TW201512310A - Display device - Google Patents

Abstract

Provided is a display device including: a primary light source emitting a primary light; a light converting part including a quantum dot absorbing at least a portion of the primary light and emitting a green light; and a green color filter transmitting the green light and including a phthalocyanine compound represented by the general formula (1).

Description

Display device

The present invention relates to a display device.

In recent years, display devices having color filters (for example, liquid crystal display devices, organic electroluminescence display devices, and the like) have been widely used as color display displays such as monitors for personal computers in addition to television image receivers. In response to the development of large-scale, thinner, and lighter display devices, technologies for achieving more vivid images and more beautiful images have also been studied.

Such a display device includes, for example, a light source that emits white light, and a display panel that displays an image by modulating white light emitted from the light source.

Generally, the display panel is provided with a plurality of pixels, the pixel having a red filter that transmits red (R) light (red light), a green filter that transmits green (G) light (green light), And a blue filter that transmits blue (B) light (blue light). Thereby, the light incident on the display panel by the light source is modulated based on the image data by the respective pixels, and the full color image is displayed.

However, in the image displayed as described above, in terms of the characteristics of the color filter, in addition to the light of R, G, and B which are easily transmitted through the color filter, although the amount of transmission is small, R, G is still contained. Light of the intermediate color of B.

Fig. 3 is a characteristic diagram showing a spectral versus transmittance spectrum of a conventional color filter. In FIG. 3, the curve R, the curve G, and the curve B respectively indicate the transmittance spectrum of the conventional red filter, the transmittance spectrum of the conventional green filter, and the transmittance spectrum of the conventional blue filter.

It is understood from Fig. 3 that the light passing through the blue filter contains light of a wavelength of an intermediate color of B and G, and the light passing through the green filter contains light of a wavelength of an intermediate color of B and G and an intermediate color of G and R. The light of the wavelength, the light passing through the red filter contains light of a wavelength of the intermediate color of G and R.

The color purity of the light of each of R, G, and B passing through the color filter is lowered, and as a result, there is a problem that it is difficult to obtain sufficient color reproducibility in the displayed image.

On the other hand, in addition to a cold cathode fluorescent lamp (CCFL), a white light source (backlight) used in a liquid crystal display device is a blue light emitting diode in response to recent thinning or power saving requirements ( Hereinafter, a light-emitting diode (also referred to as "LED" (Light Emitting Diode) or a white LED type backlight in which a yellow phosphor, a red phosphor, and a green phosphor are combined with an ultraviolet light-emitting LED Fuk.

Since these light sources include a sub-spectrum corresponding to an intermediate color of R and G, or a sub-spectrum of an intermediate color of G and B, or a spectrum itself, a large amount of light corresponding to a wavelength of an intermediate color is also emitted. This is a cause of a decrease in the color reproducibility of the image (reduction of the color reproduction region).

For example, Figure 3 also shows the blue light from the blue LED. The spectroscopic relative luminescence spectrum (curve LED-BL) of white light emitted from a yttrium aluminum garnet (YAG) phosphor is used as an example of a spectroscopic relative luminescence spectrum of a conventional backlight. The curve LED-BL includes light having a wavelength corresponding to 580 nm or more and 610 nm or less of an intermediate color of R and G.

A method of increasing the color reproducibility of an image displayed by a display device (that is, a method of enlarging a color reproduction region of an image) is generally a method of increasing the color purity of a color filter of each color.

Specifically, a method of improving the coloring photosensitive composition for forming a color filter can be mentioned.

However, from the viewpoint of maintaining properties such as pattern formation property and reliability of the coloring photosensitive composition, the amount of the coloring material contained in the coloring photosensitive composition is limited, and a large color purity cannot be expected to be improved.

Further, a method of improving the color reproducibility of an image may be a method in which an array including a blue LED, a red LED, and a green LED, which are respectively grown by epitaxy, emits red light and blue light, respectively. And the green light, which is used as the light incident on the display panel (for example, refer to the specification of US Pat. No. 6,608,614 and the specification of US Pat. No. 6,685,255).

Further, a method of improving the color reproducibility of an image may be exemplified by using a single-color LED as a primary light source to inject light from the monochromatic LED to convert all or a part of the light into A medium of other wavelengths of light (for example, a phosphor), thereby generating white light, and injecting the generated white light into the display panel.

For example, a method is known in which a blue light generated by a blue LED as a primary light source is irradiated to a quantum dot (QD; quantum dot) emitting light emitted between the light guide plates as a phosphor and emitting light A quantum dot of green light is emitted to generate white light, and the generated white light is incident on the display panel (for example, refer to Japanese Laid-Open Patent Publication No. 2012-169271).

In addition, a liquid crystal display panel and a liquid crystal display device in which a light conversion layer including the quantum dots is disposed in a liquid crystal display panel are known (for example, refer to Japanese Laid-Open Patent Publication No. 2013-15812).

Further, a method of using a light conversion sheet (also referred to as "QDEF" (quantum dot enhancement film) or "quantum dot sheet") using the quantum dots is also known (for example, referring to "secondary imaging" Secondary Imagery Dissemination (SID) Sympium Digest of Technical Papers, June 2012, Vol. 43, No. 1, pp. 895-896).

However, a method using an array including various blue LEDs, red LEDs, and green LEDs (for example, U.S. Patent No. 6,608,614 and U.S. Patent No. 6,685,255) can achieve a high NTSC (National Television System Committee). Committee), but there is a problem with the cost of manufacturing. In addition, there is a concern that color mixing may occur or an electronic circuit required to drive an LED may become complicated. Further, there is a concern that the deterioration speed of each of the three colors of LEDs is different, and therefore, there is a long time The cause of color change in the operation. Further, there is a problem that manufacturing an efficient green LED is still a problem.

In addition, according to the study by the inventors of the present invention, a method of obtaining white light using quantum dots has been found (for example, Japanese Patent Laid-Open No. Hei. No. 2012-169271 and Japanese Patent Laid-Open No. Hei. No. 2013-15812, and "Second Imaging Propagation ( Secondary Imagery Dissemination, SID) Symposium Digest of Technical Papers, June 2012, Vol. 43, No. 1, pp. 895-896), although the color purity of light of various colors can be greatly improved, There is a case where the brightness of light (green light) transmitted through the green filter is lowered.

Regarding the influence on the brightness of the entire image and the color reproducibility of the image, among the red light, the green light, and the blue light, particularly the brightness of the green light has the greatest influence.

Therefore, in order to improve the brightness of the entire image and the color reproducibility of the image, it is particularly important to increase the brightness of the green light.

Aspects of the invention include the following aspects.

<1> A display device comprising: a primary light source that emits primary light; a light conversion portion that includes quantum dots that absorb at least a portion of the primary light to emit green light; and a green filter that transmits the green color Light, and containing a phthalocyanine compound represented by the formula (1),

In the general formula (1), a plurality of X atoms independently represent a halogen atom; and a plurality of R ¹ each independently represent a group represented by the following formula (2) or (3); A plurality of R each independently represent a hydrogen atom or a monovalent substituent; M represents Cu, Zn, V(=O), Mg, Ni, Ti(=O), Sn, or Si; and a plurality of a are independently represented An integer of 0 to 4, a plurality of n each independently represent an integer of 0 to 4, and a plurality of r independently represent an integer of 0 to 4; wherein at least one of the plurality of a is 1 or more, and at least one of the plurality of n 1 is 1 or more; the sum of multiple a, multiple n and multiple r is 16]

[In the general formula (2) and the general formula (3), the presence of b of R ² independently represents a monovalent substituent selected from the group consisting of the following general formulae (4) to (6); R ³ represents a monovalent substituent; b represents an integer of 1 to 5, and c represents an integer of 0 to 4; wherein, in the general formula (2), the total of b and c does not exceed 5; Y represents -O-, -S-, -SO ₂ -, or -NR ⁸ -; R ⁸ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent]

[In the formula (4), R ⁴ represents a hydrogen atom, an alkyl group which may have a substituent, an oxyalkyl group which may have a substituent, an aryl group which may have a substituent, an alkylamine group which may have a substituent, and a dialkylamino group having a substituent, an arylamine group which may have a substituent, a diarylamine group which may have a substituent, or an alkylarylamine group which may have a substituent; in the formula (5) d represents an integer of 0 to 2, and when d is 0 or 1, R ⁵ represents an alkyl group which may have a substituent, or an aryl group which may have a substituent, and in the case where d is 2, R ⁵ represents An alkyl group which may have a substituent, an aryl group which may have a substituent, a dialkylamino group which may have a substituent, a diarylamine group which may have a substituent, or an alkylarylamine group which may have a substituent In the formula (6), R ⁶ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, and a substituent which may have a substituent An alkylsulfonyl group, an arylsulfonyl group which may have a substituent, R ⁷ represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic group which may have a substituent base].

<2> The display device according to <1>, wherein the primary light is blue light.

<3> The display device according to <2>, wherein the primary light source comprises a blue light emitting diode.

The display device according to any one of <1>, wherein the light conversion unit further includes an inorganic phosphor that absorbs a part of the primary light and emits red light, and The primary light is converted to white light by transmitting a portion of the primary light.

<5> The display device according to <4>, wherein the inorganic phosphor is a quantum dot.

The display device according to any one of <1> to <5> wherein the light emission spectrum of the green light has a maximum value in a wavelength range of 500 nm to 550 nm.

<7> The display device according to <4>, wherein the luminescence spectrum of the green light The full width at half maximum is 20 nm to 80 nm.

The display device according to any one of <1> to <7>, wherein the transmission spectrum of the green filter has a peak having a maximum value in a wavelength range of 460 nm to 550 nm.

<9> The display device according to <7>, wherein a half-height of the peak in a transmission spectrum of the green filter is 80 nm to 200 nm.

<10> The display device according to <8>, wherein a transmittance in a range of wavelengths of 500 nm to 530 nm is 90% or more in a transmission spectrum of the green filter.

The display device according to any one of <1> to <10> wherein the green filter further contains a yellow dye.

The display device according to any one of <1> to <11> wherein the quantum dot is selected from the group consisting of a group II-VI compound, a group III-V compound, a group IV-VI compound, and IV At least one type of semiconductor nanoparticle in a group consisting of a group of compounds.

The display device according to any one of <1> to <12> wherein the quantum dot is selected from the group consisting of CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, At least one semiconductor nanoparticle of a group consisting of SnPbSeTe, SnPbSTe, Si, Ge, SiC, and SiGe.

The display device according to any one of <1> to <11>, comprising: the primary light source, the light conversion portion, and a liquid crystal display panel or the organic battery including the green filter A light-emitting display panel.

According to the present invention, a display device capable of displaying an image of high luminance of green light is provided.

10B‧‧‧Blue filter

10G‧‧‧Green Filter

10R‧‧‧Red Filter

12‧‧‧Transmissive substrate

14‧‧‧Substrate with color filter

20‧‧‧Liquid layer

22‧‧‧ Alignment substrate

30‧‧‧LCD panel

40‧‧‧Blue LED (primary light source)

42‧‧‧Light conversion member (light conversion unit)

46‧‧‧Light guiding members

52‧‧‧Light conversion film

60‧‧‧Multiple blue LEDs

61‧‧‧Shell

62‧‧‧Direct type blue LED unit

100, 200, 300‧‧‧ liquid crystal display device

R, G, B‧‧· Quantum dots

Fig. 1A is a schematic cross-sectional view conceptually showing a display device according to a first embodiment.

Fig. 1B is a schematic cross-sectional view conceptually showing a display device of a second embodiment.

Fig. 1C is a schematic cross-sectional view conceptually showing a display device according to a third embodiment.

2 is a characteristic diagram showing a transmittance spectrum of a substrate with a green filter in Example 1 and Comparative Example 2. FIG.

