JP2007312374A - Color image display device - Google Patents

Abstract

Wide color reproducibility is achieved as a whole image without impairing the brightness of the whole image.
A color image display device is configured by combining an optical shutter, a color filter having at least three color elements of red, green, and blue corresponding to the optical shutter, and a backlight for transmitted illumination. The The light source used for the backlight is a combination of a blue or deep blue LED and a phosphor, and the relationship between the NTSC ratio W, which is the color reproduction range of the color image display element, and the light use efficiency Y is Y ≧ −0.38 W + 51. (W ≧ 87).
[Selection] Figure 2

Description

  The present invention relates to a color image display device. More specifically, the present invention relates to a color image display device for realizing an image with high color purity corresponding to the emission wavelength of the improved LED backlight.

In recent years, liquid crystal display elements are expected to be used not only as conventional monitors for personal computers but also as ordinary color televisions. The color reproduction range of the color liquid crystal display element is determined by the color of light emitted from the red, green, and blue pixels, and the chromaticity point in the CIE XYZ color system of each pixel is set to (x _R , y _R ), ( When x _G , y _G ) and (x _B , y _B ), they are represented by the area of a triangle surrounded by these three points on the xy chromaticity diagram. That is, the larger the area of the triangle, the more vivid color image can be reproduced. The area of this triangle is usually American National
Three primary colors defined by the Television System Committee (NTSC): red (0.67, 0.33), green (0.21, 0.71), and blue (0.14, 0.08) A triangle formed by dots is used as a reference and expressed as a ratio (unit%, hereinafter abbreviated as “NTSC ratio”) to the area of the triangle. This value is about 40 to 50% for general notebook personal computers, 50 to 60% for desktop personal computer monitors, and about 70% for current liquid crystal TVs.

  A color image display device using such a color liquid crystal display element is mainly composed of an optical shutter using liquid crystal, a color filter having red, green and blue pixels, and a backlight for transmitted illumination. The color of light emitted from the green and blue pixels is determined by the emission wavelength of the backlight and the spectral curve of the color filter.

  In the color liquid crystal display element, only the wavelength of the part necessary for the color filter is extracted from the light emission distribution from the backlight, and the red, green, and blue pixels are obtained.

  As a method for producing this color filter, methods such as a dyeing method, a pigment dispersion method, an electrodeposition method, a printing method, and an ink jet method have been proposed. As a coloring material for coloration, a dye was initially used, but a pigment is currently used from the viewpoint of reliability and durability as a liquid crystal display element. Therefore, at present, the pigment dispersion method is most widely used as a method for producing a color filter in terms of productivity and performance. In general, when the same color material is used, the NTSC ratio and brightness are in a trade-off relationship, and are used properly according to the application. That is, if the color filter is adjusted to increase the NTSC ratio in order to reproduce a vivid color image, the screen becomes dark. On the other hand, if the brightness is too important, the NTSC ratio is lowered, so that a vivid image cannot be reproduced.

  On the other hand, as a backlight, a cold cathode tube having an emission wavelength in the red, green, and blue wavelength regions is generally used as a light source, and light emitted from the cold cathode tube is converted into a white surface light source by a light guide plate. . In recent years, light emitting diodes (LEDs) have come to be used from the viewpoints of long life, no need for an inverter, high brightness, and mercury-free.

  Here, the conventional LED type backlight uses a blue light emission from the LED and a yellow phosphor obtained by excitation using the blue light as a white surface light source.

  However, since the above-mentioned light source has a yellow phosphor, it emits light with unnecessary wavelengths in terms of red and green color purity, and it is difficult to obtain a display with high color reproducibility (High Gamut). It was. On the other hand, it is possible in principle to increase the color purity of red and green by cutting light of unnecessary wavelength with a color filter, but to reproduce a vivid color image as described above. When trying to increase the NTSC ratio by adjusting the color filter, there is a problem that most of the light emission of the backlight is cut and the luminance is remarkably lowered. In particular, in this method, since red light emission is remarkably reduced, it is practically impossible to reproduce a strong reddish color.

  In order to overcome this problem, a method of combining LEDs emitting red, green, and blue has recently been proposed (Non-Patent Document 1), and a display with extremely high color reproducibility has been prototyped by this method. However, since this color image display device combines independent LED chips for red, green, and blue, 1) it takes time to mount, and 2) each LED chip for red, green, and blue is installed at a finite distance. Therefore, it is necessary to increase the distance of the light guide plate in order to sufficiently mix the light emission from each LED chip. 3) Adjust the white chromaticity by combining each LED chip with an integer multiple of the distance. For this reason, there is a problem that white balance cannot be adjusted continuously.

In addition, a color image display device having a NTSC ratio of 60% or more configured by combining a blue or deep blue LED and a phosphor is disclosed (Patent Document 2). However, although this color image display device has achieved a wide color reproducibility compared with the above-mentioned yellow phosphor, it still emits light with unnecessary wavelengths in terms of red and green color purity, and further widens the color. Color reproducibility was desired.
Monthly display April 2003, pages 42 to 46 WO2005 / 111707 International Publication Pamphlet

  The present invention has been made in view of such circumstances, and achieves wide color reproducibility as a whole image by adjusting with a color filter without impairing the brightness of the image even with an LED backlight, and red, green, An object of the present invention is to provide a color image display device that can easily adjust white balance without impairing mounting productivity by performing blue light emission by one chip.

  As a result of intensive studies, the present inventors have found that the NTSC ratio and light utilization efficiency are closely related to achieve the performance of the entire color image display device. Conventionally, as described above, the NTSC ratio and the light use efficiency are in a trade-off relationship. When the performance of the color image display device is to be improved, the NTSC ratio is improved at the expense of the light use efficiency. The main focus has been on either improving the light utilization efficiency at the expense of the NTSC ratio.

  On the other hand, the present inventors can set the light emission efficiency higher than before by combining a plurality of phosphors having an improved emission wavelength, which efficiently emits (excites) light by an LED having a specific emission wavelength. Found the backlight. Furthermore, by combining the backlight with a color filter that is optimal for the emission wavelength of the backlight, it is possible to realize an image display with high color purity, that is, a color image with higher light utilization efficiency than before even at a high NTSC ratio. It has been found that a display device can be realized.

  This invention is made | formed based on such knowledge, and makes the following (A)-(F) the summary.

(A) In a color image display device configured by combining an optical shutter, a color filter having at least three color elements of red, green, and blue corresponding to the optical shutter, and a backlight for transmitted illumination, The light source used for the backlight is a combination of a blue or deep blue LED and a phosphor, and the relationship between the NTSC ratio W, which is the color reproduction range of the color image display element, and the light utilization efficiency Y is expressed by the following equation. A color image display device characterized by the above.
Y ≧ −0.38W + 51 (W ≧ 87)

ここで、各符号、記号の定義は以下の通りである。

Here, the definition of each symbol and symbol is as follows.

(B) In a color image display device configured by combining an optical shutter, a color filter having at least three color elements corresponding to the optical shutter, red, green, and blue, and a backlight for transmitted illumination, source is a combination of a blue or deep blue LED and a phosphor to be used in the backlight, the light use efficiency Y ₁ color reproduction range of the color image display device is shown in the following when the NTSC ratio 74% 28% or more A color image display device characterized by that.

ここで、各符号、記号の定義は以下の通りである。

Here, the definition of each symbol and symbol is as follows.

(C) In a color image display device configured by combining an optical shutter, a color filter having color elements of at least three colors of red, green, and blue corresponding to the optical shutter, and a backlight for transmitted illumination. source is a combination of a blue or deep blue LED and a phosphor to be used in the backlight, the light use efficiency Y ₂ color reproduction range of the color image display device is shown in the following when the 85% NTSC ratio of 25% or more A color image display device characterized by that.

ここで、各符号、記号の定義は以下の通りである。

Here, the definition of each symbol and symbol is as follows.

(D) In a color image display device configured by combining an optical shutter, a color filter having color elements of at least three colors of red, green, and blue corresponding to the optical shutter, and a backlight for transmitted illumination. becomes a light source used in the backlight a combination of a blue or deep blue LED and a phosphor, the light use efficiency Y ₃ color reproduction range of the color image display device is shown in the following when the 94% NTSC ratio is 15% or more A color image display device characterized by that.

ここで、各符号、記号の定義は以下の通りである。

Here, the definition of each symbol and symbol is as follows.

(E) In a color image display device configured by combining an optical shutter, a color filter having at least three color elements corresponding to the optical shutter, red, green, and blue, and a backlight for transmitted illumination, The backlight has a phosphor layer or a phosphor film, the phosphor layer or the phosphor film contains a crystal phase represented by the following general formula (2A), and the object color is set to L ^* a ^* b ^{* When} expressed in the color system,
L ^* ≧ 90,
a ^* ≦ −20,
b ^* ≧ 30 and {a ^* / b ^* } ≦ −0.45
A color image display device comprising a compound characterized by satisfying
(M ^I _(1-x) M ^II x) _α SiO _β (2A)
(In the general formula (2A), M ^I represents one or more elements selected from the group consisting of Ba, Ca, Sr, Zn and Mg. M ^II takes a divalent and trivalent valence. It represents one or more metal elements that may. However, the molar ratio of divalent element is 0.5 or more to the whole M ^II, is 1 or less.
x, α and β are each
0.01 ≦ x <0.3,
1.5 ≦ α ≦ 2.5, and
3.5 ≦ β ≦ 4.5
Represents a number that satisfies )

(F) In a color image display apparatus configured by combining an optical shutter, a color filter having at least three color elements corresponding to the optical shutter, red, green, and blue, and a backlight for transmitted illumination. The color image display device, wherein the backlight has a phosphor layer or a phosphor film, and the phosphor layer or the phosphor film contains a compound represented by the following general formula (2B).
_{M1 x Ba y M2 z L u} O v N w (2B)
(In the general formula (2B), M1 is at least one kind selected from the group consisting of Cr, Mn, Fe, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm and Yb. Represents an active element, M2 represents at least one divalent metal element selected from Sr, Ca, Mg and Zn, and L represents a metal element selected from metal elements belonging to Group 4 or Group 14 of the periodic table. X, y, z, u, v, and w are numerical values in the following ranges, respectively.
0.00001 ≦ x ≦ 3
0 ≦ y ≦ 2.99999
2.6 ≦ x + y + z ≦ 3
0 <u ≦ 11
6 <v ≦ 25
0 <w ≦ 17)

  In each of the above inventions, the “color image display device” refers to a color image that is controlled in accordance with an input signal including an optical shutter, a color filter, a backlight, and their drive circuit and control circuit. "Color image display element" means the light from the backlight through the optical shutter and color filter, excluding the configuration that controls the drive of the optical shutter and backlight in the "color image display device". Means a configuration for emitting

  According to the color image display device of the present invention, even with an LED backlight, the reproduction of deep red and green can be achieved without impairing the brightness of the image, and high color reproducibility can be achieved as a whole image. Further, it is possible to provide a color image display device in which white balance can be easily adjusted without impairing mounting productivity by emitting green and blue light on a single chip.

  Embodiments of the color image display device of the present invention will be described in detail below, but these are examples of embodiments of the present invention, and the present invention is not limited to these contents.

  The color image display device of the present invention is configured by combining an optical shutter, a color filter having at least three color elements of red, green, and blue corresponding to the optical shutter, and a backlight for transmitted illumination. Is. The specific configuration is not particularly limited, and examples thereof include a TFT (thin film transistor) type color liquid crystal display device in which the optical shutter shown in FIG. 1 is an optical shutter using liquid crystal.

  FIG. 1 shows an example of a TFT type color liquid crystal display device using a sidelight type backlight device and a color filter. In this liquid crystal display device, light emitted from the light source (light emitting diode) 1 is converted into a surface light source by the light guide plate 2, further increased in uniformity by the light diffusion sheet 3, and then incident on the polarizing plate 4 after passing through the prism sheet. To do. The incident light is incident on the color filter 9 by controlling the polarization direction for each pixel by the TFT 6. Finally, the polarizing plate 4 reaches the observer through the polarizing plate 10 arranged so that the polarization direction is vertical. Here, when the degree of change in the polarization direction of the incident light is changed by the voltage applied to the TFT 6, the amount of light passing through the polarizing plate 10 is changed, and a color image can be displayed. 5 and 8 are transparent substrates (glass substrates), and 7 is a liquid crystal.

The color image display apparatus of the present invention, the configuration which will be described further below, in light use efficiency Y ₁ color reproduction range of the color image display device is shown in the following when the NTSC ratio 74% 28% or more Yes, preferably 30% or more. The higher the upper limit of the light utilization efficiency Y ₁ (100%), the better, but it is usually 50% or less.

ここで、各符号、記号の定義は以下の通りである。

Here, the definition of each symbol and symbol is as follows.

Or, a color image display device of the present invention, the color reproduction range of the color image display device when the 85% NTSC ratio, in the light use efficiency Y ₂ calculated in the same manner as the light use efficiency Y ₁ is 25% or more Yes, preferably 27% or more. The upper limit of the Y ₂ are more excellent high (100%), but is usually 50%.

Or, a color image display device of the present invention, the color reproduction range of the color image display device when the 94% NTSC ratio, in the light use efficiency Y ₃ calculated in the same manner as the light use efficiency Y ₁ is 15% or more Yes, preferably 18% or more. The upper limit of the Y ₃ is more excellent high (100%), but is usually 50%.

Alternatively, in the color image display device of the present invention, when the relationship between the NTSC ratio W, which is the color reproduction range of the color image display element, and the light utilization efficiency Y is W ≧ 87, the following formula (a), preferably: It is characterized by being represented by the formula (b), more preferably the following formula (c), particularly preferably the following formula (d).
Y ≧ −0.38W + 50 (a)
Y ≧ −0.38W + 53 (b)
Y ≧ −0.38W + 56 (c)
Y ≧ −0.38W + 57 (d)

ここで、各符号、記号の定義は以下の通りである。

Here, the definition of each symbol and symbol is as follows.

  That is, in the past, it was possible to control the light utilization efficiency to some extent up to 85% of the NTSC ratio, but in a color image display device having a design exceeding the NTSC ratio of 85%, particularly an NTSC ratio of 87% or more, especially 90% or more. In light of the nature of pigments used in conventional color filter resists, phosphor emission spectra, and backlight spectra combining semiconductor light-emitting elements and phosphors, it is easy for those skilled in the art to increase the light utilization efficiency. I couldn't think of it.

  In the color image display device of the present invention, the relationship between the NTSC ratio W and the light utilization efficiency Y was set as follows.

  (I) A color image display based on the emission spectrum (actual measurement value) of a backlight in a color image display device having a NTSC ratio exceeding 85%, which is formed by a combination of a specific novel backlight and a color filter. The virtual color filter is simulated by calculation so that the NTSC ratio of the device is about 85% and 94%.

  (Ii) In the virtual color image display device having the virtual color filter simulated in (i) above, the light utilization efficiency at two points where the NTSC ratio is about 85% and 94% is calculated. In the present invention, two points of (NTSC ratio, light utilization efficiency) = (85.4%, 25.1%) and (94.2%, 21.7%) are calculated.

(Iii) The slope of the straight line connecting the two points calculated in (ii) above is defined as the slope in the relational expression between the NTSC ratio W and the light utilization efficiency Y, and the light utilization efficiency Y ₃ when the NTSC ratio is 94%. linear function fitted the color image display device of the but the present invention which is a linear function fitted the color image display device of the present invention is 15% or more formula (a), over 18% of the preferred range of the light use efficiency Y ₃ (B), a linear function passing through the actual measurement value (NTSC ratio 93.4%, light utilization efficiency 21.5%) of the color image display device actually produced by the combination of the above (i), The linear functions that pass through the simulation values (94.2%, 21.7%) of the virtual color image display device of (ii) above are calculated as equations (d).

More preferably, when the relationship between the NTSC ratio W and the light utilization efficiency Y is W ≧ 87, a color image display device represented by the following formula (e), more preferably the following formula (f) is given. be able to.
Y = −0.38W + 58 (e)
Y = −0.40W + 61 (f)
The above formulas (e) and (f) are formed by a combination of a specific new backlight and a color filter, which are different from the color image display device that is the basis for calculating the formulas (a) to (d). Further, in a color image display device having an NTSC ratio exceeding 85%, it is obtained by calculating the relationship between the NTSC ratio W and the light utilization efficiency Y in the same manner.

  FIG. 2 is a graph showing the relationship between the NTSC ratio and the light utilization efficiency, which represents the expressions (a) to (f).

In the present invention, Y, Y ₁ , Y ₂ , and Y ₃ specifically represent the relative emission distribution spectrum S (λ) of the backlight and the transmittance spectrum T (λ) of the color filter using a high luminance measuring device. It can be calculated by measuring with a spectrophotometer and applying to the above equation.

