JP2009212508A - Semiconductor light emitting device, backlighting device, and color image display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a semiconductor light-emitting device which attains wide color reproducibility for an image as a whole, without impairing the brightness of the image as a whole. <P>SOLUTION: A light source 1 with which a backlight of a color image display is provided includes a semiconductor light-emitting device which is a combination of a solid-state light-emitting element that emits light of a blue or deep blue region or an ultraviolet region and a fluorescent substance. The fluorescent substance includes a green fluorescent substance and a red fluorescent substance. When the wavelength of the exciting light for the green fluorescent substance and the red fluorescent substance is 400 nm or 455 nm, the ratios of the change in the emitting light peak intensity of the green fluorescent substance and the emitting light peak intensity of the red fluorescent substance at 100°C to respective those at 25°C are 40% or smaller. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a semiconductor light emitting device suitably used for a color image display device that realizes an image with high color purity and a backlight using the same. Furthermore, the present invention relates to a color image display device for realizing an image with high color purity corresponding to the improved emission wavelength of the 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 of each pixel in the CIE XYZ color system (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 the three primary colors defined by the US National Television System Committee (NTSC): red (0.67, 0.33), green (0.21, 0.71), blue ( 0.14, 0.08), which is expressed as a ratio (unit%, hereinafter abbreviated as “NTSC ratio”) with respect 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 as light sources from the viewpoints of long life, no need for inverters, high brightness, and mercury free.

  Here, in a backlight using a conventional LED, an LED that emits blue light is used, and a part of the light emitted from the LED is converted into yellow light by a yellow phosphor, and a mixed color of blue light and yellow light is obtained. The white light obtained by the above is used as a surface light source by the light guide plate.

  However, since the above-mentioned light source uses a yellow phosphor, there are many unnecessary wavelengths of light emission from the viewpoint of red and green color purity, and it is difficult to obtain a display with high color reproducibility (High Gamut). there were. On the other hand, it is possible in principle to increase the color purity of red and green by cutting light of unnecessary wavelengths with a color filter. However, as described above, when the NTSC ratio is increased by adjusting the color filter in order to reproduce a vivid color image, most of the light emission of the backlight is cut and the luminance is remarkably lowered. there were. 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 configuration combining a red LED, a green LED, and a blue LED has been proposed in recent years (Non-Patent Document 1), and a display with extremely high color reproducibility has been prototyped with this configuration. . However, this color image display device combines independent LED chips for red, green and blue,
1) It takes time to implement,
2) Since the LED chips of red, green and blue are installed at a finite distance, 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) Since the white chromaticity is adjusted by combining each chip of the LED with an integral multiple of the number, white balance cannot be adjusted continuously.
There was a problem.

  Patent Document 1 discloses 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. However, although this color image display device has achieved 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. Wide color reproducibility was desired.

  Further, Patent Documents 2 and 3 disclose semiconductor light-emitting devices that combine specific phosphors that can be used for backlight light sources such as liquid crystal displays. However, when these semiconductor light emitting devices are actually combined with a color filter to form a color image display device such as a liquid crystal display, there is a case where the light emission of the backlight is insufficient or the chromaticity is shifted. there were.

On the other hand, Patent Document 4 describes an image display device having a high NTSC ratio, in which a backlight light source that satisfies a specific condition and a color filter are combined. However, under the recent demand for higher performance, 3.5MgO.0.5MgF ₂ .GeO ₂ : Mn ⁴⁺ system, Y ₂ O ₃ : Eu system and YVO ₄ specifically disclosed in Patent Document ₄ : A light emitting device using Eu ³⁺ phosphor is insufficient in terms of luminous efficiency and the like, and the appearance of a device having higher performance is desired.

WO2005 / 111707 International Publication Pamphlet JP 2002-171000 A US Patent 6,809,781 WO 2004/025359 International Publication Pamphlet

Monthly Display April 2003, pages 42 to 46

  The present invention has been made in view of such circumstances, and particularly when used as a backlight for a color image display device, the entire image has a wide color by adjusting with a color filter without impairing the brightness of the image. An object of the present invention is to provide a semiconductor light emitting device that achieves reproducibility and makes it easy to adjust white balance without impairing mounting productivity by emitting red, green, and blue light on a single chip. To do. Furthermore, the present invention provides a backlight and a color image display device using this semiconductor light emitting device.

  As a result of intensive studies, the present inventors have found that the cause of insufficient light emission from the backlight of the color image display device or chromaticity deviation is due to the characteristics of the phosphor. It was found that the problem can be solved by improving the phosphor. In addition, the present inventors have found that the NTSC ratio and the light utilization efficiency are closely related to 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 set the light emission efficiency higher than before by combining a plurality of phosphors having improved emission wavelengths, which efficiently emit (excite) light by a light emitting element having a specific emission wavelength. The semiconductor light emitting device to be obtained was found. Further, when the semiconductor light emitting device is used for a backlight, an image display with high color purity can be realized by combining a color filter optimal for the light emission wavelength of the backlight with the backlight, that is, at a high NTSC ratio. In addition, the present inventors have found that a color image display device having higher light utilization efficiency than the conventional one can be realized.

  This invention is made | formed based on such knowledge, and makes the following the summary.

[1] A semiconductor light-emitting device comprising a solid-state light emitting element that emits light in a blue or deep blue region or an ultraviolet region, and a phosphor,
The phosphor has a green phosphor having one or more emission peaks in a wavelength region of 515 to 550 nm, and an emission peak having a half width of 10 nm or less in the wavelength region of 610 to 650 nm, and A red phosphor containing substantially no excitation spectrum in the emission wavelength region of the green phosphor and containing Mn ⁴⁺ as an activating element;
The green phosphor and the red phosphor have an emission peak intensity at 100 ° C. with respect to an emission peak intensity when the temperature of the green phosphor and the red phosphor is 25 ° C. when the wavelength of excitation light is 400 nm or 455 nm. The semiconductor light emitting device characterized in that the rate of change of is 40% or less.

  [2] The semiconductor light emitting device according to [1], wherein the green phosphor includes one or more compounds selected from the group consisting of aluminate phosphors, sialon phosphors, and oxynitride phosphors.

  [3] In the above [1], the red phosphor has a rate of change of the emission peak intensity at 100 ° C. of 18% or less with respect to the emission peak intensity when the temperature is 25 ° C. when the wavelength of the excitation light is 455 nm. The semiconductor light-emitting device as described.

  [4] The semiconductor light emitting device according to any one of [1] to [3], wherein the red phosphor has a main light emission peak having a half width of 10 nm or less in a wavelength region of 610 to 650 nm.

  [5] The above-mentioned [1] to [4], wherein the red phosphor contains a crystal phase having a chemical composition represented by any of the following general formulas [r1] to [r8]. Semiconductor light emitting device.

M ^I ₂ [M ^IV _1-x R _x F ₆ ]... [R1]
M ^I ₃ [M ^III _1-x R _x F ₆ ] ... [r2]
M ^II [M ^IV _1-x R _x F ₆ ] ... [r3]
M ^I ₃ [M ^IV _1-x R _x F ₇ ] ... [r4]
M ^I ₂ [M ^III _1-x R _x F ₅ ] ... [r5]
_{^{Zn 2 [M III 1-x}} R x F 7] ··· [r6]
M ^I [M ^III _2-2x R _2x F ₇ ] ... [r7]
Ba _0.65 Zr _0.35 F _2.70 : Mn ⁴⁺ ... [R8]
(In the general formulas [r1] to [r8], M ^I represents one or more monovalent groups selected from the group consisting of Li, Na, K, Rb, Cs, and NH ₄ , and M ^II represents an alkali M ^III represents at least one metal element selected from the group consisting of earth metal elements, M ^III represents at least one metal element selected from the group consisting of Groups 3 and 13 of the periodic table, and M ^IV represents One or more metal elements selected from the group consisting of groups 4 and 14 of the periodic table are represented, R represents an activator containing at least Mn, and x is represented by 0 <x <1. It is a numerical value in the range.)

  [6] A backlight including the semiconductor light-emitting device according to any one of [1] to [5] as a light source.

[7] Color image display constituted by combining an optical shutter, a color filter having at least three color elements corresponding to the optical shutter, red, green, and blue, and the backlight according to the above [6] A device,
A color image display device, wherein 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.
Y ≧ −0.4W + 64 (W ≧ 85)

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.

  [8] The color image display device according to [7], wherein the green pixel of the color filter includes a brominated zinc phthalocyanine pigment.

  [9] The color image display device according to [7] or [8], wherein a film thickness of each pixel of the color filter is 0.5 μm or more and 3.5 μm or less.

  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

  ADVANTAGE OF THE INVENTION According to this invention, the semiconductor light-emitting device which can achieve wide color reproducibility can be provided by combining the light emitting element which emits the light of a specific wavelength, and the fluorescent substance which has a specific property. In addition, the color image display device of the present invention uses the semiconductor light emitting device of the present invention as a light source and appropriately defines the relationship between the NTSC ratio and the light utilization efficiency, so that the brightness of the image is not impaired. A certain red and green reproduction can be realized, and a wide color reproducibility can be achieved as an entire image. In addition, since red, green, and blue light can be emitted on a single chip, it is possible to provide a color image display device that can easily adjust white balance without impairing mounting productivity.

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. It is sectional drawing which shows the structure of an example of the semiconductor light-emitting device of this invention. It is sectional drawing which shows the structure of the other example of the semiconductor light-emitting device of this invention. It is the transmittance | permeability spectrum of the color filter for Examples 1, 3, 5, and 7. FIG. It is the transmittance | permeability spectrum of the color filter for Examples 2, 4, 6, 8-10, and Comparative Examples 3 and 4. FIG.

  Hereinafter, embodiments of the semiconductor light emitting device, the backlight, and the color image display device of the present invention will be described in detail, but these are examples of the embodiment 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. Although there is no particular limitation on the specific configuration, for example, a TFT (thin film transistor) type color liquid crystal display device using an optical shutter using liquid crystal as shown in FIG.

  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 a light source 1 having a solid light-emitting element and a phosphor is converted into a surface light source by a light guide plate 2, further increased in uniformity by a light diffusion sheet 3, and then passed through a prism sheet. , Enters the polarizing plate 4. The incident light is controlled in the polarization direction for each pixel by the TFT 6 and enters the color filter 9. The light incident on the color filter 9 finally reaches the observer through the polarizing plate 10 disposed so that the polarization direction is perpendicular to the polarizing plate 4. The TFT 6 and the color filter 9 are provided on glass substrates 5 and 8 which are transparent substrates, respectively, and a liquid crystal 7 is sealed between the glass substrates 5 and 8. 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.

In the color image display device of the present invention, the relationship between the color reproduction range (NTSC ratio) W of the color image display element and the light utilization efficiency Y shown below is expressed by the following formula (a) by the configuration described in detail below. ), Preferably represented by formula (b), more preferably represented by formula (c), and most preferably represented by formula (d). In particular, the solid-state light emitting device included in the backlight has a deep blue region or an ultraviolet region. In the case of using a solid light emitting element that emits light of the above, light utilization efficiency tends to be high, which is preferable.
Y ≧ −0.4W + 64 (a) (W ≧ 85)
Y ≧ −0.4W + 66 (b) (W ≧ 85)
Y ≧ −0.4W + 71 (c) (W ≧ 85)
Y ≧ −0.4W + 73 (d) (W ≧ 85)

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 NTSC ratio 85%, but the design exceeding NTSC ratio 85%, that is, NTSC ratio 85% or more, especially 87% or more, especially 90% or more. In color image display devices, it is concrete for those skilled in the art to improve light utilization efficiency due to the properties of pigments used in conventional color filter resists, phosphor emission spectra, and backlight spectra combining solid light emitting elements and phosphors. A typical configuration could not be easily conceived.

  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) In a color image display device having a NTSC ratio of more than 85% formed by a combination of a specific novel backlight and a color filter, the emission spectrum of each phosphor used and the light emission of the solid state light emitting device (LED chip) The emission spectrum of the backlight is created by combining the spectra. Based on the emission spectrum of the backlight, a virtual color filter is simulated by calculation so that the NTSC ratio of the color image display device is about 85% or more.

(Ii) In the virtual color image display device having the virtual color filter simulated in (i) above, the light utilization efficiency at two points at which the NTSC ratio is about 85% or more is calculated. In the present invention, as a simulation value when β-SiAlON is used as the green phosphor and K ₂ TiF ₆ : Mn is used as the red phosphor, (NTSC ratio, light utilization efficiency) = (87.2%, 29.5) ) And (91.6%, 27.7) are calculated.

(Iii) From the above (ii), a linear function Y = −0.4W + 64 passing through the two points.
Thus, the above formula (a), that is, Y ≧ −0.4W + 64 (a) (W ≧ 85)
Is obtained.

Further, the relationship between the NTSC ratio W and the light utilization efficiency Y in the preferred color image display device is as follows when Ba ₃ Si ₆ O ₁₂ N ₂ : Eu is used as the green phosphor and K ₂ TiF ₆ : Mn is used as the red phosphor. Two points of (NTSC ratio, light utilization efficiency) = (87.2%, 29.5) and (91.6%, 27.7) are calculated as simulation values, and a linear function Y passing through these two points is calculated. = -0.4W + 66
From the above formula (b), that is, Y ≧ −0.4W + 66 (b) (W ≧ 85)
As obtained.

Further, more preferably a color image display relationship NTSC ratio W and the light use efficiency Y in the apparatus uses a near-ultraviolet LED as the solid light emitting device, _BaMgAl 10 _O 17 as a blue phosphor: Eu, BaMgAl ₁₀ O as a green phosphor ₁₇ : Eu, Mn, K ₂ TiF ₆ : Mn as the red phosphor was similarly simulated,
The above formula (c), that is, Y ≧ −0.4W + 71 (c) (W ≧ 85)
Is obtained.