3 is a characteristic diagram showing a spectroscopic versus transmittance spectrum of a conventional color filter.

Hereinafter, specific embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

The display device of the present invention includes: a primary light source that emits primary light; and a light conversion portion that includes quantum dots that absorb at least a portion of the primary light to emit green light (hereinafter also referred to as "quantum dot G"); The filter transmits green light emitted from the quantum dot and contains a phthalocyanine compound represented by the following formula (1). The display device of the present invention may also include other components.

That is, the display device of the present invention arranges the light conversion portion and the green filter in order from the primary light source along the optical path from the primary light source. The optical path referred to here is not necessarily limited to a linear shape (see FIGS. 1A and 1B described later).

In the present invention, "green light" refers to all light that is considered to be green (all light having intensity in a green wavelength region), and is of course not limited to light of a single wavelength. The same applies to "red light" and "blue light" which will be described later.

In the display device of the present invention, the brightness of green light (specifically, green light after being transmitted through the green filter) can be improved by the above configuration. Therefore, an image with high luminance of green light can be displayed.

Further, in the display device of the present invention, by using the quantum dot G, the color purity of green light (specifically, green light after being transmitted through the green filter) can be improved.

Therefore, according to the display device of the present invention, the brightness of the entire image can be improved as well Color reproducibility of an image (enlarged color reproduction area of an image).

The reason why the brightness of green light can be improved in the display device of the present invention is presumed as follows.

The luminescence spectrum of green light (hereinafter also referred to as "existing green light") of white light emitted from a conventional white LED (for example, a white LED using a YAG phosphor) is more desirable than a green wavelength region. The long wavelength side has a maximum value and has a broad spectrum (for example, refer to FIG. 2 and FIG. 3 described later). On the other hand, compared with the luminescence spectrum of the conventional green light, the luminescence spectrum of the green light emitted from the quantum dot G has a maximum value on the short-wavelength side and becomes a sharp (semi-high-width-small) spectrum (for example, reference) Figure 2) described later. Therefore, by using the green light emitted from the quantum dot G as a light source of the display device, the luminance and color purity of the green light in the displayed image can be improved.

Here, the display device of the present invention includes a green filter containing a phthalocyanine compound represented by the general formula (1). The green filter has a maximum value of transmittance on the short-wavelength side and a green wavelength region as a whole, compared with a green filter containing a conventional colored material (for example, CI Pigment Green 58, CI Pigment Green 36, etc.). The transmittance is improved (for example, refer to FIG. 2 described later).

According to the above, in the display device of the present invention in which the quantum dot G and the green filter containing the phthalocyanine compound represented by the general formula (1) are combined, the luminance of the green light by the quantum dot G is improved. The effect becomes more remarkable, and as a result, it is considered that the brightness of the green light after being transmitted through the green filter can be improved.

Preferred aspects of the quantum dots in the present invention will be described later.

In the display device of the present invention, the primary light is preferably blue light.

As is well known, blue light is more energy than green light, and therefore, by the primary light being blue light, the efficiency of light conversion by the light conversion portion is further improved.

Further, when the primary light is blue light, there is an advantage that it is not necessary to include a phosphor (for example, a quantum dot B to be described later) that generates blue light in the light conversion portion.

The aspect in which the primary light is blue light is particularly preferably a state in which the primary light source includes a blue light emitting diode (blue LED). Since the blue LED can emit blue light having excellent excellent purity, the primary light source includes the blue LED, and the brightness of the blue light can be further increased in the displayed image, thereby further improving the brightness of the entire image and The color reproducibility of the image.

The display device of the present invention preferably has a state in which the light conversion portion further contains an inorganic phosphor that absorbs a part of the primary light and emits red light, and converts the primary light into white light by transmitting a part of the primary light.

Here, "white light" means light in which at least blue light, red light, and green light are mixed.

In this aspect, for example, when blue light is used as the primary light, part of the blue light (primary light) incident on the light conversion portion is partially transmitted through the light conversion portion in the state of blue light, and the other portion is quantum. The point G is converted into green light and emitted by the light converting portion, and the other portion is converted into red light by the inorganic phosphor and emitted by the light converting portion. As a result, white light in which at least the blue light, the green light, and the red light are mixed is emitted by the light conversion unit. In this way, in the light conversion unit, the primary light is converted into white light.

In this aspect, the inorganic phosphor that emits red light by absorbing a part of the primary light is not particularly limited, and a known inorganic phosphor other than the quantum dot (for example, a YAG-based phosphor to be described later or a ruthenium) may be used. Aluminium garnet (TAG) is a phosphor, a sialon-based phosphor, a barium orthosilicate (BOS) phosphor, etc., but is preferably used. A quantum dot that absorbs a part of the primary light and emits red light (hereinafter also referred to as "quantum dot R"). Thereby, since the color purity of the red light contained in the white light can be improved, the brightness of the red light can be further increased in the displayed image, and the brightness of the entire image and the color reproduction of the image can be further improved. Sex.

In the light conversion unit of the present invention, an inorganic phosphor that absorbs primary light and emits blue light (for example, an inorganic phosphor other than a quantum dot to be described later, preferably a quantum dot that absorbs primary light and emits blue light) may be contained. (hereinafter also referred to as "quantum dot B")). Among them, in particular, when blue light is used as the primary light, it is not necessary to include the inorganic phosphor that emits blue light in the light conversion portion.

In the display device of the present invention, the emission spectrum (peak) of the green light emitted from the quantum dot G preferably has a maximum value in the range of wavelengths of 500 nm to 550 nm. In this aspect, since the color purity of the green light corresponding to the peak is particularly high, the luminance of the green light after being transmitted through the green filter can be further improved.

The maximum value is preferably in the range of 500 nm to 540 nm, and particularly preferably in the range of 510 nm to 540 nm.

In the present invention, the luminescence spectrum of the green light emitted by the quantum dot G (or the luminescence spectrum of the white light emitted by the light conversion portion) means the use of spectroscopic radiation The spectrum measured from the spectroradiometer to the sample (light conversion unit) was set to 70 mm, and the measurement angle was set to 0.2 degrees.

For the spectrum of the white light and the spectrum of the green light, for example, a spectroradiometer "SR-3" manufactured by Topcon Co., Ltd. can be used, and the measurement mode is set to "automatic" for the measurement wavelength range of 380 nm to 780 nm. The measurement was carried out under the measurement conditions described above.

In addition, the light emission spectrum of the green light is preferably a full width at half maximum (FWHM; 20 nm to 80 nm).

If the full width at half maximum is 80 nm or less, the color purity of the green light is particularly high, so that the brightness of the green light after being transmitted through the green filter can be further improved. On the other hand, if the full width at half maximum is 20 nm or more, the amount of transmission of the green light transmitted through the green color filter can be further increased, so that the luminance of the green light after being transmitted through the green color filter can be further improved.

The full width at half maximum of the light emission spectrum of the green light is preferably 20 nm to 60 nm, and particularly preferably 20 nm to 50 nm.

Further, in the display device of the present invention, it is preferable that the display layer of the green filter has a peak having a maximum value in a wavelength range of 460 nm to 550 nm.

By the maximum value of the peak being present in the range of the wavelength of 460 nm or more, the luminance of the green light after being transmitted through the green filter can be further improved.

By the maximum value of the peak being present in the range of 550 nm or less, the color purity of the green light after being transmitted through the green filter can be further improved.

The maximum value of the peak is more preferably in the range of 460 nm to 540 nm. In particular, it is preferably present in the range of 460 nm to 520 nm, and more preferably in the range of 470 nm to 510 nm, and particularly preferably in the range of 480 nm to 500 nm.

Further, the full width at half maximum of the peak in the transmission spectrum of the green filter is preferably from 80 nm to 200 nm.

If the full width at half maximum of the peak is 80 nm or more, the brightness of the green light after being transmitted through the green filter can be further increased.

If the full width at half maximum of the peak is 200 nm or less, the color purity of the green light after being transmitted through the green filter can be further improved.

The full width at half maximum of the peak is preferably from 80 nm to 190 nm, more preferably from 80 nm to 170 nm, and particularly preferably from 80 nm to 150 nm.

In the present invention, the transmission spectrum of the green filter means a transmission spectrum measured by a spectrophotometer for a measurement wavelength range of 200 nm to 800 nm.

For the spectrophotometer, for example, a spectrophotometer "MCPD-3700" manufactured by Otsuka Electronics Co., Ltd. can be used.

Further, in the transmission spectrum of the green filter, the transmittance in the wavelength range of 500 nm to 530 nm is particularly preferably 90% or more. Thereby, the brightness of the green light after being transmitted through the green filter can be further improved. It is difficult to achieve the transmittance characteristics in a green filter containing a known colored material (for example, C.I. Pigment Green 58, C.I. Pigment Green 36, etc.) instead of the phthalocyanine compound represented by the general formula (1).

When the green filter contains a phthalocyanine compound represented by the following formula (1), a preferable range of the transmittance characteristics of the green filter described above can be more easily achieved.

Next, an embodiment of a display device of the present invention will be described with reference to FIGS. 1A to 1C. However, the display device of the present invention is not limited to the following embodiments.

In the respective embodiments, members having substantially the same functions are given the same conformity in all the drawings, and the description thereof will be omitted.

<First embodiment>

FIG. 1A is a schematic configuration diagram of a display device (liquid crystal display device 100) according to the first embodiment.

The liquid crystal display device 100 shown in FIG. 1A includes a blue LED 40 (primary light source) that generates blue light as primary light, and a light conversion member 42 (light conversion portion) that generates blue light (arrow B) generated by the blue LED 40. Converted to white light; light guiding member 46 for guiding white light emitted by the light converting member 42 to the liquid crystal display panel 30; and liquid crystal display panel 30 having white light for converting the light emitted by the light guiding member 46 into green light Green filter 10G.

In the liquid crystal display device 100, the light conversion member 42, the light guide member 46, and the liquid crystal display panel 30 are sequentially disposed in the optical path from the blue LED 40 (primary light source).

The green filter 10G contains a phthalocyanine compound represented by the following formula (1) as a colored material.

In FIG. 1A, red light, green light, and blue light are respectively indicated by an arrow R, an arrow G, and an arrow B.

The liquid crystal display device 100 is a liquid crystal display device with a side edge backlight system example of.

In the liquid crystal display device 100, the liquid crystal display panel 30 includes a substrate 14 with a color filter, and a red filter 10R and a green filter on a light-transmissive substrate 12 such as a glass substrate or a plastic substrate. 10G and the blue filter 10B; the opposite substrate 22 is disposed opposite to the substrate 14 with the color filter; and the liquid crystal layer 20 is disposed on the substrate 14 with the color filter and the pair Between the substrates 22 .

Regarding the other aspects, the substrate 14 with the color filter can be formed into a known configuration. Therefore, although the illustration is omitted, the substrate 14 with the color filter may appropriately include a known constituent element such as a black matrix or an overcoat film.

The counter substrate 22 can be an active matrix substrate provided with a thin film transistor (TFT) or the like on a light-transmissive substrate such as a glass substrate or a plastic substrate, or a light-transmissive substrate such as a glass substrate or a plastic substrate. A passive matrix substrate or the like which is formed by a strip electrode or the like is provided.

Regarding the other aspects, the liquid crystal display panel 30 can be configured as a well-known one. Therefore, although not shown in the drawings, the liquid crystal display panel 30 may of course have a known member such as a polarizing plate, an alignment film, a spacer, and a sealing material.

For the configuration of the liquid crystal display panel, for example, a known configuration described in Japanese Laid-Open Patent Publication No. 2013-15812 or the like can be appropriately referred to.

The liquid crystal display device 100 includes a light guiding member 46 that faces the opposite substrate 22 of the liquid crystal display panel 30.

The liquid crystal display device 100 further includes a light turn opposite to an end surface of the light guiding member 46. The member 42 is replaced.