  The color image display device of the present invention is characterized by having wide color reproducibility. That is, the color image display device of the present invention is configured by combining an optical shutter, a color filter having at least three color elements of red, green, and blue corresponding to the optical shutter, and a backlight for transmitted illumination. In the color image display device, the backlight light source is a combination of a blue or deep blue LED and a phosphor, and each of the main light sources emits light in the wavelength range of 430 to 470 nm, 500 to 540 nm, and 600 to 680 nm. The color reproduction range of the color image display element is 60% or more of NTSC ratio. The NTSC ratio is preferably 70% or more.

  The color image display device of the present invention has a color temperature of usually 5,000 to 10,000K, preferably 5,500 to 9,500K, more preferably 6,000 to 9,000K. If the color temperature is too low, the entire image will be reddish. On the other hand, if the color temperature is too high, the luminance is lowered.

[1] Backlight Device First, the configuration of the backlight device used in such a color liquid crystal display device will be described.

  The backlight device used in the present invention refers to a planar light source device that is disposed on the back surface of a liquid crystal panel and is used as a back light source means of a transmissive or transflective color liquid crystal display device.

  The configuration of the backlight device includes an LED that emits white light and a light uniformizing unit that converts the light source light into a substantially uniform surface light source.

  As a light source installation method, a light source is disposed directly under the back surface of the liquid crystal element (directly under method), or a light source is disposed on the side surface to transmit light using a translucent light guide such as an acrylic plate. A method of obtaining a surface light source by converting into a shape (side light method) is representative. Among them, as a surface light source that is thin and excellent in luminance distribution uniformity, a sidelight system as shown in FIGS. 3 and 4 is suitable, and is currently most widely used.

  In the backlight device of FIG. 3, the light emitting diode 1 is disposed along the side end surface 11a on the one end surface 11a of the light guide 11 that is a light-transmitting flat plate. The light guide 11 is made incident from the side end face 11a. One plate surface 11b of the light guide 11 is used as a light emitting surface, and a light control sheet 13 having a substantially triangular prism-shaped array 12 formed on the light emitting surface 11b, the apex angle of the array 12 is observed by an observer. It is arranged toward the side. A light extraction mechanism 14 formed by printing and forming a large number of dots 14a in a predetermined pattern with light scattering ink is provided on a plate surface 11c opposite to the light emitting surface 11b in the light guide 11. On the plate surface 11c side, a reflection sheet 15 is disposed adjacent to the plate surface 11c.

  In the backlight device of FIG. 4, a light control sheet 13 in which a substantially triangular prism-like prism array 12 is formed is arranged with the apex angle of the array 12 facing the light output surface 11 b side of the light guide 11. Further, the light extraction mechanism 14 ′ provided on the plate surface 11c opposed to the light emitting surface 11b of the light guide 11 is constituted by a rough surface pattern 14b in which each surface is formed into a rough surface. Different from the backlight device shown in FIG.

  With such a sidelight type backlight device, it is possible to more effectively bring out the characteristics of a liquid crystal display device that is lightweight and thin.

  As a light source of the backlight device of the present invention, an LED (hereinafter also referred to as a light emitting diode) may be included in the structure. In general, any light source may be used as long as it emits light in the red, green, and blue wavelength regions, that is, in the range of 580 to 700 nm, 500 to 550 nm, and 400 to 480 nm.

  In order for the backlight to satisfy such conditions, the light source is a combination of a blue or deep blue LED and a phosphor, and the red region (usually 600 nm or more, preferably 610 nm or more, more preferably 620 nm or more, Usually 680 nm or less, preferably 670 nm or less), green region (usually 500 nm or more, preferably 510 nm or more, usually 540 nm or less, preferably 535 nm or less, more preferably 530 nm or less, particularly preferably 525 nm or less, particularly preferably 520 nm or less region), blue region (usually 430 nm or more, preferably 440 nm or more, usually 470 nm or less, preferably 460 nm or less), so that each wavelength region has one or more main components of light emission. There is a way to adjust.

  The amount of light in each of the red, green, and blue regions in the transmissive or transflective transmission mode is determined by the product of the light emission from the backlight and the spectral transmittance of the color filter. Therefore, it is necessary to select a backlight that satisfies the conditions described later in the section (c) Colorant of the color filter composition.

  Although the specific example of the backlight apparatus of this invention is described below, if the backlight light source of this invention satisfy | fills the above-mentioned conditions, it will not be limited to this.

  The light source is preferably a blue or deep blue LED. The emission wavelength of the light source is usually 440 nm or more, preferably 450 nm or more, and usually 490 nm or less, preferably 480 nm. Blue or deep blue LEDs are preferably used in that a light source with high luminous efficiency can be obtained.

  As the light source, for example, an InGaN-based, GaAlN-based, InGaAlN-based, ZnSeS-based semiconductor or the like that is crystal-grown on a substrate of silicon carbide, sapphire, gallium nitride, or the like by MOCVD or the like is suitable. In order to achieve high output, the light source size may be increased or the number of light sources may be increased. Further, it may be an edge emitting type or a surface emitting type laser diode.

  The frame for fixing the light source has at least positive and negative electrodes for energizing the light source. When a concave cup is provided on the frame and a light source is arranged on the bottom surface thereof, the emitted light can be given directivity and light can be used effectively. Also, by plating the inner surface or the entire recess of the frame with a highly reflective metal such as silver, platinum, or aluminum, or an equivalent alloy, the reflectance in the entire visible light range can be increased, and the light utilization efficiency can be increased. So even better. The same effect can be obtained even if the surface of the concave portion of the frame or the entire surface is made of a resin for injection molding containing a highly reflective substance such as white glass fiber, alumina powder or titania powder.

  For fixing the light source, epoxy-based, imide-based, acrylic-based adhesives, solders such as AuSn and AgSn, bumps such as Au, and the like can be used.

  When the light source is energized through the adhesive, it is preferable to apply a thin and uniform coating containing a conductive filler such as silver fine particles, such as silver paste or carbon paste. Also, soldering is effective for large current type light emitting diodes and laser diodes where heat dissipation is particularly important. In addition, any adhesive may be used for fixing in the case of a light source that is not energized through an adhesive, but silver paste or solder is still preferable in view of heat dissipation.

  When a plurality of light sources are used, the use of solder is not preferable because the light source must be repeatedly exposed to a high temperature or exposed for a long time, and the life of the light source may be deteriorated. On the other hand, when bumps are used, it is possible to work at a temperature lower than that of solder, and bonding can be easily and reliably performed. In particular, when a flip-chip type LED is used, an adhesive of silver paste may cause the p-type and n-type electrodes to be short-circuited.

  The light source and the electrode of the frame are connected by wire bonding. As the wire, a gold or aluminum wire having a diameter of 20 to 40 μm is used. As a method of connecting the light source and the electrode of the frame, there is a flip chip mounting method without using a wire.

  The phosphor that emits the blue band, the phosphor that emits the green band, and the phosphor that emits the red band are mixed in a transparent binder such as an epoxy resin or a silicone resin and applied to the light emitting diode. The mixing ratio may be appropriately changed so as to obtain a desired chromaticity. Further, the phosphor emitting the blue band, the phosphor emitting the green band, and the phosphor emitting the red band may be separately applied to the light emitting diode. When a diffusing agent is further added to the transparent binder, the emitted light can be made more uniform. The diffusing agent is preferably a colorless substance having an average particle size of 100 nm to several tens of μm. Alumina, zirconia, yttria and the like are more preferable because they are stable in a practical temperature range of −60 to 120 ° C. A higher refractive index is more preferable because the effect of the diffusing agent is increased. Further, when a phosphor having a large particle size is used, it is preferable to use an anti-settling agent because color unevenness or color misregistration is likely to occur due to sedimentation of the phosphor. As an anti-settling agent, fumed silica is generally used.

  When the completed light emitting device is energized, the light emitting diode first emits blue or deep blue light. The phosphor absorbs part of it and emits light in the green or red band. As the light emitted from the light emitting device, the original blue band of the light emitting diode is mixed with the green band and the red band that have been wavelength-converted by the phosphor, and approximately white light is obtained.

[2] Phosphor Next, the phosphor will be described. In the color image display device of the present invention, it is preferable that the above-mentioned backlight has a phosphor layer or a phosphor film, and the phosphor layer or phosphor film uses the following phosphors.

[2-1] Red phosphor The red phosphor used in the phosphor layer or phosphor film used in the color image display device of the present invention has an emission peak wavelength in the wavelength range of 620 nm ≦ λ _n ≦ 680 nm. It is possible to use various phosphors. As a red phosphor for realizing such an image with high color purity, a phosphor activated with europium is preferable. Examples of phosphors activated with europium include nitride phosphors, oxynitride phosphors, sulfide phosphors, and oxysulfide phosphors. Among these, nitride phosphors and oxynitride phosphors are preferable. .
Further, among nitride phosphors and oxynitride phosphors, nitride phosphors including activating element M ¹ , divalent metal element M ² , and tetravalent metal element M ⁴ including at least Si, oxynitride A phosphor is preferred.

  Hereinafter, specific examples of the red phosphor preferably used will be described.

[2-1-1] Nitride phosphor and oxynitride phosphor Specific examples of the nitride phosphor and the oxynitride phosphor according to the present invention include an activating element M ¹ and a divalent metal element M ^2. A trivalent metal element M ³ and a tetravalent metal element M ⁴ containing at least Si can be included, and includes a compound represented by the following general formula (1A) based on a nitride or oxynitride Examples include phosphors.

_{^{M 1 a M 2 b M 3}} c M 4 d N e O f (1A)
(However, a, b, c, d, e, and f are values in the following ranges, respectively.

0.00001 ≦ a ≦ 0.15
a + b = 1
0.5 ≦ c ≦ 1.5
0.5 ≦ d ≦ 1.5
2.5 ≦ e ≦ 3.5
0 ≦ f ≦ 0.5
As the activator element M ¹ , various light-emitting ions that can be contained in a crystal matrix constituting a phosphor having a nitride or oxynitride as a matrix can be used, but Cr, Mn, Fe, Ce, Pr It is preferable to use one or more elements selected from the group consisting of Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb because a phosphor with high emission characteristics can be produced. The activator element M ¹ preferably contains one or more of Mn, Ce, Pr and Eu, and particularly contains Ce and / or Eu to obtain a phosphor exhibiting high-luminance red light emission. More preferable, and Eu is particularly preferable. Further, in order to provide a variety of functions such as to impart the or phosphorescent increasing the brightness, even if one or more is contained coactivated element other than Ce and / or Eu as activator elements M ¹ good.

The elements other than the activating element ^{M 1,} divalent various trivalent, but tetravalent metal elements may be used, the divalent metal elements ^{M 2} is Mg, Ca, Sr, Ba, and from Zn one or more elements selected from the group consisting of trivalent metal elements M ³ is Al, Ga, in, and at least one element selected from the group consisting of Sc, tetravalent metal elements M4 including at least Si One or more elements selected from the group consisting of Si, Ge, Sn, Ti, Zr, and Hf are preferable because a phosphor with high emission characteristics can be obtained.

Also preferred since divalent and 50 mol% or more of the metal elements M ² to adjust the composition so that the Ca and / or Sr emission characteristics of high phosphor obtained, more than 80 mole% of M ² Ca And / or Sr, more preferably 90 mol% or more is Ca and / or Sr, and most preferably all M ² is Ca and / or Sr.

Also, if more than 50 mol% of the divalent metal elements M ² to adjust the composition so that Ca, is preferred because a good phosphor color purity and long emission wavelength of the phosphor is obtained, M ² More preferably, 80 mol% or more of Ca is Ca, more preferably 90 mol% or more is Ca, and most preferably all M ² is Ca.

Further, it is preferable to adjust the composition so that 50 mol% or more of the trivalent metal element M ³ is Al, because a phosphor having high emission characteristics can be obtained. However, 80 mol% or more of M ³ is preferably Al. Preferably, 90 mol% or more is more preferably Al, and most preferably all M ³ is Al.

Further, it is preferable to adjust the composition so that at least 50 mol% of the tetravalent metal element M ⁴ containing Si becomes Si, so that a phosphor with high emission characteristics can be obtained. However, 80 mol% or more of M ⁴ is preferably Si mol. More preferably, 90 mol% or more is Si, and all M ⁴ is preferably Si.

  In particular, 50 mol% or more of the divalent metal element M2 is Ca and / or Sr, and 50 mol% or more of the trivalent metal element M3 is Al, and a tetravalent metal containing at least Si. It is preferable that 50 mol% or more of the element M4 is Si because a phosphor having particularly high emission characteristics can be manufactured.

  In addition, the reason why the numerical range of a to f in the general formula (1A) is preferable is as follows.

  When a is smaller than 0.00001, sufficient light emission intensity tends to be not obtained, and when a is larger than 0.15, concentration quenching increases and the light emission intensity tends to decrease. Accordingly, the raw materials are mixed so that a is in the range of 0.00001 ≦ a ≦ 0.15. For the same reason, 0.0001 ≦ a ≦ 0.1 is preferable, 0.001 ≦ a ≦ 0.05 is more preferable, 0.002 ≦ a ≦ 0.04 is further preferable, and 0.004 ≦ a ≦ 0. .02 is most preferred.

Also, when using Eu as activator elements M ^1, in order to improve the red color purity and long emission wavelength of the phosphor is preferably 0.005 ≦ a ≦ 0.1, 0 .01 ≦ a ≦ 0.05 is more preferable, and 0.015 ≦ a ≦ 0.04 is even more preferable.

the sum of a and b, since the activator elements M ¹ in the crystal matrix of the phosphor replaces the atom positions of the metal element M2, to adjust the raw material mixed composition to be 1.

  When c is smaller than 0.5 or when c is larger than 1.5, a heterogeneous phase is produced during production, and the yield of the phosphor tends to be low. Therefore, the raw materials are mixed so that c is in the range of 0.5 ≦ c ≦ 1.5. From the viewpoint of emission intensity, 0.5 ≦ c ≦ 1.5 is preferable, 0.6 ≦ c ≦ 1.4 is more preferable, and 0.8 ≦ c ≦ 1.2 is most preferable.

  Whether d is smaller than 0.5 or d is larger than 1.5, a heterogeneous phase is produced during production, and the yield of the phosphor tends to be low. Accordingly, the raw materials are mixed so that d is in the range of 0.5 ≦ d ≦ 1.5. From the viewpoint of light emission intensity, 0.5 ≦ d ≦ 1.5 is preferable, 0.6 ≦ d ≦ 1.4 is more preferable, and 0.8 ≦ d ≦ 1.2 is most preferable.

  e is a coefficient indicating the nitrogen content;

となる。この式に０．５≦ｃ≦１．５，０．５≦ｄ≦１．５を代入すれば、ｅの範囲は
１．８４≦ｅ≦４．１７
となる。しかしながら、前記一般式（１Ａ）で表される蛍光体組成において、窒素の含有量を示すｅが２．５未満であると蛍光体の収率が低下する傾向にある。また、ｅが３．５を超えても蛍光体の収率が低下する傾向にある。従って、ｅは通常２．５≦ｅ≦３．５である。

It becomes. If 0.5 ≦ c ≦ 1.5 and 0.5 ≦ d ≦ 1.5 are substituted into this equation, the range of e is 1.84 ≦ e ≦ 4.17.
It becomes. However, in the phosphor composition represented by the general formula (1A), if the e indicating the nitrogen content is less than 2.5, the yield of the phosphor tends to decrease. Even if e exceeds 3.5, the yield of the phosphor tends to decrease. Therefore, e is usually 2.5 ≦ e ≦ 3.5.

The oxygen in the phosphor represented by the general formula (1A) may be mixed as an impurity in the raw metal, or may be introduced during a manufacturing process such as a pulverization process or a nitriding process. The ratio of oxygen f is preferably in the range of 0 ≦ f ≦ 0.5 within a range in which a decrease in the light emission characteristics of the phosphor is acceptable. When Eu is used as the activating element M ¹ , 0 ≦ f ≦ 0.2 is preferable and 0 ≦ f in order to increase the emission wavelength of the phosphor and improve the red color purity. ≦ 0.15 is more preferable, and 0 ≦ f ≦ 0.1 is particularly preferable.

  Among the phosphors represented by the general formula (1A), a phosphor represented by the following general formula (1B) can be used.