Further, the relationship between the NTSC ratio W and the light utilization efficiency Y in the most preferable color image display device uses a near-ultraviolet LED as a solid state light emitting device, Sr ₅ (PO ₄ ) ₃ Cl: Eu as a blue phosphor, and a green phosphor. In the same manner, a simulation was performed using BaMgAl ₁₀ O ₁₇ : Eu, Mn as the red phosphor and K ₂ TiF ₆ : Mn as the red phosphor.
The above formula (d), that is, Y ≧ −0.4W + 73 (d) (W ≧ 85)
Is obtained.

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

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

  Further, the color image display device 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 apparatus, the backlight light source includes a semiconductor light emitting device in which a solid light emitting element that emits light in a blue, deep blue region, or ultraviolet region and a phosphor are combined. It has one or more emission main components in the wavelength regions of 470 nm, 500 to 550 nm, and 600 to 680 nm, respectively, and the color reproduction range of the color image display element is usually 60% or more of NTSC ratio. The NTSC ratio is preferably 70% or more, more preferably 80% or more, still more preferably 85% or more, still more preferably 87% or more, and particularly preferably 90% or more.

  The color image display device usually has a color temperature of 4,000 to 10,000K, preferably 4,500 to 9,500K, and more preferably 5,000 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 and Semiconductor Light-Emitting Device First, the configuration of the backlight device used in such a color liquid crystal display device and the semiconductor light-emitting device provided in the backlight 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 a light source that emits white light and light uniformizing means that converts light from the light source 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 source 1 is disposed along the side end surface 11a on the one side end surface 11a of the light-transmitting plate 11 that is a light-transmitting flat plate, and one side that is a light incident end surface. It is configured to enter the light guide 11 from the end surface 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-shaped array 12 is formed is arranged with the apex angle of the array 12 facing the light exit surface 11 b side of the light guide 11, and FIG. 3 shows that the light extraction mechanism 14 ′ provided on the plate surface 11c opposed to the light emitting surface 11b of the light guide 11 is composed of a rough surface pattern 14b in which each surface is formed into a rough surface. Unlike the backlight device shown, the other configuration is the same.

  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 sometimes 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 includes a semiconductor light-emitting device in which one or a plurality of solid-state light-emitting elements that emit light in the blue or deep blue region or the ultraviolet region and a phosphor are combined. . This phosphor may be directly excited by light from the solid light-emitting element, or may be excited (indirect excitation) by light emission from a different phosphor that receives light from the solid light-emitting element.

  A semiconductor light emitting device in which a solid light emitting element and a phosphor are combined is realized in various forms, and among them, a form called a shell type and a form called a surface mount type are mainstream. These forms will be briefly described with reference to FIGS. 5A and 5B.

  The semiconductor light emitting device shown in FIG. 5A is a typical example of a form called a shell type. In FIG. 5A, the semiconductor light emitting device 24 includes a solid light emitting element 27 mounted on the mount lead 25 and a phosphor containing portion 28 formed so as to cover the solid light emitting element 27. An inner lead 26 is located adjacent to the mount lead 25, and the solid light emitting element 27 is electrically connected to the inner lead 26 by a conductive wire 29. These structures are covered with the transparent mold member 20 with a part of the mount lead 25 and a part of the inner lead 26 exposed.

  The semiconductor light emitting device shown in FIG. 5B is a typical example of a form called a surface mount type. In FIG. 5B, the solid state light emitting device 32 is mounted in a recess formed on the upper surface of the frame 34. Two electrodes 36 and 37 are formed in the recess, and one electrode 37 is electrically connected to the solid light emitting element 32 by directly mounting the solid light emitting element 32, and the other electrode 36 is It is electrically connected to the solid state light emitting device 32 through the conductive wire 35. Further, a phosphor-containing portion 33 is formed in the recess of the frame 34 so as to cover the solid light emitting element 32.

  The semiconductor light emitting device has a 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, more preferably 650 nm or less), a green region (usually 500 nm or more, Preferably 510 nm or more, usually 550 nm or less, preferably 542 nm or less, more preferably 540 nm or less, further preferably 535 nm or less, particularly preferably 530 nm or less, particularly preferably 525 nm or less, most preferably 520 nm or less), blue It is adjusted so that each wavelength region in the region (usually 430 nm or more, preferably 440 nm or more, and usually 470 nm or less, preferably 460 nm or less) has one or more main components of light emission.

  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.

  The light emission wavelength of the solid light-emitting element is not particularly limited as long as it overlaps with the absorption wavelength of the phosphor, and a solid light-emitting element having a wide light emission wavelength region can be used. Among these, when blue light is used as excitation light, it is usually 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, still more preferably 450 nm or more, and usually 490 nm or less, preferably 480 nm or less, more preferably 470 nm. Hereinafter, it is more preferable to use a light emitter having an emission peak wavelength of 460 nm or less. On the other hand, when using deep blue light (hereinafter sometimes referred to as near-ultraviolet light) or ultraviolet light as excitation light, it is usually 300 nm or more, preferably 330 nm or more, more preferably 360 nm or more, and usually 420 nm or less. It is desirable to use a light emitter having an emission peak wavelength of preferably 410 nm or less, more preferably 400 nm or less.

  The preferred red phosphor and green phosphor used in the present invention are usually excited by blue light, and are usually combined with a solid light emitting element that emits blue light. By the blue light emitted from the solid light emitting element, Directly excited to emit red light and green light. Alternatively, the red phosphor and the green phosphor can be excited by near ultraviolet light or ultraviolet light. However, in that case, depending on the type of phosphor, the emission peak intensity may be smaller than that when excited with blue light. Therefore, when the red phosphor and the green phosphor are combined with a solid light emitting element that emits near ultraviolet light or ultraviolet light, a blue phosphor that emits blue light when excited by light from the solid light emitting element is used as necessary. Further, it is preferable to excite the red phosphor and the green phosphor with the blue light emitted from the blue phosphor in order to improve the light emission efficiency. In this case, the red phosphor and the green phosphor are excited by light from another phosphor that converts the wavelength of the light from the solid state light emitting device into light suitable for excitation of the red phosphor and the green phosphor. Thus, it can be said that the light is indirectly excited by light from the solid state light emitting device. As described above, when the red phosphor and the green phosphor are indirectly excited by light from the solid state light emitting device using the blue phosphor, the excitation having a wavelength that matches the excitation band of the blue phosphor. It is preferable to choose light.

  Examples of the solid light-emitting element include an organic electroluminescence light-emitting element, an inorganic electroluminescence light-emitting element, and a semiconductor light-emitting element. Preferably, a semiconductor light-emitting element is used, and for example, a substrate such as silicon carbide, sapphire, or gallium nitride is used. InGaN-based, GaAlN-based, InGaAlN-based, and ZnSeS-based semiconductor light-emitting elements grown by MOCVD or the like are 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. Blue or deep blue LEDs are preferably used in that a light source with a large amount of light can be obtained because they have a wavelength that can excite phosphors efficiently.

Among these, GaN-based LEDs and LDs using GaN-based compound semiconductors are preferable as the semiconductor light emitting device. This is because GaN-based LEDs and LDs have significantly higher emission output and external quantum efficiency than SiC-based LEDs that emit light in this region, and emit very bright light with low power when combined with the phosphor. It is because it is obtained. For example, for a current load of 20 mA, GaN LEDs and LDs usually have a light emission peak intensity that is 100 times or more that of SiC. As the GaN-based LED and LD, those having an Al _X Ga _Y N light emitting layer, a GaN light emitting layer, or an In _X Ga _Y N light emitting layer are preferable. Among them, since the emission peak intensity is very high, the GaN-based LED is particularly preferably one having an In _X Ga _Y N light emitting layer, and one having a multiple quantum well structure of an In _X Ga _Y N layer and a GaN layer. Further preferred.

  In the above, the value of X + Y is usually a value in the range of 0.8 to 1.2. In the GaN-based LED, those in which the light emitting layer is doped with Zn or Si or those without a dopant are preferable for adjusting the light emission characteristics.

A GaN-based LED has these light-emitting layer, p-layer, n-layer, electrode, and substrate as basic components, and the light-emitting layer is an n-type and p-type Al _X Ga _Y N layer, GaN layer, or In _X Those having a heterostructure sandwiched between Ga _Y N layers and the like are preferable because of high light emission efficiency, and those having a heterostructure having a quantum well structure are more preferable because of high light emission efficiency.

  In the case of a surface-mounted semiconductor light-emitting element, the solid light-emitting element is fixed to a frame. The frame has at least positive and negative electrodes for energizing the light source of the solid light emitting element, and the electrode of the solid light emitting element and the electrode of the frame are electrically connected. These electrodes can be electrically connected by wire bonding or flip chip mounting. When connecting by a wire bonding method, a gold wire with a diameter of 20 to 40 μm or an aluminum wire can be used.

  When a concave cup is provided on the frame and a solid light emitting element is disposed on the bottom surface, 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 solid light-emitting element, an epoxy, imide, or acrylic adhesive, a solder such as AuSn or AgSn, or a bump such as Au can be used.

  When the solid light emitting element 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. It is also effective to use a solder to fix a large current type light emitting diode or laser diode in which heat dissipation is particularly important. In addition, any adhesive may be used for fixing in the case of a solid light emitting element that is not energized through an adhesive, but silver paste or solder is still preferable in view of heat dissipation.

  When a plurality of solid state light emitting devices are used, the use of solder is not preferable because the solid state light emitting device needs to be repeatedly exposed to a high temperature or exposed for a long time, and the life of the solid state light emitting device may be deteriorated. On the other hand, when the bump is used, it is possible to work at a temperature lower than that of the solder, and the solid light emitting element and the frame can be connected easily and reliably. 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.

  In order for the semiconductor light emitting device to have one or more main components of light emission in each of the wavelength regions of the red region, the green region, and the blue region, the phosphor that emits the green band (green phosphor), and the red band It is preferable to combine two or more kinds of phosphors including a phosphor emitting red light (red phosphor). These color phosphors are preferably mixed in a transparent binder such as an epoxy resin or a silicone resin, and applied so as to cover the solid light emitting element. The mixing ratio of each color phosphor may be changed as appropriate so that a desired chromaticity is obtained. Further, the phosphor that emits the green band and the phosphor that emits the red band may be separately applied to the solid-state light emitting device. When a diffusing agent is further added to the 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. Since alumina, zirconia, yttria and the like are stable in a practical temperature range of −60 to 120 ° C., they can be more preferably used as a diffusing agent. 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 add an anti-settling agent to the binder because color unevenness and color deviation are likely to occur due to the sedimentation of the phosphor. As an anti-settling agent, fumed silica is generally used.

  The solid light emitting element is preferably sealed with a sealing material. When sealing a solid light emitting element with a sealing material, the phosphor may be contained in the sealing material, and the sealing material may also serve as the binder.

  The kind of sealing material is not specifically limited, Usually, the curable material which can be molded by covering a solid light emitting element can be used. The curable material is a fluid material that is cured by performing some kind of curing treatment. Here, the fluid state means, for example, a liquid state or a gel state. The curable material is not particularly limited as long as it secures the role of guiding the light emitted from the solid light emitting element to the phosphor. Moreover, only 1 type may be used for a curable material and it may use 2 or more types together by arbitrary combinations and a ratio. Therefore, as the curable material, any of inorganic materials, organic materials, and mixtures thereof can be used.

  As the inorganic material, for example, a solution obtained by hydrolytic polymerization of a solution containing a metal alkoxide, a ceramic precursor polymer or a metal alkoxide by a sol-gel method, or a combination thereof is solidified (for example, a siloxane bond). Inorganic materials having

  On the other hand, examples of the organic material include a thermosetting resin and a photocurable resin. Specific examples include (meth) acrylic resins such as poly (meth) acrylic acid methyl; styrene resins such as polystyrene and styrene-acrylonitrile copolymers; polycarbonate resins; polyester resins; phenoxy resins; butyral resins; Cellulose resins such as cellulose acetate and cellulose acetate butyrate; epoxy resins; phenol resins; silicone resins and the like.

  Among these curable materials, it is particularly preferable to use a silicon-containing compound that has little deterioration with respect to light emission from the light emitting element and is excellent in heat resistance. The silicon-containing compound is a compound having a silicon atom in the molecule, organic materials such as polyorganosiloxane (silicone compound), inorganic materials such as silicon oxide, silicon nitride, silicon oxynitride, borosilicate, phosphosilicate Examples thereof include glass materials such as salts and alkali silicates. Of these, silicone materials are preferred from the viewpoints of transparency, adhesion, ease of handling, mechanical and thermal adaptability relaxation characteristics, and the like.

  The silicone-based material usually refers to an organic polymer having a siloxane bond as a main chain, and for example, condensation-type, addition-type, improved sol-gel type, photo-curing type silicone-based materials can be used.

  As the condensed silicone material, for example, semiconductor light-emitting device members described in JP-A-2007-112973 to 112975, JP-A-2007-19459, JP-A-2008-34833, and the like can be used. Condensation-type silicone materials have excellent adhesion to components such as packages, electrodes, and light-emitting elements used in semiconductor light-emitting devices, so the addition of adhesion-improving components can be minimized, and crosslinking is mainly due to siloxane bonds. There is an advantage of excellent heat resistance and light resistance.

  Examples of the addition-type silicone material include potting silicone materials described in JP-A-2004-186168, JP-A-2004-221308, JP-A-2005-327777, JP-A-2003-183881, Organically modified silicone materials for potting described in JP-A-2006-206919, silicone materials for injection molding described in JP-A-2006-324596, silicone materials for transfer molding described in JP-A-2007-231173, etc. Can be suitably used. The addition-type silicone material has advantages such as a high degree of freedom in selection such as a curing speed and a hardness of a cured product, a component that does not desorb during curing, hardly shrinking due to curing, and excellent deep part curability.