The liquid crystal display device 100 further includes a blue LED 40 disposed on the side opposite to the light guiding member 46 from the light conversion member 42.

The blue LED 40 is a primary light source that generates blue light as primary light.

As described above, the blue LED (blue light) is advantageous in terms of the efficiency of generation of red light and green light by the light conversion member 42.

The light conversion member 42 is a member that converts blue light (primary light) generated by the blue LED 40 into white light.

The light conversion member 42 has a configuration in which a composition in which a quantum dot G and a quantum dot R are dispersed in a resin as a binder is sealed in a case made of glass.

Here, the quantum dot G is a semiconductor nanoparticle that emits green light by absorbing blue light (primary light), and the quantum dot R is a semiconductor nanoparticle that emits red light by absorbing blue light (primary light). Preferred aspects of the quantum dots will be described later.

A part of the blue light (primary light) incident on the light conversion member 42 is transmitted through the light conversion member 42 in the state of blue light (arrow B), and the other portion is converted into green light (arrow G) by the quantum dot G The light conversion member 42 emits, and the other portion is emitted by the light conversion member 42 by the quantum dot R being converted into red light (arrow R).

As described above, the light conversion member 42 that emits blue light (primary light) emits white light including blue light, green light, and red light.

The white light emitted by the light conversion member 42 is compared with the white light emitted by the cold cathode fluorescent lamp or the white LED, and the respective blue light, green light, and red light Excellent purity.

That is, in the light emission spectrum of the white light emitted from the light conversion member 42, there are sharp peaks corresponding to the blue light, the green light, and the red light, respectively. The preferred form of the peak (luminescence spectrum) of green light is as described above.

The liquid crystal display device 100 may also be provided with a light source member including the blue LED 40 and the light conversion member 42.

The light source member is referred to as a "quantum dot backlight."

The light guiding member 46 is a flat member for guiding the white light emitted from the light conversion member 42 to the liquid crystal display panel 30, and has a function as a surface light source of the liquid crystal display panel 30.

Although not shown in the drawings, the light guide member 46 has a configuration including a light guide plate that receives light from the end surface and emits the light from the upper surface and the lower surface; the raft is disposed on the light guide plate a surface; and a reflective sheet disposed opposite to the lower surface of the light guide plate. With the above configuration, white light can be emitted only from the upper surface of the light guiding member 46.

For the configuration of the light guiding member 46, for example, a known configuration described in Japanese Laid-Open Patent Publication No. 2013-15812 or the like can be referred to.

The liquid crystal display device 100 may be provided with one member (quantum dot backlight unit) including the blue LED 40, the light conversion member 42, and the light guiding member 46.

The quantum dot backlight unit is, for example, a backlight unit of a commercially available liquid crystal display device (manufactured by Sony Corporation, trade name KDL46W900A). The backlight unit includes a blue LED and Color IQ ^TM (U.S. quantum dots quantum dot image member (QD Vision) Co., Ltd.) (refer to Example 1).

In the liquid crystal display device 100 described above, blue light (primary light) from the blue LED 40 is incident on the light conversion member 42, and white light is emitted from the light conversion member 42 that is incident on the blue light (primary light) (including The white light emitted from the light conversion member 42 is incident on the light guide member 46 from the end surface of the light guide member 46 in the red light, the green light, and the white light of the blue light. The white light incident into the light guiding member 46 is emitted from the upper surface (the surface facing the liquid crystal display panel) of the light guiding member 46. The emitted white light is incident into the liquid crystal display panel 30, and then, as the red light, the green light, and the blue light, from the red color filter 10R, the green color filter 10G, and the blue color filter 10B, respectively. And fired out. The emitted red light, green light, and blue light are regarded as color images.

The liquid crystal display device 100 includes a combination of a light conversion member 42 including a quantum dot G and a green filter 10G containing a phthalocyanine compound represented by the following formula (1). Here, as described above, the effect of improving the luminance of the green light in the image of the light conversion member 42 is excellent, and the transmittance of the wavelength region of the green light emitted from the quantum dot G of the green color filter 10G is high.

Therefore, in the liquid crystal display device 100, the effect of improving the luminance of the green light by the quantum dot G is more remarkable, and thus the luminance of the green light after being transmitted through the green color filter 10G can be remarkably improved. Further, by using the quantum dot G, the color purity of the green light after being transmitted through the green color filter 10G can be remarkably improved.

Further, since the liquid crystal display device 100 uses the blue LED 40 as a primary light source, the luminance and color purity of the blue light after being transmitted through the blue color filter 10B high. Further, in the liquid crystal display device 100, since the light conversion member 42 contains the quantum dot R, the luminance and color purity of the red light transmitted through the red color filter 10R are high.

Therefore, the liquid crystal display device 100 can display an image having high luminance and high color purity of green light, red light, and blue light (that is, an image excellent in luminance and color reproducibility of the entire image).

The liquid crystal display device 100 may include a member known as a member for a liquid crystal display device, in addition to the member.

<Second embodiment>

FIG. 1B is a schematic configuration diagram of a display device (liquid crystal display device 200) according to the second embodiment.

In the liquid crystal display device 200, the liquid crystal display device 100 is not provided with the light conversion member 42, and the light conversion sheet 52 as the light conversion portion is disposed between the light guide member 46 and the liquid crystal display panel 30, and the liquid crystal display device. The composition of 100 is the same.

In the liquid crystal display device 200, the light conversion sheet 52 is not shown, but includes a resin layer in which the quantum dots G and the quantum dots R are dispersed, and a pair of protective films that protect both surfaces of the resin layer. That is, the light conversion sheet 52 is a quantum dot sheet (QDEF).

The quantum dot G and the quantum dot R are the same semiconductor nanoparticles as the quantum dot G and the quantum dot R in the liquid crystal display device 100.

The white light emitted from the light conversion sheet 52 is superior to the white light emitted from the cold cathode fluorescent lamp or the white LED, and each of the blue light, the green light, and the red light is excellent in purity.

That is, in the spectrum of the white light emitted from the light conversion sheet 52, there are sharp peaks corresponding to the respective blue light, green light, and red light. The preferred form of the peak of green light is as described above.

Similarly to the liquid crystal display device 100, the liquid crystal display device 200 is an example of a liquid crystal display device of a side edge backlight system.

In the liquid crystal display device 200, the blue light (primary light) from the blue LED 40 is directly incident on the end surface of the light guiding member 46, and the upper surface of the light guiding member 46 does not emit white light, but is emitted. In the blue light, the emitted blue light is converted into white light (white light including red light, green light, and blue light) by the light conversion sheet 52, and the converted white light is incident on the liquid crystal display panel 30. In these respects, the liquid crystal display device 200 is different from the liquid crystal display device 100.

Similarly to the case of the liquid crystal display device 100, the white light incident on the liquid crystal display panel 30 is red light, green light, and blue light, and is emitted by the liquid crystal display panel 30, and the emitted red light, green light, and The blue light is regarded as a color image as in the case of the liquid crystal display device 100.

Similarly to the liquid crystal display device 100, the liquid crystal display device 200 includes a combination of a quantum dot G and a green filter containing a phthalocyanine compound represented by the general formula (1), and further includes a blue LED and a quantum dot R.

Therefore, the liquid crystal display device 200 also exhibits the same effects as the liquid crystal display device 100.

<Third embodiment>

1C is a schematic diagram of a display device (liquid crystal display device 300) according to a third embodiment. Slightly composed.

The configuration of the liquid crystal display device 300 is the same as that of the liquid crystal display device 200 except that the blue LED 40 and the light guiding member 46 are changed to the direct blue LED unit 62 in the liquid crystal display device 200.

In the liquid crystal display device 300, the direct type blue LED unit 62 includes a case 61 and a plurality of blue LEDs 60 disposed in the case 61.

The direct-type blue LED unit 62 is disposed on the opposite side of the liquid crystal display panel 30 from the light conversion sheet 52, and is disposed such that the plurality of blue LEDs 60 and the light conversion sheet 52 face each other. Thereby, blue light (primary light) can be irradiated from the normal direction of the liquid crystal display panel 30 without passing through the light guiding member.

In the liquid crystal display device 300, the blue light generated by the plurality of blue LEDs 60 is converted into white light including blue light, green light, and red light by the light conversion sheet 52, and the converted white light is incident on the liquid crystal display panel 30. .

This liquid crystal display device 300 is an example of a liquid crystal display device of a direct type backlight system.

In addition to the above, the configuration of the liquid crystal display device including the direct type blue LED unit 62 and the direct type backlight system can be a known configuration.

Similarly to the liquid crystal display device 100, the liquid crystal display device 300 includes a combination of a quantum dot G and a green filter containing a phthalocyanine compound represented by the general formula (1), and further includes a blue LED and a quantum dot R.

Therefore, the liquid crystal display device 300 also exhibits the same effects as those of the liquid crystal display device 100.

Although the first embodiment to the third embodiment of the present invention have been described above, the present invention is not limited to the embodiments.

For example, the light conversion unit in the above embodiment may be changed to a light conversion layer including quantum dots R and quantum dots G disposed in the liquid crystal display panel. For the light conversion layer to be disposed in the liquid crystal display panel, for example, the configuration described in Japanese Laid-Open Patent Publication No. 2013-15812 or the like can be referred to.

Further, the liquid crystal display panel in the above embodiment can be replaced with an organic electroluminescence (organic EL) display panel including the red color filter 10R, the green color filter 10G, and the blue color filter 10B. That is, the display device of the present invention may be an organic EL display device.

In the case where the display device of the present invention is a liquid crystal display device including a liquid crystal display panel having the green filter (for example, in the case of the first embodiment to the third embodiment), it is not only a liquid crystal display device. Further, an image excellent in brightness and color reproducibility comparable to the organic EL display device can be displayed.

Next, each member of the display device of the present invention will be described.

<primary light source>

The primary light source in the present invention is a light source that emits primary light.

In addition to the blue LED described above, the primary light source may use other LEDs such as an ultraviolet LED, a red LED, and a green LED.

LEDs have great advantages in terms of low power, small size, and low cost.

Among the LEDs, blue LEDs and ultraviolet LEDs are preferred in terms of efficiency of light conversion by the light converting portion.

Among them, the blue LED also has an advantage of reducing the type of the phosphor that can be contained in the light conversion portion. For example, when a blue LED is used as a primary light source and a primary light (blue light) emitted from a blue LED is converted into white light by a light conversion unit, the light conversion unit includes a quantum that converts blue light into green light. Points and inorganic phosphors that convert blue light into red light. In this case, a part of the blue light generated by the blue LED is used in a state of blue light by directly passing through the light conversion unit.

<Light Conversion Unit>

The light conversion portion in the present invention includes a quantum dot G that absorbs at least a part of the primary light emitted from the primary light source and emits green light. The light conversion unit may contain other inorganic phosphors as needed (specifically, for example, described later).

Preferably, the light converting portion includes an inorganic phosphor that absorbs a part of the primary light emitted from the primary light source and emits red light (preferably, absorbs a part of the primary light emitted by the primary light source and emits the light as described above). The quantum point of red light R).

Further, as described above, the light converting portion may include an inorganic phosphor that absorbs a part of the primary light emitted from the primary light source and emits blue light (preferably, absorbs a part of the primary light emitted by the primary light source and emits a quantum dot of blue light B). Among them, in the case where the primary light is blue light, it is not necessary to emit a blue light fluorescent body.

Here, the quantum dots (quantum dots G and, if necessary, quantum dots R and quantum dots B) in the present invention will be described.

The so-called quantum dot refers to the quantum encapsulation effect (quantum confinement) Semiconductor nanoparticle.

The particle diameter of the quantum dot (semiconductor nanoparticle) is usually in the range of 1 nm to 10 nm.