M ^{1 ′} _{a ′} Sr _{b ′} Ca _{c ′} M ^{2 ′} _{d ′} Al _{e ′} Sif _′ N _{g ′} (1B)
(However, a ′, b ′, c ′, d ′, e ′, f ′, and g ′ are values in the following ranges, respectively.
0.00001 ≦ a ′ ≦ 0.15
0 ≦ b ′ ≦ 0.99999
0 ≦ c ′ <1
0 ≦ d ′ <1
a ′ + b ′ + c ′ + d ′ = 1
0.5 ≦ e ′ ≦ 1.5
0.5 ≦ f ′ ≦ 1.5
0.8 × (2/3 + e ′ + 4/3 × f ′) ≦ g ′ ≦ 1.2 × (2/3 + e ′ + 4/3 × f ′))
Here, M ^{1 ′} is a group consisting of Cr, Mn, Fe, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb, similarly to M ¹ in the general formula (1A). Represents an activation element selected from Among them, the activator element M ^{1 ′} preferably includes one or more of Mn, Ce, Pr, and Eu, particularly preferably Eu and / or Ce, and particularly preferably Eu.

M ^{2 ′} represents Mg and / or Ba, and is preferably Mg. Inclusion of Mg can increase the emission wavelength of the phosphor.

  When a 'is smaller than 0.00001, sufficient light emission intensity tends to be not obtained, and when a' is larger than 0.15, concentration quenching increases and the light emission intensity tends to decrease. Accordingly, the raw materials are mixed so that a ′ is in the range of 0.00001 ≦ a ′ ≦ 0.15. For the same reason, 0.0001 ≦ a ′ ≦ 0.1 is preferable, 0.001 ≦ a ′ ≦ 0.05 is more preferable, 0.002 ≦ a ′ ≦ 0.04 is further preferable, and 0.004 ≦ Most preferably, a ′ ≦ 0.02.

Also, when using Eu as activator elements M ^1, in order to improve the red color purity and long emission wavelength of the phosphor is preferably 0.005 ≦ a '≦ 0.1, 0.01 ≦ a ′ ≦ 0.05 is more preferable, and 0.015 ≦ a ′ ≦ 0.04 is even more preferable.

  The range of b ′ is usually 0 ≦ b ′ ≦ 0.99999. If b ′ is large, the emission wavelength of the phosphor tends to be shortened.

  The range of c ′ is normally 0 ≦ c ′ <1. Preferably 0.1 ≦ c ′ <1, more preferably 0.15 ≦ c ′ <1. If this value is too small, the structure tends to be unstable.

  The range of d is usually 0 ≦ d ′ <1, preferably 0 ≦ d ′ ≦ 0.5, and more preferably 0 ≦ d ′ ≦ 0.2.

The relationship between a ′, b ′, c ′, d ′ is usually
a ′ + b ′ + c ′ + d ′ = 1
Satisfied.
The range of e ′ is usually 0.5 ≦ e ′ ≦ 1.5, preferably 0.8 ≦ e ′ ≦ 1.2, and more preferably 0.9 ≦ e ′ ≦ 1.1.

  The range of f ′ is usually 0.5 ≦ f ′ ≦ 1.5, preferably 0.8 ≦ f ′ ≦ 1.2, and more preferably 0.9 ≦ f ′ ≦ 1.1.

  The range of g ′ is usually 0.8 (2/3 + e ′ + 4/3 × f ′) ≦ g ′ ≦ 1.2 × (2/3 + e ′ + 4/3 × f ′), preferably 0.8. 9 × (2/3 + e ′ + 4/3 × f ′) ≦ g ′ ≦ 1.1 × (2/3 + e ′ + 4/3 × f ′), more preferably 2.5 ≦ g ′ ≦ 3.5 is there.

  Oxygen contained in the phosphor of the present invention may be mixed as an impurity in the raw metal, or mixed during a manufacturing process such as a pulverization process or a nitriding process.

  The oxygen content is usually 5% by weight or less, preferably 2% by weight or less, and most preferably 1% by weight or less as long as the reduction in the light emission characteristics of the phosphor is acceptable.

[2-1-2] Other nitride phosphors As specific examples of other nitride phosphors, nitride silicate type MxSiyNz: Eu [where M is selected from the group consisting of Ca, Sr, and Ba. And a phosphor emitting yellow to red, characterized by having a host lattice of at least one alkaline earth metal or Zn, and z = 2 / 3x + 4 / 3y].

  Preferably, the phosphor is of the type where x = 2 and y = 5. In another preferred embodiment, the phosphor is of the type where x = 1 and y = 7.

  Preferably, the metal M in the phosphor is strontium because the resulting phosphor emits a relatively short wavelength from yellow to red. Thus, the efficiency is much higher compared to most of the other selected metals M.

  In another embodiment, the phosphor uses a mixture of different metals as component M, for example Ca (10 atomic%) together with Ba (balance).

  These materials exhibit high absorption and good excitation, high quantum efficiency and low temperature quenching up to 100 ° C. in the UV and blue visible spectrum (up to 450 nm).

  Specific examples of the phosphor according to the present invention include known phosphors described in, for example, JP-T-2003-515655, JP-A-2005-11705, and the like.

[2-1-3] Sulfide phosphor A specific example of the sulfide phosphor includes a compound represented by the general formula (1C).

_{Eu h Ca i Sr j M k} S l ...... (1C)
Here, M represents at least one element selected from Ba, Mg, and Zn, and h to l are values in the following ranges, respectively.

0.0002 ≦ h ≦ 0.02
0.3 ≦ i ≦ 0.9998
d is 0 ≦ j ≦ 0.1
h + i + j + k = 1
0.9 ≦ l ≦ 1.1
From the viewpoint of thermal stability, the preferable range of the chemical formula amount h of Eu in the formula (1C) is preferably in the range of 0.0002 ≦ h ≦ 0.02, and in the range of 0.0004 ≦ h ≦ 0.02. Is more preferable.

  From the viewpoint of temperature characteristics, the preferable range of the chemical formula amount h of Eu in the formula (1C) is preferably 0.0004 ≦ h ≦ 0.01, and 0.0004 ≦ h ≦ 0.007. More preferably, the range of 0.0004 ≦ h <0.005 is more preferable, and the range of 0.0004 ≦ h ≦ 0.004 is more preferable.

From the viewpoint of emission intensity, the preferable range of the chemical formula amount h of Eu in the formula (1C) is preferably 0.0004 ≦ h ≦ 0.02, and 0.001 ≦ h ≦ 0.008. More preferred. If the content of the luminescent center ion Eu ²⁺ is too small, the luminescence intensity tends to decrease, whereas if too much, the luminescence intensity tends to decrease due to a phenomenon called concentration quenching.

  Speaking of a preferable range of the chemical formula amount h of Eu in the formula (1C) that has all of thermal stability, temperature characteristics, and emission intensity, a range of 0.0004 ≦ h ≦ 0.004 is preferable, and 0.001 ≦ The range of h ≦ 0.004 is more preferable.

In the basic crystal Eu _h Ca _i Sr _j M _k S ₁ of the general formula (1C), the molar ratio of the cation site occupied by Eu, Ca, Sr or M and the anion site occupied by S is 1: 1. Even if some cation deficiency or anion deficiency occurs, there is no significant influence on the fluorescence performance for this purpose. Therefore, the molar ratio l of the anion sites occupied by S is in the range from 0.9 to 1.1. The basic crystals can be used.

  In the chemical substance of the general formula (1C), M representing at least one element selected from Ba, Mg, and Zn is not necessarily an essential element for the present invention, but 0 ≦ k ≦ 0. Even if it is contained in the chemical substance of the general formula (1C) at a ratio of 1, the object of the present invention can be achieved.

  Even if an element other than Eu, Ca, Sr, Ba, Mg, Zn, and S is contained in the chemical substance of the general formula (1C) in an amount of 1% by weight or less as an impurity, there is no problem in use.

[2-2] Green phosphor The green phosphor used in the phosphor layer or phosphor film used in the color image display device of the present invention has an emission peak wavelength in the wavelength range of 500 nm ≦ λ _n ≦ 530 nm. It is possible to use various phosphors. The green phosphor for realizing such an image with high color purity preferably includes a phosphor activated with cerium and / or europium. Among the phosphors activated with cerium and / or europium, oxide phosphors, nitride phosphors, and oxynitride phosphors can be mentioned. Among them, oxide phosphors activated with cerium and europium are preferred. Activated oxide phosphors and oxynitride phosphors are preferred.

  Moreover, it is preferable that the crystal structure of the phosphor has a garnet crystal structure because it tends to be excellent in terms of heat resistance and the like.

Hereinafter, specific examples of preferably used green phosphors will be described.
[2-2-1] As a specific example, the phosphor layer or the phosphor film contains a crystal phase represented by the following general formula (2A), and the object color is L ^* a ^* b ^* color system. In the case of
L ^* ≧ 90,
a ^* ≦ −20,
b ^* ≧ 30, and
{A ^* / b ^* } ≦ −0.45
The compound characterized by satisfy | filling is mentioned.

(M ^I _(1-x) M ^II x) _α SiO _β (2A)
(In the general formula (2A), M ^I represents one or more elements selected from the group consisting of Ba, Ca, Sr, Zn and Mg. M ^II takes a divalent and trivalent valence. It represents one or more metal elements that may. However, the molar ratio of divalent element is 0.5 or more to the whole M ^II, is 1 or less.
x, α and β are each
0.01 ≦ x <0.3,
1.5 ≦ α ≦ 2.5, and
3.5 ≦ β ≦ 4.5
Represents a number that satisfies ).

In the general formula (2A), M ^I represents one or more elements selected from the group consisting of Ba, Ca, Sr, Zn and Mg. As M ^I , any one of these elements may be contained alone, or two or more may be contained in any combination and ratio.

Among them, ^{M I} preferably contains at least Ba. In this case, the molar ratio of Ba to the total ^{M I} is usually 0.5 or more and preferably 0.55 or more, further 0.6 or more, particularly 0.7 or more, particularly 0.8 or more, particularly 0.9 or more, Moreover, it is usually less than 1, preferably 0.97 or less, more preferably 0.95 or less, and further preferably 0.93 or less. If the molar ratio of Ba is too low, the emission peak wavelength tends to shift to the longer wavelength side and the light emission efficiency tends to decrease. On the other hand, if the molar ratio of Ba is too high, the emission peak wavelength tends to shift to the short wavelength side and the green color purity tends to decrease.

In particular, M ^I preferably contains at least Ba and Sr. Here, when the respective molar ratios of Ba and Sr for the entire ^{M I} [Ba] and [Sr], the ratio of [Ba] to the total of [Ba] and [Sr], i.e., [Ba] / ([Ba ] + [Sr]) is usually larger than 0.5, especially 0.6 or more, more preferably 0.65 or more, further 0.7 or more, especially 0.8 or more, especially 0.9 or more. Also, it is usually 1 or less, preferably 0.9 or less, more preferably 0.95 or less, and further preferably 0.93 or less. If the value of [Ba] / ([Ba] + [Sr]) is too small (that is, the ratio of Ba is too small), the emission peak wavelength of the phosphor obtained shifts to the long wavelength side, and the half-value width is Since it tends to increase, it is not preferable. On the other hand, if the value of [Ba] / ([Ba] + [Sr]) is too large (that is, the ratio of Ba is too large), the emission peak wavelength is shifted to the short wavelength side and the green color purity is lowered. Since there is a tendency, it is not preferable.

  Further, the relative ratio between [Ba] and [Sr], that is, the value represented by [Ba] / [Sr] is usually larger than 1, especially 1.2 or more, further 1.5 or more, especially 1. It is preferably 8 or more, particularly 2.5 or more, particularly 4 or more, particularly 10 or more, and usually 35 or less, especially 20 or less, especially 15 or less, especially 13 or less. If the value of [Ba] / [Sr] is too small (ie, the ratio of Ba is too small), the emission peak wavelength of the obtained phosphor tends to shift to the longer wavelength side, and the half-value width tends to increase. It is not preferable. On the other hand, if the value of [Ba] / [Sr] is too large (that is, the ratio of Ba is too large), the emission peak wavelength tends to shift to the short wavelength side and the green color purity tends to decrease, which is not preferable. .

In the general formula (2A), when M ^I contains at least Sr, a part of Sr is preferably substituted with Ca. In this case, the amount of substitution with Ca is a value of the molar ratio of the amount of substitution of Ca with respect to the total amount of Sr, and is usually 10% or less, preferably 5% or less, more preferably 2% or less. When the ratio of the substitution amount with Ca is too high, the light emission efficiency tends to decrease.

  Further, Si may be partially substituted by other elements such as Ge. However, from the standpoint of green emission intensity and the like, it is preferable that the ratio of Si substituted by other elements is as low as possible. Specifically, other elements such as Ge may be contained in an amount of 20 mol% or less of Si, and it is more preferable that all are made of Si.

In the general formula (2A), M ^II is intended listed as an activator element, a divalent and at least one metal element can take the trivalent valence. Specific examples include transition metal elements such as Cr and Mn; rare earth elements such as Eu, Sm, Tm, and Yb. The M ^II, may contain any one of these elements alone or may also be having both of two or more kinds in any combination and in any ratio. Among ^them, as the ^{M II} Sm, Eu, Yb are preferred, Eu is particularly preferable. The molar ratio of the divalent element to the entire M ^II (total of divalent element and trivalent element) is usually 0.5 or more, preferably 0.7 or more, more preferably 0.8 or more, Usually, it is less than 1, and the closer to 1, the better. If the molar ratio of the divalent element to the entire M ^II is too low, the light emission efficiency tends to decrease. This is because a divalent element and a trivalent element are taken into the crystal lattice, but it is considered that the trivalent element absorbs emission energy in the crystal.

In the general formula (2A), x is a number representing the number of moles of M ^II , and specifically, is usually 0.01 or more, preferably 0.03 or more, more preferably 0.04 or more, particularly preferably. Represents a number of 0.05 or more, usually less than 0.3, preferably 0.2 or less, more preferably 0.15 or less. If the value of x is too small, the emission intensity tends to be small. On the other hand, if the value of x is too large, the emission intensity tends to decrease.

  In the general formula (2A), α is preferably close to 2, but usually 1.5 or more, preferably 1.8 or more, more preferably 1.9 or more, and usually 2.5 or less, preferably It represents a number in the range of 2.2 or less, more preferably 2.1 or less. If the value of α is too small or too large, heterogeneous crystals appear and the light emission characteristics tend to deteriorate.

  In the general formula (2A), β is usually 3.5 or more, preferably 3.8 or more, more preferably 3.9 or more, and usually 4.5 or less, preferably 4.4 or less, more preferably Represents a number in the range of 4.1 or less. If the value of β is too small or too large, heterogeneous crystals appear and the light emission characteristics tend to deteriorate.

  Specific examples of preferred compositions of the phosphor according to the present invention are listed in Table 1 below, but the composition of the phosphor of the present invention is not limited to the following examples.

Further, among the phosphors represented by the general formula (2A), the relative ratio of [Ba] and [Sr], the ratio of [Ba] to the sum of [Ba] and [Sr], the mole of M ^II When the number x representing the number is in the following range, an image display apparatus having a relatively short emission peak wavelength, a narrow half-value width, a high luminance, and a wide color reproduction range can be realized. is there.

  The relative ratio between [Ba] and [Sr], that is, the value represented by [Ba] / [Sr] is 8.5 or more, especially 9 or more, particularly 10 or more, and 100 or less, especially 50 or less, The range of 25 or less is particularly preferable. If the value of [Ba] / [Sr] is too small (that is, the ratio of Ba is too small), the emission peak wavelength of the phosphor tends to shift to the longer wavelength side and the half-value width tends to increase. On the other hand, if the value of [Ba] / [Sr] is too large (that is, the ratio of Ba is too large), the emission peak wavelength of the phosphor tends to shift to the short wavelength side.

  Further, the ratio of [Ba] to the sum of [Ba] and [Sr], that is, the value represented by [Ba] / ([Ba] + [Sr]) is greater than 0.5, and more than 0.8. Further, it is preferably 0.9 or more, and less than 1, especially 0.98 or less, particularly 0.97 or less. If the value of [Ba] / ([Ba] + [Sr]) is too small (that is, the ratio of Ba is too small), the emission peak wavelength of the phosphor shifts to the longer wavelength side, and the half-value width increases. Tend. On the other hand, if the value of [Ba] / ([Ba] + [Sr]) is too large (that is, the ratio of Ba is too large), the emission peak wavelength of the phosphor tends to shift to the short wavelength side.

  Further, x is a number of 0.04 or more, more preferably 0.05 or more, particularly preferably 0.06 or more, and 0.3 or less, preferably 0.2 or less, more preferably 0.15 or less. Represent. If the value of x is too small, the emission intensity tends to decrease. On the other hand, if the value of x is too large, the emission intensity tends to decrease.