  Moreover, as an improved sol-gel type silicone material that is one of the condensation types, for example, the silicone materials described in JP-A-2006-077234, JP-A-2006-291018, JP-A-2007-119569 and the like can be used. It can be used suitably. The improved sol-gel type silicone material has an advantage that it has a high degree of crosslinking, heat resistance, light resistance and durability, and is excellent in the protective function of a phosphor having low gas permeability and low moisture resistance.

  As the photocurable silicone material, for example, silicone materials described in JP 2007-131812 A, JP 2007-214543 A, and the like can be suitably used. The ultraviolet curable silicone material has advantages such as excellent productivity because it cures in a short time, and it is not necessary to apply a high temperature for curing, so that the light emitting element is hardly deteriorated.

  These silicone materials may be used alone, or a mixture of a plurality of silicone materials may be used if curing inhibition does not occur when mixed.

  As long as the effects of the present invention are not significantly impaired, the curable material may be used by further mixing other components with the above-described inorganic material and / or organic material. In addition, only 1 type may be used for another component and it may use 2 or more types together by arbitrary combinations and ratios.

The curable material may further contain inorganic particles for the purpose of improving optical characteristics and workability and for the purpose of obtaining any of the following effects [1] to [5]. In addition, inorganic particle | grains may use only 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
[1] By making the curable material contain inorganic particles as a light scattering agent, a layer formed of the curable material is used as a scattering layer. Thereby, the light transmitted from the light source can be scattered in the scattering layer, and the directivity angle of the light emitted from the light guide member to the outside can be widened. If inorganic particles are contained as a light scattering agent in combination with the phosphor, the amount of light hitting the phosphor can be increased and the wavelength conversion efficiency can be improved.
[2] By containing inorganic particles as a binder in the curable material, it is possible to prevent the occurrence of cracks in the layer formed of the curable material.
[3] By containing inorganic particles as a viscosity modifier in the curable material, the viscosity of the curable material can be increased.
[4] By containing inorganic particles in the curable material, shrinkage of the layer formed of the curable material can be reduced.
[5] By incorporating inorganic particles in the curable material, the refractive index of the layer formed of the curable material can be adjusted, and the light extraction efficiency can be improved.

  However, when inorganic particles are included in the curable material, the effect obtained depends on the type and amount of the inorganic particles.

  When the completed semiconductor light emitting device is energized, the solid state light emitting element first emits light in the blue, deep blue or ultraviolet region. The phosphor absorbs part of it and emits light in the green or red band, respectively. The light emitted from the light emitting device includes the light of the original blue or deep blue region or ultraviolet region of the solid state light emitting device, the green and red bands that have been wavelength-converted by the phosphor, and, if necessary, the light of the blue band. Are mixed to obtain an approximately white one.

[2] Phosphor Next, the phosphor will be described. As described above, the semiconductor light emitting device of the present invention has a phosphor, but when the semiconductor light emitting device has a red phosphor and a green phosphor, each color phosphor has the characteristics described below. It is preferable.

[Temperature dependence of emission peak intensity]
In the red phosphor and the green phosphor used in the present invention, the change in emission peak intensity at 100 ° C. with respect to the emission peak intensity when the temperature of each phosphor is 25 ° C. when the wavelength of excitation light is 400 nm or 455 nm. The rate is 40% or less, preferably 30% or less, more preferably 25% or less, and still more preferably 22% or less. Among them, the red phosphor preferably has a change rate of 18% or less, particularly preferably 15% or less.

  The light emitted from the solid state light emitting device is absorbed by the phosphor and the binder holding the phosphor. As a result, the binder generates heat and heats the phosphor. In addition, the phosphor itself generates heat by the light emitted from the solid state light emitting element being absorbed by the phosphor. Furthermore, when the solid light emitting element is energized and emits light, the light emitting element generates heat due to the electric resistance inside the solid light emitting element, and the temperature rises, whereby the phosphor is heated by heat transfer. The temperature of the phosphor reaches about 100 ° C. by these heating actions. The emission peak intensity of the phosphor depends on the temperature, and the emission peak intensity tends to decrease as the temperature of the phosphor increases. Therefore, in order to prevent the overall color tone from changing even when light is continuously emitted from the solid state light emitting device, even if the emission peak intensity of each color phosphor changes due to a temperature rise, the balance is greatly lost. It is important not to.

  Therefore, in the present invention, the red phosphor and the green phosphor have a rate of change of the emission peak intensity at 100 ° C. with respect to the emission peak intensity at 25 ° C. when the wavelength of the excitation light is 400 nm or 455 nm. The composition etc. are prepared. As a result, even if the emission peak intensity of each color phosphor changes due to the temperature rise of each color phosphor, the change is relatively small between the color phosphors, so the color tone of light emitted from the light emitting device does not change as a whole. .

  Here, specifically, the temperature dependence of the phosphor can be measured, for example, as follows.

[Temperature dependence measurement example]
The temperature dependence measurement is carried out by using, for example, an MCPD7000 multi-channel spectrum measurement device manufactured by Otsuka Electronics as a light emission spectrum measurement device, a stage equipped with a cooling mechanism using a color luminance meter BM5A, a Peltier element, and a heating mechanism using a heater, The following procedure is performed using an apparatus equipped with a 150 W xenon lamp as a light source.

  Place the cell containing the phosphor sample on the stage, change the temperature to 25 ° C and 100 ° C, check the surface temperature of the phosphor, and then remove the spectrum from the light source with a diffraction grating, wavelength 400nm or 455nm The phosphor is excited with the light, and the luminance value and the emission spectrum are measured. The emission peak intensity is obtained from the measured emission spectrum. Here, as a measured value of the surface temperature on the excitation light irradiation side of the phosphor, a value corrected using a measured temperature value by a radiation thermometer and a thermocouple is used.

  Further, in the above, when the wavelength of the excitation light is 400 nm or 455 nm, the change rate of the emission peak intensity at 100 ° C. with respect to the emission peak intensity at 25 ° C. is 40% or less for both the green phosphor and the red phosphor. More preferably. Thereby, when the temperature of the phosphor rises, the decrease in the emission peak intensity as a whole is suppressed while suppressing the change in the color tone of the light from the light emitting device.

  Hereinafter, the red phosphor and the green phosphor that are preferably used in the present invention will be described in detail.

[2-1] Red phosphor The red phosphor combined with the solid state light emitting device in the semiconductor light emitting device of the present invention has an emission peak of 1 or more and a half width of 10 nm or less in a wavelength region of 610 to 650 nm, And it is the fluorescent substance which does not have an excitation spectrum substantially in the light emission wavelength range of the green fluorescent substance mentioned later, and contains Mn4 ⁺ as an activating element. Moreover, it is preferable that a red fluorescent substance has the main light emission peak whose half value width is 10 nm or less in a wavelength range of 610-650 nm. Further, as described above, when the wavelength of the excitation light is 400 nm or 455 nm, the rate of change of the emission peak intensity at 100 ° C. with respect to the emission peak intensity when the phosphor temperature is 25 ° C. is 40% or less, preferably 30%. Below, more preferably 25% or less, still more preferably 22% or less, and particularly preferably 18% or less.

  The red phosphor used in the present invention has an emission peak of 1 or more and a half-value width of 10 nm or less in the wavelength region of 610 to 650 nm, thereby increasing red color purity and realizing a high NTSC ratio. Can do. The full width at half maximum is preferably 8 nm or less, more preferably 7 nm or less.

  In addition, the red phosphor used in the present invention is characterized in that it does not substantially have an excitation spectrum in the emission wavelength region of the green phosphor described later. Thereby, since the light emission of the green phosphor is not used for the light emission of the red phosphor, the light emission of the green phosphor can be used efficiently, and the usage amount of the green phosphor can be reduced. In addition, since the amount of heat generation is also reduced, the rate of change of the emission peak intensity due to the temperature of the phosphor can be suppressed, and the deterioration of the mold part molded with the above-mentioned curable material and the surrounding members are also suppressed. be able to.

  Here, “substantially having no excitation spectrum in the emission wavelength region of the green phosphor” is 1/10 of the maximum excitation intensity of the excitation spectrum of the red phosphor, although it depends on the type of the green phosphor to be combined. Is usually 535 nm or less, preferably 530 nm or less, more preferably 520 nm or less, and even more preferably 515 nm or less. For example, when a phosphor represented by the general formula [G1] described later is used as the green phosphor, a red phosphor having a wavelength that is 1/10 of the maximum excitation intensity of the excitation spectrum at 520 nm or less is used. Is preferred.

As a red phosphor having such characteristics, a phosphor containing Mn ⁴⁺ as an activating element is used in the present invention. Preferably, at least one element selected from alkali metal elements and alkaline earth metal elements and Zn, at least one element selected from Si, Ti, Zr, Hf, Sn, Al, Ga, and In, and halogen Examples include phosphors containing at least one selected from elements. More preferably, the fluorescent substance shown by the following general formula [r1]-[r8] is mentioned.

M ^I ₂ [M ^IV _1-x R _x F ₆ ]... [R1]
M ^I ₃ [M ^III _1-x R _x F ₆ ] ... [r2]
M ^II [M ^IV _1-x R _x F ₆ ] ... [r3]
M ^I ₃ [M ^IV _1-x R _x F ₇ ] ... [r4]
M ^I ₂ [M ^III _1-x R _x F ₅ ] ... [r5]
_{^{Zn 2 [M III 1-x}} R x F 7] ··· [r6]
M ^I [M ^III _2-2x R _2x F ₇ ] ... [r7]
Ba _0.65 Zr _0.35 F _2.70 : Mn ⁴⁺ ... [R8]
(In the general formulas [r1] to [r8], M ^I represents one or more monovalent groups selected from the group consisting of Li, Na, K, Rb, Cs, and NH ₄ , and M ^II represents an alkali M ^III represents at least one metal element selected from the group consisting of earth metal elements, M ^III represents at least one metal element selected from the group consisting of Groups 3 and 13 of the periodic table, and M ^IV represents One or more metal elements selected from the group consisting of groups 4 and 14 of the periodic table are represented, R represents an activator containing at least Mn, and x is represented by 0 <x <1. It is a numerical value in the range.)

Among them, the M ^I, it is particularly preferable to contain one or more elements selected from the group consisting of K and Na. Further, M ^II preferably contains at least Ba, and particularly preferably Ba. Preferred examples of ^{M III, Al, Ga, In} , include one or more metal elements selected from the group consisting of Y and Sc. Among these, Al, Ga, In and combinations thereof are preferable, and among these, it is preferable to contain at least Al, and Al is particularly preferable. Preferred examples of M ^IV, Si, Ge, Sn, include one or more metal elements selected from the group consisting of Ti and Zr, among others Si, Ge, Ti and Zr are preferred, of which at least Si In particular, Si is preferable. x is preferably 0.004 or more, more preferably 0.010 or more, particularly preferably 0.020 or more, and the upper limit is preferably 0.30 or less, more preferably 0.25 or less, and still more preferably 0.08 or less. Especially preferably, it is 0.06 or less.

Preferable specific examples of the compounds represented by the above general formulas [r1] to [r8] include K ₂ [AlF ₅ ]: Mn ⁴⁺ , K ₃ [AlF ₆ ]: Mn ⁴⁺ , K ₃ [GaF ₆ ]: Mn ⁴⁺ , Zn ₂ [AlF ₇ ]: Mn ⁴⁺ , K [In ₂ F ₇ ]: Mn ⁴⁺ , K ₂ [SiF ₆ ]: Mn ⁴⁺ , Na ₂ [SiF ₆ ]: Mn ⁴⁺ , K ₂ [TiF ₆ ]: Mn ⁴⁺ , K ₃ [ZrF ₇ ]: Mn ⁴⁺ , Ba [TiF ₆ ]: Mn ⁴⁺ , K ₂ [SnF ₆ ]: Mn ⁴⁺ , Na ₂ [TiF ₆ ]: Mn ⁴⁺ , Na ₂ [ZrF ₅ ]: Mn ^{_{4+, KRb [TiF 6]:}} Mn 4+, K 2 [Si 0.5 Ge 0.5 F 6]: Mn 4+ and the like.

Of these, the red _{phosphor, K 2 [SiF 6]:} Mn 4+, or _K 2 _[TiF 6]: preferably contains ^{_{Mn 4+, K 2 [SiF 6}} ]: Mn 4+ is more preferable.

In particular, the red phosphor contains a crystal phase having a chemical composition represented by the following formula [R1],
The ratio of Mn to the total number of moles of M ⁴ and Mn is 0.1 mol% or more and 40 mol% or less, and
A phosphor having a specific surface area of 1.3 m ² / g or less is preferred.

M ¹ ₂ M ⁴ F ₆ : R ... [R1]
(In the formula [R1], M ¹ contains one or more elements selected from the group consisting of K and Na, M ⁴ contains Si, and R contains an activation containing at least Mn. Represents an element.)

In the above formula [R1], M ¹ contains an element selected from the group consisting of potassium (K) and sodium (Na). Any one of these elements may be contained alone, or two of them may be contained in any ratio. In addition to the above, an alkali metal element such as Li, Rb, and Cs or a part of (NH ₄ ) may be contained as long as the performance is not affected. The content of Li, Rb, Cs and (NH ₄ ) is usually 10 mol% or less based on the total amount of M ¹ .

Of these, M ¹ preferably contains at least K. Usually, K accounts for 90 mol% or more, preferably 97 mol% or more, and more preferably with respect to the total amount of M ^1. Occupies 98 mol% or more, more preferably 99 mol% or more, and it is particularly preferable to use only K.

