pixel, and Nz is the refractive index in the thickness direction of the colored pixel. , Nx is a slow axis where Nx ≧ Ny, and d is the thickness (nm) of the colored pixel.)
Table 4 below shows the thickness direction retardation value Rth of each color coating film prepared from each colored composition shown in Table 3 above.

[contrast]
A polarizing plate was placed on both sides of the substrate on which the coating film was formed, and the ratio of luminance (Lp) when the polarizing plate was parallel and luminance (Lc) when it was orthogonal, Lp / Lc was calculated as contrast (C).

  Further, contrast of only the substrate without colored pixels = Lp / Lc is CS, CR is a red pixel, CY is a yellow pixel, CG is a green pixel, and CB is a blue pixel.

  The luminance was measured using a color luminance meter (“BM-5A” manufactured by Topcon Corporation) under the condition of a 2 ° visual field, and “NPF-SEG1224DU” manufactured by Nitto Denko Corporation was used as the polarizing plate.

  In addition, Table 4 shows the results of evaluating the storage stability, patterning characteristics, and coating film resistance of the photosensitive coloring composition.

ｇ）カラーフィルタ及び液晶表示装置の作製
上記表３に示した各着色組成物を組み合わせて、下記に示す方法により、カラーフィルタを作製した。

g) Preparation of color filter and liquid crystal display device A color filter was prepared by the method shown below by combining the colored compositions shown in Table 3 above.

[Example 8]
First, the red coloring composition 1 was applied by spin coating to a glass substrate on which a black matrix had been previously formed, and then prebaked at 70 ° C. for 20 minutes in a clean oven. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp.

  Thereafter, the substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, and air-dried. Further, post-baking was performed at 230 ° C. for 30 minutes in a clean oven to form striped red pixels on the substrate.

  Next, the green coloring composition 4 was similarly formed to form a green pixel, and further, the blue coloring composition 6 was used to similarly form a blue pixel to obtain a color filter. The film thickness of each color pixel was 2.0 μm.

  An overcoat layer was formed on the obtained color filter, and a polyimide alignment layer was formed thereon. And the polarizing plate was formed in the other surface of this glass substrate.

  On the other hand, a TFT array and a pixel electrode were formed on one surface of another glass substrate, and a polarizing plate was formed on the other surface.

  The two glass substrates prepared in this manner face each other so that the electrode layers face each other, and are aligned while using a spacer bead to keep the distance between the two substrates constant, leaving a liquid crystal composition injection opening. The periphery was sealed with a sealant. Next, a liquid crystal composition for VA was injected from the opening, and the opening was sealed. Furthermore, an optical compensation layer optimized so that a wide viewing angle display is possible is provided on the polarizing plate.

  The liquid crystal display device thus fabricated was combined with a backlight unit to obtain a VA display mode liquid crystal panel.

[Example 9]
The red coloring composition is changed from the coloring composition 1 to the coloring composition 3, the green coloring composition is changed from the coloring composition 4 to the coloring composition 5, and the blue coloring composition is changed from the coloring composition 6 to the coloring composition 7. A liquid crystal display device was obtained in the same manner as in Example 8 except for the change.

[Comparative Example 8]
The blue colored composition is colored from the colored composition 6 except that the red colored composition is changed from the colored composition 1 to the colored composition 8 and the green colored composition is changed from the colored composition 4 to the colored composition 12. A liquid crystal display device was obtained in the same manner as the embodiment 8 except that the composition 14 was changed.

[Comparative Example 9]
The red coloring composition is changed from the coloring composition 1 to the coloring composition 10, the green coloring composition is changed from the coloring composition 4 to the coloring composition 13, and the blue coloring composition is changed from the coloring composition 6 to the coloring composition 14. A liquid crystal display device was obtained in the same manner as in Example 1 except for the change.

h) Visibility evaluation at the time of black display of the liquid crystal display device The produced liquid crystal display device is displayed in black and leaks from the normal direction (substantially vertical direction) of the liquid crystal panel and from the direction (oblique) inclined by 45 ° from the normal direction. The amount of light (orthogonal transmitted light; leakage light) was visually observed. Also, the chromaticity (u (、), v (⊥)) when viewed from a substantially vertical direction when displaying black and the chromaticity when viewed from an orientation inclined up to 60 ° from the normal direction of the display surface ( u (45), v (45)) were measured with Topcon BM-5A, the color difference Δu′v ′ was calculated, and the maximum value of Δu′v ′ at 0 ≦ θ ≦ 60 ° was determined. The evaluation rank is as follows, and the results are shown in Table 5 below.