Another feature of the phosphor according to the present invention is that when the object color is represented by the L ^* a ^* b ^* color system, the a ^* value and the b ^* value satisfy the following expressions: .
L ^* ≧ 90
a ^* ≦ −20
b ^* ≧ 30
{A ^* / b ^* } ≦ −0.45
When the phosphor according to the present invention has an object color that satisfies the above conditions, a light emitting device with high luminous efficiency can be realized when used in a light emitting device described later.

Specifically, the upper limit value of a ^* of the phosphor according to the present invention is usually −20 or less, preferably −22 or less, and more preferably −24 or less. A phosphor in which a ^* is too large is not preferable because the total luminous flux tends to be small. Also, from the viewpoint of increasing luminance, it is desirable that the value of a ^* is small.

The b ^* of the phosphor according to the present invention is usually 30 or more, preferably 33 or more. If b ^* is too small, the luminance tends to decrease, which is not preferable. On the other hand, the upper limit of b ^* is theoretically 200 or less, but is usually preferably 120 or less. If b ^* is too large, the emission wavelength tends to shift to the longer wavelength side and the luminance tends to decrease, which is not preferable.

The ratio of a ^* and b ^* of the phosphor according to the present invention, that is, the value represented by a ^* / b ^* is usually −0.45 or less, preferably −0.5 or less, more preferably − The range is 0.55 or less. If the value of a ^* / b ^* is too large, the object color is yellowish and the luminance tends to decrease, which is not preferable.

The L ^* of the phosphor according to the present invention is usually 90 or more, preferably 95 or more. If the value of L ^* is too small, the emission tends to be weak, which is not preferable. On the other hand, the upper limit value of L ^* generally does not exceed 100 because it deals with an object that does not emit light by irradiation light, but the phosphor according to the present invention emits light generated by being excited by irradiation light. Since it is superimposed on the reflected light, the value of L ^* may exceed 100. Specifically, the upper limit value of L ^* of the phosphor of the present invention is usually 115 or less.

  In addition, the measurement of the object color of the phosphor according to the present invention can be performed by using, for example, a commercially available object color measurement device (for example, CR-300 manufactured by Minolta).

[2-2-2] Another specific example is a compound in which the phosphor layer or the phosphor film is represented by the following general formula (2B).
_{M1 x Ba y M2 z L u} O v N w (2B)
(In the general formula (2B), M1 is at least one kind selected from the group consisting of Cr, Mn, Fe, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm and Yb. Represents an active element, M2 represents at least one divalent metal element selected from Sr, Ca, Mg and Zn, and L represents a metal element selected from metal elements belonging to Group 4 or Group 14 of the periodic table. X, y, z, u, v, and w are numerical values in the following ranges, respectively.
0.00001 ≦ x ≦ 3
0 ≦ y ≦ 2.99999
2.6 ≦ x + y + z ≦ 3
0 <u ≦ 11
6 <v ≦ 25
0 <w ≦ 17)
In the general formula (2B), M1 is an activation element.

  M1 includes at least one kind of transition metal element or rare earth element selected from the group consisting of Cr, Mn, Fe, Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm and Yb in addition to Eu. It is done. As M1, any one of these elements may be contained alone, or two or more may be contained in any combination and ratio. Among these, in addition to Eu, Ce, Sm, Tm or Yb, which are rare earth elements, can be mentioned as preferable elements. Among them, the M1 is preferably one containing at least Eu or Ce from the viewpoint of light emission quantum efficiency. Among them, in particular, those containing at least Eu are more preferable in terms of emission peak wavelength, and it is particularly preferable to use only Eu.

The activator element M1 is present as a divalent cation and / or a trivalent cation in the phosphor of the present invention. At this time, it is preferable that the activation element M1 has a higher abundance ratio of divalent cations. When M1 is Eu, specifically, the ratio of Eu ^{2+ to} the total Eu amount is usually 20 mol% or more, preferably 50 mol% or more, more preferably 80 mol% or more, particularly preferably 90 mol%. That's it.

In addition, the ratio of Eu < ²⁺ > in the total Eu contained in the phosphor of the present invention can be examined, for example, by measuring the X-ray absorption fine structure (X-ray Absorption Fine Structure). That is, when the L3 absorption edge of Eu atom is measured, Eu ²⁺ and Eu ³⁺ show separate absorption peaks, and the ratio can be quantified from the area. Further, the ratio of Eu ^{2+ in} the total Eu contained in the phosphor of the present invention can also be known by measuring electron spin resonance (ESR).

  In the general formula (2B), x is a numerical value in the range of 0.00001 ≦ x ≦ 3. Among these, x is preferably 0.03 or more, more preferably 0.06 or more, and particularly preferably 0.12 or more. On the other hand, if the content ratio of the activating element M1 is too large, concentration quenching may occur. Therefore, it is preferably 0.9 or less, more preferably 0.7 or less, and particularly preferably 0.45 or less.

  Moreover, the phosphor of the present invention can substitute the position of Ba with Sr, Ca, Mg and / or Zn while maintaining the BSON phase crystal structure. Therefore, in the general formula (2B), M2 represents at least one divalent metal element selected from Sr, Ca, Mg, and Zn. In this case, M2 is preferably Sr, Ca and / or Zn, more preferably Sr and / or Ca, and further preferably Sr. Further, Ba and M2 may be partially substituted with these ions.

  In addition, as said M2, any one of these elements may be contained independently and you may have 2 or more types together by arbitrary combinations and ratios.

  In the substitution with the Ca ions, the ratio of Ca to the total amount of Ba and Ca is preferably 40 mol% or less. If the Ca content is increased more than this, the emission wavelength may become longer and the emission intensity may be reduced.

  In the substitution with the Sr ions, the ratio of Sr to the total amount of Ba and Sr is preferably 50 mol% or less. If the amount of Sr increases more than this, the emission wavelength may become longer and the emission intensity may decrease.

  In the substitution with Zn ions, the abundance ratio of Zn with respect to the total amount of Ba and Zn is preferably 60 mol% or less. If the Zn content is increased more than this, the emission wavelength may become longer and the emission intensity may be reduced.

  Therefore, in the general formula (2B), the amount of z may be set according to the type of the metal element M2 to be substituted and the amount of y. Specifically, in the general formula (2B), y is a numerical value in the range of 0 ≦ y ≦ 2.9999. In the general formula (2B), x + y + z is 2.6 ≦ x + y + z ≦ 3.

  In the phosphor of the present invention, the Ba or M2 element may be lost together with oxygen or nitrogen. For this reason, in the general formula (2B), the value of x + y + z may be less than 3, and x + y + z can normally take a value of 2.6 ≦ x + y + z ≦ 3, but ideally x + y + z = 3. It is.

  The phosphor of the present invention preferably contains Ba from the viewpoint of the stability of the crystal structure. Accordingly, in the above general formula (2B), y is preferably larger than 0, more preferably 0.9 or more, particularly preferably 1.2 or more, and from the relationship with the content ratio of the inactivating agent element. It is preferably smaller than 2.9999, more preferably 2.99 or less, further preferably 2.98 or less, and particularly preferably 2.95 or less.

  In the general formula (2B), L represents a metal element selected from a metal element of Group 4 of the periodic table such as Ti, Zr, and Hf, or a metal element of Group 14 of the periodic table such as Si and Ge. Represent. In addition, L may contain any 1 type among these metal elements independently, and may have 2 or more types together by arbitrary combinations and ratios. Of these, L is preferably Ti, Zr, Hf, Si or Ge, more preferably Si or Ge, and particularly preferably Si. Here, L is a metal element that can be a trivalent cation such as B, Al, and Ga, as long as it does not adversely affect the performance of the phosphor in terms of the charge balance of the phosphor crystal. It may be mixed. The mixing amount is usually 10 atomic% or less, preferably 5 atomic% or less with respect to L.

  In the general formula (2B), u is usually 11 or less, preferably 9 or less, more preferably 7 or less, and is a value greater than 0, preferably 3 or more, more preferably 5 or more. .

  The amounts of O ions and N ions are represented by numerical values v and w in the general formula (2B). Specifically, in the general formula (2B), v is usually a value greater than 6, preferably greater than 7, more preferably greater than 8, even more preferably greater than 9, and particularly preferably greater than 11. It is usually 25 or less, preferably less than 20, more preferably less than 15, and still more preferably less than 13.

  Further, since the phosphor of the present invention is an oxynitride, N is an essential component. For this reason, in the above general formula (2B), w is a numerical value greater than zero. Moreover, w is a numerical value of 17 or less normally, Preferably it is smaller than 10, More preferably, it is smaller than 4, More preferably, it is a numerical value smaller than 2.4.

  Therefore, from the above viewpoint, in the general formula (2B), it is particularly preferable that u, v, and w are 5 ≦ u ≦ 7, 9 <v <15, and 0 <w <4, respectively. Thereby, the light emission intensity can be increased.

  In the phosphor of the present invention, the ratio of oxygen atoms to metal elements such as (M1 + Ba + M2) and L is preferably larger than the ratio of nitrogen atoms, and the amount of nitrogen atoms relative to the amount of oxygen atoms (N / O) is: It is 70 mol% or less, preferably 50 mol% or less, more preferably 30 mol% or less, and still more preferably less than 20 mol%. Moreover, as a minimum, it is larger than 0 mol% normally, Preferably it is 5 mol% or more, More preferably, it is 10 mol% or more.

  Specific examples of preferred compositions of the phosphor of the present invention are listed below, but the composition of the phosphor of the present invention is not limited to the following examples.

In the following examples, the parentheses indicate a composition containing one or more elements separated by commas (,). For example, (Ca, Sr, Ba) ₃ (Si, Ge) ₆ O ₁₂ N ₂ : (Eu, Ce, Mn) is one or more atoms selected from the group consisting of Ca, Sr and Ba, Si and Ge A phosphor composed of one or more atoms selected from the group consisting of O, and N, and further activated by one or more atoms selected from the group consisting of Eu, Ce and Mn.

Preferable specific examples of the phosphor of the present invention include (Ca, Sr, Ba) ₃ (Si, Ge) ₆ O ₁₂ N ₂ : (Eu, Ce, Mn), (Ca, Sr, Ba) ₃ (Si, Ge) ₆ O ₉ N ₄ : (Eu, Ce, Mn), (Ca, Sr, Ba) ₃ (Si, Ge) ₆ O ₃ N ₈ : (Eu, Ce, Mn), (Ca, Sr, Ba) ₃ (Si, Ge) ₇ O ₁₂ N _8/3 : (Eu, Ce, Mn), (Ca, Sr, Ba) ₃ (Si, Ge) ₈ O ₁₂ N _14/3 : (Eu, Ce, Mn) , (Ca, Sr, Ba) ₃ (Si, Ge) ₈ O ₁₂ N ₆ : (Eu, Ce, Mn), (Ca, Sr, Ba) ₃ (Si, Ge) _28/3 O ₁₂ N _22/3 : (Eu, Ce, Mn), (Ca, Sr, Ba) ₃ (Si, Ge) _29/3 O ₁₂ N _26/3 : (Eu, Ce, Mn), (Ca, Sr, Ba) ₃ (Si _{, Ge) 6.5 O 13 N 2} : Eu, Ce, Mn), ( Ca, Sr, Ba) 3 (Si, Ge) 7 O 14 N 2: (Eu, Ce, Mn), (Ca, Sr, Ba) 3 (Si, Ge) 8 O 16 N ₂ : (Eu, Ce, Mn),
(Ca, Sr, Ba) ₃ (Si, Ge) ₉ O ₁₈ N ₂ : (Eu, Ce, Mn), (Ca, Sr, Ba) ₃ (Si, Ge) ₁₀ O ₂₀ N ₂ : (Eu, Ce , Mn) or (Ca, Sr, Ba) ₃ (Si, Ge) ₁₁ O ₂₂ N ₂ : (Eu, Ce, Mn), and more preferable specific examples include Ba ₃ Si ₆ O ₁₂ N ₂ : Eu, Ba ₃ Si ₆ O ₉ N ₄ : Eu, Ba ₃ Si ₆ O ₃ N ₈ : Eu, Ba ₃ Si ₇ O ₁₂ N _8/3 : Eu, Ba ₃ Si ₈ O ₁₂ N _14/3 : Eu, Ba ₃ Si ₈ O ₁₂ N ₆ : Eu, Ba ₃ Si _28/3 O ₁₂ N _22/3 : Eu, Ba ₃ Si _29/3 O ₁₂ N _26/3 : Eu, Ba ₃ Si _6.5 O ₁₃ N ₂ : Eu, Ba ₃ Si ₇ O ₁₄ N ₂ : Eu, Ba ₃ Si ₈ O ₁₆ N ₂ : Eu, Ba ₃ Si ₉ O ₁₈ N ₂ : Eu, Ba ₃ Si ₁₀ O ₂₀ N ₂ : Eu, Ba ₃ Si ₁₁ O ₂₂ N _2: Eu _{Ba 3 Si 6 O 12 N 2} : Eu, Mn, Ba 3 Si 6 O 9 N 4: Eu, Mn, Ba 3 Si 6 O 3 N 8: Eu, Mn, Ba 3 Si 7 O 12 N 8/3: _{Eu, Mn, Ba 3 Si 8} O 12 N 14/3: Eu, Mn, Ba 3 Si 8 O 12 N 6: Eu, Mn, Ba 3 Si 28/3 O 12 N 22/3: Eu, Mn, Ba ₃ Si _29/3 O ₁₂ N _26/3 : Eu, Mn, Ba ₃ Si _6.5 O ₁₃ N ₂ : Eu, Mn, Ba ₃ Si ₇ O ₁₄ N ₂ : Eu, Mn, Ba ₃ Si ₈ O ₁₆ N ₂ : Eu, Mn, Ba ₃ Si ₉ O ₁₈ N ₂ : Eu, Mn, Ba ₃ Si ₁₀ O ₂₀ N ₂ : Eu, Mn, Ba ₃ Si ₁₁ O ₂₂ N ₂ : Eu, Mn, Ba ₃ Si ₆ O _{12 N 2: Ce, Ba 3 Si} 6 O 9 N 4: Ce, Ba 3 Si 6 O 3 N 8: Ce, Ba 3 Si 7 O 12 N 8/3: Ce, Ba 3 Si 8 O 12 N 14/3 : Ce, Ba ₃ Si ₈ O ₁₂ N ₆ : Ce, Ba ₃ Si _28/3 O ₁₂ N _22/3 : Ce, Ba ₃ Si _29/3 O ₁₂ N _26/3 : Ce, Ba ₃ Si _6.5 O ₁₃ N ₂ : Ce, Ba ₃ Si ₇ O ₁₄ N ₂ : Ce, Ba ₃ Si ₈ O ₁₆ N ₂ : Ce, Ba ₃ Si ₉ O ₁₈ N ₂ : Ce, Ba ₃ Si ₁₀ O ₂₀ N ₂ : Ce, Ba ₃ Si ₁₁ O ₂₂ N ₂ : Ce, etc. Can be mentioned.

[2-2-3] Other specific examples include, for example, MSi ₂ N ₂ O ₂ activated with europium (where M is one or more alkaline earth metals), 2005 At Europium described in Tsukuba Research Academy City Press Association, MEXT Press Conference, Science Press Conference materials “Succeeded in developing green phosphor for white LED” published by National Institute for Materials Science Examples include activated β-SiAlON.

[2-2-4] As another embodiment, for example, for example, the formula _{(Sr 1-m-n Ca} n Ba o) Si x N y O z: Eu m (m = 0.002~0 .2, n = 0.0-0.25, o = 0.0-0.25, x = 1.5-2.5, y = 1.5-2.5, z = 1.5-2 And 5), Eu ²⁺ active Sr-SiON, which can be excited by light in the wavelength range from UV to blue.

  Specific examples of the phosphor according to the present invention include known phosphors described in, for example, EP1413618, JP-T-2005-530917, and JP-A-2004-134805.

[3] Color filter The color filter used in the color image display device of the present invention is not particularly limited. For example, the following can be used.

  The color filter is obtained by forming fine pixels such as red, green, and blue on a transparent substrate such as glass by a dyeing method, a printing method, an electrodeposition method, a pigment dispersion method, or the like. In order to block the leakage of light from these pixels and obtain a higher quality image, a light shielding pattern called a black matrix is often provided between the pixels.