In the above formula [R1], M ⁴ contains at least Si. Usually, Si accounts for 90 mol% or more based on the total M ⁴ amount is preferably when account for more than 97 mol%, more preferably if the account for at least 98 mol%, more preferably at least 99 mol% It is particularly preferable to use only Si. That is, it is particularly preferable that the phosphor containing a crystal phase having the chemical composition represented by the formula [R1] contains a crystal phase having a chemical composition represented by the following formula [R2].

M ¹ ₂ SiF ₆ : R ... [R2]
(In the formula [R2], M ¹ contains one or more elements selected from the group consisting of K and Na, and R represents an activation element containing at least Mn.)

As good activation element be contained in addition to Si as ^{M 4, Ti, Zr, Ge} , Sn, Al, Ga, B, In, Nb, Ta, W, Re, Mo, Zn, and Mg 1 type or 2 types or more chosen from the group which consists of are mentioned.

  In the above formulas [R1] and [R2], R is an activation element containing at least Mn, and as R, an activation element that may be contained in addition to Mn is Cr, Fe, Co, Ni, 1 type, or 2 or more types chosen from the group which consists of Cu, Ru, and Ag is mentioned.

  R preferably contains 90 mol% or more of Mn relative to the total amount of R, more preferably 95 mol% or more, particularly preferably 98 mol% or more, and particularly preferably contains only Mn.

  In the phosphor of the present invention, the ratio of Mn to the total number of moles of Si and Mn (in the present invention, this ratio is hereinafter referred to as “Mn concentration”) is 0.1 mol% or more and 40 mol% or less. It is characterized by. If the Mn concentration is too low, the absorption efficiency of the excitation light by the phosphor decreases, so the luminance tends to decrease. If it is too high, the absorption efficiency increases, but the internal quantum efficiency and luminance decrease due to concentration quenching. Tend to. More preferable Mn concentration is 0.4 mol or more, more preferably 1 mol% or more, particularly preferably 2 mol% or more, 30 mol% or less, more preferably 25 mol% or less, and still more preferably 8 mol%. Hereinafter, it is particularly preferably 6 mol% or less.

  The phosphor represented by the above formula [R1] or [R2] is preferably produced by the method described in the phosphor production method described later. In the phosphor production method, for the following reason: There is a slight difference between the charged composition of the phosphor raw material and the composition of the obtained phosphor. The phosphor of the present invention is characterized by having the above-mentioned specific composition as the composition of the obtained phosphor, not the raw material composition at the time of phosphor production.

Here, the ionic radius of ^{Mn 4+} (0.53 Å) is larger than the ionic radius (0.4 Å) of ^{Si 4+, Mn 4+} _is not totally dissolved in K 2 SiF _6, since the partial solid solution, In the phosphor of the present invention, the substantially activated Mn ⁴⁺ concentration is limited and reduced as compared with the charged composition. However, even when the concentration of Mn ⁴⁺ contained in the phosphor is low, according to the manufacturing method described later, since the particle growth is promoted, sufficient absorption efficiency and luminance can be provided.

  In addition, the chemical composition analysis of the Mn concentration contained in the phosphor in the present invention can be measured by, for example, SEM-EDX. In this method, in scanning electron microscope (SEM) measurement, the phosphor is irradiated with an electron beam (for example, an acceleration voltage of 20 kV), and characteristic X-rays emitted from each element contained in the phosphor are detected to detect the element. Analyze. As a measuring apparatus, SEM (S-3400N) manufactured by Hitachi, Ltd. and an energy dispersive X-ray analyzer (EDX) EX-250x-act manufactured by Horiba, Ltd. can be used.

  In addition to the elements constituting the phosphor, the phosphor includes one or two selected from the group consisting of Al, Ga, B, In, Nb, Ta, W, Re, Mo, Zn, and Mg. More than one element may be contained in a range that does not adversely affect the performance of the phosphor.

  The phosphor represented by the above formula [R1] or [R2] can be produced according to a known method by mixing raw materials containing each constituent element. Specifically, a method in which each reagent is dissolved in hydrofluoric acid and then the solution is heated to evaporate and dry the phosphor (J. Electrochem. Soc. Vol. 120, No. 7, (1973). ), 942-947, U.S. Patent Application Publication No. 2006/169998), and by dissolving each reagent in HF acid and then adding a poor solvent to deposit a phosphor (US) Patent No. 3576756) can be used.

Moreover, in the case of the phosphor represented by the above formula [R1], those produced by the following method using no poor solvent are preferable to the above poor solvent precipitation method. Here, the method without using a poor solvent means that “a mixture of two or more solutions containing one or more elements selected from the group consisting of K, Na, Si, Mn, and F was deposited by mixing. A method for obtaining a precipitate (phosphor) ”, and in this method, it is preferable that the mixed solution contains all of the elements constituting the target phosphor. Specific examples of the combination of the solutions to be mixed include the following 2-1) and the following 2-2).

  2-1) A method of mixing a solution containing at least Si and F and a solution containing at least K (and / or Na), Mn and F.

  2-2) A method of mixing a solution containing at least Si, Mn and F with a solution containing at least K (and / or Na) and F.

Examples of the “solution containing at least Si and F” include hydrofluoric acid containing an SiF ₆ source (hereinafter referred to as “HF aqueous solution”), and the above “at least K (and / or Na)”. Examples of the “solution containing Mn, M and F” include an HF aqueous solution containing a K (and / or Na) source and a Mn source.

The “solution containing at least Si, Mn, and F” includes an HF aqueous solution containing a SiF ₆ source and a Mn source, and contains the above “at least K (and / or Na) and F. Examples of the “solution” include an aqueous HF solution containing a K (and / or Na) source.

  After the reaction, crystals of the target phosphor are precipitated. The crystals are recovered by solid-liquid separation by filtration or the like, washed with a solvent such as ethanol, water, acetone, etc., and usually 100 ° C. or higher, preferably 120 It is preferable to dry at a temperature of not less than 150 ° C, more preferably not less than 150 ° C, and usually not more than 300 ° C, preferably not more than 250 ° C, more preferably not more than 200 ° C. The drying time is not particularly limited as long as the water adhering to the phosphor can be evaporated, but for example, it is dried for about 1 to 2 hours.

The phosphor represented by the above formula [R1] or [R2] used in the present invention has a specific surface area of usually 1.3 m ² / g or less, preferably 1.1 m ² / g or less, particularly preferably. in 1.0 m ² / g or less, typically 0.05 m ² / g or more and among them 0.1 m ² / g or more. If the specific surface area of the phosphor is too small, the phosphor particles are large, which tends to cause coating unevenness and clogging of the dispenser, etc. If too large, the phosphor particles are small, so the contact area with the outside increases and durability It becomes inferior.

  The specific surface area of the phosphor is measured by the BET 1-point method, for example, using a fully automatic specific surface area measuring device (flow method) AMS1000A manufactured by Okura Riken Co., Ltd.

Furthermore, it is preferable that the peak value of the particle size distribution is one. More preferably, the peak width of the particle size distribution is narrow, and the quadrature deviation of the particle size distribution is 0.60 or less, preferably 0.40 or less, more preferably 0.35 or less, more preferably 0.30 or less, Particularly preferably, it is 0.25, usually 0.18 or more, preferably 0.20 or more. The quadrature deviation of the particle size distribution can be calculated using a particle size distribution curve measured using a laser diffraction / scattering particle size distribution measuring device.

[2-2] Green phosphor As the green phosphor combined with the solid state light emitting device in the semiconductor light emitting device of the present invention, various phosphors having one or more emission peak wavelengths in a wavelength region of 515 to 550 nm, preferably 515 to 535 nm. It is possible to use a phosphor. Examples of the green phosphor for realizing such an image with high color purity include oxynitride phosphors, sialon phosphors, aluminate phosphors and orthosilicate phosphors, among which europium and phosphor And / or cerium-activated oxynitride phosphor, europium-activated sialon phosphor, europium-activated Mn-containing aluminate-based phosphor and europium-activated orthosilicate-based fluorescence The body is preferred.

Hereinafter, specific examples of preferably used green phosphors will be described.
[2-2-1] Oxynitride phosphors activated with europium and / or cerium Another specific example of the green phosphor includes a compound represented by the following general formula [G1].
_{M1 x Ba y M2 z L u} O v N w [G1]
(However, in general formula [G1], 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 above general formula [G1], M1 is an activating 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 above general formula [G1], 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.

  In addition, the phosphor of the present invention maintains the specific phase crystal structure described below (hereinafter sometimes referred to as “BSON phase crystal structure”), and the position of Ba is Sr, Ca, Mg and / or Zn. Can be substituted. Therefore, in the general formula [G1], 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 M2 in the said general formula [G1], any one of these elements may be contained independently, and two or more may be included in any combination and ratio.

  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 amount of Ca increases more than this, the emission wavelength may become longer and the emission peak 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 peak 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 peak intensity may be lowered.

  Therefore, in the above general formula [G1], 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 [G1], y is a numerical value in a range of 0 ≦ y ≦ 2.9999. In the general formula [G1], 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 above general formula [G1], the value of x + y + z may be less than 3, and x + y + z can usually 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 [G1], 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 [G1], 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 above general formula [G1], 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 [G1]. Specifically, in the general formula [G1], 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 general formula [G1], 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 [G1], it is particularly preferable that u, v, and w are 5 ≦ u ≦ 7, 9 <v <15, and 0 <w <4, respectively. Thereby, the emission peak 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 green phosphor used in 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) 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, and the like.

  The oxynitride phosphor used in the present invention preferably includes a specific crystal structure, that is, a BSON phase crystal structure defined below.

[2-2-1-1] BSON phase A crystal in which a diffraction peak is observed in a diffraction angle (2θ) range of 26.9 to 28.2 ° (R0) in an X-ray diffraction measurement using a CuKα X-ray source. 5 diffraction peaks derived from the Bragg angle (θ0) of P0 (provided that the diffraction peak is in the angle range of 20.9 ° to 22.9 °). Are, in order from the low angle side, P1, P2, P3, P4, and P5, and the angle ranges of diffraction angles of these diffraction peaks are R1, R2, R3, R4, and R5, R1, R2 , R3, R4 and R5 are R1 = R1s to R1e, respectively.
R2 = R2s to R2e,
R3 = R3s to R3e,
R4 = R4s to R4e,
R5 = shows the angular range of R5s to R5e,
At least one diffraction peak exists in all the ranges of R1, R2, R3, R4, and R5, and the height of the diffraction peak having the highest diffraction peak height among P0, P1, P2, P3, P4, and P5 On the other hand, the intensity of P0 has a diffraction peak height ratio of 20% or more, and at least one of P1, P2, P3, P4 or P5 has a diffraction peak height ratio of 5 or more. % Or more, preferably 9% or more.

  Here, when there are two or more diffraction peaks in each angular range of the angular ranges R0, R1, R2, R3, R4, and R5, the peak having the highest peak intensity among these is P0, P1, Let P2, P3, P4 and P5.

R1s, R2s, R3s, R4s and R5s are the start angles of R1, R2, R3, R4 and R5, respectively. R1e, R2e, R3e, R4e and R5e are the ends of R1, R2, R3, R4 and R5, respectively. An angle is shown, and the following angles are shown.
R1s: 2 × arcsin {sin (θ0) / (1.994 × 1.015)}
R1e: 2 × arcsin {sin (θ0) / (1.994 × 0.985)}
R2s: 2 × arcsin {sin (θ0) / (1.412 × 1.015)}
R2e: 2 × arcsin {sin (θ0) / (1.412 × 0.985)}
R3s: 2 × arcsin {sin (θ0) / (1.155 × 1.015)}
R3e: 2 × arcsin {sin (θ0) / (1.155 × 0.985)}
R4s: 2 × arcsin {sin (θ0) / (0.894 × 1.015)}
R4e: 2 × arcsin {sin (θ0) / (0.894 × 0.985)}
R5s: 2 × arcsin {sin (θ0) / (0.756 × 1.015)}
R5e: 2 × arcsin {sin (θ0) / (0.756 × 0.985)}

  The phosphor used in the present invention contains an impurity phase such as cristobalite, α-silicon nitride, β-silicon nitride which is a single crystal form of silicon dioxide in X-ray diffraction measurement using a CuKα X-ray source. Also good. The content of these impurities can be known by X-ray diffraction measurement using a CuKα X-ray source. That is, the strongest peak intensity of the impurity phase in the X-ray diffraction measurement result is usually 40% or less, preferably 30% or less with respect to the strongest peak intensity of the P0, P1, P2, P3, P4 and P5. More preferably, it is 20% or less, and more preferably 10% or less. In particular, it is preferable that the peak of the impurity phase is not observed and the BSON phase exists as a single phase. Thereby, the emission peak intensity can be increased.

  As the oxynitride phosphor used in the present invention, the phosphor described in International Publication No. 2007/088966 Pamphlet can be used.

As another specific example of the green phosphor, 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 = 1.5-2.5) Eu ²⁺ active Sr-SiON that can be excited by light having a wavelength in the range from ultraviolet to blue.

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

[2-2-2] Sialon phosphor activated by europium Another specific example of the green phosphor was announced by the National Institute for Materials Science, March 23, 2005, for example. Examples include β-SiAlON activated by europium as described in Tsukuba Research Academy City Press Association, MEXT Press Association, Science Press Association materials "Successfully developed green phosphor for white LED".

[2-2-3] Europium-activated Mn-containing aluminate-based phosphor Another specific example of the green phosphor includes a compound represented by the following general formula [G2].
R _1-a Eu _a M _1-b Mn _b A ₁₀ O ₁₇ [G2]
(In the general formula [G2], a and b are numbers satisfying 0.05 <a ≦ 1, 0.6 <a / b <5 and 0.01 <b ≦ 0.9, respectively, and R is , Ba, Sr, Ca represents at least one element selected from the group, M represents Mg and / or Zn, and A represents at least one element selected from the group of Al, Ga, Sc, B .)