上記表５より、実施例１から実施例２に係るカラーフィルタの赤色画素、緑色画素、および青色画素層の厚み方向位相差値が、２以下であるように形成されているので、得られたカラーフィルタを液晶表示装置に用いることで、表示面の法線方向と斜め方向の色度差が上述の式（１）を満たし、正面および斜め方向の視認性が良好な液晶表示装置を得ることができる。

From Table 5 above, the red, green, and blue pixel layer thickness direction retardation values of the color filters according to Example 1 to Example 2 were formed to be 2 or less. By using a color filter in a liquid crystal display device, a liquid crystal display device in which the chromaticity difference between the normal direction and the oblique direction of the display surface satisfies the above-described formula (1) and the visibility in the front and oblique directions is good. Can do.

  On the other hand, in the liquid crystal display device including the color filter according to Comparative Examples 1 and 2, the condition that the absolute value of the thickness direction retardation of the red pixel, the green pixel, and the blue pixel layer is 2 or less is not satisfied. A color shift occurs in an oblique direction, resulting in poor visibility.

  DESCRIPTION OF SYMBOLS 1 ... Transparent substrate, 2 ... Black matrix, 3 ... Colored pixel, 4 ... Liquid crystal display device, 5 ... 1st board | substrate, 7 ... TFT array, 8, 12, ...・ Transparent electrode, 9, 13 ... Alignment layer, 10, 14 ... Polarizing plate, 15 ... Three-wavelength lamp, 16 ... Backlight unit

Claims (6)

A photosensitive coloring composition for forming a colored pixel of a color filter for a liquid crystal display device, comprising a pigment, a resin, a monomer and a solvent,
Containing two or more pigments as the pigment,
50% or more of the solvents are solvents having an evaporation rate of 10 to 35 when the evaporation rate of butyl acetate is 100.
The mass ratio of monomer to resin (monomer / resin) is in the range of 0.3 to 1.0;
And, when this photosensitive coloring composition is applied on a glass substrate, and the film stress σ of the coating film obtained through the steps of drying, exposure, development, and post-baking is calculated by the formula (1), the film A photosensitive coloring composition for a color filter, wherein the stress σ is in the range of 0 to +30.
σ = E · h ² / [6 (1-λ) R · t] Formula (1)
(Wherein, E represents the Young's modulus of the substrate, h represents the substrate thickness (m), λ represents the Poisson's ratio of the substrate, and t represents the coating thickness (m). R represents the effective radius of curvature (m). This is a numerical value satisfying 1 / R = 1 / R ₂ −1 / R ₁ , where R ₁ is the radius of curvature of the substrate before forming the colored coating film and R ₂ is the radius of curvature of the substrate after forming the colored coating film. is there.)   The photosensitive coloring composition according to claim 1, comprising a retardation adjusting agent.   3. The retardation adjusting agent is one or more organic compounds selected from organic compounds having a planar structure group having one or more crosslinkable groups, melamine compounds, and benzylic compounds. The photosensitive coloring composition as described in 2. It is a color filter which formed the colored pixel using the photosensitive coloring composition in any one of Claims 1-3, Comprising: The thickness direction phase difference Rth of the said colored pixel is computed by Formula (2) A color filter for a liquid crystal display device, wherein the absolute value of the thickness direction retardation Rth is 2.0 or less.
Rth = {(Nx + Ny) / 2−Nz} × d (2)
(Where Nx is the refractive index in the x direction in the plane of the colored pixel layer, Ny is the refractive index in the y direction in the plane of the colored pixel layer, and Nz is the refractive index in the thickness direction of the colored pixel layer. There is a slow axis where Nx is Nx ≧ Ny, and d is the thickness (nm) of the colored pixel layer. In a liquid crystal display device comprising a liquid crystal cell comprising the color filter according to claim 4, polarizing plates respectively disposed on both outer surfaces of the liquid crystal cell, and an optical compensation layer provided on the inner side of these polarizing plates.
The liquid crystal display device is displayed in black, and the chromaticity (u, v) expressed in the CIE 1960 color system is measured, and the chromaticity (u (⊥), v (⊥)) when viewed from the vertical direction, When the chromaticity difference Δuv with respect to the chromaticity (u (θ), v (θ)) viewed from an orientation inclined by θ ° from the normal direction of the display surface is calculated by the following equation (3), 0 <θ A liquid crystal display device having a chromaticity difference Δuv of 0.02 or less within a range of ≦ 60.
Δuv = [{u (⊥) −u (θ)} ² + {v (⊥) −v (θ)} ² ] ^1/2 Equation (3)   6. The liquid crystal display device according to claim 5, wherein the liquid crystal display device is a VA method or an IPS method.

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