  A color filter by a dyeing method is manufactured by forming an image with a photosensitive resin obtained by mixing dichromate as a photosensitizer with gelatin, polyvinyl alcohol or the like, and then dyeing the image. The color filter by printing method is a method such as screen printing method, gravure printing method, flexographic printing method, reversal printing method, soft lithography method (imprint printing), etc., and transfers thermosetting or photo-curing ink to a transparent substrate such as glass. Manufactured. In the electrodeposition method, a transparent substrate such as glass provided with an electrode is immersed in a bath containing a pigment or dye, and a color filter is formed by electrophoresis. A color filter by the pigment dispersion method forms a coating film on a transparent substrate such as glass by applying a composition in which a color material such as a pigment is dispersed or dissolved in a photosensitive resin, and is irradiated with radiation through a photomask. Exposure is performed, and unexposed portions are removed by development processing to form a pattern. In addition to these methods, a polyimide resin composition in which a color material is dispersed or dissolved is applied and a pixel image is formed by an etching method, and a film on which a resin composition containing the color material is applied is attached to a transparent substrate. It can also be manufactured by a method of peeling and image exposure, developing to form a pixel image, a method of forming a pixel image with an ink jet printer, and the like.

  In the manufacture of color filters for liquid crystal display elements in recent years, the pigment dispersion method has become the mainstream from the viewpoint of high productivity and excellent microfabrication, but the color filter according to the present invention is in any of the above manufacturing methods. Is also applicable.

  As a black matrix formation method, a chromium and / or chromium oxide (single layer or multilayer) film is formed on the entire surface by a method such as sputtering on a transparent substrate such as glass, and then only the color pixel portion is removed by etching. A photosensitive composition in which a light-shielding component is dispersed or dissolved is coated on a transparent substrate such as glass to form a coating film, which is exposed to radiation through a photomask, and unexposed portions are There is a method of forming a pattern by removing it by development processing.

[3-1] Method for Manufacturing Color Filter Specific examples of the method for manufacturing a color filter according to the present invention are shown below. The color filter according to the present invention can be usually produced by forming red, green and blue pixel images on a transparent substrate provided with a black matrix. When forming each color pixel on the transparent substrate, basically, the pigment and the film thickness are optimized so that the peak wavelengths in the red region, blue region, and green region of the emission spectrum of the backlight are best transmitted. More specifically, the white point, the chromaticity index of the backlight spectrum, and the required NTSC ratio are calculated by the color matching system, and the optimum pigment and film thickness are set.

  The material of the transparent substrate is not particularly limited. Examples of the material include heat such as polyester such as polyethylene terephthalate, polyolefin such as polypropylene and polyethylene, thermoplastic sheet of polycarbonate, polymethyl methacrylate, polysulfone, epoxy resin, unsaturated polyester resin, and poly (meth) acrylic resin. Examples thereof include curable plastic sheets and various glass plates. Among these, a glass plate and a heat resistant plastic are preferable from the viewpoint of heat resistance.

  The transparent substrate may be previously subjected to corona discharge treatment, ozone treatment, thin film treatment of various polymers such as silane coupling agents and urethane polymers in order to improve physical properties such as surface adhesion.

  The black matrix is formed on a transparent substrate using a metal thin film or a black matrix pigment dispersion.

  The black matrix using a metal thin film is formed of, for example, a chromium single layer or two layers of chromium and chromium oxide. In this case, first, a thin film of the metal or metal / metal oxide is formed on the transparent substrate by vapor deposition or sputtering. Subsequently, a photosensitive film is formed thereon, and then the photosensitive film is exposed and developed using a photomask having a repetitive pattern such as a stripe, a mosaic, and a triangle to form a resist image. Thereafter, the thin film is etched to form a black matrix.

  When the black matrix pigment dispersion is used, a black matrix is formed using a color filter composition containing a black color material as a color material. For example, carbon black, bone black, graphite, iron black, aniline black, cyanine black, red or the like appropriately selected from inorganic or organic pigments and dyes, or a plurality of black color materials such as titanium black A black matrix is formed using a color filter composition containing a black color material by mixing green, blue, etc., in the same manner as in the following method for forming red, green, and blue pixel images.

  After applying the above color filter composition containing a color material of one of red, green and blue on a transparent substrate provided with a black matrix and drying, a photomask is placed on this coating film. Through the photomask, a pixel image is formed by image exposure, development, and if necessary, heat curing or photocuring to produce a colored layer. This operation is carried out for each of the three color filter compositions of red, green and blue to form a color filter image.

  Application of the color filter composition can be performed by an application apparatus such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, or a spray.

  Drying after application may be performed using a hot plate, IR oven, convection oven or the like. The higher the drying temperature is, the higher the adhesion to the transparent substrate is. However, if the drying temperature is too high, the photopolymerization initiation system is decomposed and heat polymerization is likely to cause development failure. It is the range of -150 degreeC. The drying time is usually in the range of 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes. Also, prior to drying with heat, a drying method using reduced pressure can be applied.

  The film thickness of the coating after drying is usually in the range of 0.5 to 3.5 μm, preferably 1.0 to 3.0 μm. If the film thickness is too thick, the dispersion of the film thickness tends to increase, and if it is too thin, the pigment concentration increases and pixel formation becomes difficult.

  In the present invention, since the light utilization efficiency of the backlight is particularly excellent, it is possible to reduce the thickness of the color filter. Thinning the color filter shortens and simplifies the manufacturing process, leading to improved productivity and lower prices, and can also save power consumption of the backlight when operated as a display panel. become. In addition, since a thin image display device can be realized, it is particularly suitable for a mobile phone or the like in which the device itself is required to be thin.

  In addition, when the composition for a color filter to be used uses a binder resin and an ethylenic compound in combination, and the binder resin is an acrylic resin having an ethylenic double bond and a carboxyl group in the side chain, Since this material has very high sensitivity and high resolving power, it is preferable that an image can be formed by exposure and development without providing an oxygen barrier layer such as polyvinyl alcohol.

  The exposure light source that can be applied to image exposure is not particularly limited. For example, a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, A lamp light source such as a fluorescent lamp or a laser light source such as an argon ion laser, a YAG laser, an excimer laser, a nitrogen laser, a helium cadmium laser, or a semiconductor laser is used. When only a specific wavelength is used, an optical filter can be used.

  After image exposure with such a light source, an image can be formed on the substrate by developing with an organic solvent or an aqueous solution containing a surfactant and an alkali agent. This aqueous solution can further contain an organic solvent, a buffer, a dye or a pigment.

  Although there is no restriction | limiting in particular about the image development processing method, Usually, methods, such as immersion image development, spray image development, brush image development, and ultrasonic image development, are used at 10-50 degreeC, Preferably it is 15-45 degreeC.

  Examples of alkali agents used for development include sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate, and sodium bicarbonate. Or organic amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetraalkylammonium hydroxide, and the like. The above can be used in combination.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters; alkylbenzenesulfonic acid Anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinate esters; amphoteric surfactants such as alkylbetaines and amino acids can be used.

  For example, isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like can be used as the organic solvent when used alone or in combination with an aqueous solution.

[3-2] Color filter composition
The color filter composition (resist) used in the color image display device of the present invention is not particularly limited, and for example, the following can be used.

  In the following, the pigment dispersion method, which has been the mainstream in recent years, will be described as an example of raw materials for producing color filters.

  In the pigment dispersion method, as described above, a composition in which a color material such as a pigment is dispersed in a photosensitive resin (hereinafter referred to as “color filter composition”) is used. This color filter composition is generally formed by dissolving or dispersing (a) a binder resin and / or (b) a monomer, (c) a coloring material, and (d) other components as constituents in a solvent. The coloring composition for color filters.

  Each component will be described in detail below. In the following, “(meth) acryl”, “(meth) acrylate”, and “(meth) acrylo” represent “acryl or methacryl”, “acrylate or methacrylate”, and “acrylo or methacrylo”, respectively.

(A) Binder resin When a binder resin is used alone, an appropriate one is selected in consideration of the target image formability and performance, the production method desired to be employed, and the like. When the binder resin is used in combination with a monomer described later, the binder resin is added for the purpose of modifying the color filter composition and improving the physical properties after photocuring. Therefore, in this case, the binder resin is appropriately selected according to the purpose of improvement such as compatibility, film-forming property, developability, and adhesiveness.

  Examples of commonly used binder resins include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, maleic acid, (meth) acrylonitrile, styrene, vinyl acetate, vinylidene chloride, maleimide and the like. Examples of the polymer include polyethylene oxide, polyvinyl pyrrolidone, polyamide, polyurethane, polyester, polyether, polyethylene terephthalate, acetyl cellulose, novolac resin, resol resin, polyvinyl phenol, and polyvinyl butyral.

  Among these binder resins, those containing a carboxyl group or a phenolic hydroxyl group in the side chain or main chain are preferable. If a resin having these functional groups is used, development with an alkaline solution becomes possible. Among them, a resin having a carboxyl group, such as an acrylic acid (co) polymer, a styrene / maleic anhydride resin, a novolak epoxy acrylate acid anhydride-modified resin, and the like, which are highly alkaline developable.

  Particularly preferred are (meth) acrylic acid or (co) polymers containing (meth) acrylic acid esters having a carboxyl group (herein these are referred to as “acrylic resins”). That is, this acrylic resin is preferable in that it has excellent developability and transparency, and various copolymers can be obtained by selecting various monomers, so that the performance and production method can be easily controlled.

  Examples of the acrylic resin include (meth) acrylic acid and / or succinic acid (2- (meth) acryloyloxyethyl) ester, adipic acid (2-acryloyloxyethyl) ester, phthalic acid (2- (meta ) Acryloyloxyethyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxyethyl) ester, maleic acid (2- (meth) acryloyloxyethyl) ester, succinic acid (2- (meth) acryloyl) Roxypropyl) ester, adipic acid (2- (meth) acryloyloxypropyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxypropyl) ester, phthalic acid (2- (meth) acryloyloxypropyl) Ester, maleic acid (2- (meth) acryloyloxypropyl) ester, succinic acid (2 (Meth) acryloyloxybutyl) ester, adipic acid (2- (meth) acryloyloxybutyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxybutyl) ester, phthalic acid (2- (meth) (Acryloyloxybutyl) ester, maleic acid (2- (meth) acryloyloxybutyl) ester, hydroxyalkyl (meth) acrylate, (anhydrous) succinic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, etc. A compound to which an acid (anhydride) is added is an essential component, and if necessary, styrene monomers such as styrene, α-methylstyrene, vinyltoluene; cinnamic acid, maleic acid, fumaric acid, maleic anhydride, itaconic acid, etc. Of unsaturated group-containing carboxylic acids; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth Acrylate), allyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate , Esters of (meth) acrylic acid such as methoxyphenyl (meth) acrylate; (meth) acrylic acid added with lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone A compound that is: acrylonitrile; (meth) acrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N-methacryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N- Acrylamide such as methyl aminoethyl acrylamide; vinyl acetate, vinyl versatate, vinyl propionate, vinyl cinnamate, vinyl acids such as vinyl pivalate or the like, a resin obtained by copolymerizing various monomers.

  In addition, styrene, α-methylstyrene, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate, hydroxyphenyl (meth) acrylamide, hydroxyphenyl (meth) for the purpose of increasing the strength of the coating film. A monomer having a phenyl group such as acrylic sulfoamide is 10 to 98 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%, and (meth) acrylic acid or succinic acid (2- (meta ) Acryloyloxyethyl) ester, adipic acid (2-acryloyloxyethyl) ester, phthalic acid (2- (meth) acryloyloxyethyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxyethyl) Ester, maleic acid (2- (meth) acryloyloxy 2 to 90 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol of at least one monomer selected from the group consisting of (meth) acrylic acid esters having a carboxyl group such as (til) ester An acrylic resin copolymerized at a ratio of% is also preferably used.

  These resins preferably have an ethylenic double bond in the side chain. By using a binder resin having a double bond in the side chain, the photocurability of the obtained color filter composition is increased, so that the resolution and adhesion can be further improved.

  As a means for introducing an ethylenic double bond into the binder resin, for example, a method described in JP-B-50-34443, JP-B-50-34444, or the like, that is, a glycidyl group or an epoxy is added to the carboxyl group of the resin. Examples thereof include a method of reacting a compound having both a cyclohexyl group and a (meth) acryloyl group, and a method of reacting an acrylic acid chloride with a hydroxyl group of the resin.

  For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (meth) By reacting a compound such as acrylic acid chloride or (meth) acrylic chloride with a resin having a carboxyl group or a hydroxyl group, a binder resin having an ethylenic double bond group in the side chain can be obtained. In particular, a resin obtained by reacting an alicyclic epoxy compound such as (3,4-epoxycyclohexyl) methyl (meth) acrylate is preferable as the binder resin.

  Thus, when an ethylenic double bond is introduced into a resin having a carboxylic acid group or a hydroxyl group in advance, the ethylenic double bond is added to 2 to 50 mol%, preferably 5 to 40 mol% of the carboxyl group or hydroxyl group of the resin. It is preferable to bind a compound having a bond.

  The preferable range of the weight average molecular weight of these acrylic resins measured by GPC (gel permeation chromatography) is 1,000 to 100,000. When the weight average molecular weight is less than 1,000, it is difficult to obtain a uniform coating film, and when it exceeds 100,000, the developability tends to decrease. Moreover, the range of preferable content of a carboxyl group is 5-200 in an acid value (mgKOH / g). When the acid value is less than 5, it becomes insoluble in an alkaline developer, and when it exceeds 200, the sensitivity may be lowered.

  A particularly preferred specific example of the binder resin will be described below.

(A-1): “Unsaturated monobasic acid in at least part of the epoxy group of the copolymer with respect to the copolymer of epoxy group-containing (meth) acrylate and other radical polymerizable monomer And an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction "
Examples of such a resin include resins described in paragraphs 0090 to 0110 of JP-A-2005-154708.

(A-2): Carboxyl group-containing linear alkali-soluble resin The carboxyl group-containing linear alkali-soluble resin is not particularly limited as long as it has a carboxyl group, and is usually a polymerizable monomer containing a carboxyl group. It is obtained by polymerizing a monomer. Examples of such a resin include resins described in paragraphs 0055 to 0066 of JP-A-2005-232432.

(A-3): Resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the (a-2) resin. (A-2) The carboxyl group portion of the carboxyl group-containing resin does not contain an epoxy group. A resin to which a saturated compound is added is also particularly preferable.

  The epoxy group-containing unsaturated compound is not particularly limited as long as it has an ethylenically unsaturated group and an epoxy group in the molecule.

  For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, N- (3,5-dimethyl-4-glycidyl) benzylacrylamide, 4- Acyclic epoxy group-containing unsaturated compounds such as hydroxybutyl (meth) acrylate glycidyl ether can also be mentioned, but from the viewpoints of heat resistance and dispersibility of the pigment described later, alicyclic epoxy group-containing unsaturated compounds are used. preferable.

  Here, as the alicyclic epoxy group-containing unsaturated compound, as the alicyclic epoxy group, for example, 2,3-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, 7,8-epoxy [tricyclo [5 .2.1.0] dec-2-yl] group and the like. Further, the ethylenically unsaturated group is preferably derived from a (meth) acryloyl group.

Among these, 3,4-epoxycyclohexylmethyl (meth) acrylate is particularly preferable.
Examples of such a resin include resins described in paragraphs 0055 to 0066 of JP-A-2005-232432.

(A-4): Acrylic resin (a-4) The acrylic resin is a polymer obtained by polymerizing acrylic acid and / or acrylic acid ester as monomer components.

  Examples of preferable acrylic resins include the resins described in JP-A-2006-161035, paragraphs 0067 to 0086.

  These binder resins are usually contained in the range of 10 to 80% by weight, preferably 20 to 70% by weight in the total solid content of the color filter composition.

(B) Monomer The monomer is not particularly limited as long as it is a polymerizable low molecular compound, but an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Are abbreviated). The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of a photopolymerization initiation system described later when the composition for a color filter is irradiated with actinic rays. In addition, the monomer in this invention means the concept which opposes what is called a polymeric substance, and means the concept also containing a dimer, a trimer, and an oligomer other than the monomer of a narrow sense.

  Examples of the ethylenic compound include an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid and a monohydroxy compound, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an aromatic polyhydroxy compound and an unsaturated carboxylic acid, Esters, polyisocyanate compounds and (meth) acryloyl obtained by esterification reaction with unsaturated carboxylic acid and polyvalent carboxylic acid and polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds described above Examples thereof include an ethylenic compound having a urethane skeleton obtained by reacting the containing hydroxy compound.

  Examples of the unsaturated carboxylic acid include (meth) acrylic acid, (anhydrous) maleic acid, crotonic acid, itaconic acid, fumaric acid, 2- (meth) acryloyloxyethyl succinic acid, and 2-acryloyloxyethyl adipic acid. 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid 2- (meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyl hydrophthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, -(Meth) acryloyloxybutyl hydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid, (meth) acrylic acid with ε-caprolactone, β-propio Monomers obtained by adding lactones such as lactone, γ-butyrolactone, δ-valerolactone, or hydroxyalkyl (meth) acrylate to (anhydrous) succinic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, etc. And monomers added with an acid (anhydride). Among these, (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferable, and (meth) acrylic acid is more preferable. A plurality of these may be used.

  Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, penta Acrylic esters such as erythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate and the like can be mentioned. In addition, the acrylic acid part of these acrylates is a methacrylic acid ester replaced with a methacrylic acid part, an itaconic acid ester replaced with an itaconic acid part, a crotonic acid ester replaced with a crotonic acid part, or a maleic acid replaced with a maleic acid part Examples include esters.

  Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.

  The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. Representative examples include condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol and glycerin. And the like.

  Examples of ethylenic compounds having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanate; aromatic diisocyanate such as tolylene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3-hydroxy ( Reaction products with (meth) acryloyl group-containing hydroxy compounds such as 1,1,1-trimethacryloyloxymethyl) propane And the like.

  Other examples of the ethylenic compound used in the present invention include acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate.

  The blending ratio of these ethylenic compounds is usually 10 to 80% by weight, preferably 20 to 70% by weight, based on the total solid content of the color filter composition.

(C) Coloring material In order to use the light from the backlight as efficiently as possible, the colorant is adjusted to the emission wavelength of the red, green, and blue backlights at the emission wavelength of the phosphor in each pixel. It is necessary to select the transmittance as high as possible and the transmittance at other emission wavelengths as low as possible.

  Since the present invention is characterized by high color reproducibility not particularly found in conventional LED backlights, special attention is required in selecting a color material. That is, the following conditions must be satisfied so that the characteristics of the backlight having deep red and green emission wavelengths characteristic of the present invention are fully utilized.

[3-2-1] Red Composition First, the red composition (red resist) constituting the red pixel will be described.

  In addition to organic pigments such as azo-based, quinacridone-based, benzimidazolone-based, isoindoline-based, perylene-based, and diketopyrrolopyrrole-based pigments, various inorganic pigments can be used for the red composition according to the present invention. Is available.

  Specifically, for example, pigments having the following pigment numbers can be used. In addition, the term “CI” mentioned below means a color index (CI).

  Red color material: C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276.

  Further, the following yellow color material may be mixed with the red color material for fine color adjustment.

  Yellow color material: C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 17 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203 204, 205, 206, 207, 208.

[3-2-2] Green Composition Next, the green composition (green resist) constituting the green pixel will be described.

  As the pigment used in the green composition according to the present invention, various inorganic pigments can be used in addition to azo and phthalocyanine organic pigments.

  Specifically, for example, pigments having the following pigment numbers can be used.

  Green color material: C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55.

  The above-mentioned yellow color material may be mixed with the green color material for fine color adjustment.

  Specific examples of the green pixel that satisfy the above conditions include, in particular, Pigment Green 36 and / or Pigment Green 7 as a green pigment, and Pigment Yellow 150, Pigment Yellow 138, and Pigment Yellow 139 as a yellow pigment for toning. It is preferable that one or more are included.

  In the present invention, when a color image display device having an NTSC ratio of 87% or more, particularly 90% or more is produced, it is preferable to use Pigment Green 7 instead of Pigment Green 36 from the viewpoint of film formability. When Pigment Green 36 is used, the pigment concentration becomes high, so that problems such as poor development and foreign matter defects in die coating may occur. That is, for example, when using the backlight of Example 3 to be described later, as shown in Table 2, if it is designed to produce a color filter with a green resist using Pigment Green 7 (Formulation Example 1), the total pigment concentration Is 37.7% by weight. On the other hand, when the color filter is designed to be produced with a green resist using Pigment Green 36 (Formulation Example 2), the total pigment concentration is 53.1% by weight. These Formulation Examples 1 and 2 correspond to Examples 3A and 3B described later, respectively.

  In the present invention, a particularly preferable combination of green pigments for producing a color image display device having an NTSC ratio of 87% or more, particularly 90% or more is a combination of Pigment Green 7 and Pigment Yellow 150. Pigment Green 7: Pigment Yellow 150 is usually 9: 1 to 1: 9, preferably 8: 2 to 2: 8, and more preferably 7: 3 to 3: 7.

[3-2-3] Blue Composition Next, the blue composition (blue resist) constituting the blue pixel will be described.

  As the pigment used in the blue composition according to the present invention, for example, pigments having the following pigment numbers can be used.

  Blue color material: C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79.

  Violet color material: C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50.

[3-2-4] Adjustment of coloring composition In addition, the following pigments may be further used as necessary for fine adjustment of color regardless of red, green, and blue.

  Orange color material: C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79.

  Brown color material: C.I. I. Pigment Brown 1, 6, 11, 22, 23, 24, 25, 27, 29, 30, 31, 33, 34, 35, 37, 39, 40, 41, 42, 43, 44, 45.

  Of course, other coloring materials such as dyes may be used.

  Examples of the dye include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

  Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

  Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.

  Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

  In addition, as a color material that can be used for the color filter composition, inorganic color materials such as barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, chromium oxide, carbon black, and the like are used.

  These colorants are preferably used after being dispersed to an average particle size of 1.0 μm or less, preferably 0.5 μm or less, more preferably 0.3 μm or less.

  These coloring materials are usually contained in the range of 5 to 60% by weight, preferably 10 to 50% by weight, based on the total solid content of the color filter composition.

(D) Other components The color filter composition may further include a photopolymerization initiation system, a thermal polymerization inhibitor, a plasticizer, a storage stabilizer, a surface protective agent, a smoothing agent, a coating aid, and other additives as necessary. Can be added.

(D-1) Photopolymerization initiation system When the color filter composition contains an ethylenic compound as the monomer (b), it directly absorbs light or is photosensitized to undergo a decomposition reaction or a hydrogen abstraction reaction. A photopolymerization initiating system having a function of generating and generating a polymerization active radical is required.

  The photopolymerization initiation system is composed of a system in which an addition agent such as an accelerator is used in combination with the polymerization initiator. Examples of the polymerization initiator include metallocene compounds including titanocene compounds described in JP-A Nos. 59-152396 and 61-151197, and 2- (2 ′) described in JP-A-10-39503. Hexachlorobiimidazole derivatives such as -chlorophenyl) -4,5-diphenylimidazole, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N -Radical activators such as aryl-α-amino acid esters. Examples of the accelerator include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, complex such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole. A mercapto compound having a ring or an aliphatic polyfunctional mercapto compound is used. A plurality of types of photopolymerization initiators and additives may be combined.

  The blending ratio of the photopolymerization initiation system is usually 0.1 to 30% by weight, preferably 0.5 to 20% by weight, more preferably 0.7 to 10% by weight in the total solid content of the composition of the present invention. . When the blending ratio is extremely low, sensitivity is lowered. On the other hand, when the blending ratio is extremely high, the solubility of the unexposed portion in the developer is lowered, and development failure tends to be induced.

(D-2) Thermal polymerization inhibitor Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, and β-naphthol. The blending amount of the thermal polymerization inhibitor is preferably in the range of 0 to 3% by weight with respect to the total solid content of the composition.

(D-3) Plasticizer As the plasticizer, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like are used. It is done. The blending amount of these plasticizers is preferably in the range of 10% by weight or less with respect to the total solid content of the composition.
(D-4) Sensitizing dye Moreover, in the composition for color filters, the sensitizing dye according to the wavelength of the image exposure light source can be mix | blended in the composition for color filters as needed for the purpose of improving a sensitivity.

  Examples of these sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, and heterocyclic rings described in JP-A-3-239703 and JP-A-5-289335. Coumarin dyes, 3-ketocoumarin compounds described in JP-A-3-239703, JP-A-5-289335, pyromethene dyes described in JP-A-6-19240, and others, JP-A 47-2528, JP JP 54-155292, JP 45-37377, JP 48-84183, JP 52-112681, JP 58-15503, JP 60-88005, JP 59- 56403, JP-A-2-69, JP-A-57-168088, JP-A-5-107761, JP-A-5-210240, JP-A-4-2888 Dyes having a dialkyl aminobenzene skeleton as described in 8 JP can be exemplified.

  Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3 Benzophenone compounds such as 3,3'-diaminobenzophenone and 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) ) Benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- ( p-dimethylaminophenyl) benzothiazole, 2- ( -Diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, ( p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, etc. P-dialkylaminophenyl group-containing compounds. Of these, 4,4′-dialkylaminobenzophenone is most preferred.

  The blending ratio of the sensitizing dye is usually 0 to 20% by weight, preferably 0.2 to 15% by weight, and more preferably 0.5 to 10% by weight in the total solid content of the color filter composition.

(D-5) Other additives Further, an adhesion improver, a coatability improver, a development improver, and the like can be appropriately added to the color filter composition.

  The color filter composition may be used after being dissolved in a solvent in order to dissolve additives such as viscosity adjustment and a photopolymerization initiation system.

  The solvent may be appropriately selected according to the constituents of the composition, such as (a) a binder resin or (b) monomer, such as diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, valsol # 2, apco # 18 solvent, diisobutylene, amyl acetate, butyl acetate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, Methyl nonyl ketone, propyl ether, dodecane, soak solvent No. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, (n, sec, t-) butyl acetate, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, Amylformate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methylamino Ketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropionic acid, 3-ethoxy Methyl propionate, 3-ethoxypropyl Ethyl pionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether , Propylene glycol-t-butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate and the like. Two or more of these solvents may be used in combination.

  The solid content concentration in the color filter coloring composition is appropriately selected according to the coating method to be applied. In the spin coat, slit & spin coat, and die coat widely used in the production of color filters at present, the range of 1 to 40% by weight, preferably 5 to 30% by weight is appropriate.

  The combination of solvents is selected in consideration of the dispersion stability of the pigment, the solubility of the resin, monomer, photopolymerization initiator and other soluble components in the solid content, the drying property during coating, and the drying property in the vacuum drying process. The

  A color filter composition using the above-described blending components is produced, for example, as follows.

  First, a color material is dispersed and adjusted to an ink state. The dispersion treatment is performed using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. Since the color material is finely divided by the dispersion treatment, the transmittance of transmitted light is improved and the coating characteristics are improved.

  The dispersion treatment is preferably performed in a system in which a colorant and a solvent are appropriately combined with a binder resin having a dispersion function, a dispersant such as a surfactant, a dispersion aid, and the like. In particular, it is preferable to use a polymer dispersant because it is excellent in dispersion stability over time.

  For example, when the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.05 to several millimeters. The temperature during the dispersion treatment is usually set in the range of 0 ° C to 100 ° C, preferably room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the ink (coloring material, solvent, dispersant) and the device specifications of the sand grinder.

  Next, the colored ink obtained by the above dispersion treatment is mixed with a binder resin, a monomer, a photopolymerization initiation system, and the like to obtain a uniform solution. In addition, in each process of a dispersion process and mixing, since a fine dust is often mixed, it is preferable to filter the obtained solution with a filter etc.

  Next, although a manufacture example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded. In the following examples, “part” represents “part by weight”.

[1] Synthesis of phosphor [1-1] Synthesis of red phosphor Ca _0.992 Eu _0.008 AlSiN ₃ (hereinafter also referred to as “CASN”) The metal element composition ratio is Eu: Ca: Al: Si = 0.008: 0. 992: 1: 1 Eu ₂ O ₃ (rare metallic), Ca ₃ N ₂ (SERAC 200 mesh pass), AlN (Tokuyama grade F), and Si ₃ N ₄ (Ube Industries SN) -E10) was weighed in a nitrogen atmosphere and mixed manually for 20 minutes using an alumina mortar in a nitrogen atmosphere to obtain a phosphor material.

The obtained phosphor material was filled into a boron nitride crucible. This was placed within a resistance heating vacuum pressurized-atmosphere heat-treating furnace (manufactured by Fuji Telecommunications Industry), under a reduced pressure of <5 × ¹⁰ -3 Pa (i.e., less than ^{5 × 10 -3 Pa), 800} ℃ from room Until the heating rate was 10 ° C./min. When the temperature reached 800 ° C., high-purity nitrogen gas (99.9995%) was introduced over 30 minutes until the pressure was maintained at 0.5 MPa. After the introduction, while maintaining 0.5 MPa, the temperature was further increased to 1800 ° C. at a rate of temperature increase of 5 ° C./min, held at that temperature for 2 hours, and then allowed to cool to room temperature. When the fluorescence characteristics were evaluated, the emission peak wavelength at 455 nm excitation was 648 nm.

[1-2] Synthesis of red phosphor Ca _0.97 Eu _0.03 AlSi _1.03 N ₃ (hereinafter also referred to as “CASN2”) The metal element composition ratio is Eu: Ca: Al: Si = 0.03: 0.97: 1: Ca ₃ N ₂ , AlN, Si ₃ N ₄ , and EuF ₃ (manufactured by Shin-Etsu Chemical) were weighed in a nitrogen atmosphere so as to be 1.03. A CASN phosphor was obtained in the same manner as in [1-1] except that the holding time at 0.75 MPa and 1800 ° C. was 3 hours. When the fluorescence characteristics were evaluated, the emission peak wavelength at 455 nm excitation was 666 nm.

[1-3] Synthesis of green phosphor Ba _1.39 Sr _0.46 Eu _0.15 SiO ₄ (hereinafter also referred to as “BSS”) As phosphor raw materials, barium carbonate (BaCO ₃ ), strontium carbonate (SrCO ₃ ), europium oxide (Eu) ₂ O ₃ ) and silicon dioxide (SiO ₂ ) powders were used. Each of these phosphor materials may also, at a purity of 99.9% or more, _{the weight-average} median diameter _{D 50} is 10nm or more, was used in a range below 5 [mu] m. These phosphor materials were weighed so that the molar ratio would be Ba: Sr: Eu: Si = 1.39: 0.46: 0.15: 1. These phosphor raw material powders were mixed in an automatic mortar until sufficiently uniform, filled in an alumina crucible, and fired at 1100 ° C. for 12 hours in air at atmospheric pressure.

Next, the contents of the crucible were taken out, SrCl ₂ was added as a flux so that the molar ratio was 0.1, and the mixture was pulverized by a dry ball mill. The obtained mixed pulverized product was again filled into an alumina crucible. Raw materials were packed in a crucible during firing, and solid carbon (block shape) was placed on the crucible and covered. After reducing the pressure to 5 Pa or less with a vacuum pump in a vacuum furnace, hydrogen-containing nitrogen gas (nitrogen: hydrogen = 96: 4 (volume ratio)) was introduced until atmospheric pressure was reached. After repeating this operation again, firing was performed by heating at 1200 ° C. for 4 hours under atmospheric pressure under flowing hydrogen-containing nitrogen gas (nitrogen: hydrogen = 96: 4 (volume ratio)).

  After the obtained fired product is crushed by a ball mill, coarse particles are removed through a sieve while in a slurry state, then washed with water, rinsed with water, washed away with fine particles, dried, and sieved to break up the agglomerated particles. The phosphor was manufactured by finishing. When the fluorescence characteristics were evaluated, the emission peak wavelength at 455 nm excitation was 525 nm.

[1-4] Synthesis of green phosphor Ba _1.65 Sr _0.2 Eu _0.15 SiO ₄ (hereinafter also referred to as “BSS2”) The molar ratio is Ba: Sr: Eu: Si = 1.65: 0.2: 0.15: A phosphor was produced in the same manner as in [1-3] except that the sample was collected to be 1. When the fluorescence characteristics were evaluated, the emission peak wavelength with excitation at 455 nm was 520 nm.

[1-5] Synthesis of green phosphor Ba _1.88 Eu _0.12 Si ₆ O ₈ N ₄ (hereinafter also referred to as “BSON”) The composition ratio of charged composition is Ba: Eu: Si = 1.88: 0.12: 6 So that BaCO ₃ is 6.02 g, SiO ₂ is 2.87 g, Si ₃ N ₄ is 2.23 g, Eu ₂ O ₃ is 0.34 g, and the charged composition is Ba _1.88 Eu _0.12 Si ₆ O ₈ N _The phosphor ₄ was synthesized as follows.

  All of these raw material powders were put in an agate automatic mortar, ethanol was added, and they were mixed by a wet mixing method until uniform. The paste-like mixture thus obtained was dried and then filled into alumina crucibles, and lightly loaded to compress the filling. This was placed in a resistance heating tubular electric furnace with a temperature controller, and the temperature was raised at 4.8 ° C./min in a mixed air stream of 96 volume% nitrogen + 4 volume% hydrogen at 0.5 l / min under atmospheric pressure. After heating at a rate of 1200 ° C. and holding at that temperature for 4 hours, it was allowed to cool to room temperature. The obtained sample was pulverized in an aluminum mortar, and the pulverized sample was once again filled into an alumina crucible, and a light load was applied to compress the filled material.