  Among these, when a is 0.05 or less, the emission peak intensity of the crystal phase when excited by light having a wavelength of 400 nm tends to be low. A crystal phase having a chemical composition with a number satisfying 0.05 <a ≦ 1 is preferable because the emission peak intensity is high. For the same reason, a is preferably 0.1 ≦ a ≦ 1, more preferably 0.2 ≦ a ≦ 1, particularly preferably 0.25 ≦ a ≦ 1, and most preferably 0.3 ≦ a ≦ 1. preferable.

  When the ratio of a to b, a / b, is 0.6 or less, excitation light having a wavelength of 400 nm cannot be sufficiently absorbed, and the emission peak intensity from the second light emitter tends to be small. On the other hand, when a / b is 5 or more, the blue light emission peak intensity is stronger than the green light emission peak intensity, and it is difficult to obtain green light emission with good color purity. A crystal phase having a chemical composition in which a / b satisfies 0.6 <a / b <5 has a high ratio of green emission peak intensity near wavelength 515 nm to blue emission peak intensity near wavelength 450 nm, and green purity. Is preferable because a light emitting device having a high color rendering property and a high color rendering property can be obtained. For the same reason, the lower limit of a / b is preferably a / b ≧ 0.8, and more preferably a / b ≧ 1. The upper limit is preferably a / b ≦ 4, more preferably a / b ≦ 3.

  The element represented by R in the general formula [G2] is at least one element selected from the group of Ba, Sr, and Ca, but contains a crystal phase having a chemical composition that becomes Ba and / or Sr. It is preferable because high emission peak intensity can be obtained. Further, it is more preferable that Ba be 50 mol% or more of R and Sr be 10 mol% or more of R because a high emission peak intensity can be obtained.

  The element represented by M in the general formula [G2] is Mg and / or Zn, but it is preferable to contain a crystal phase having a chemical composition of Mg because a high emission peak intensity can be obtained.

  The element represented by A in the general formula [G2] is at least one element selected from the group consisting of Al, Ga, Sc, and B, but has a chemical composition in which 50 mol% or more of A is Al. It is preferable that a phase is contained in order to obtain a high emission peak intensity. Furthermore, it is more preferable that 99% or more of A is Al because the light emission characteristics are good.

  Among them, a phosphor containing an alkali metal in the crystal phase of the phosphor having the above composition and having an alkali metal element content of 3% or less with respect to the number of sites that can be substituted by Eu was excited by near-ultraviolet light. Even in such a case, it is preferable because it has a stable high emission peak intensity and luminance and is excellent in temperature characteristics.

  As the alkali metal element, Li, Na and K are preferable, and Na and K are particularly preferable.

  The content of the alkali metal element is preferably 0.1% or more, more preferably 0.2% or more, still more preferably 0.3% or more, particularly preferably 0.5% or more, preferably Is not more than 2.6%, more preferably not more than 2.3%, still more preferably not more than 2%, particularly preferably not more than 1.8%, particularly preferably not more than 1.6%.

  Furthermore, as said fluorescent substance, what contains F as an anion element is preferable. The content of F element is greater than 0%, preferably 0.01% or more, more preferably 0.05% or more, with respect to the number of sites that can be substituted by Eu in the crystal phase of the phosphor having the above composition. More preferably, it is 0.1% or more, usually 10% or less, preferably 5% or less, more preferably 3% or less.

  Such a phosphor can be obtained by allowing a monovalent metal halide to coexist at a predetermined concentration as a flux during firing of the raw material mixture, as described in International Publication No. 2008/123498.

  These phosphors have a reduction rate of the emission peak intensity at an excitation wavelength of 400 nm with respect to the emission peak intensity at an excitation wavelength of 340 nm measured at a temperature of 25 ° C. of 29% or less, preferably 26% or less. More preferably, it is 23% or less. The reduction rate of the emission peak intensity at the excitation wavelength of 390 nm with respect to the emission peak intensity at the excitation wavelength of 382 nm measured at a temperature of 25 ° C. is 3.1% or less, preferably 2.5% or less, More preferably, it is 2% or less, and further preferably 1.5% or less. In addition, the reduction rate of these luminescence peak intensity | strength is 0 or more normally.

  The excitation spectrum can be performed, for example, using a 150 W xenon lamp as an excitation light source and a fluorescence measurement device (manufactured by JASCO Corporation) equipped with a multichannel CCD detector C7041 (manufactured by Hamamatsu Photonics) as a spectrum measurement device. .

[2-2-4] Orthosilicate phosphor activated by europium Another specific example of the green phosphor is a compound represented by the following general formula [G3].
(M1 _(1-x) M2 _x ) _α SiO _β [G3]
(In General Formula [G3], M1 represents one or more elements selected from the group consisting of Ba, Ca, Sr, Zn, and Mg, and M2 is a kind that can take a divalent and trivalent valence. The above metal elements are represented.
x, α, and β are 0.01 <x <0.3, 1.5 ≦ α ≦ 2.5, and 3.5 ≦ β ≦ 4.5, respectively.
Represents a number that satisfies )

  Among these, M1 preferably contains at least Ba. In this case, the molar ratio of Ba to the entire M1 is usually 0.5 or more, particularly 0.55 or more, more preferably 0.6 or more, and usually less than 1, particularly 0.97 or less, more preferably 0.9 or less, The range of 0.8 or less is particularly preferable.

  Further, M1 preferably contains at least Ba and Sr. Here, when the molar ratios of Ba and Sr to the entire M1 are [Ba] and [Sr], respectively, the ratio of [Ba] to the sum of [Ba] and [Sr], that is, [Ba] / ([Ba] + [Sr]) is usually greater than 0.5, especially 0.6 or more, more preferably 0.65 or more, and usually 1 or less, especially 0.9 or less, and further 0.8 or less. A range is 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, usually 15 or less, especially 10 or less, more preferably 5 or less, and particularly preferably 3.5 or less.

  In the general formula [G3], when M1 contains at least Sr, part of Sr may be 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.

  Further, Si may be partially substituted by other elements such as Ge. However, from the standpoint of green emission peak 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 [G3], M2 is listed as an activator element and represents one or more metal elements that can have a divalent and trivalent valence. Specific examples include transition metal elements such as Cr and Mn; rare earth elements such as Eu, Sm, Tm, and Yb. As M2, any one of these elements may be contained alone, or two or more may be contained in any combination and ratio. Among these, as M2, Sm, Eu, and Yb are preferable, and Eu is particularly preferable.

  In the general formula [G3], x is a number that represents the number of moles of M2, and is specifically greater than 0.01, preferably greater than or equal to 0.04, more preferably greater than or equal to 0.05, and particularly preferably. Represents a number of 0.06 or more, usually less than 0.3, preferably 0.2 or less, more preferably 0.16 or less.

  In the general formula [G3], α is preferably close to 2, usually 1.5 or more, preferably 1.7 or more, more preferably 1.8 or more, and usually 2.5 or less, preferably 2. It represents a number in the range of 2 or less, more preferably 2.1 or less, particularly preferably 2.

  In the general formula [G3], 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.

  The specific composition phosphor includes alkali metal elements, alkaline earth metal elements, zinc other than the elements described in the above formula (general formula [G3], that is, M1, M2, Si (silicon), and O (oxygen)). (Zn), Yttrium (Y), Aluminum (Al), Scandium (Sc), Phosphorus (P), Nitrogen (N), Rare earth elements, Halogen elements and other monovalent elements, Divalent elements, Trivalent elements It may contain an element selected from the group consisting of an element, a −1 valent element, and a −3 valent element (hereinafter referred to as “trace element” as appropriate), and particularly contains an alkali metal element or a halogen element. Are preferred.

  The total content of the trace elements is usually 1 ppm or more, preferably 3 ppm or more, more preferably 5 ppm or more, and usually 100 ppm or less, preferably 50 ppm or less, more preferably 30 ppm or less. When the specific composition phosphor contains plural kinds of trace elements, the total amount thereof satisfies the above range.

Examples of the phosphor represented by the general formula [G3] as described above include those described in the pamphlet of International Publication No. 2007/052405, and in particular, the raw material mixture or the fluorescence obtained by firing the mixture. The precursor is fired, and after the firing, in a strongly reducing atmosphere, 0.05 moles or more of SrCl ₂ is used alone or further 0.1 mole as a flux with respect to silicon (Si) in the phosphor. What was obtained through the process of baking in the presence of the above CsCl is preferable because it has a high external quantum efficiency.

  Moreover, what baked in strong reducing atmospheres, such as coexisting solid carbon, is preferable at the time of baking.

The phosphor represented by the general formula [G3] has an emission peak half-value width of 75 nm or less when excited with light having a peak wavelength of 400 nm or 455 nm, and when excited with light having a peak wavelength of 400 nm or 455 nm. The external quantum efficiency defined by the following formula is 0.59 or more, preferably 0.60 or more, more preferably 0.63 or more, and further preferably 0.65 or more.
(External quantum efficiency) = (internal quantum efficiency) x (absorption efficiency)

[2-3] Blue phosphor As a blue phosphor combined with a solid-state light emitting element as necessary in the semiconductor light emitting device of the present invention, one or more emission peak wavelengths in a wavelength region of 420 nm to 490 nm, preferably 430 nm to 480 nm. It is possible to use various phosphors having Examples of blue phosphors for realizing such images with high color purity include halophosphate phosphors, aluminate phosphors, and merwinite phosphors. Among them, halophosphorus activated with europium. Preference is given to acid-based phosphors, aluminate-based phosphors activated with europium, and merwinite-based phosphors activated with europium.

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

[2-3-1] Europium-activated halophosphate-based phosphor As a specific example of a blue phosphor, a phosphor having a chemical composition represented by the following general formula [B1] can be given.
_{(Sr 10-x-y-} z M x Eu y Mn z) (PO 4) 6 (Cl 1-a Q a) 2 [B1]
(In the general formula [B1],
“M” represents at least one element selected from the group consisting of Ba, Ca, Mg, and Zn;
“Q” represents at least one element selected from the group consisting of F, Br, and I;
“X”, “y”, “z”, and “a” are each
0 ≦ x <10,
0.3 ≦ y ≦ 1.5,
0 ≦ z ≦ 3,
0 ≦ a ≦ 1,
x + y + z ≦ 10,
Represents a number that satisfies )

  In the general formula [B1], “M” represents one or more elements selected from the group consisting of Ba, Ca, Mg, and Zn. As the “M”, any one of these elements may be contained alone, or two or more may be used in any combination and ratio.

  In the general formula [B1], “x” is a numerical value representing the amount of substitution of “M” for the Sr site. The numerical value is usually 0 or more, and usually less than 10, preferably 5 or less, more preferably 2 or less. In particular, when the phosphor of the present invention is used for illumination, etc., when it is desired to obtain a phosphor having a wide emission peak half width and high brightness, “x” is usually 0.1 or more, preferably 0.5 or more. Also, it is usually less than 10. On the other hand, when the phosphor of the present invention is used for backlighting of an image display device, it is preferable that the half width of the emission peak is narrow, so “x” is preferably 0.3 or less, more preferably 0. .

  In the general formula [B1], “y” is a numerical value representing the amount of substitution of Eu for the Sr site. The lower limit of the numerical value is usually 0.3 or more, preferably 0.4 or more, particularly preferably 0.5 or more. Here, if the substitution amount of Eu is small, sufficient emission peak intensity may not be obtained. On the other hand, if the Eu substitution amount is large, the emission peak intensity increases, but the temperature characteristics may be lowered. Therefore, the upper limit of the Eu substitution amount is usually 1.5 or less, more preferably 1.2 or less. More preferably, it is less than 1, particularly preferably less than 0.9.

  In the general formula [B1], “z” is a numerical value representing the amount of substitution of Mn for the Sr site. The numerical value is usually 0 or more and usually 3 or less. In particular, when obtaining a blue-emitting phosphor, it is more preferable that “z = 0”.

The relationship between “x”, “y”, and “z” is preferably “x + y + z ≦ 10”, but more preferably “x + y + z <10”. This means that at least Sr is preferably included in the chemical composition represented by the general formula [B1].

  In the general formula [B1], “Q” represents one or more elements selected from the group consisting of F, Br, and I. As the “Q”, any one of these elements may be contained alone, or two or more kinds may be used in any combination and ratio.

  In the formula (B1), “a” is a numerical value representing the amount of substitution of Q for Cl sites. “A” is usually 0 or more, and usually 1 or less, preferably 0.1 or less. If it exceeds this range, the emission peak wavelength may shift. In particular, when a phosphor emitting blue light is desired, “a = 0” is preferable.

  As described above, the Sr site in the general formula [B1] can be substituted with a divalent metal element such as Ba, Ca, Mg, Zn, or Mn. The Cl site can be replaced with F, Br, I, or the like. Since the alkaline earth metal is often located at the Sr site, the site can also be called an alkaline earth metal site.

  Furthermore, as long as the amount is small, elements other than the elements described above may be substituted. For example, metallic elements having different valences such as Na and La may be substituted at the Sr site.

  Specific examples of the preferred composition of the blue phosphor that can be used in the present invention are given below, but the composition of the blue phosphor that can be used in the present invention is not limited to the following examples.

Examples of the blue phosphor include (Sr _9.2 Eu _0.8 ) (PO ₄ ) ₆ Cl ₂ , (Sr ₉ Eu) (PO ₄ ) ₆ Cl ₂ , (Sr _8.2 CaEu _0.8 ) ( PO ₄ ) ₆ Cl ₂ , (Sr _7.2 BaCaEu _0.8 ) (PO ₄ ) ₆ Cl ₂ , (Sr ₉ Eu) (PO ₄ ) ₆ Cl _1.8 F _0.2 , (Sr _9.1 Eu) _{0.8 Mn 0.1) (PO 4)} 6 Cl 2, include _{(Sr 6 BaCaMgEu) (PO 4} ) 6 Cl 1.8 F 0.2 and the like.