When a quantum dot absorbs light from an excitation source and reaches an energy excitation state, it emits energy equivalent to an energy band gap of a quantum dot. Therefore, if the size of the quantum dots or the composition of the substance is adjusted, the energy band gap can be adjusted, and energy of a plurality of levels of wavelength bands can be obtained.

For example, when the quantum dot has a particle diameter of 5.5 nm to 10 nm, the quantum dot emits red light, and when the quantum dot has a particle diameter of 2.5 nm to 5 nm, green light is emitted, and the quantum dot has a particle diameter of 1 nm to 2 nm. In the case of blue light. Quantum dots that emit yellow light have an intermediate dimension that emits red quantum dots and green quantum dots.

Therein, there may be some variation in the particle size.

Here, the quantum dot emitting red light is the quantum dot R, the quantum dot emitting green light is the quantum dot G, and the quantum dot emitting blue light is the quantum dot B.

From the quantum dots described above, light of a plurality of colors such as red light, green light, and blue light can be easily obtained by a quantum size effect. Therefore, colors that emit light at various wavelengths can also be produced, and red, green, and blue can be mixed to generate. Achieve white or multiple colors.

For example, when the light emitted from the primary light source is blue light, the light conversion unit preferably includes the quantum dot R and the quantum dot G.

The quantum dot R converts a part of the blue light into red light having a wavelength of 600 nm to 750 nm (preferably 600 nm to 670 nm), and the quantum dot G converts a part of the blue light into green light having a wavelength of 495 nm to 570 nm. Further, blue light that is not converted into red light and green light is directly transmitted through the light conversion portion.

Therefore, blue light, red light, and green light are emitted from the light conversion portion, and the light is mixed to generate white light.

On the other hand, in a case where the light emitted from the primary light source is red light, the light conversion portion may include the quantum dot B and the quantum dot G, and in the case where the light emitted by the primary light source is green light, the light conversion portion Quantum dots B and quantum dots R may be included.

In addition, when the light emitted from the primary light source is not blue light, red light, or green light but is other monochromatic light, ultraviolet light, or infrared light, the light conversion portion, the quantum dot R, and the quantum dot G may be included. And all of the quantum dots B, the light passing through the light conversion portion is filtered into blue, red, and green.

Among them, in terms of the efficiency of light conversion, it is preferable that the primary light source is blue light, and the light conversion portion includes the quantum dot R and the quantum dot G.

The quantum dot preferably contains at least one semiconductor nanoparticle selected from the group consisting of a II-VI compound, a III-V compound, a IV-VI compound, and a group IV compound.

The quantum dot is particularly preferably a semiconductor nanoparticle selected from at least one of the following group of compounds.

- compound group -

CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe (above "II-VI compound"), GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaN, GaNAs, GaNSb, GaPAs, GaPSb, AlNP , AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb (above "III-V compound"), SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe (above "IV -VI compound"), Si, Ge, SiC, SiGe (above "Group IV compound").

Quantum dots can be synthesized using chemical wet methods.

The chemical wet method is a method in which a precursor substance is added to an organic solvent to grow the particles.

In addition, quantum dots can also have a core. Shell structure.

An organic ligand may exist on the surface of the semiconductor nanoparticle as a quantum dot.

The organic ligand includes pyridine, mercapto alcohol, thiol, phosphine, and phosphine oxide, and functions to stabilize unstable quantum dots after synthesis.

The light conversion unit may contain other inorganic phosphors in addition to quantum dots (at least the quantum dots G).

Examples of other inorganic phosphors include a yttrium aluminum garnet (YAG)-based phosphor, a terbium aluminum garnet (TAG)-based phosphor, and a sialon-based sialon system. A phosphor or a barium orthosilicate (BOS)-based phosphor.

The light conversion portion may contain a resin.

A preferred embodiment of the light conversion unit is a form in which quantum dots are dispersed in a resin.

The resin is preferably one which does not absorb primary light.

More specifically, the resin is preferably at least one selected from the group consisting of an epoxy resin, an anthrone resin, an acrylic resin, and a carbonate polymer.

In the case where the resin has elasticity, the durability of the display device against external impact can also be improved.

Further, the light conversion unit may contain glass in addition to the resin.

Specific examples of the light-converting member include a light-converting member in which a resin in which quantum dots (and other inorganic phosphors as needed) are dispersed in a translucent container such as a glass case (for example, the light-converting member) 42) a light conversion layer containing a resin in which quantum dots (and other inorganic phosphors as needed) are dispersed, and a light conversion sheet including the light conversion layer and a light transmissive protective film covering both surfaces of the light conversion layer (Quantum dot; for example, the light conversion sheet 52).

The method of forming the light conversion layer may be exemplified by using a well-known molding method. A method of resin molding in which quantum dots (and other inorganic phosphors as needed) are dispersed, and a coating liquid containing a resin in which quantum dots (and other inorganic phosphors as needed) and an organic solvent are dispersed is applied to A method of drying a support (the protective film or the like) and the like.

<green filter>

The green filter contains at least one phthalocyanine compound represented by the following formula (1) as a colored material.

The green filter may also contain other colored materials or components other than the colored materials as needed.

<phthalocyanine compound represented by the formula (1)>

The phthalocyanine compound represented by the following general formula (1) is a dye having a high transmittance of green light emitted from the quantum dot G. In more detail, the phthalocyanine compound is a dye that easily achieves the above-described preferred transmittance characteristics. The reason for this is presumed to be a structure in which a halogen atom and a specific group containing an aromatic ring structure (a group represented by the following general formula (2) or the general formula (3)) are substituted on the phthalocyanine skeleton.

Therefore, the green filter contains a phthalocyanine compound represented by the following formula (1) as a colored material, and the light conversion portion contains the quantum dots G, whereby the luminance of the green light after being transmitted through the green filter can be improved.

In addition, the coloring composition (the composition for forming a green filter) containing the phthalocyanine compound represented by the formula (1) is excellent in the solubility of the phthalocyanine compound in an organic solvent when the coloring composition is prepared. When the colored composition is stored in a liquid state or when the colored composition forms a colored film on the substrate, the time is The precipitation of the dye or the like does not occur, the storage stability is good, and the heat resistance and light resistance are good. Further, the coloring composition is also excellent in pattern formability.

In the general formula (1), a plurality of X atoms independently represent a halogen atom. A plurality of R ¹ are each independently represented by a group represented by the following formula (2) or (3). A plurality of R's independently represent a hydrogen atom or a monovalent substituent. M represents Cu, Zn, V(=O), Mg, Ni, Ti(=O), Sn, or Si. The plurality of a each independently represent an integer of 0 to 4, and the plurality of n independently represent integers of 0 to 4, and the plurality of r independently represent integers of 0 to 4, respectively. Among them, at least one of the plurality of a is 1 or more, and at least one of the plurality of n is 1 or more. Of course, in the case where the sum of a plurality of n is 1, X also represents a halogen atom. When the total of a plurality of a is 1, the R ¹ also represents a group represented by the following formula (2) or (3). In the case where the total of a plurality of r is 1, R also represents a hydrogen atom or a monovalent substituent. The sum of a plurality of a, a plurality of n, and a plurality of r is 16.

In the general formulae (2) and (3), b of R ² each independently represents a monovalent substituent selected from the group consisting of the following general formulae (4) to (6). R ³ represents a monovalent substituent. b represents an integer from 1 to 5, and c represents an integer from 0 to 4. However, in the general formula (2), the total of b and c does not exceed 5. Y represents -O-, -S-, -SO ₂ -, or -NR ⁸ -. R ⁸ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.

In the formula (4), R ⁴ represents a hydrogen atom, an alkyl group which may have a substituent, an oxyalkyl group which may have a substituent, an aryl group which may have a substituent, an alkylamine group which may have a substituent, and may have A dialkylamino group of a substituent, an arylamine group which may have a substituent, a diarylamine group which may have a substituent, or an alkylarylamine group which may have a substituent. In the formula (5), d represents an integer of 0 to 2, and when d is 0 or 1, R ⁵ represents an alkyl group which may have a substituent, or an aryl group which may have a substituent, and wherein d is 2 In the case, R ⁵ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a dialkylamino group which may have a substituent, a diarylamine group which may have a substituent, or may have a substituent Alkylarylamino group. In the formula (6), R ⁶ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, and an alkyl group which may have a substituent A sulfonyl group, an arylsulfonyl group which may have a substituent, and R ⁷ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.

When the phthalocyanine compound represented by the formula (1) used in the present invention is a mixture of two or more kinds, a, n, and r each represent an average value of the compounds in the mixture.

Although many studies have been conducted on the use of phthalocyanine compounds as color filters for color filters (refer to Japanese Patent No. 3476208 and International Publication No. 2011/105603), coloring for color filters having green color in particular has not been obtained. A coloring composition having satisfactory color purity and transmittance, and further satisfying heat resistance, light resistance, hardening sensitivity, and storage stability over time. From the standpoint of the above, the meaning of the present invention is large.

Further, the phthalocyanine compound used in the present invention preferably has a ratio of absorption intensity at 550 nm to absorption intensity at 650 nm (550 nm / 650 nm) in the range of 0 to 0.2. In the area, it is especially in the range of 0~0.1.

In the formula (1), X represents a halogen atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom. Further, when the substitution position of X is the α position of the phthalocyanine skeleton, the absorption wavelength is long-wavelength, and it can be suitably used for green color filter applications.

The plurality of n independently represent an integer of 0 to 4, and preferably an integer of 2 to 4. The total of a plurality of n is preferably 2 to 15, more preferably 6 to 15, and particularly preferably 9 to 15.

R ¹ represents a group represented by the formula (2) or the formula (3), and more preferably a group represented by the formula (2).

When the substitution position of R ¹ is the β position of the phthalocyanine skeleton, it is preferable to maintain an appropriate association of the phthalocyanine skeleton in the coloring layer of the color filter and to easily provide the above-described absorption intensity ratio. In addition, when the substitution position of R ¹ is the α position of the phthalocyanine skeleton, precipitation of the phthalocyanine compound in the colored composition is suppressed, and storage stability of the colored composition is improved, which is preferable.

The plurality of a independently represent an integer of 0 to 4, preferably 0 or 1. The total of a plurality of a is preferably from 1 to 14, particularly preferably from 1 to 8, and particularly preferably from 1 to 5.

M represents Cu, Zn, V(=O), Mg, Ni, Ti(=O), Sn, or Si, preferably Zn or Cu.

R represents a hydrogen atom or a monovalent substituent. The substituent T which will be described later can be exemplified as an example of the monovalent substituent. R is preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aryloxy group, more preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a phenoxy group. Especially good for hydrogen atoms.

The plurality of r independently represent integers of 0 to 4, respectively.

In the general formula (1), the substitution position of R in the phthalocyanine skeleton may be any of the α-position and the β-position of the phthalocyanine skeleton, but the effect of inhibiting the association of the α-position substituent is large, and the colored layer is improved. The aspect of the absorption coefficient is preferred.

R ² in the general formula (2) and the general formula (3) each independently represents a monovalent substituent selected from the group consisting of the general formulae (4) to (6), and particularly preferably a general formula ( 4) or a monovalent substituent represented by the formula (5).

b is an integer of 1 to 5, preferably 1 or 2. When b is 2 or more, a plurality of R ² may be the same or different.

R ³ in the general formula (2) and the general formula (3) represents a monovalent substituent. The monovalent substituent represented by R ³ may be selected from the substituent T described later, and is preferably a halogen atom (preferably a chlorine atom or a bromine atom), a cyano group, a nitro group, a hydroxyl group, an amine group, an aryl group, and a total. Alkoxycarbonyl group having 2 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms, arylthio group having 6 to 20 carbon atoms, and total carbon number 1 An alkyl group of ~20 or an alkoxy group having a total carbon number of 1 to 20 is more preferably a methyl group or a methoxy group.

c is an integer from 0 to 4, preferably 0 or 1, more preferably 0. When c is 2 or more, a plurality of R ³ may be the same or different.