This alumina crucible is placed in a resistance heating type tubular electric furnace with a temperature controller, and is 4.8 ° C./min in a mixed air stream of 96 volume% nitrogen + 4 volume% hydrogen at 0.5 l / min under atmospheric pressure. The temperature was raised to 1350 ° C. at a rate of temperature increase, maintained at that temperature for 72 hours, and then allowed to cool to room temperature.
When the fluorescence characteristics of the obtained phosphor were evaluated, the emission peak wavelength at 455 nm excitation was 526 nm.

Here, using the _Si 3 _β-Si 3 _{N 4} which were subjected to the following processing as _{N 4.} 292 g of α-Si ₃ N ₄ (manufactured by Ube Industries) was filled in a boron nitride crucible as a powder, and compression molded by applying a light load. This boron nitride crucible was placed in a resistance heating type vacuum pressure atmosphere heat treatment furnace (manufactured by Fuji Denpa Kogyo Co., Ltd.) and heated from room temperature to 800 ° C. under a reduced pressure of <5 × 10 ⁻³ Pa at a heating rate of 20 ° C./min. Heated in vacuo. When the temperature reached 800 ° C., high-purity nitrogen gas (99.9995%) was introduced for 30 minutes until the pressure was 0.92 MPa while maintaining the temperature. After the introduction, the temperature was further increased to 1200 ° C. at a rate of temperature increase of 20 ° C./min while maintaining 0.92 MPa.

  The temperature was maintained for 5 minutes and the thermocouple was changed to a radiation thermometer, and further heated to 2000 ° C. at a rate of temperature increase of 20 ° C./min. When the temperature reached 2000 ° C., the temperature was maintained for 2 hours, and further heated to 1800 ° C. at 20 ° C./min, and maintained at that temperature for 3 hours.

After firing, the mixture was cooled to 1200 ° C. at a temperature lowering rate of 20 ° C./min, and then allowed to cool. When the fluorescence characteristics were evaluated, the emission peak wavelength at 455 nm excitation was 526 nm.
X-ray diffraction measurement and reflection spectrum measurement were performed on Si ₃ N ₄ before and after the above treatment. A comparison of each of the X-ray diffraction pattern PDF and (Powder Diffraction File) 76-1407 and _α-Si 3 _{N 4} and _β-Si 3 _{N 4} peaks in 75-0950, pretreatment is _α-Si 3 N ₄ was confirmed to be completely phase transitioned to β-Si ₃ N ₄ by the above treatment.

[2] Manufacture of Backlight [2-1] Manufacture Example 1: Manufacture of Backlight 1 (BL-1) A light emitting device is manufactured by the following procedure.

  A blue light emitting diode having a peak emission wavelength of 454 nm is die-bonded to the bottom of the cup of the frame, and then the light emitting diode and the electrode of the frame are connected by wire bonding.

  BSS is used as the phosphor emitting the green band, and CASN is used as the phosphor emitting the red band. These are kneaded with a silicone resin “JCR6101UP” manufactured by Toray Dow Co., Ltd. and applied to a light emitting diode in a cup and cured.

  Next, a wedge-shaped cyclic polyolefin resin plate having a size of 289.6 × 216.8 mm as a light guide, a thickness of 2.0 mm, a thickness of 0.6 mm, and a thickness changing in the short side direction ( Nippon Zeon's product name “ZEONOR”) is used, and the light source consisting of the above light emitting diodes is arranged on the long side of the thick wall side, and the light source is efficiently connected to the thick wall side (light incident surface). The light source emitted from the light source is incident.

  On the surface facing the light emitting surface of the light guide, a fine circular pattern having a rough surface, the diameter of which gradually increases with distance from the linear light source, is transferred from the mold and patterned. The diameter of the rough surface pattern is 130 μm in the vicinity of the light source, gradually increases as the distance from the light source increases, and is 230 μm at the farthest distance.

  Here, a mold used for forming a fine circular pattern having a rough surface is obtained by laminating a dry film resist having a thickness of 50 μm on a SUS substrate, forming an opening at a portion corresponding to the pattern by photolithography, and The mold is obtained by uniformly blasting the mold with a # 600 spherical glass bead at a projection pressure of 0.3 MPa by sandblasting and then peeling off the dry film resist.

  In addition, the light guide is provided with a triangular prism array having an apex angle of 90 ° and a pitch of 50 μm on its light exit surface so that the ridge line is substantially perpendicular to the light incident surface of the light guide. A structure that enhances the light collecting property of the light beam emitted from the light guide. A mold used for forming a condensing element array composed of a triangular prism array is obtained by machining a stainless steel substrate subjected to M nickel electroless plating with a single crystal diamond bite.

  A light reflecting sheet (“Lumirror E60L” manufactured by Toray Industries, Inc.) is disposed on the side of the light guide that faces the light emitting surface, and a light diffusion sheet is disposed on the light emitting surface. Further, on this light diffusion sheet, a sheet (“BEFIII” manufactured by Sumitomo 3M Co., Ltd.) on which a triangular prism array having an apex angle of 90 ° and a pitch of 50 μm is formed is stacked so that the ridgelines of each prism sheet are orthogonal to each other. To obtain Backlight 1 (BL-1).

  FIG. 4 shows the relative emission spectrum of the backlight 1 (BL-1) obtained as described above. As can be seen from FIG. 4, the backlight 1 has one emission wavelength peak in each of the wavelength regions of 455 m, 531 nm, and 642 nm.

[2-2] Production Example 2: Production of Backlight 2 (BL-2) Same as Production Example 1 except that the blending ratio of BSS and CASN in Production Example 1 is the emission spectrum shown in FIG. Thus, the backlight 2 (BL-2) is manufactured. As can be seen from FIG. 5, the backlight 2 has one emission wavelength peak in each of the wavelength regions of 455 nm, 530 nm, and 639 nm.

[2-3] Production Example 3: Production of Backlight 3 (BL-3) Same as Production Example 1 except that the blending ratio of BSS and CASN in Production Example 1 is the emission spectrum shown in FIG. Thus, the backlight 3 (BL-3) is manufactured. As can be seen from FIG. 6, the backlight 3 has one emission wavelength peak in each of the wavelength regions of 455 m, 531 nm, and 641 nm.

[2-4] Production Example 4: Production of Backlight 4 (BL-4) In Production Example 1, BSS2 is used as a phosphor emitting a green band, and the blending ratio of BSS2 and CASN is shown in FIG. A backlight 4 (BL-4) is produced in the same manner as in Production Example 1 except that the composition is blended so that the emission spectrum is obtained. As can be seen from FIG. 7, the backlight 4 has one emission wavelength peak in each of the wavelength regions of 456 nm, 516 nm, and 642 nm.

[2-5] Production Example 5: Production of Backlight 5 (BL-5) In Production Example 1, BSON is used as a phosphor emitting a green band, and the blending ratio of BSON and CASN is shown in FIG. A backlight 5 (BL-5) is produced in the same manner as in Production Example 1 except that the composition is blended so that the emission spectrum is obtained. As can be seen from FIG. 8, the backlight 7 has one emission wavelength peak in each of the wavelength regions of 456 nm, 532 nm, and 641 nm.

[2-6] Production Example 6: Production of Backlight 6 (BL-6) In Production Example 1, BSS2 was used as the phosphor emitting the green band, and CASN2 was used as the phosphor emitting the red band. A backlight 6 (BL-6) is produced in the same manner as in Production Example 1, except that the blending ratio of CASN2 and CASN2 is such that the emission spectrum shown in FIG. 9 is obtained. As can be seen from FIG. 9, the backlight 4 has one emission wavelength peak in each of the wavelength regions of 456 nm, 531 nm, and 666 nm.

[2-7] Production Example 7: Production of Conventional Backlight 7 for Comparative Example A light emitting device is produced by the following procedure.

A blue light emitting diode having a peak emission wavelength of 460 nm is die-bonded to the bottom of the cup of the frame, and then the light emitting diode and the electrode of the frame are connected by wire bonding. Y _2.8 Tb _0.1 Ce _0.1 Al ₅ O ₁₂ is used as a phosphor emitting a yellow band. These are kneaded with an epoxy resin to form a paste, which is applied to the light emitting diode in the cup and cured. Thereafter, the conventional backlight 7 for the comparative example is obtained by using the same method as in Production Example 1. The relative emission spectrum of the backlight 7 obtained in this way is shown in FIG.

[3] Production of binder resin [3-1] Production Example 8: Binder resin A
55 parts by weight of benzyl methacrylate, 45 parts by weight of methacrylic acid and 150 parts by weight of propylene glycol monomethyl ether acetate are put into a 500 ml separable flask, and the inside of the flask is sufficiently substituted with nitrogen. Thereafter, 6 parts by weight of 2,2′-azobisisobutyronitrile is added and stirred at 80 ° C. for 5 hours to obtain a polymer solution. The weight average molecular weight of the synthesized polymer is 8000, and the acid value is 176 mgKOH / g.

[3-2] Production Example 9: Binder resin B
Stirring while 145 parts by weight of propylene glycol monomethyl ether acetate is replaced with nitrogen, the temperature is raised to 120 ° C. 20 parts by weight of styrene, 57 parts by weight of glycidyl methacrylate and 82 parts by weight of monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) are added dropwise thereto, and the mixture is further stirred at 120 ° C. for 2 hours.

  Next, the inside of the reaction vessel is changed to air substitution, 27 parts by weight of acrylic acid, 0.7 part by weight of trisdimethylaminomethylphenol and 0.12 part by weight of hydroquinone are added, and the reaction is continued at 120 ° C. for 6 hours. Thereafter, 52 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine are added and reacted at 120 ° C. for 3.5 hours.

  The polymer thus obtained has a weight average molecular weight Mw of about 8000.

[4] Production Example 10: Production of Clear Resist Solution Each component shown below is prepared at the following ratio and stirred with a stirrer until each component is completely dissolved to obtain a resist solution.

Binder resin B produced in Production Example 9: 2.0 parts,
Dipentaerythritol hexaacrylate: 1.0 part,
Photopolymerization initiation system,
2- (2′-chlorophenyl) -4,5-diphenylimidazole: 0.06 part,
2-mercaptobenzothiazole: 0.02 part,
4,4′-bis (diethylamino) benzophenone: 0.04 part,
Solvent (propylene glycol monomethyl ether acetate): 9.36 parts,
Surfactant (“FC-430” manufactured by Sumitomo 3M): 0.0003 part.

[5] Production of Color Filter [5-1] Production Example 11: Red Pixel Production for Examples 1 to 12 and Comparative Examples 1 to 2 75 parts of propylene glycol monomethyl ether acetate, red pigment P.I. R. 16.7 parts of 254, 4.2 parts of the acrylic dispersant “DB2000” manufactured by Big Chemie, and 5.6 parts of the binder resin A produced in Production Example 8 were mixed and stirred for 3 hours with a stirrer to give a solid content concentration of 25% by weight. To prepare. This mill base was subjected to dispersion treatment using 600 parts of 0.5 mmφ zirconia beads in a bead mill device at a peripheral speed of 10 m / s and a residence time of 3 hours.
254 dispersion ink is obtained.

  Also, except that the pigment was changed to P.Y.139, a mill base was prepared with the same composition as the above-mentioned P.R.254, and subjected to a dispersion treatment for 2 hours under the same dispersion conditions with a residence time. A dispersed ink is obtained. In addition, the pigment is changed to P.I. Y. 150 except for the change to 150. R. A mill base was prepared with the same composition as that of H.254 and dispersed for 2 hours under the same dispersion conditions with a residence time. Y. 150 dispersion inks are obtained.

  In addition, the pigment is changed to P.I. R. 177 except for the change to P.177. R. A mill base was prepared with the same composition as that of H.254, and dispersion treatment was performed for 3 hours with a residence time under the same dispersion conditions. R. 177 dispersion ink is obtained.

  The dispersion ink obtained as described above and the resist solution obtained in Production Example 9 were mixed and stirred at the blending ratio shown in Table 3 below, and the solvent ( Propylene glycol monomethyl ether acetate) is added to obtain a red color filter composition.

The color filter composition thus obtained is applied onto a 10 cm × 10 cm glass substrate (“AN635” manufactured by Asahi Glass Co., Ltd.) using a spin coater and dried. The entire surface of the substrate is irradiated with ultraviolet rays having an exposure amount of 100 mJ / cm ² , developed with an alkali developer, and post-baked in an oven at 230 ° C. for 30 minutes to prepare a red pixel sample for measurement. The thickness of the red pixel after fabrication is set to 2.5 μm.

[5-2] Production Example 12: Green Pixel Production for Examples 1-12 and Comparative Examples 1-2 The same as PR.254 in Production Example 13 except that the pigment was changed to P.G.36. A mill base is prepared with the composition, and subjected to a dispersion treatment under the same dispersion conditions with a residence time of 1 hour to obtain a dispersion ink of P.G.36. Pigment is changed to P.I. G. In the same manner, a mill base was prepared and subjected to dispersion treatment under the same dispersion conditions with a residence time of 2 hours. G. 7 dispersion ink is obtained.

  Further, a mill base was prepared with the same composition as in Production Example 11 except that the pigment was changed to P.Y.150, and subjected to dispersion treatment under the same dispersion conditions with a residence time of 2 hours. Obtain dispersed ink.

  The dispersion ink obtained as described above and the resist solution produced in Production Example 12 were mixed and stirred at a blending ratio shown in Table 4 below, and a solvent (so that the final solid content concentration was 25% by weight. Propylene glycol monomethyl ether acetate) is added to obtain a green color filter composition.

The color filter composition thus obtained is applied onto a 10 cm × 10 cm glass substrate (“AN635” manufactured by Asahi Glass Co., Ltd.) with a spin coater and dried. The entire surface of the substrate is irradiated with ultraviolet rays having an exposure amount of 100 mJ / cm ² , developed with an alkali developer, and post-baked in an oven at 230 ° C. for 30 minutes to prepare a green pixel sample for measurement. The film thickness of the green pixel after fabrication is set to 2.5 μm.

[5-3] Production Example 13: Blue Pixel Production for Examples 1 to 12 and Comparative Examples 1 to 2 PR.254 of Production Example 11 except that the pigment was changed to P.G.15: 6. A mill base is prepared with the same composition and subjected to a dispersion treatment under the same dispersion conditions with a residence time of 1 hour to obtain a dispersion ink of P.G.15: 6.

  Further, except that the pigment was changed to P.V.23, a mill base was prepared with the same composition as P.R.254 in Production Example 13, and subjected to a dispersion treatment under the same dispersion conditions with a residence time of 2 hours. PV 23 dispersion inks are obtained.

  The dispersion ink obtained as described above and the resist solution produced in Production Example 9 were mixed and stirred at the blending ratio shown in Table 5 below, and the solvent ( Propylene glycol monomethyl ether acetate) is added to obtain a blue color filter composition.

The color filter composition thus obtained is applied onto a 10 cm × 10 cm glass substrate (“AN635” manufactured by Asahi Glass Co., Ltd.) with a spin coater and dried. The entire surface of the substrate is irradiated with ultraviolet rays having an exposure amount of 100 mJ / cm ² , developed with an alkali developer, and post-baked in an oven at 230 ° C. for 30 minutes to prepare a blue pixel sample for measurement. The film thickness of the blue pixel after fabrication is set to 2.5 μm.

[5-4] Color filter The red, green, and blue pixels having the same names shown in Tables 3 to 5 are combined to form color filters for Examples 1 to 12 and Comparative Examples 1 and 2. About the color filter for Examples 1-12, the result of having calculated the transmittance | permeability spectrum of each of a red pixel sample, a green pixel sample, and a blue pixel sample is shown to FIGS.

[6] Color image display device [6-1] Examples 1-3 and Comparative Examples 1-2
Backlights (BL-1, BL-2, BL-3, BL-7) shown in Production Examples 1-3, 7 and color filters for Examples 1-3, 3A, 3B, and Comparative Examples 1-2 To obtain color image display devices of Examples 1 to 3 and Comparative Examples 1 and 2. For these color image display devices, chromaticity (x, y, Y) is calculated from the calculated transmittance spectrum and backlight emission spectrum, and color reproducibility (NTSC ratio) and brightness (color temperature) are calculated. Also asked. Here, the Y value corresponds to the utilization efficiency of light emission from the backlight. The results are shown in Table 6.