Moreover, among the phosphors represented by the general formula [B1], it is preferable that the external quantum efficiency is high. Specifically, the external quantum efficiency η _o when the phosphor is excited with light having a wavelength of 400 nm is usually 77% or more, preferably 78% or more, more preferably 79% or more, and further preferably 80% or more.

Further, as the phosphor represented by the general formula [B1], in the excitation spectrum at room temperature (25 ° C.), the intensity of the excitation peak at a wavelength of 400 nm is I _ex (400), and the intensity of the excitation peak at a wavelength of 350 nm. the when the _I ex _(350), the value of _{I ex (400) / I ex} (350) is preferably 0.8 or more, more preferably 0.85 or more, more preferably 0.86 or more, 0 .9 or more is particularly preferable, and the closer to 1, the more preferable. The value of I _ex (400) / I _ex (350) is a value characterizing the shape of the excitation spectrum. The closer the value is to 1, the flatter the excitation band.

As a manufacturing method of the phosphor represented by the general formula [B1], a manufacturing method described in International Publication No. 2009/005035 pamphlet (for example, a manufacturing method as represented by Synthesis Example 8 in Examples described later). It is preferable that it was manufactured by.

[2-3-2] Europium-activated aluminate-based phosphor Another specific example of the blue phosphor includes a compound represented by the following general formula [B2].

R _1-a Eu _a Mg _1-b Mn _b Al ₁₀ O ₁₇ (B2)
(In the general formula [B2], a and b are numbers satisfying 0.2 <a ≦ 0.5 and 0 ≦ b ≦ 0.1, respectively, R includes at least Ba, and Sr, Or the element which may contain Ca is shown.)

  In the general formula [B2], since the emission peak intensity is high, a is particularly preferably 0.25 ≦ a ≦ 0.5, and most preferably 0.3 ≦ a ≦ 0.5.

  Among the phosphors represented by the general formula [B2], the alkali metal is contained in the crystal phase of the phosphor having the above composition, and the content of the alkali metal element with respect to the number of sites that Eu can substitute is 3% or less. Even when the phosphor is excited by near ultraviolet light, it is preferable because it has a stable high emission peak intensity and luminance and is excellent in temperature characteristics.

  The alkali metal element is the same as that of the green phosphor represented by the general formula [G2].

  Furthermore, as said fluorescent substance, what contains F as an anion element is preferable. The content of F element is the same as that of the green phosphor represented by the general formula [G2].

  The method for producing such a phosphor is the same as that for the green phosphor represented by the above general formula [G2].

[2-3] Preferred Combinations of Each Color Phosphor While the red phosphor and the green phosphor have been described above, Table 1 illustrates preferred combinations of the above-described color phosphors.

  Table 2 shows more preferable combinations among the combinations shown in Table 1.

  Further, particularly preferred combinations are shown in Table 3.

  Each color phosphor shown in Tables 1-3 is excited by light in the blue or deep blue region, emits light in a narrow band in the red region and the green region, respectively, and is excellent in that the change in emission peak intensity due to temperature change is small. Temperature characteristics.

  Therefore, the color image display device of the present invention, which can set the luminous efficiency higher than the conventional one by combining two or more kinds of phosphors including these color phosphors with a solid light emitting element that emits light in a blue or deep blue region. It is possible to provide a semiconductor light emitting device suitable for a light source used for a general purpose backlight.

When a solid light emitting element that emits light in the near ultraviolet or ultraviolet region and a phosphor are used in combination, the combination of phosphors described in Tables 1 to 3 above is further added to (Sr, Ca, Ba, Mg) ₁₀ ( PO ₄ ) ₆ (Cl, F): Eu, and (Sr, Ba) ₃ MgSi ₂ O ₈ : Eu, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu selected from the group consisting of Eu It is preferable to combine phosphors, and it is more preferable to combine (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F): Eu or (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu. preferable. At this time, it is preferable to combine BaMgAl ₁₀ O ₁₇ : Eu, Mn as the green phosphor.

  When a sealing material is used for a semiconductor light emitting device, it is preferable to use the above-mentioned silicone material as the sealing material from the viewpoints of deterioration resistance and heat resistance. It is more preferable to use a condensation type silicone material having a Si—O—Si bond obtained by condensation at a crosslinking point.

  In addition, an image display with high color purity can be realized by combining a color filter optimal for the emission wavelength of the semiconductor light emitting device. That is, by using the above semiconductor light emitting device combining a red phosphor and a green phosphor having a high emission peak intensity in a narrow band and excellent temperature characteristics as a light source for a backlight, even at a high NTSC ratio, compared with the conventional technology. In addition, since a solid light emitting element that has high light utilization efficiency and generates heat when driven is used, it is possible to obtain an excellent color image display device in which the emission peak intensity is stable and the color shift is small even when the temperature of the semiconductor light emitting device becomes high. it can.

[3] Color filter Although 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 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, graphite, iron black, aniline black, cyanine black, titanium black and other black color materials used alone or in combination, or red, green, blue appropriately selected from inorganic or organic pigments and dyes A black matrix is formed in the same manner as the method for forming red, green, and blue pixel images described below using a color filter composition containing a black color material by mixing the above.

  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 coated film after drying, that is, the film thickness of each pixel 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; and alkylbenzene sulfonic acids. Anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinic acid ester salts; 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. 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. A coloring composition for a color filter.

  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 JP-A-2005-232432, paragraphs 0055 to 0066.

(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, trimethylol propane 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, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 17 176, 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, etc.

[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, brominated zinc phthalocyanine pigment.

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

  Specific examples of the green pixel satisfying the above conditions include, in particular, Pigment Green 36, Pigment Green 7 and / or brominated zinc phthalocyanine pigment as a green pigment, and JP-A-2007-25687 as a yellow pigment for toning. It is preferable to include any one or more of the described azo nickel complex yellow pigment (hereinafter simply referred to as “azo nickel complex yellow pigment”), pigment yellow 138, and pigment yellow 139. As the brominated zinc phthalocyanine green pigment, Pigment Green 58 is preferable.

  In the present invention, when producing a color image display device having an NTSC ratio of 85% or more, particularly 90% or more, Pigment Green 7 or brominated zinc phthalocyanine pigment is used instead of Pigment Green 36 from the viewpoint of transmittance. It is preferable to use it. As the brominated zinc phthalocyanine, brominated zinc phthalocyanine containing 13 or more bromine atoms on average in one molecule is preferable because it exhibits high transmittance and is suitable for forming a green pixel of a color filter. Furthermore, brominated zinc phthalocyanine having 13 to 16 bromine atoms in one molecule and not containing chlorine or having an average of 3 or less in one molecule is preferable, and in particular, an average of 14 bromine atoms in one molecule is 14 Brominated zinc phthalocyanine having ˜16 and not containing chlorine atoms in one molecule or having an average of 2 or less is preferred. Table 4 shows a preferable blending example of the color material constituting the green pixel.

[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-59-152396 and JP-A-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 having the above, 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, 54-155292, JP 45-37377, JP 48-84183, JP 52-112681, JP 58-15503, JP 60 JP-A-88005, JP-A-59-56403, JP-A-2-69, JP-A57-168088, JP-A-5-1077. 1, JP-A No. 5-210240, JP-can be mentioned dyes having a dialkyl aminobenzene skeleton described in JP-A-4-288818.

  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.

[4] Other Configurations The color image display device preferably has an absorption portion containing an absorbent that absorbs ultraviolet to near ultraviolet light emitted from the semiconductor light emitting device. It may be provided in a panel portion that displays an image, or may be provided in a backlight.

  When the absorption part is provided in the panel part, for example, in FIG. 1, the absorption part is formed between the light diffusion sheet 3 and the polarizing plate 4, between the polarizing plate 4 and the glass substrate 5, and between the glass substrate 8 and the polarizing plate 10. It can arrange | position in any one or more places, such as between and the surface of the polarizing plate 10. Moreover, when providing an absorption part in a backlight, an absorption part is a light control between the light source 1 and the light guide 11, between the light guide 11 and the light control sheet 13, for example in FIG.3 and FIG.4. It can arrange | position in any one or more places among the surfaces of the sheet | seat 13, etc.

  In both cases where the absorbing portion is provided in the panel portion and in the backlight, the absorbing portion can be provided as a sheet formed from a resin containing an absorbent, or a coating film, and the absorbent may be provided as described above. It can also be provided by mixing in the member.

  As described above, by providing the color image display device with the absorbing portion, it is possible to suppress the influence of ultraviolet to near-ultraviolet light on various members and observers constituting the color image display device. From the viewpoint of suppressing the influence on the observer, the position where the absorption portion is provided is arbitrary, but from the viewpoint of suppressing the influence on the members constituting the color image display device, the absorption portion is formed from the semiconductor light emitting device. It is preferable to provide as close to the semiconductor light emitting device as possible in the light traveling direction. In particular, in order to suppress deterioration of the liquid crystal and the color filter due to ultraviolet to near-ultraviolet light, it is preferable to provide an absorption portion in front of the liquid crystal in the traveling direction of light from the semiconductor light emitting device.

  Here, the absorbent contained in the absorption part will be described in detail. The absorbent used in the present invention is not particularly limited as long as it has an action of absorbing ultraviolet to near ultraviolet light. For example, o-hydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2 Benzophenone series such as -hydroxy-4-methoxybenzophenone; 2- (2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy Benzotriazoles such as -3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole; ethyl-2-cyano-3 , 3-Diphenyl acrylate, 5-ethylhexyl-2-cyano-3,3-diphenyl acrylate Cyanoacrylates such as carbonates; salicylic acids such as phenylsulcylate and 4-t-butylphenylsulcylate; 2-ethyl-5′-t-butyl-2′-ethoxy-N, N′-di Examples thereof include oxalic anilides such as phenyloxalamide; and inorganic oxides such as zinc oxide, titanium oxide, and zirconium oxide. These inorganic oxides may be contained in glass and used as ultraviolet shielding glass.

  Since the absorbent can be used by dissolving in the resin, the transparency is good. Moreover, the inorganic absorber can obtain the absorption part excellent in transparency by using dispersed particles having an average particle diameter of 100 nm or less. Moreover, it is preferable that the surface of particles of a photoactive compound such as titanium oxide is treated with an inert substance such as silica. These absorbents can adjust the ultraviolet shielding effect by adjusting the amount added to the resin. Among them, examples of the absorbent that shields ultraviolet rays of 350 nm or less include benzophenone-based and zinc oxide, and may be used alone or in combination of two or more thereof. By using these absorbers, light having a wavelength of 350 nm or less can be substantially blocked, but further, deterioration of an organic compound such as a binder resin is prevented, and durability of the color image display device is improved. For this purpose, it is preferable to shield near-ultraviolet light having a wavelength of 400 nm or less, and this can be achieved by appropriately selecting from the above-mentioned absorbents.

  The absorbent is usually used by mixing with an appropriate resin. Examples of the resin to be used include thermoplastic resins, thermosetting resins, and photocurable resins. Specifically, for example, acrylic resin such as polymethylmethacrylate; styrene resin such as polystyrene and styrene-acrylonitrile copolymer; polycarbonate resin, polyester resin; phenoxy resin; butyral resin; polyvinyl alcohol; ethyl cellulose, cellulose acetate And cellulose resins such as cellulose acetate butyrate; epoxy resins, phenol resins, silicone resins, and the like. Among these, epoxy resin, butyral resin, polyvinyl alcohol, and the like are preferable from the viewpoint of transparency, heat resistance, and light fastness.

  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 example 1: red phosphor K ₂ TiF ₆ : Mn (hereinafter also referred to as “KTF”)
K ₂ TiF ₆ (4.743 g) and K ₂ MnF ₆ (0.2596 g) were used as raw material compounds so that the raw material synthesis of the phosphors was K ₂ Ti _0.95 Mn _0.05 F _6. Under atmospheric pressure and room temperature, it was slowly added to 40 ml of hydrofluoric acid (47.3% by weight) with stirring and dissolved. After all the raw material compounds were dissolved, 60 ml of acetone was added at a rate of 240 ml / hr while stirring the solution to precipitate the phosphor in a poor solvent. The obtained phosphors were washed with pure water and acetone, respectively, and dried at 100 ° C. for 1 hour. From the X-ray diffraction pattern of the obtained phosphor, it was confirmed that K ₂ TiF ₆ : Mn was synthesized.

[1-2] Synthesis Example 2: Red phosphor K ₂ SiF ₆ : Mn (hereinafter also referred to as “KSF”)
K ₂ SiF ₆ (1.77783 g) and K ₂ MnF ₆ (0.2217 g) are used as the raw material compounds so that the raw material composition of each phosphor becomes K ₂ Si _0.9 Mn _0.1 F _6. Under atmospheric pressure and room temperature, it was slowly added to 70 ml of hydrofluoric acid (47.3% by weight) with stirring and dissolved. After all the raw material compounds were dissolved, 70 ml of acetone was added at a rate of 240 ml / hr while stirring the solution to precipitate the phosphor in a poor solvent. Each of the obtained phosphors was washed with ethanol and dried at 130 ° C. for 1 hour to obtain 1.7 g of the phosphor. From the X-ray diffraction pattern of the obtained phosphor, it was confirmed that K ₂ SiF ₆ : Mn was synthesized.

[1-3] Synthesis Example 3: Red phosphor CaAlSiN ₃ : Eu (hereinafter also referred to as “CASN660”)
A red phosphor “BR-101B” (CaAlSiN ₃ : Eu) manufactured by Mitsubishi Chemical Corporation having an emission peak wavelength of 660 nm was used.