In the general formula (2) and the general formula (3), Y represents -O-, -S-, -SO ₂ -, or -NR ⁸ -, preferably -O- or -SO ₂ -, more preferably - O-.

By setting Y to -O- or -SO ₂ -, the absorption of the Soret band can be shortened, and the contrast of absorption can be more effectively exhibited.

R ⁸ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, more preferably a hydrogen atom or a methyl group. Especially preferred is a hydrogen atom. Examples of the alkyl group or the like which may have a substituent are as described later.

R ⁴ in the formula (4) represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, an alkylamine group which may have a substituent, and may have a dialkylamino group of a substituent, an arylamine group which may have a substituent, a diarylamine group which may have a substituent, or an alkylarylamine group which may have a substituent, preferably a hydrogen atom, total An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a diarylamine group having a total carbon number of 12 to 20, or a total carbon number of 7 ~20 alkylarylamine group, particularly preferably an alkyl group having a total carbon number of 1 to 20, a dialkylamino group having a total carbon number of 2 to 20, a diarylamino group having a total carbon number of 12 to 20, or a total The carbon number is 7 to 20 alkylarylamine groups, particularly preferably a diarylamine group having a total carbon number of 12 to 20 or a dialkylamino group having a total carbon number of 2 to 20.

The alkyl moiety and the aryl moiety of the alkyl group, the aryl group and the like may further have a substituent, and the substituent is preferably an alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, or an aromatic group. A thiol group, a halogen atom or the like is more preferably an alkoxy group, and particularly preferably a methoxy group or an ethoxy group. Further, a form having no substituent is also preferable. Examples of the alkyl group or the like which may have a substituent are as described later.

In the formula (5), d represents an integer of 0 to 2, and when d is 0 or 1, R ⁵ is an alkyl group which may have a substituent or an aryl group which may have a substituent, and when d is 2, it represents An alkyl group which may have a substituent, an aryl group which may have a substituent, a dialkylamino group which may have a substituent, a diarylamine group which may have a substituent, or an alkylarylamine group which may have a substituent . When d is 2, R ^{5 is} preferably a dialkylamino group having 2 to 20 carbon atoms, a diarylamine group having 12 to 20 carbon atoms, or an alkylarylamine group having 7 to 20 carbon atoms.

The alkyl moiety and the aryl moiety of the alkyl group, the aryl group and the like may further have a substituent, and the substituent may be exemplified by the substituent T described later, preferably an alkoxy group, an aryl group, an aryloxy group or an alkoxycarbonyl group. An alkylthio group, an arylthio group or a halogen atom, etc., more preferably an alkoxy group, particularly preferably a methoxy group or an ethoxy group. Further, a form having no substituent is also preferable. Examples of the alkyl group or the like which may have a substituent are as described later.

In the formula (6), R ⁶ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, and an alkyl group which may have a substituent A sulfonyl group, an arylsulfonyl group which may have a substituent, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylcarbonyl group having 2 to 20 carbon atoms, and a carbon number of 7 ~20 arylcarbonyl, alkyl 1-20 sulfonyl, or 6 to 20 arylsulfonyl, more preferably 2 to 20 carbon carbonyl, carbon number 7-20 An arylcarbonyl group, an alkylsulfonyl group having 1 to 20 carbon atoms, or an arylsulfonyl group having 6 to 20 carbon atoms.

The alkyl moiety and the aryl moiety of the alkyl group, the aryl group and the like may further have a substituent, and the substituent may be exemplified by the substituent T described later, preferably an alkoxy group, an aryl group, an aryloxy group or an alkoxycarbonyl group. An alkylthio group, an arylthio group or a halogen atom, etc., more preferably an alkoxy group, particularly preferably a methoxy group or an ethoxy group. Further, a form having no substituent is also preferable. Examples of the alkyl group or the like which may have a substituent are as described later.

In the formula (6), R ⁷ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, preferably an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms. base.

The alkyl moiety and the aryl moiety of the alkyl group, the aryl group and the like may further have a substituent, and the substituent may, for example, be a substituent T described later, preferably an alkoxy group, an aryl group, an aryloxy group or an alkoxycarbonyl group. An alkylthio group, an arylthio group or a halogen atom, etc., more preferably an alkoxy group, particularly preferably a methoxy group or an ethoxy group. Further, it is also preferred that the alkyl moiety and the aryl moiety have no substituent. Examples of the alkyl group or the like which may have a substituent are as described later.

Preferred examples of the alkyl group which may have a substituent in the above formula (2) to formula (6) are shown.

The alkyl group which may have a substituent may, for example, be methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 1-ethylpentyl, 2-ethyl Hexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl, phenoxymethyl, phenoxyethyl, benzyl, Phenylethyl, 4-phenylbutyl, N-butylaminosulfonylpropyl, N-butylaminocarbonylmethyl, N,N-dibutylaminosulfonylpropyl, B Oxyethoxyethyl, 2-chloroethyl, particularly preferably: methyl, ethyl, propyl, isopropyl, tert-butyl, phenoxyethyl, benzyl, phenyl Base, N-butylaminosulfonylpropyl, N-butylaminocarbonylmethyl, N,N-dibutylaminosulfonylpropyl, ethoxyethoxyethyl, especially To be mentioned, methyl, ethyl, propyl, tert-butyl, 2-ethylhexyl, phenoxyethyl, benzyl, phenylethyl, 4-phenylbutyl, N-butylamine Sulfosylpropyl, N-butylaminocarbonylmethyl, N,N-dibutylaminosulfonylpropyl, ethoxyethoxyethyl.

Preferred examples of the alkoxy group which may have a substituent in the above formula (2) to formula (6) are shown.

Examples of the alkoxy group which may have a substituent include a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, a propoxy group, an isopropoxy group, a third butoxy group, and a dodecyl group. Further, examples of the cycloalkyloxy group include a cyclopentyloxy group and a cyclohexyloxy group, and particularly preferably a methoxy group, an ethoxy group, a 1-butoxy group, and an isopropoxy group. Base, third butoxy.

Preferred examples of the aryl group which may have a substituent in the above formula (2) to formula (6) are shown.

Examples of the aryl group which may have a substituent include a phenyl group, a 2-chlorophenyl group, a 2-methoxyphenyl group, a 4-butoxycarbonylphenyl group, and a 4-N,N-dibutylaminocarbonylphenyl group. 4-N-butylaminosulfonylphenyl, 4-N,N-dibutylaminosulfonylphenyl, more preferably phenyl, 4-butoxycarbonylphenyl, 4-N,N-dibutylaminocarbonylphenyl, 4-N-butylaminosulfonylphenyl, 4-N,N-dibutylaminosulfonylphenyl, especially preferably Listed: phenyl, 4-butoxycarbonylphenyl, 4-N,N-dibutylaminocarbonylphenyl, 4-N,N-dibutylaminosulfonylphenyl.

Preferred examples of the alkylamino group which may have a substituent in the above formula (2) to formula (6) are shown.

Examples of the alkylamino group which may have a substituent include a methylamino group, an ethylamino group, a butylamino group, a tetradecylamino group, a 2-ethylhexylamino group, and a cyclohexylamino group. Examples thereof include an ethylamino group, a butylamino group, and a 2-ethylhexylamino group.

Preferred examples of the dialkylamino group which may have a substituent in the above formula (2) to formula (6) are shown.

Examples of the dialkylamino group which may have a substituent include N,N-dimethylamino group, N,N- Dibutylamino, N,N-dioctylamino, N,N-bis(2-ethylhexyl)amine, N-methyl-N-benzylamine, N,N-di(2 -Ethoxyethyl)amino, N,N-bis(2-hydroxyethyl)amine.

Preferred examples of the arylamine group which may have a substituent in the above formula (2) to formula (6) are shown.

Examples of the arylamine group which may have a substituent include an anilino group, a 2-methylanilino group, a 2-ethylanilino group, a 2-isopropylanilino group, a 2,6-dimethylanilino group, and 2, 4,6-trimethylanilino, 3-methylanilino, 4-methylanilino, 2-methoxyanilino, particularly preferred are anilino, 2-methylanilino, 2, 6-dimethylanilino.

Preferred examples of the diarylamine group which may have a substituent in the above formula (2) to formula (6) are shown.

Examples of the diarylamine group which may have a substituent include N,N-diphenylamino group, N,N-bis(4-methoxyphenyl)amino group, and N,N-bis(4-fluorenyl group). Phenyl)amine group.

Preferred examples of the alkylarylamine group which may have a substituent in the above formula (2) to formula (6) are shown.

The alkylarylamine group which may have a substituent may, for example, be N-methyl-N-phenylamino, N-benzyl-N-phenylamine, N-methyl-N-(4-methoxy Alkyl phenyl)amino group.

Preferred examples of the alkylcarbonyl group which may have a substituent in the above formula (2) to formula (6) are shown.

The alkylcarbonyl group which may have a substituent may, for example, be an ethyl fluorenyl group, a propylcarbonyl group, a heptyl-3-carbonyl group, a 2-ethylhexyloxymethylcarbonyl group, a phenoxymethylcarbonyl group or a 2-ethylhexyloxy group. Alkylcarbonylmethylcarbonyl.

Preferred examples of the arylcarbonyl group which may have a substituent in the above formula (2) to formula (6) are shown.

Examples of the arylcarbonyl group which may have a substituent include a benzamidine group, a 4-methoxybenzylidene group, and a 4-ethoxycarbonylbenzylidene group.

Preferred examples of the alkylsulfonyl group which may have a substituent in the above formula (2) to formula (6) are shown.

The alkylsulfonyl group which may have a substituent may, for example, be a methylsulfonyl group, a butasulfonyl group, an octylsulfonyl group, a dodecylsulfonyl group, a benzylsulfonyl group or a phenoxypropylsulfonyl group. .

Preferred examples of the arylsulfonyl group which may have a substituent in the above formula (2) to formula (6) are shown.

Examples of the arylsulfonyl group which may have a substituent include a phenylsulfonyl group, a 4-methylphenylsulfonyl group, a 2-methoxyphenylsulfonyl group, and a 4-ethoxycarbonylphenylsulfonyl group. base.

Preferred examples of the alkylsulfonylamino group which may have a substituent in the above formula (2) to formula (6) are shown.

Examples of the alkylsulfonylamino group which may have a substituent include a methylsulfonylamino group, a butylsulfonylamino group, a hydroxypropylsulfonylamino group, and a 2-ethylhexylsulfonylamino group. , n-octylsulfonylamino, phenoxyethylsulfonylamino, allylsulfonylamino.

The vinylsulfonylamino group which may have a substituent in the general formula (2) to the general formula (6) may, for example, be a vinylsulfonylamino group or a 1-methylvinylsulfonylamino group.

Examples of the arylsulfonylamino group which may have a substituent in the general formulae (2) to (6) include a phenylsulfonylamino group and a p-methoxyphenylsulfonylamino group. P-ethoxycarbonylsulfonylamino group and the like.

The alkylcarbonylamino group which may have a substituent in the general formula (2) to the general formula (6) may, for example, be a methylcarbonylamino group, a 2-ethylhexylamino group or a n-heptylcarbonylamino group. Ethoxyethoxymethylcarbonylamino group and the like.

The arylcarbonylamino group which may have a substituent in the general formula (2) to the general formula (6) may, for example, be a benzindylamino group, a 2-methoxybenzhydrylamino group or a 4-ethylene group. Benzobenzamide or the like.

R ¹ in the above formula (1) is particularly preferably represented by the following formula (7).

In the formula (7), R ⁸ and R ⁹ each independently represent an alkyl group which may have a substituent, and an aryl group which may have a substituent. R ³¹ represents a substituent. C1 represents an integer from 0 to 4.