  In Example 3, a backlight and a color filter were actually produced according to the above manufacturing method, and a color image display device was obtained by combining them. Then, the emission spectrum of the backlight, the transmittance spectrum of each color pixel sample in the color filter, and the NTSC ratio and color temperature of the color image display device were measured. The transmittance spectrum of each pixel sample was measured with a spectrophotometer (“U-3500” manufactured by Hitachi, Ltd.). The emission spectrum of the backlight was measured with a light luminance measuring device (“CS-1000” manufactured by Konica Minolta). Furthermore, chromaticity was calculated from the measured transmittance spectrum and the emission spectrum of the backlight.

  Table 3 shows the chromaticity (x, y, Y) calculated based on the measured NTSC ratio and color temperature, and the measurement results of the transmittance spectrum and backlight emission spectrum of each color pixel sample for Example 3. It is shown in parentheses at the bottom of the corresponding column of 6.

表６中の白色のＹ値がカラー画像表示装置全体としてのバックライト光の利用効率を表す。表６の通り、EBU規格（NTSC比７２％）、NTSC比８５％という高い色再現範囲のカラー画像表示装置を設計した場合に、従来バックライトではＹ値の著しい低下をもらすのに対し、本発明の技術を用いれば高いＹ値を達成できる。即ち、低消費電力でより高い輝度を得ることが可能となる。

The white Y value in Table 6 represents the utilization efficiency of the backlight light as the entire color image display device. As shown in Table 6, when a color image display device with a high color reproduction range of EBU standard (NTSC ratio 72%) and NTSC ratio 85% is designed, the conventional backlight has a significant decrease in the Y value. High Y values can be achieved using the inventive technique. That is, higher luminance can be obtained with low power consumption.

  In addition, about Example 3, when the result obtained by simulation and the result obtained by actually measuring were compared, both were substantially the same result. Therefore, also in Examples 1 and 2 and Comparative Examples 1 and 2, when a color image display device was actually produced and various characteristics were measured, the results similar to those shown in Table 5 were obtained. It is done. That is, it is considered that the characteristics such as the NTSC ratio and the light utilization efficiency of the actual color image display device may be judged from the simulation results of the examples and the comparative examples.

Furthermore, even with conventional backlights, the color filter film thickness becomes too thick (> 10 μm), and even the Adobe-RGB (NTSC ratio 94%), which could not be achieved because the plate-making performance cannot be obtained, is the technology of the present invention. This can be achieved if used. Moreover, about Example 3, when the coating film of the composition for color filters of each color prepared by the said manufacture examples 11-13 was exposed and developed at 100 mJ / cm < ² > using the test pattern mask, in all the samples, It was confirmed that a good pattern was obtained. The film thickness after drying of the color filter composition of each color actually produced in Example 3 was 2.50 μm.

[6-2] Examples 4 to 6
The backlight (BL-4) shown in Production Example 4 and the color filters for Examples 4 to 6 are combined to form color image display devices of Examples 4 to 6. About these color image display apparatuses, chromaticity (x, y, Y), NTSC ratio, and color temperature were calculated | required by calculation similarly to the above-mentioned Examples 1-3. The results are shown in Table 7.

  In particular, for Example 6, a backlight and a color filter were actually produced, and a color image display device was obtained by combining them. And about the obtained color image display apparatus, while measuring the transmittance | permeability spectrum of each color pixel sample, the emission spectrum of a backlight, the NTSC ratio of a color image display apparatus, and color temperature similarly to the above-mentioned Example 3, each color Chromaticity (x, y, Y) is calculated based on the measurement results of the transmittance spectrum of the pixel and the emission spectrum of the backlight, and these are shown in parentheses at the bottom of the corresponding column in Table 7.

表７より、実施例４〜６についても、実施例１〜３と同様、高いＮＴＳＣ比においても従来と比較して高い光利用効率を達成できることがわかる。また、実施例６についてシミュレーション結果と実際に測定することによって得られた結果がほぼ同じ結果であったことから、実際のカラー画像表示装置のＮＴＳＣ比、光利用効率といった特性を判断して差し支えないと考えられる。また、実施例６について、実際に作製した各色のカラーフィルター用組成物の乾燥後の膜厚は、いずれも２．５０μｍであり、実施例３と同様、良好なパターンが得られることを確認した。

From Table 7, it can be seen that in Examples 4 to 6, as in Examples 1 to 3, higher light utilization efficiency can be achieved even at a higher NTSC ratio than in the past. Further, since the simulation result and the result obtained by actually measuring the sixth example were almost the same result, the characteristics such as the NTSC ratio and the light utilization efficiency of the actual color image display device may be judged. it is conceivable that. Moreover, about Example 6, the film thickness after drying of the color filter composition actually produced for each color was 2.50 μm, and it was confirmed that a good pattern was obtained as in Example 3. .

[6-3] Examples 7 to 9
The backlight (BL-5) shown in Production Example 5 and the color filters for Examples 7-9 are combined to provide color image display devices of Examples 7-9. About these color image display apparatuses, chromaticity (x, y, Y), NTSC ratio, and color temperature were calculated | required by calculation similarly to the above-mentioned Examples 1-3. The results are shown in Table 8.

  In particular, for Example 9, a backlight and a color filter were actually produced, and a color image display device was obtained by combining them. And about the obtained color image display apparatus, while measuring the transmittance | permeability spectrum of each color pixel sample, the emission spectrum of a backlight, the NTSC ratio of a color image display apparatus, and color temperature similarly to the above-mentioned Example 3, each color Chromaticity (x, y, Y) is calculated based on the measurement results of the transmittance spectrum of the pixel and the emission spectrum of the backlight, and these are shown in parentheses at the bottom of the corresponding column in Table 8.

表８より、実施例７〜９についても、実施例１〜３と同様、高いＮＴＳＣ比においても従来と比較して高い光利用効率を達成できることがわかる。また、実施例９についてシミュレーション結果と実際に測定することによって得られた結果がほぼ同じ結果であったことから、実際のカラー画像表示装置のＮＴＳＣ比、光利用効率といった特性を判断して差し支えないと考えられる。また、実施例９について、実際に作製した各色のカラーフィルター用組成物の乾燥後の膜厚は、いずれも２．５０μｍであり、実施例３と同様、良好なパターンが得られることを確認した。

From Table 8, it can be seen that also in Examples 7 to 9, high light utilization efficiency can be achieved compared to the conventional case even at a high NTSC ratio, as in Examples 1 to 3. In addition, since the simulation result and the result obtained by actually measuring Example 9 were almost the same, the characteristics such as the NTSC ratio and the light utilization efficiency of the actual color image display device may be judged. it is conceivable that. Moreover, about Example 9, the film thickness after drying of the color filter composition actually produced for each color was 2.50 μm, and it was confirmed that a good pattern was obtained as in Example 3. .

[6-4] Examples 10 to 12
The backlight (BL-6) shown in Production Example 6 and the color filters for Examples 10 to 12 are combined to provide color image display devices of Examples 10 to 12. About these color image display apparatuses, chromaticity (x, y, Y), NTSC ratio, and color temperature were calculated | required by calculation similarly to the above-mentioned Examples 1-3. The results are shown in Table 9.

表９より、実施例１０〜１２についても、実施例１〜３と同様、高いＮＴＳＣ比においても従来と比較して高い光利用効率を達成できることがわかる。

From Table 9, it can be seen that also in Examples 10 to 12, high light utilization efficiency can be achieved compared to the conventional case even at a high NTSC ratio, as in Examples 1 to 3.

  According to the present invention, a wide color reproducibility is achieved as a whole image by adjusting with a color filter without impairing the brightness of an image even with an LED backlight, and red, green, and blue light emission can be performed in one chip. Therefore, it is possible to provide a color image display device in which white balance adjustment is easy without impairing mounting productivity, so in the fields of color filter compositions, color filters, color image display devices, etc. Industrial applicability is extremely high.

It is a figure which shows the structure of a color liquid crystal display device of a TFT system. It is a graph which shows the relationship between the NTSC ratio and light utilization efficiency of the color image display apparatus by this invention. It is sectional drawing which shows an example of the backlight apparatus suitable for this invention. It is sectional drawing which shows the other example of the backlight apparatus suitable for this invention. 3 is a relative emission spectrum of the backlight 1 obtained in Production Example 1. 6 is a relative emission spectrum of the backlight 2 obtained in Production Example 2. 4 is a relative emission spectrum of the backlight 3 obtained in Production Example 3. 6 is a relative emission spectrum of the backlight 4 obtained in Production Example 4. 6 is a relative emission spectrum of the backlight 5 obtained in Production Example 5. 7 is a relative emission spectrum of the backlight 6 obtained in Production Example 6. 7 is a relative emission spectrum of the backlight 7 obtained in Production Example 7. 2 is a transmittance spectrum of a color filter for Example 1. FIG. 4 is a transmittance spectrum of a color filter for Example 2. 10 is a transmittance spectrum of a color filter for Example 3. It is the transmittance | permeability spectrum of the color filter for Example 3A. It is the transmittance | permeability spectrum of the color filter for Example 3B. 7 is a transmittance spectrum of a color filter for Example 4. 7 is a transmittance spectrum of a color filter for Example 5. 7 is a transmittance spectrum of a color filter for Example 6. FIG. 10 is a transmittance spectrum of a color filter for Example 7. It is the transmittance | permeability spectrum of the color filter for Example 8. FIG. It is the transmittance | permeability spectrum of the color filter for Example 9. FIG. It is the transmittance | permeability spectrum of the color filter for Example 10. FIG. It is the transmittance | permeability spectrum of the color filter for Example 11. FIG. It is the transmittance | permeability spectrum of the color filter for Example 12. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Light emitting diode 2 Light guide plate 3 Light diffusion sheet 4,10 Polarizing plate 5,8 Glass substrate 6 TFT
7 Liquid crystal 9 Color filter 11 Light guide 12 Array 13 Light control sheet 14, 14 'Light extraction mechanism 15 Reflection sheet

Claims (12)

In a color image display device configured by combining an optical shutter, a color filter having at least three color elements of red, green, and blue corresponding to the optical shutter, and a backlight for transmitted illumination, the backlight The light source used in the above is a combination of a blue or deep blue LED and a phosphor, and the relationship between the NTSC ratio W, which is the color reproduction range of the color image display element, and the light utilization efficiency Y is represented by the following formula: Color image display device.
Y ≧ −0.38W + 51 (W ≧ 87)

Here, the definition of each symbol and symbol is as follows.

In a color image display device configured by combining an optical shutter, a color filter having at least three color elements of red, green, and blue corresponding to the optical shutter, and a backlight for transmitted illumination, the backlight source is a combination of a blue or deep blue LED and a phosphor for use in, that the light use efficiency Y ₁ color reproduction range of the color image display device is shown in the following when the NTSC ratio of 74% is 28% or more A color image display device characterized by the above.

Here, the definition of each symbol and symbol is as follows.

In a color image display device configured by combining an optical shutter, a color filter having at least three color elements of red, green, and blue corresponding to the optical shutter, and a backlight for transmitted illumination, the backlight source is a combination of a blue or deep blue LED and a phosphor for use in, that the light use efficiency Y ₂ color reproduction range of the color image display device is shown in the following when the 85% NTSC ratio is 25% or more A color image display device characterized by the above.

Here, the definition of each symbol and symbol is as follows.

In a color image display device configured by combining an optical shutter, a color filter having at least three color elements of red, green, and blue corresponding to the optical shutter, and a backlight for transmitted illumination, the backlight source is a combination of a blue or deep blue LED and a phosphor for use in, that the light use efficiency Y ₃ color reproduction range of the color image display device is shown in the following when the 94% NTSC ratio is 15% or more A color image display device characterized by the above.

Here, the definition of each symbol and symbol is as follows.

5. The color image display device according to claim 1, wherein a light source used for the backlight has one or more emission wavelength peaks in wavelength regions of 430 to 470 nm, 500 to 540 nm, and 600 to 680 nm, respectively. .
  The backlight includes a phosphor layer or a phosphor film, and the phosphor layer or the phosphor film includes a phosphor having a light emitting component in a wavelength region of 600 to 680 nm and activated with europium. The color image display device according to claim 1, wherein: The said backlight has a fluorescent substance layer or a fluorescent substance film, and this fluorescent substance layer or this fluorescent substance film contains the compound represented by following General formula (1A), Any one of Claims 1-5 characterized by the above-mentioned. 2. A color image display device according to claim 1.
_{^{M 1 a M 2 b M 3}} c M 4 d N e O f (1A)
(Wherein, ^{M 1} is Cr, Mn, Fe, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and one or more activator elements selected from the group consisting of Yb, ^{M 2} is Mg, Ca, Sr, Ba, and one or more divalent metal element selected from the group consisting of Zn, ^{M 3} is Al, Ga, in, and at least one trivalent element selected from the group consisting of Sc M ⁴ is one or more elements selected from the group consisting of Si, Ge, Sn, Ti, Zr, and Hf containing at least Si, and a, b, c, d, e, and f are respectively The value is in the following range.
0.00001 ≦ a ≦ 0.15
a + b = 1
0.5 ≦ c ≦ 1.5
0.5 ≦ d ≦ 1.5
2.5 ≦ e ≦ 3.5
0 ≦ f ≦ 0.5) The said backlight has a fluorescent substance layer or a fluorescent substance film, and this fluorescent substance layer or this fluorescent substance film contains the compound represented by following General formula (1B), Any one of Claims 1-5 characterized by the above-mentioned. 2. A color image display device according to claim 1.
M ^{1 ′} _{a ′} Sr _{b ′} Ca _{c ′} M ^{2 ′} _{d ′} Al _{e ′} Sif _′ N _{g ′} (1B)
(However, M ^{1 ′} is one or more activation elements selected from the group consisting of Cr, Mn, Fe, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb, M ^{2 ′} is one or more divalent metal elements selected from the group consisting of Mg, Ba and Zn, and a ′, b ′, c ′, d ′, e ′, f ′ and g ′ are respectively It is a value in the range.
0.00001 ≦ a ′ ≦ 0.15
0 ≦ b ′ ≦ 0.99999
0 ≦ c ′ <1
0 ≦ d ′ <1
a ′ + b ′ + c ′ + d ′ = 1
0.5 ≦ e ′ ≦ 1.5
0.5 ≦ f ′ ≦ 1.5
0.8 × (2/3 + e ′ + 4/3 × f ′) ≦ g ′ ≦ 1.2 × (2/3 + e ′ + 4/3 × f ′))   The phosphor layer or the phosphor film includes a phosphor having a light emitting component in a wavelength region of 500 to 540 nm and activated with cerium and / or europium. Color image display device. In a color image display device configured by combining an optical shutter, a color filter having at least three color elements of red, green, and blue corresponding to the optical shutter, and a backlight for transmitted illumination, the backlight Has a phosphor layer or phosphor film, the phosphor layer or phosphor film contains a crystal phase represented by the following general formula (2A), and the object color is L ^* a ^* b ^* color When expressed in a system,
L ^* ≧ 90,
a ^* ≦ −20,
b ^* ≧ 30 and {a ^* / b ^* } ≦ −0.45
A color image display device comprising a compound characterized by satisfying
(M ^I _(1-x) M ^II x) _α SiO _β (2A)
(In the general formula (2A), M ^I represents one or more elements selected from the group consisting of Ba, Ca, Sr, Zn and Mg. M ^II takes a divalent and trivalent valence. It represents one or more metal elements that may. However, the molar ratio of divalent element is 0.5 or more to the whole M ^II, is 1 or less.
x, α and β are each
0.01 ≦ x <0.3,
1.5 ≦ α ≦ 2.5, and
3.5 ≦ β ≦ 4.5
Represents a number that satisfies ) In a color image display device configured by combining an optical shutter, a color filter having at least three color elements of red, green, and blue corresponding to the optical shutter, and a backlight for transmitted illumination, the backlight Has a phosphor layer or phosphor film, and the phosphor layer or phosphor film contains a compound represented by the following general formula (2B).
_{M1 x Ba y M2 z L u} O v N w (2B)
(In the general formula (2B), M1 is at least one kind selected from the group consisting of Cr, Mn, Fe, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm and Yb. Represents an active element, M2 represents at least one divalent metal element selected from Sr, Ca, Mg and Zn, and L represents a metal element selected from metal elements belonging to Group 4 or Group 14 of the periodic table. X, y, z, u, v, and w are numerical values in the following ranges, respectively.
0.00001 ≦ x ≦ 3
0 ≦ y ≦ 2.99999
2.6 ≦ x + y + z ≦ 3
0 <u ≦ 11
6 <v ≦ 25
0 <w ≦ 17)   The color image display device according to claim 1, wherein a film thickness of each pixel of the color filter is 0.5 μm or more and 3.5 μm or less.

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