[1-4] Synthesis Example 4: Red phosphor BaTiF ₆ : Mn (hereinafter also referred to as “BTF”)
K ₂ TiF ₆ (4.743 g) and K ₂ MnF ₆ (0.25569 g) are used as raw material compounds so that the raw material synthesis of the phosphors becomes K ₂ Ti _0.95 Mn _0.05 F _6. Under atmospheric pressure and room temperature, it was slowly added to 50 ml of hydrofluoric acid (47.3% by weight) with stirring and dissolved. After all the starting compounds were dissolved, BaCO3 (3.8987 g) was added to the solution while stirring the solution to precipitate phosphor BaTiF ₆ : Mn. The obtained phosphors were washed with pure water and acetone, respectively, and dried at 100 ° C. for 1 hour. From the X-ray diffraction pattern of the obtained phosphor, it was confirmed that BaTiF ₆ : Mn was synthesized.

[1-5] Synthesis Example 5: Green phosphor Ba ₃ Si ₆ O ₁₂ N ₂ : Eu (hereinafter also referred to as “BSON”)
The raw material compounds were BaCO ₃ (267 g), SiO ₂ (136 g), and Eu ₂ so that the charged composition of each raw material of the phosphor was Ba _2.7 Eu _0.3 Si _6.9 O ₁₂ N _3.2. O ₃ (26.5 g) was sufficiently stirred and mixed, and then filled in an alumina mortar. This was placed in a resistance heating type electric furnace equipped with a temperature controller, heated to 1100 ° C. at a heating rate of 5 ° C./min under atmospheric pressure, held at that temperature for 5 hours, and then allowed to cool to room temperature. The obtained sample was pulverized to 100 μm or less on an alumina mortar.

The sample (295 g) obtained above and Si ₃ N ₄ (45 g) as a raw material compound were sufficiently stirred and mixed, and then filled in an alumina mortar as primary firing, and this was 96% by volume of nitrogen under atmospheric pressure. The mixture was heated to 1200 ° C. under a flow rate of a mixed gas of 4% by volume of hydrogen at 0.5 L / min, kept at that temperature for 5 hours, and then allowed to cool to room temperature. The obtained fired powder was pulverized on an alumina mortar until it became 100 μm or less.

After sufficiently stirring and mixing 300 g of the calcined powder obtained by the primary firing and BaF ₂ (6 g), which is a flux, and BaHPO ₄ (6 g), the mixture is filled in an alumina mortar and subjected to nitrogen under atmospheric pressure as secondary firing. The mixture was heated to 1350 ° C. under a flow rate of 0.5 L / min of 96% by volume of hydrogen and 4% by volume of hydrogen, held at that temperature for 8 hours, and then allowed to cool to room temperature. The obtained fired powder was pulverized on an alumina mortar until it became 100 μm or less.

The sample (70 g) obtained by the above secondary firing, BaCl ₂ (5.6 g), which is a flux, and BaHPO ₄ (3.5 g) are sufficiently stirred and mixed, and then filled into an alumina mortar, followed by tertiary firing. And heated to 1200 ° C. under a flow of 0.5 L / min of a mixed gas of 96% by volume of nitrogen and 4% by volume of hydrogen under atmospheric pressure, kept at that temperature for 5 hours, and then allowed to cool to room temperature. The obtained fired powder was slurried and dispersed using glass beads, sieved to 100 μm or less, washed, and surface coated with a calcium phosphate salt using a calcium solution and a phosphate solution.

2 g of the obtained phosphor was heated in the atmosphere to 700 ° C. in about 40 minutes using a quartz container having a diameter of 30 mm, held at 700 ° C. for 10 minutes, and then the quartz container was taken out of the furnace and heat-resistant brick Cooled to room temperature above. From the X-ray diffraction pattern of the fired product obtained, it was confirmed that Ba ₃ Si ₆ O ₁₂ N ₂ : Eu was synthesized.

[1-6] Synthesis Example 6: Green phosphor Eu-activated β sialon phosphor (hereinafter also referred to as “β-SiAlON”)
α-type silicon nitride powder 95.5 wt%, aluminum nitride powder 3.3 wt%, aluminum oxide powder 0.4 wt%, and europium oxide powder 0.8 wt% were thoroughly mixed in an agate mortar. This raw material powder was filled in a boron nitride crucible and subjected to heat treatment at 1950 ° C. for 12 hours in a pressurized nitrogen atmosphere having a carbon heater in a pressurized nitrogen atmosphere of 0.92 MPa. The obtained fired powder was crushed, passed through a sieve, washed, and then dried to obtain a phosphor powder. It was found by powder X-ray diffraction measurement that the synthesized powder was a single-phase Eu-activated β sialon phosphor.

[1-7] Synthesis Example 7: Green phosphor BaMgAl ₁₀ O ₁₇ : Eu, Mn (hereinafter also referred to as “GBAM”)
As phosphor materials, barium carbonate (BaCO ₃ ), europium oxide (Eu ₂ O ₃ ), basic magnesium carbonate (mass per mol of 93.17), manganese carbonate (MnCO ₃ ), α-alumina (Al ₂ O ₃₎ In addition, aluminum fluoride (AlF3) was used as a baking aid. These phosphor raw materials are weighed in such an amount as to have a chemical composition represented by Ba _0.455 Sr _0.245 Eu _0.3 Mg _0.7 Mn _0.3 Al ₁₀ O ₁₇ , and a firing aid is used as the phosphor. They were weighed so as to be 0.8% by weight based on the total weight of the raw materials, mixed for 30 minutes in a mortar, and filled in an alumina crucible. In order to create a reducing atmosphere at the time of firing, alumina crucibles were doubled and beaded graphite was placed in the space around the inner crucible and fired at 1550 ° C. for 2 hours in the atmosphere. The obtained fired product was crushed to obtain a green phosphor (GBAM). The obtained green phosphor (GBAM) had an emission peak wavelength of 517 nm and an emission peak half width of 27 nm.

[1-8] Synthesis Example 8: Blue phosphor Sr ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu (hereinafter also referred to as “SCA”)
SrCO ₃ (Kanto Chemical Co., Ltd.) 0.2 mol, SrHPO ₄ (Kanto Chemical Co., Ltd.) 0.605 mol, Eu ₂ O ₃ (Shin-Etsu Chemical 99.99% purity) 0.050 mol, SrCl ₂ (Kanto Chemical Co., Ltd.) 0.1 mol was weighed and dry mixed with a small V-type blender.

  The obtained raw material mixture was filled in an alumina crucible and set in a box-type electric furnace. In the atmosphere, under atmospheric pressure, the temperature was raised to 1050 ° C. at a rate of temperature increase of 5 ° C./min and held for 5 hours to obtain a fired product (primary firing). Next, after the contents in the crucible were cooled to room temperature, they were taken out from the crucible and crushed.

0.05 mol of SrCl ₂ was added to the obtained fired product, mixed with a small V-type blender, filled in an alumina crucible, and the crucible was set in the same electric furnace as the primary firing. While flowing hydrogen-containing nitrogen gas (hydrogen: nitrogen = 4: 96 (volume ratio)) at a rate of 2.5 liters per minute, the temperature was raised to 950 ° C. at a heating rate of 5 ° C./min in a reducing atmosphere at atmospheric pressure. And held for 3 hours (secondary firing). Subsequently, after the content part in a crucible was cooled to room temperature, it was taken out from the crucible and crushed.

0.05 mol of SrCl ₂ was added to the obtained fired product, mixed with a small V-type blender, and then filled into an alumina crucible. Again, the crucible was set in the same electric furnace as the secondary firing. While flowing hydrogen-containing nitrogen gas (hydrogen: nitrogen = 4: 96 (volume ratio)) at a rate of 2.5 liters per minute, the temperature was raised to 1050 ° C. at a heating rate of 5 ° C./min in a reducing atmosphere at atmospheric pressure. And held for 3 hours. The obtained calcined mass was coarsely pulverized to a particle size of about 5 mm and then treated with a ball mill for 6 hours to obtain a phosphor slurry.

  In order to wash the phosphor, the phosphor slurry is stirred and mixed in a large amount of water, allowed to stand until the phosphor particles settle, and then the supernatant liquid is discarded. The electrical conductivity of the supernatant liquid is 3 mS / m. Repeat until: After confirming that the electrical conductivity of the supernatant was 3 mS / m or less, the fine particles and coarse particles of the phosphor were removed by classification.

The obtained phosphor slurry was dispersed in an aqueous Na ₃ PO ₄ solution having pH = 10, and small particles were classified and removed, followed by a calcium phosphate treatment. After dehydration, the phosphor Sr ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu was obtained by drying at 150 ° C. for 10 hours. The obtained blue phosphor had an emission peak wavelength of 450 nm and an emission peak half width of 29 nm.

[1-9] Temperature dependence evaluation of phosphors Luminance and emission peak intensity when excited at a wavelength of 400 nm or 455 nm for the red phosphors and green phosphors produced in the above [1-1] to [1-7] Temperature dependence (hereinafter, these may be collectively referred to as “temperature characteristics”).

  The temperature characteristics are measured using an Otsuka Electronics MCPD7000 multi-channel spectrum measurement device as an emission spectrum measurement device, a color luminance meter BM5A as a luminance measurement device, a stage equipped with a cooling mechanism using a Peltier element and a heating mechanism using a heater, and a 150 W xenon lamp as a light source. The following procedure was used.

The cell containing the phosphor sample was placed on the stage, the temperature was changed from 25 ° C. to 150 ° C., the surface temperature of the phosphor was confirmed, and then the wavelength of 400 nm extracted from the light source by spectroscopy with a diffraction grating Alternatively, the phosphor was excited with 455 nm light, and the emission spectrum was measured. From the measured emission spectrum, the emission peak intensity at 25 ° C. and the emission peak intensity at 100 ° C. were obtained, and the change rate (%) of the emission peak intensity was obtained from the following formula [A].
{1- (luminescence peak intensity at 100 ° C.) / (Luminescence peak intensity at 25 ° C.)} × 100 (A)
In addition, as a measured value of the surface temperature on the excitation light irradiation side of the phosphor, a value corrected using a temperature measured value by a radiation thermometer and a thermocouple was used. The measurement results of the temperature characteristics for Synthesis Examples 1 to 7 are shown in Table 5 below. The SCA, which is the blue phosphor manufactured in Synthesis Example 8, had a rate of change in emission peak intensity of 14% as a result of measuring temperature characteristics when excited with light having a wavelength of 400 nm.

[2] Manufacture of backlight The manufacture example of the backlight of the present invention is shown.

[2-1] Production Example 1: Production of Backlight 1 (BL-1) A light emitting device is produced according to the following procedure.

  A blue light emitting diode having an emission peak 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.

  BSON is used as the phosphor emitting the green band, and KTF 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. Thus, a semiconductor light emitting device is obtained.

  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 ( The product name “ZEONOR” manufactured by ZEON CORPORATION is used, and the semiconductor light emitting device (light source) composed of the above-mentioned light emitting diode is arranged on the long side of the thick side, and the thick side of the light guide (light incident surface) ) So that the outgoing light source from the linear light source is efficiently 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).

  The backlight 1 (BL-1) obtained as described above has one emission peak wavelength in each of the wavelength regions of 455 m, 529 nm, and 631 nm.

[2-2] Production Example 2: Production of Backlight 2 (BL-2) In Production Example 1, the same phosphor as in Production Example 1 except that β-SiAlON was used instead of BSON as a phosphor emitting a green band. Thus, the backlight 2 (BL-2) is manufactured. The backlight 2 has one emission peak wavelength in each of the wavelength regions of 455 nm, 542 nm, and 631 nm.

[2-3] Production Example 3: Production of Backlight 3 (BL-3) Production Example 1 was the same as Production Example 1 except that BaTiF ₆ : Mn was used instead of KTF as a phosphor emitting a red band. Similarly, the backlight 3 (BL-3) is manufactured. BaTiF ₆ : Mn is a phosphor described in US 2006/0169998 A1, and its emission spectrum is described in the same document. As can be seen from this document, the backlight 3 has one emission peak wavelength in each of the wavelength regions of 455 m, 529 nm, and 631 nm.

[2-4] Production Example 4: Production of Backlight 4 (BL-4) In Production Example 1, the same phosphor as in Production Example 3 except that β-SiAlON was used instead of BSON as the phosphor emitting the green band. Thus, the backlight 4 (BL-4) is produced. The backlight 4 has one emission peak wavelength in each of the wavelength regions of 456 nm, 542 nm, and 631 nm.

[2-5] Production Example 5: Production of Conventional Backlight 5 (BL-5) for Comparative Example A light emitting device is produced by the following procedure.

A blue light emitting diode having an emission peak 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. As a phosphor emitting a yellow band, Y _2.8 Tb _0.1 Ce _0.1 Al ₅ O ₁₂ is synthesized and used according to the method described in Example 1 of JP-A-2006-265542. 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 5 for the comparative example is obtained by using the same method as in Production Example 1.

  Production Examples 1 to 5 described above have shown production examples of backlights in which blue light emitting diodes and phosphors are combined. The following Production Examples 6 to 9 show examples of production of backlights in which light-emitting diodes that emit near-ultraviolet light (hereinafter referred to as “near-ultraviolet LEDs”) and blue, green, and red phosphors are combined.

[2-6] Production Example 6: Production of Backlight 6 (BL-6) As a near-ultraviolet LED that emits light with a dominant emission wavelength of 390 to 400 nm, a 290 μm square chip C395MB290 manufactured by Cree was used. A transparent die bond paste was used to adhere to the terminal at the bottom of the recess of the 3528 SMD type PPA package. The package to which the near ultraviolet LED was bonded was heated at 150 ° C. for 2 hours to cure the transparent die bond paste. Thereafter, the near-ultraviolet LED and the electrode of the package were wire-bonded using a gold wire having a diameter of 25 μm.