R ³¹ has the same meaning as R ³ in the formula (2), and the preferred range is also the same. C1 has the same meaning as c in the formula (2), and the preferred range is also the same.

R ⁸ and R ⁹ each independently represent an alkyl group which may have a substituent, and an aryl group which may have a substituent. The alkyl group which may have a substituent, the aryl group which may have a substituent, and the alkyl group which may have a substituent in R ⁵ of the formula (5), and the aryl group which may have a substituent have the same meanings, and the preferred range is also the same .

The group represented by the formula (7) is particularly preferably a group represented by the formula (9).

In the formula (9), R ⁸¹ and R ⁹¹ each independently represent an alkyl group which may have a substituent, and an aryl group which may have a substituent.

R ⁸¹ and R ⁹¹ each independently represent an alkyl group which may have a substituent, and an aryl group which may have a substituent. The alkyl group which may have a substituent, the aryl group which may have a substituent has the same meaning as the alkyl group which may have a substituent in R ⁸ and R ⁹ of the formula (7), and the aryl group which may have a substituent, and a preferred range The same is true.

The alkyl group which may have a substituent is preferably an alkyl group which may have a substituent of 1 to 12 carbon atoms, more preferably an alkyl group which may have a substituent of 1 to 8 carbon atoms, and particularly preferably a carbon number of 1 to 6. An alkyl group which may have a substituent. The substituent T which will be described later can be exemplified as an example of the substituent. The alkyl group which may have a substituent may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a cyclopropyl group or a ring. Butyl, Cyclopentyl, cyclohexyl, 2-ethylhexyl and the like.

The substituent T means any substituent selected from the group of substituents below.

a halogen atom (preferably a chlorine atom or a bromine atom) or an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, for example, methyl group, ethyl group, propyl group or the like). Propyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1 - norbornyl, 1-adamantyl), alkenyl (preferably alkenyl having 2 to 18 carbon atoms, such as vinyl, allyl, 3-buten-1-yl), aryl (comparative Preferred are aryl groups having 6 to 24 carbon atoms, such as phenyl, naphthyl, and heterocyclic groups (preferably a heterocyclic group having 1 to 18 carbon atoms, for example, 2-thienyl, 4-pyridyl, 2 - furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), decylalkyl (preferably carbon number) a decyl group of 3 to 18, for example, a trimethyl decyl group, a triethyl decyl group, a tributyl decyl group, a tert-butyl dimethyl decyl group, a third hexyl dimethyl decyl group, a hydroxyl group, a cyanogen group a nitro group, an alkoxy group (preferably an alkoxy group having 1 to 24 carbon atoms, for example, a methoxy group, an ethoxy group, a 1-butoxy group, or a 2- An oxy group, an isopropoxy group, a tert-butoxy group, a dodecyloxy group, and, if it is a cycloalkyloxy group, for example, a cyclopentyloxy group, a cyclohexyloxy group, or an aryloxy group ( Preferred is an aryloxy group having 6 to 24 carbon atoms, for example, a phenoxy group, a 1-naphthyloxy group, a heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 18 carbon atoms, for example, 1-benzene). a tetrazole-5-oxy group, a 2-tetrahydropyranyloxy group, a decyloxy group (preferably a decyloxy group having 1 to 18 carbon atoms, for example, a trimethyl decyloxy group, Tributyl dimethyl decyloxy, diphenylmethyl fluorenyloxy), decyloxy (preferably carbon number) 2 to 24 decyloxy groups, for example: ethoxylated, trimethylethoxycarbonyl, 2-ethylhexyloxy, 2-methylpropoxy, octyloxy, butoxy , 2-methylbutanoxy, benzhydryloxy, dodecyloxy), alkoxycarbonyloxy (preferably alkoxycarbonyloxy having 2 to 24 carbon atoms, for example: ethoxylated) a carbonyloxy group, a third butoxycarbonyloxy group, and, if it is a cycloalkyloxycarbonyloxy group, for example, a cyclohexyloxycarbonyloxy group, an aryloxycarbonyloxy group (preferably a carbon) a 7 to 24 aryloxycarbonyloxy group, for example, a phenoxycarbonyloxy group, an amine methyl methoxy group (preferably an amine methoxy group having a carbon number of 1 to 24, for example, N, N-di Methylamine methyl methoxy, N-butylamine methyl methoxy, N-phenylamine methyl methoxy, N-ethyl-N-phenylamine methyl oxy), amine sulfonyloxy ( Preferred is an aminesulfonyloxy group having 1 to 24 carbon atoms, for example, N,N-diethylaminesulfonyloxy, N-propylaminesulfonyloxy), alkylsulfonyloxy (preferably). It is an alkylsulfonyloxy group having 1 to 24 carbon atoms, for example, methylsulfonyloxy group, cetylsulfonyloxy group, cyclohexylsulfonyloxy group, or arylsulfonyloxy group (preferably An arylsulfonyloxy group having 6 to 24 carbon atoms, for example, a phenylsulfonyloxy group, a fluorenyl group (preferably a fluorenyl group having 1 to 24 carbon atoms, for example, a fluorenyl group, an ethyl fluorenyl group, and a trimethyl group) Alkoxycarbonyl, benzhydryl, tetradecyl, cyclohexyl), alkoxycarbonyl (preferably alkoxycarbonyl having 2 to 24 carbon atoms, for example, methoxycarbonyl, ethoxy) Carbonyl group, octadecyloxycarbonyl group, cyclohexyloxycarbonyl group, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group, aryloxycarbonyl group (preferably carbon number 7~) An aryloxycarbonyl group of 24, for example, a phenoxycarbonyl group, an amine carbenyl group (preferably an amine carbenyl group having a carbon number of 1 to 24, for example, an amine carbenyl group, an N,N-diethylamine group) Sulfhydryl, N-ethyl-N-octylamine, mercapto, N,N-dibutylamine, mercapto, N-propylamine, N-phenylamine An anthracene group, an N-methyl-N-phenylamine methyl sulfonyl group, an N,N-dicyclohexylamine methyl fluorenyl group, an amine group (preferably an amine group having a carbon number of 24 or less, for example, an amine group, A An amino group, N,N-dibutylamino group, tetradecylamino group, 2-ethylhexylamino group, cyclohexylamino group), an anilino group (preferably an anthranyl group of 6 to 24, for example: An anilino group, an N-methylanilino group, a heterocyclic amine group (preferably a heterocyclic amino group of 1 to 18, for example, a 4-pyridylamino group), a carboguanamine group (preferably 2 to 24) Carboguanamine group, for example: acetamino group, benzammonium group, tetradecylguanidinium group, trimethylacetamidoguanyl group, cyclohexaneguanidinyl group, urea group (preferably carbon) a ureido group having 1 to 24, for example, a ureido group, an N,N-dimethylureido group, an N-phenylureido group, or a quinone imine group (preferably a quinone imine group having a carbon number of 24 or less, for example : N-butylenedimino group, N-phthalimido group, alkoxycarbonylamino group (preferably alkoxycarbonylamino group having 2 to 24 carbon atoms, for example, methoxy group) Carbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino), aryloxycarbonylamino An aryloxycarbonylamino group having 7 to 24 carbon atoms, for example, a phenoxycarbonylamino group, a sulfonylamino group (preferably a sulfonylamino group having 1 to 24 carbon atoms, for example, a methanesulfonylamino group) , butasulfonylamino, benzenesulfonylamino, hexadecanesulfonylamino, cyclohexylsulfonylamino), aminesulfonylamino (preferably amidoxime amine having a carbon number of 1 to 24) a group, for example, N,N-dipropylaminesulfonylamino, N-ethyl-N-dodecylaminesulfonylamino), azo (preferably having a carbon number of 1 to 24) An azo group, for example, a phenylazo group, a 3-pyrazolylazo group, an alkylthio group (preferably an alkylthio group having 1 to 24 carbon atoms, for example, a methylthio group or an ethyl group) Sulfur, octylthio, cyclohexylthio), arylthio (preferably arylthio having 6 to 24 carbon atoms, for example, phenylthio), hetero Cyclo-thio group (preferably a heterocyclic thio group having 1 to 18 carbon atoms, for example, 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), alkyl group a sulfonyl group (preferably an alkylsulfinylene group having 1 to 24 carbon atoms, for example, a dodecylsulfinyl group) or an arylsulfinyl group (preferably an aryl group having 6 to 24 carbon atoms) a sulfonyl group, for example, a phenylsulfinyl group, an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 24 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, and propyl Sulfosyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), aryl a sulfonyl group (preferably an arylsulfonyl group having 6 to 24 carbon atoms, for example, a phenylsulfonyl group, a 1-naphthylsulfonyl group), an aminesulfonyl group (preferably an amine having a carbon number of 24 or less) Sulfhydryl group, for example: amidoxime, N,N-dipropylaminesulfonyl, N-ethyl-N-dodecylammoniumsulfonyl, N-ethyl-N-phenylaminesulfonate Sulfhydryl, N-cyclohexylamine sulfonyl), sulfo, phosphinyl (preferably a fluorenyl group having 1 to 24 carbon atoms, for example, phenoxyphosphonium, octyloxyphosphonium, benzene Phosphine fluorenyl) Phosphinic acyl group (preferably having a carbon number of acyl group phosphinic 1 to 24, for example: diethoxy phosphonite acyl group, di-octyloxy alkylphosphonous acyl group).

Further, in particular, from the viewpoint of improving the developability of the alkaline developing solution, the substituent T is preferably a substituent forming an alkali aqueous solution solubilizing moiety, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a sulfonium group. a substituent such as an imido group, a phenolic hydroxyl group, an acetamethyleneamine group, an acetamidine acetate group, or an alkyl group, an alkyloxy group or an alkyl group substituted with any group selected from the group Substituents such as thiol, aryloxy, arylthio, alkylsulfonyl, arylsulfonyl.

In the case where the substituent T is a group which may be further substituted, Any of the groups described above is further substituted. Further, in the case of having two or more substituents, the substituents may be the same or different. Among them, the substituent in the present invention preferably has a mass of 500 daltons or less per molecule.

The phthalocyanine compound represented by the formula (1) in the present invention is preferably a phthalocyanine compound represented by the following formula (1').

In the general formula (1'), a plurality of X ^A represent a chlorine atom, and a plurality of R ^B represent a group represented by the following formula (2'), and a plurality of R ^A independently represent hydrogen. Atom or phenoxy. Q represents Cu or Zn. Each of the plurality of e independently represents an integer of 0 to 4, and the plurality of m independently represent integers of 0 to 4, and the plurality of s independently represent integers of 0 to 4, respectively. Among them, at least one of the plurality of e is 1 or more, and at least one of the plurality of m is 1 or more. Of course, in the case where the sum of a plurality of m is 1, X ^A also represents a chlorine atom. When the total of a plurality of e is 1, R ^B also represents a group represented by the following formula (2'). In the case where the sum of a plurality of s is 1, R ^A also independently represents a hydrogen atom or a phenoxy group. The sum of a plurality of e, a plurality of m, and a plurality of s is 16.

In the formula (2'), R ^C represents one monovalent substituent selected from the group consisting of the following general formulae (4') to (6'), and R ^D represents a methyl group or a methoxy group. base. f represents an integer from 1 to 5, and g represents 0 or 1. The total of f and g will not exceed 5. Y ^A represents -O-.

In the formula (4'), R ^E represents a hydrogen atom, an alkyl group having a total carbon number of 1 to 20, an aryl group having a total carbon number of 6 to 20, a dialkylamino group having a total carbon number of 2 to 20, and a total carbon number. 12 to 20 diarylamine groups or a total of 7 to 20 alkylarylamine groups. In the formula (5'), h is 2, and R ^F represents a dialkylamino group having 2 to 20 carbon atoms, a diarylamino group having 12 to 20 carbon atoms, or a 7 to 20 alkylarylamine having a carbon number of 7 to 20 base. In the formula (6'), R ^G represents an alkylcarbonyl group having 2 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, or a carbon number of 6 to 20 Arylsulfonyl. R ^H represents a methyl group.

The preferred range of each substituent, each numerical value, and the like in the above formula (1') is the same as the preferred range of each substituent and each numerical value in the above formula (1).

The molecular weight of the phthalocyanine compound represented by the formula (1) is preferably from 1,500 to 3,500, more preferably from 1,750 to 2,500.

The phthalocyanine compound represented by the formula (1) can be described in "Phase as a functional dye (issued by IPC Co., Ltd.)" and "phthalocyanine-chemistry and function - (issued by IPC Co., Ltd.)" The way to synthesize.

The phthalocyanine compound represented by the formula (1) can be synthesized by subjecting a substitutable phthalonitrile to condensation cyclization in the presence of a metal source. At this time, a phthalocyanine compound into which a plurality of substituents are introduced can be synthesized by mixing a plurality of phthalonitriles. In the case where a single phthalonitrile is used as a raw material, there are also up to four cyclized isomers.

The raw material of the phthalocyanine compound is preferably phthalonitrile, and is not particularly limited, and may be a raw material known as a raw material of phthalocyanine, for example, respectively. The phthalocyanine compound into which a plurality of substituents are introduced can be synthesized by substituting phthalic acid, phthalic anhydride, or phthalimide.

The phthalocyanine compound represented by the formula (1) can be used as a strong organic base by 1,8-diazabicyclo[5,4, by making the corresponding phthalonitrile (together with a metal salt as needed). In the presence of 0]-7-undecene, the reaction is carried out in an alcohol solvent to synthesize.

Hereinafter, an exemplary compound of the phthalocyanine compound represented by the formula (1) is shown.

However, the invention is not limited to the exemplified compounds.

In the following exemplified compounds, M, R ^1, X and R each represent the general formula (1), M, R ^1, X and R.

Further, among the following exemplified compounds, a, n and r respectively represent the sum of a plurality of a in the formula (1), the sum of a plurality of n, and the sum of a plurality of r.

Further, in the following exemplified compounds, Y and Ar are each a substituent of the formula (2) and the formula (3) represented by R ¹ and an aromatic group.

Further, in the following exemplified compounds, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, Ph represents a phenyl group, and ring-C ₆ H ₁₁ represents a cyclohexyl group.

Further, among the following exemplified compounds, Ar-1 to Ar-51 and Q-1 to Q-10 each represent a substituent described later. Among the substituents, Indicates the bond position.

Next, a synthesis example of the exemplified compound is shown.

In addition, in the following synthesis example, "parts" means "parts by mass".

(Exemplified synthesis of compound A-1)

A mixed solution of methylparaben (20 parts) and dibutylamine (30 parts) was reacted at 120 ° C for 5 hours. The reaction liquid was extracted with ethyl acetate (200 parts) and 1N hydrochloric acid (200 parts), and the organic layer was separated and concentrated, and then purified by silica gel chromatography to obtain 4-dibutylaminocarbonylphenol 30. Share.

Then, a mixed solution of the obtained substituted phenol (25 parts), tetrachlorophthalonitrile (27 parts), potassium carbonate (20 parts), and N-methylpyrrolidone (200 parts) at 60 ° C Reaction for 3 hours. The reaction liquid was subjected to a liquid separation operation using ethyl acetate and 1N aqueous hydrochloric acid. After concentrating the organic layer, it was purified by silica gel chromatography to obtain 35 parts of 4-dibutylaminocarbonylphenoxytrichlorophthalonitrile. Further, a 3-position substituent is mixed in 4-dibutylaminocarbonylphenol.

The reaction mixture of the obtained substituted phthalonitrile (20 parts), zinc chloride (8 parts), and dimethylaminoethanol (400 parts) was reacted at 120 ° C for 6 hours. The reaction liquid was subjected to an extraction operation using ethyl acetate and 1N hydrochloric acid, and the organic layer was separated and concentrated, and then purified by silica gel chromatography to obtain 14 parts of the exemplified compound A-1.

The maximum absorption wavelength of the obtained compound in chloroform was 710 nm, and the molar absorption coefficient was 125,000.

(Synthesis of exemplified compound A-2 to exemplified compound A-27, exemplified compound A-37, exemplified compound A-39, and exemplified compound A-40)

The substituted phenol corresponding to the exemplified compound Ar-2 to the exemplified compound Ar-49 and the substituted naphthol were synthesized by reference to the literature, and the substituted phenol was used to synthesize the substituted phthalate by the same method as the exemplified compound A-1. Nitrile (substituted phenol The substitution position of the hydroxyl group is a mixture of the 3 and 4 positions, and then, the zinc phthalocyanine is synthesized.

(Synthesis of Compound A-28)

4-Dibutylaminocarbonylphenoxytrichlorophthalonitrile (9.6 parts), phthalonitrile (2.5 parts), chlorine synthesized by the method described in the synthesis of the exemplified compound A-1 The reaction solution of zinc (4 parts) and dimethylaminoethanol (100 parts) was reacted at 120 ° C for 6 hours, taken out, and purified, whereby 8 parts of the exemplified compound A-28 were obtained.

(Synthesis of Compound A-29)

4-Dibutylaminosulfonylphenoxytrichlorophthalonitrile (10.2 parts (a mixture of substituted phenolic hydroxyl groups at the 3-position and 4-position)), phthalonitrile (2.5 a reaction solution of copper acetate (3.0 parts), ammonium benzoate (6.0 parts), 1-methoxy-2-propanol (100 parts), reacted at 120 ° C for 6 hours, taken out, purified, borrowed This gave 7 parts of the exemplified compound A-29.

(Synthesis of Compound A-30)

The exemplified compound A-30 was synthesized by the same method as the exemplified compound A-29 except that 3-phenoxyphthalonitrile (4.4 parts) was used instead of phthalonitrile.

(Synthesis of Compound A-31)

a mixed solution of 4-dibutylaminocarbonylphenol (25 parts), tetrachlorophthalonitrile (13.5 parts), potassium carbonate (20 parts), and N-methylpyrrolidone (200 parts). The reaction was carried out at 90 ° C for 6 hours. The reaction liquid was subjected to a liquid separation operation using ethyl acetate and 1N aqueous hydrochloric acid. After concentrating the organic layer, it was purified by silica gel chromatography to obtain 20 parts of bis(4-dibutylaminocarbonylphenoxy)dichlorophthalonitrile. In addition, 4- The dibutylaminocarbonylphenol has a substitution number of 2, and the substitution position is a mixture of the 3 position and the 4 position and the 5 position.

The bis(4-dibutylaminocarbonylphenoxy)dichlorophthalonitrile and 4-dibutylaminocarbonylphenoxytrichloroortane were used in addition to the molar ratio of 1 to 3. In the same manner as in the synthesis of the exemplified compound A-1, zinc phthalocyanine was synthesized in the same manner as the diacetonitrile to obtain the exemplified compound A-31.

(Synthesis of Compound A-32)

In addition to the 3 to 1 molar ratio, 4-dibutylaminosulfonylphenoxytrichlorophthalonitrile (the substitution position of the hydroxyl group of the substituted phenol is a mixture of 3 and 4 positions) and the adjacent In addition to the phthalonitrile, zinc phthalocyanine was synthesized by the same method as the synthesis of the exemplified compound A-28 to obtain the exemplified compound A-32.

(Synthesis of Compound A-33)

In addition to using a molar ratio of 1 to 1, 4-(bis(ethoxyethyl)aminocarbonyl)phenoxytrichlorophthalonitrile (the substitution position of the hydroxyl group of the substituted phenol is 3 and 4 positions) The exemplified compound A-33 was synthesized by the same method as the synthesis of the exemplified compound A-1 except for the mixture of 4-dibutylaminosulfonylphenoxytrichlorophthalonitrile.

(Synthesis of Compound A-34)

Synthesis of 2-bis(ethoxyethyl)aminocarbonylthiophenoxytrichloroorthophenyl using 2-bis(ethoxyethyl)aminocarbonylthiophenol and tetrachlorophthalonitrile Dimeronitrile, followed by the use of m-chloroperoxybenzoic acid in a chloroform solvent to synthesize 2-bis(ethoxyethyl)aminocarbonylphenylsulfonyltrichlorophthalonitrile. Use the resulting substitution neighbor As the phthalonitrile, the exemplified compound A-34 was synthesized by the same method as the synthesis of the exemplified compound A-1.

(Synthesis of Compound A-35)

By using 2-bis(ethoxyethyl)aminocarbonylthiophenoxytrichlorophthalonitrile, the reaction is carried out using copper acetate, ammonium benzoate and 1-methoxy-2-propanol. The exemplified compound A-35 was obtained.

(Synthesis of Compound A-36)

Synthesis of 4-dibutylaminosulfonylaminotrichlorophthalonitrile using 4-dibutylaminosulfonylaniline in the same manner as the synthesis of the exemplified compound A-1 Ear ratio of 3 to 1 using 4-dibutylaminosulfonylaminotrichlorophthalonitrile and phthalonitrile, using copper acetate, ammonium benzoate, 1-methoxy-2-propene The alcohol was reacted, whereby the exemplified compound A-36 was obtained.

(Synthesis of Compound A-37)

Synthesis of substituted trichlorophthalonitrile using the same method as the synthesis of the exemplified compound A-1 using 6-bis(ethoxyethyl)aminosulfonyl-2-naphthol, followed by synthesis of zinc Phthalocyanine, whereby the exemplified compound A-37 was obtained.

(Synthesis of Compound A-38)

4-Dibutylaminosulfonylphenoxytrichlorophthalonitrile, phenoxytrichlorophthalonitrile, and 3-phenoxyphthalonitrile to be in molar ratio 1 was mixed in a manner of 1 to 2, and the exemplified compound A-38 was obtained by the same method as the synthesis of the exemplified compound A-1.

(Synthesis of Compound A-41)

Mixing 4-dibutylaminocarbonylphenoxytrichlorophthalonitrile and phenoxytrichlorophthalonitrile in a molar ratio of 3 to 1, using and exemplified compound A-1 The same method was synthesized to obtain the exemplified compound A-41.

(Synthesis of Compound A-42)

Synthesis of 4-dibutylaminosulfonylaminotrichlorophthalonitrile using acetic acid using 4-dibutylaminosulfonylaniline in the same manner as in the synthesis of the exemplified compound A-1 Copper, ammonium benzoate, and 1-methoxy-2-propanol were allowed to react, whereby the exemplified compound A-42 was obtained.

(Synthesis of Compound A-43, Exemplary Compound A-44)

The substituted phenol corresponding to the exemplified compound A-43 and the exemplified compound A-44 was synthesized by reference to the literature, and the substituted phenol was used to synthesize the substituted phthalonitrile by the same method as the synthesis of the exemplified compound A-1. The substitution position of the hydroxyl group of phenol is a mixture of 3 and 4 positions, and then, zinc phthalocyanine is synthesized.

(Synthesis of Compound A-45)

4-Dibutylaminosulfonylphenoxytrichlorophthalonitrile (10.2 parts (a mixture of substituted phenolic hydroxyl groups at the 3-position and 4-position)), tetrachlorophthalonitrile A reaction liquid of (1.77 parts), zinc iodide (2.5 parts), and benzonitrile (30 parts) was reacted at 135 ° C for 48 hours. The reaction liquid was subjected to an extraction operation using ethyl acetate and 1N hydrochloric acid, and the organic layer was separated and concentrated, and then purified by silica gel chromatography to obtain 10.3 parts of the exemplified compound A-45.

(Synthesis of Compound A-46)

In addition to the use of phthalonitrile (0.85 parts) instead of tetrachlorophthalonitrile, The exemplified compound A-46 was synthesized by the same method as the exemplified compound A-45.