  On the other hand, 0.053 g of the blue phosphor (SCA) obtained in Synthesis Example 8, 0.088 g of the green phosphor (GBAM) obtained in Synthesis Example 6, and the red phosphor (KSF) obtained in Synthesis Example 2 ) 0.304 g, Shin-Etsu Chemical Co., Ltd. silicone resin (SCR 1011) and Nippon Aerosil Co., Ltd. Aerosil (RX200) as the binder resin were weighed in the blending amounts shown in Table 6 and the stirring deaerator AR manufactured by Shinkey Co. Mixing was performed at −100 to obtain a phosphor-containing composition.

  Next, 4 μl of the obtained phosphor-containing composition was injected using a dispenser into the concave portion of the package to which the ultraviolet LED was bonded. Thereafter, the phosphor-containing composition was cured by heating at 70 ° C. for 1 hour and then at 150 ° C. for 5 hours to obtain a semiconductor light emitting device. Thereafter, the backlight 6 (BL-6) was obtained in the same manner as in Production Example 1.

[2-7] Production Example 7: Production of Backlight 7 (BL-7) Production Example 6 except that the amounts of phosphor, silicone resin and dry silica contained in the phosphor-containing composition were changed as shown in Table 6. In the same manner, Backlight 7 (BL-7) was obtained.

[2-8] Production Example 8: Production of Backlight 8 (BL-8) As the red phosphor, the red phosphor obtained in Synthesis Example 3 (CASN660) is used, and the phosphor-containing composition is contained. A backlight 8 (BL-8) was obtained in the same manner as in Production Example 6 except that the amounts of the phosphor, silicone resin and dry silica were changed as shown in Table 6.

[2-9] Production Example 9: Production of Backlight 9 (BL-9) Production Example 8 except that the amounts of phosphor, silicone resin and dry silica contained in the phosphor-containing composition were changed as shown in Table 6. Backlight 9 (BL-9) was obtained in the same manner.

  Table 6 shows the types of phosphors used in Production Examples 6 to 9 and the amounts of materials used when producing the phosphor-containing compositions.

[3] Production of binder resin for color filter [3-1] Production Example 10: 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 11: Binder resin B
145 parts by weight of propylene glycol monomethyl ether acetate is stirred while being purged with nitrogen, and 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 12: Production of Clear Resist Solution Each component shown below is prepared in 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 11: 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 (“F-475” manufactured by Dainippon Ink & Chemicals, Inc.): 0.0003 part.

[5] Production of Color Filter [5-1] Production Example 13: Red Pixel Production for Examples 1 to 10 and Comparative Examples 1 to 4 75 parts of propylene glycol monomethyl ether acetate, red pigment pigment red (hereinafter “P”) 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 12 were mixed and stirred for 3 hours with a stirrer. A mill base having a solid content of 25% by weight is prepared. The mill base was subjected to dispersion treatment using 600 parts of 0.5 mmφ fuzirconia beads in a bead mill apparatus with a peripheral speed of 10 m / s and a residence time of 3 hours. R. 254 dispersion ink is obtained.

  Further, except that the pigment was changed to the azo nickel complex yellow pigment synthesized according to the description of the production example of Example 2 (paragraph [0066]) of JP-A-2007-25687, the above-mentioned P.I. R. A mill base is prepared with the same composition as 254, and subjected to a dispersion treatment for 2 hours under the same dispersion conditions with a residence time to obtain a dispersion ink of an azo nickel complex yellow pigment.

  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 12 are mixed and stirred at the blending ratio (% by weight) shown in Table 7 below, so that the final solid content concentration becomes 25% by weight. Thus, a 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 14: Green Pixel Production Example 13 for Examples 1 to 10 and Comparative Examples 1 to 4 Production Example 13 except that the pigment was changed to Pigment Green (hereinafter referred to as “PG”) 36 P. R. A mill base was prepared with the same composition as that of H.254 and subjected to dispersion treatment under the same dispersion conditions with a residence time of 1 hour. G. 36 dispersion inks are obtained.

  Further, a mill base was prepared with the same composition as in Production Example 13 except that the pigment was changed to an azo nickel complex yellow pigment, and subjected to a dispersion treatment under the same dispersion conditions with a residence time of 2 hours. Get.

  Similarly, a mill base was prepared with the same composition as in Production Example 13 except that the pigment was changed to brominated zinc phthalocyanine and the dispersant was changed to Big Chemie's acrylic dispersant “LPN6919”, and the same dispersion conditions were used. Then, a dispersion treatment is performed with a residence time of 3 hours to obtain a dispersed ink of brominated zinc phthalocyanine. The brominated zinc phthalocyanine pigment was synthesized by the method shown in [5-2-1] below.

[5-2-1] Synthesis example of brominated zinc phthalocyanine Zinc phthalocyanine was produced using phthalodinitrile and zinc chloride as raw materials. This 1-chloronaphthalene solution had light absorption at 600 to 700 nm. For halogenation, 3.1 parts by weight of sulfuryl chloride, 3.7 parts by weight of anhydrous aluminum chloride, 0.46 parts by weight of sodium chloride, and 1 part by weight of zinc phthalocyanine were mixed at 40 ° C., and 4.4 parts by weight of bromine was added dropwise. I went. The mixture was reacted at 80 ° C. for 15 hours, and then the reaction mixture was poured into water to precipitate a brominated zinc phthalocyanine crude pigment. The aqueous slurry was filtered, washed with hot water at 80 ° C., and dried at 90 ° C. to obtain 3.0 parts by mass of a purified brominated zinc phthalocyanine crude pigment.

  1 part by weight of this brominated zinc phthalocyanine pigment, 12 parts by weight of crushed sodium chloride, 1.8 parts by weight of diethylene glycol, and 0.09 part by weight of xylene were charged into a double-arm kneader and kneaded at 100 ° C. for 6 hours. After kneading, it was taken out into 100 parts by weight of water at 80 ° C., stirred for 1 hour, and then filtered, washed with hot water, dried and ground to obtain a brominated zinc phthalocyanine pigment.

The obtained brominated zinc phthalocyanine pigment had an average composition of ZnPcBr ₁₄ Cl ₂ (Pc: phthalocyanine) based on a halogen content analysis by mass spectrometry and contained an average of ₁₄ bromines in one molecule. Moreover, the average value of the primary particle size measured with a transmission electron microscope (H-9000UHR manufactured by Hitachi, Ltd.) was 0.023 μm. The average primary particle diameter of the pigment is determined by dispersing the pigment ultrasonically in chloroform, dropping it onto a mesh with a collodion film, drying it, and observing the primary particle image of the pigment by observation with a transmission electron microscope (TEM). From this image, the primary particle size was measured to determine the average particle size.

  The dispersion ink obtained as described above and the resist solution produced in Production Example 12 are mixed and stirred at a blending ratio (% by weight) shown in Table 8 below, so that the final solid content concentration becomes 25% by weight. Thus, a solvent (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 alkaline 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 15: Blue Pixel Production for Examples 1 to 10 and Comparative Examples 1 to 4 PR.254 of Production Example 13 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 Pigment Violet (hereinafter referred to as “P.V.”) 23, a mill base was prepared with the same composition as P.R.254 in Production Example 13 and retained under the same dispersion conditions. Dispersion treatment was performed in 2 hours, and PV was applied. 23 dispersion inks are obtained.

  The dispersion ink obtained as described above and the resist solution produced in Production Example 12 are mixed and stirred at a blending ratio (% by weight) shown in Table 9 below, resulting in a final solid content concentration of 25% by weight. Thus, a 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 (“AN100” 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 same named pixels of red, green, and blue shown in Tables 7 to 9 are combined to form color filters for Examples 1 to 10 and Comparative Examples 1 to 4. FIG. 6 shows the result of calculating the transmittance spectrum of each of the red pixel sample, the green pixel sample, and the blue pixel sample for the color filters for Examples 1, 3, 5, and 7. FIG. 7 shows the result of calculating the transmittance spectrum of each of the red pixel sample, the green pixel sample, and the blue pixel sample for the color filters for Examples 2, 4, 6, 8 to 10 and Comparative Examples 3 and 4. .

[6] Color image display device [6-1] Examples 1-8, Comparative Examples 1-2
Examples 1 to 8 and Comparative Example 1 were combined with the backlights (BL-1 to BL-5) shown in Production Examples 1 to 5 and the color filters for Examples 1 to 8 and Comparative Examples 1 to 2. The color image display device of ~ 2 was made. For these color image display devices, chromaticity (x, y, Y) was measured, and color reproducibility (NTSC ratio) and brightness (color temperature) were also determined. Here, the Y value corresponds to the utilization efficiency of light emitted from the backlight. The results are shown in Table 10.

  The white Y value in Table 10 represents the utilization efficiency of the backlight light as the entire color image display device. As shown in Table 10, when designing a color image display device that exceeds the EBU standard (NTSC ratio 72%) and has a high color reproduction range of 85% NTSC ratio, the conventional backlight has a significant decrease in the Y value. If the technique of the present invention is used, a higher Y value can be achieved. That is, higher luminance can be obtained with low power consumption.

Furthermore, with the conventional backlight, the color filter film thickness becomes too thick (> 10 μm), and the NTSC ratio exceeding Adobe-RGB (NTSC ratio 94%), which could not be achieved because the plate-making property is not obtained, This can be achieved by using the technology of the invention. When the coating film of each color filter composition prepared in Production Examples 13 to 15 is exposed and developed at 100 mJ / cm ² using a test pattern mask, good patterns can be obtained in all samples. It was confirmed. In addition, the film thickness after drying of the color filter compositions of each color actually produced was 2.50 μm.

[6-2] Examples 9 to 10 and Comparative Examples 3 to 4
In combination with the backlights (BL-6 to BL-9) shown in Production Examples 6 to 9 and the color filters for Examples 9 to 10 and Comparative Examples 3 to 4, Examples 9 to 10 and Comparative Example 3 -4 color image display devices were obtained. For these color image display devices, chromaticity (x, y, Y) was measured, and color reproducibility (NTSC ratio) and brightness (color temperature) were also determined. Here, the Y value corresponds to the utilization efficiency of light emitted from the backlight. The results are shown in Table 11.

  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.

DESCRIPTION OF SYMBOLS 1 Light source 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 Reflective sheet 20 Mold member 24 Semiconductor light emitting device 25 Mount lead 26 Inner lead 27 Solid light emitting element 28 Phosphor containing part 29 Conductivity Wire 32 Solid light emitting device 33 Phosphor-containing portion 34 Frame 35 Conductive wire 36, 37 Electrode

Claims (9)

A solid state light emitting device that emits light in a blue or deep blue region or an ultraviolet region and a phosphor, and a semiconductor light emitting device,
The phosphor has a green phosphor having one or more emission peaks in a wavelength region of 515 to 550 nm, and an emission peak having a half width of 10 nm or less in the wavelength region of 610 to 650 nm, and A red phosphor containing substantially no excitation spectrum in the emission wavelength region of the green phosphor and containing Mn ⁴⁺ as an activating element;
The green phosphor and the red phosphor have an emission peak intensity at 100 ° C. with respect to an emission peak intensity when the temperature of the green phosphor and the red phosphor is 25 ° C. when the wavelength of excitation light is 400 nm or 455 nm. The semiconductor light emitting device characterized in that the rate of change of is 40% or less.   2. The semiconductor light emitting device according to claim 1, wherein the green phosphor includes one or more compounds selected from the group consisting of an aluminate phosphor, a sialon phosphor, and an oxynitride phosphor.   2. The semiconductor light emitting device according to claim 1, wherein the red phosphor has a rate of change of the emission peak intensity at 100 ° C. of 18% or less with respect to the emission peak intensity when the temperature is 25 ° C. when the wavelength of the excitation light is 455 nm. apparatus.   4. The semiconductor light emitting device according to claim 1, wherein the red phosphor has a main light emission peak having a half width of 10 nm or less in a wavelength region of 610 to 650 nm. 5. The semiconductor light-emitting device according to claim 1, wherein the red phosphor contains a crystal phase having a chemical composition represented by any one of the following general formulas [r1] to [r8]. .
M ^I ₂ [M ^IV _1-x R _x F ₆ ]... [R1]
M ^I ₃ [M ^III _1-x R _x F ₆ ] ... [r2]
M ^II [M ^IV _1-x R _x F ₆ ] ... [r3]
M ^I ₃ [M ^IV _1-x R _x F ₇ ] ... [r4]
M ^I ₂ [M ^III _1-x R _x F ₅ ] ... [r5]
_{^{Zn 2 [M III 1-x}} R x F 7] ··· [r6]
M ^I [M ^III _2-2x R _2x F ₇ ] ... [r7]
Ba _0.65 Zr _0.35 F _2.70 : Mn ⁴⁺ ... [R8]
(In the general formulas [r1] to [r8], M ^I represents one or more monovalent groups selected from the group consisting of Li, Na, K, Rb, Cs, and NH ₄ , and M ^II represents an alkali M ^III represents at least one metal element selected from the group consisting of earth metal elements, M ^III represents at least one metal element selected from the group consisting of Groups 3 and 13 of the periodic table, and M ^IV represents One or more metal elements selected from the group consisting of groups 4 and 14 of the periodic table are represented, R represents an activator containing at least Mn, and x is represented by 0 <x <1. It is a numerical value in the range.) The backlight provided with the semiconductor light-emitting device of any one of Claim 1 to 5 as a light source. 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 the backlight according to claim 6. ,
A color image display device, wherein 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.
Y ≧ −0.4W + 64 (W ≧ 85)

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

  The color image display device according to claim 7, wherein the green pixel of the color filter contains a brominated zinc phthalocyanine pigment.   9. The color image display device according to claim 7, 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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