(Synthesis of Compound A-47)

4-{bis(methoxyethyl)aminosulfonyl}phenoxytrichlorophthalonitrile (13.83 parts (the substitution position of the hydroxyl group of the substituted phenol is a mixture of the 3 and 4 positions)), The reaction solution of zinc iodide (2.5 parts) and benzonitrile (30 parts) was reacted at 135 ° C for 48 hours. The reaction mixture was subjected to an extraction operation using ethyl acetate and 1N hydrochloric acid, and the organic layer was separated and concentrated, and then purified by silica gel chromatography to obtain 9.8 parts of the exemplified compound A-47.

(Synthesis of Compound A-48~ Exemplary Compound A-76)

Reference information was used to synthesize a substituted phenol corresponding to the exemplified compound A-48 to the exemplified compound A-76, and the substituted phenol was used to synthesize a substituted phthalonitrile by the same method as the synthesis of the exemplified compound A-1. The substitution position of the hydroxyl group of phenol is a mixture of 3 and 4 positions).

Then, in the case of synthesizing zinc phthalocyanine having "a" of 3 in the general formula (1), the zinc phthalocyanine having "a" of 4 in the general formula (1) is synthesized by the same method as the exemplified compound A-46. The synthesis was carried out in the same manner as in the exemplified compound A-47.

(Synthesis of Compound A-77)

Sodium hydroxybenzenesulfonate (20 parts) was added to sulfoxide (49 parts), and dimethylformamide (1.4 parts) was added dropwise thereto, followed by heating under reflux for 2 hours. The reaction solution was crystallized from ice water, extracted with ethyl acetate, and the organic layer was separated and concentrated to obtain 19.7 parts of hydroxybenzenesulfonyl chloride.

Next, N-methylpyrrolidine dissolved in 2-(ethylamino)ethanol (9 parts) To the ketone (50 parts) solution, hydroxybenzenesulfonium chloride (19.2 parts) was added dropwise thereto in an ice bath, followed by stirring at 50 °C for 2 hours. After adding water to the reaction liquid, a liquid separation operation was carried out using ethyl acetate and a 1 N aqueous hydrochloric acid solution. After concentrating the organic layer, 200 ml of a 30% aqueous sodium hydroxide solution was added, and the mixture was stirred under heating at 80 ° C for 5 hours. The reaction liquid was subjected to a liquid separation operation using ethyl acetate and 1N aqueous hydrochloric acid. The organic layer was concentrated, and then purified by silica gel chromatography to obtain 15.1 parts of 4-(N-ethyl-N-hydroxyethylaminesulfonyl)phenol.

Next, a mixed solution of 4-(N-ethyl-N-hydroxyethylaminesulfonyl)phenol (12.2 parts), pyridine (4.7 parts), and tetrahydrofuran (100 parts) was cooled to 0 ° C, and acetonitrile was added dropwise. Chlorine (4.7 parts), stirred for 3 hours. The reaction liquid was subjected to a liquid separation operation using ethyl acetate and 1N aqueous hydrochloric acid. The organic layer was concentrated and purified by silica gel chromatography to give 12.5 parts of 4-(N-ethyloxyethyl-N-ethylaminesulfonyl) phenol.

Then, a mixed solution of the obtained substituted phenol (14.4 parts), tetrachlorophthalonitrile (13.3 parts), potassium carbonate (8.3 parts), and N-methylpyrrolidone (100 parts) was reacted at 60 ° C. 3 hours. The reaction liquid was subjected to a liquid separation operation using ethyl acetate and 1N aqueous hydrochloric acid. After concentrating the organic layer, it was purified by silica gel chromatography to obtain 35 parts of 4-(N-acetoxyethyl-N-ethylaminesulfonyl)phenoxytrichlorophthalonitrile. Further, the substitution position of the hydroxyl group of 4-(N-acetoxyethyl-N-ethylaminesulfonyl)phenol is a mixture of the 3 position and the 4 position.

The reaction mixture of the obtained substituted phthalonitrile (13.8 parts), zinc iodide (2.5 parts), and benzonitrile (30 parts) was reacted at 135 ° C for 48 hours. The reaction mixture was subjected to an extraction operation using ethyl acetate and 1N hydrochloric acid, and the organic layer was separated and concentrated, and then purified by silica gel chromatography to obtain 8.2 parts of the exemplified compound A-77.

(Synthesis of Compound A-78)

The substituted phthalonitrile (10.3 parts), tetrachlorophthalonitrile (1.77 parts), zinc iodide (2.5 parts), benzonitrile (30 parts) used in the synthesis of the compound <A-77> were synthesized. The reaction solution was reacted at 135 ° C for 48 hours. The reaction mixture was subjected to an extraction operation using ethyl acetate and 1N hydrochloric acid, and the organic layer was separated and concentrated, and then purified by silica gel chromatography to obtain 11.1 parts of the exemplified compound A-78.

(Synthesis of Compound A-79~ Exemplary Compound A-112)

The reference literature and the exemplified compound A-77 were used to synthesize a substituted phenol corresponding to the exemplified compound A-79 to the exemplified compound A-112, and the substituted phenol was used to synthesize the substitution by the same method as the synthesis of the exemplified compound A-77. Phthalonitrile (the substitution position of the hydroxyl group of the substituted phenol is a mixture of the 3 and 4 positions).

Then, when the zinc phthalocyanine in which a is 3 in the general formula (1) is synthesized, the zinc phthalocyanine in which a is 4 in the general formula (1) is synthesized and exemplified by the same method as the synthesis of the exemplary compound A-78. The synthesis of Compound A-77 was carried out in the same manner as in the synthesis.

The content of the phthalocyanine compound represented by the formula (1) in the green filter is preferably from 1% by mass to 80% by mass, more preferably from 1% by mass to 70% by mass, based on the total mass of the green filter. It is preferably from 3% by mass to 50% by mass, particularly preferably from 10% by mass to 50% by mass.

By setting the content in the above range, a good color density is obtained, which is advantageous in that the patterning of the pixels is good.

<yellow dye>

The green filter preferably contains, in addition to the phthalocyanine compound represented by the general formula (1), In addition, it also contains a yellow dye.

Thereby, the brightness of the green light after being transmitted through the green filter and the color purity of the green light are further improved.

The yellow dye is preferably a methine dye having a pyrazolotriazole ring in one molecule and a pyridone ring in one molecule from the viewpoint of further increasing the brightness of the green light after being transmitted through the green filter. An azo dye, an azo dye having a pyrazole ring in one molecule.

For the yellow dyes (methine dyes, azo dyes), for example, the description of JP-A-2011-164564 can be referred to.

The yellow dye is preferably a methine dye having a pyrazolotriazole ring in one molecule, and particularly preferably a yellow dye represented by the following formula (I) or the following formula (II).

When the green filter contains a yellow dye represented by the following formula (I) or the following formula (II), the green filter may contain only one type of the yellow dye, or may contain two or more kinds.

In the formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aminomethyl group, an amine sulfonyl group, a cyano group, or the like. The aryl group or the heteroaryl group may have the same or different R ¹ and R ² in the molecule.

In the formula (II), R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an amine carbaryl group, an amine sulfonyl group, The sulfonylamino group, the carbonylamino group, the cyano group, the aryl group or the heteroaryl group may have the same or different R ⁵ groups in the molecule.

In the formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aminomethyl group, an amine sulfonyl group, a cyano group, or the like. The aryl group or the heteroaryl group may have the same or different R ¹ and R ² in the molecule.

In the formula (II), R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an amine carbaryl group, an amine sulfonyl group, The sulfonylamino group, the carbonylamino group, the cyano group, the aryl group or the heteroaryl group may have the same or different R ⁵ groups in the molecule.

In the general formula (I) or the general formula (II), the alkyl group represented by R ¹ to R ⁸ may further have a monovalent substituent, may be linear, may be branched, or may be cyclic. The total carbon number of the alkyl group is preferably from 1 to 30, particularly preferably from 1 to 16. Specific examples thereof include a methyl group, an ethyl group, a butyl group, an isopropyl group, a tert-butyl group, a hydroxyethyl group, a methoxyethyl group, a cyanoethyl group, a trifluoromethyl group, and a 3-sulfo group. Propyl, 4-sulfobutyl, cyclohexyl and the like.

The alkoxy group represented by R ¹ to R ⁸ is represented by -OR ^A (R ^A is an alkyl group), and R ^A has the same meaning as the alkyl group represented by R ¹ to R ⁸ , and the specific examples are also the same.

The alkoxycarbonyl group represented by R ¹ to R ⁸ is represented by -COOR ^A (R ^A is an alkyl group), and R ^A has the same meaning as the alkyl group represented by R ¹ to R ⁸ , and the specific examples are also the same.

The amine forminyl group represented by R ¹ to R ⁸ may further have a monovalent substituent, preferably an amine formamidine group having a total carbon number of 1 to 30, and particularly preferably an amine formamidine group having 1 to 16 carbon atoms. Specific examples thereof include a methylamine methyl sulfonyl group, a dimethylamine methyl fluorenyl group, a phenylamine methyl fluorenyl group, and an N-methyl-N-phenylamine methyl fluorenyl group.

The amine sulfonyl group represented by R ¹ to R ⁸ may further have a monovalent substituent, preferably a total carbon number of 0 to 30, and particularly preferably a total carbon number of 0 to 16. Specific examples thereof include an aminesulfonyl group, a dimethylaminesulfonyl group, and a bis-(2-hydroxyethyl)aminesulfonyl group.

The aryl group represented by R ¹ to R ⁸ may further have a monovalent substituent (excluding a heterocyclic group), preferably an aryl group having a total carbon number of 6 to 30, particularly preferably an aryl group of 6 to 16. Specific examples thereof include a phenyl group, a 4-methylphenyl group, a 4-methoxyphenyl group, a 2-chlorophenyl group, a 3-(3-sulfopropylamino)phenyl group, and a 4-amine sulfonium oxime. A group, a 4-ethoxyethylamine sulfonyl group, a 3-dimethylaminecarbamyl group or the like.

The heteroaryl group represented by R ¹ to R ⁸ has a structure in which a monovalent heterocyclic group is substituted with the above-mentioned aryl group. The monovalent heterocyclic group which may be substituted with an aryl group may be saturated or unsaturated, and examples thereof include the following aromatic heterocyclic group and include a hetero atom such as a nitrogen atom, a sulfur atom or an oxygen atom in the ring. The group of one may further have a substituent, and is preferably a heterocyclic group having a total carbon number of from 1 to 30, particularly preferably a heterocyclic group of from 1 to 15. Specific examples thereof include a 2-pyridyl group, a 2-thienyl group, a 2-thiazolyl group, a 2-benzothiazolyl group, a 2-benzoxazolyl group, and a 2-furyl group.

Further, specifically, R ¹ to R ⁸ may further contain a monovalent substituent represented by a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, an amine carbenyl group, or an aliphatic oxycarbonyl group. , aryloxycarbonyl, fluorenyl, hydroxy, aliphatic oxy, aryloxy, decyloxy, amine methyl methoxy, heterocyclic oxy, amine, aliphatic amine, aryl amine, heterocyclic Amine, mercaptoamine, amine, mercaptoamine, aminesulfonylamino, aliphatic oxycarbonylamino, aryloxycarbonylamino, aliphatic sulfonylamino, arylsulfonyl Amino, nitro, aliphatic thio, arylthio, aliphatic sulfonyl, arylsulfonyl, sulfonyl, sulfo, quinone, or heterocyclic thio, aliphatic A aryl group, an aryl group, a heterocyclic group, a cyano group, an amine carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a fluorenyl group, an aliphatic oxy group, an aryloxy group, an aliphatic amine group, and an arylamine group.

A more preferable substituent of the structure of the compound represented by the formula (I) or the formula (II) will be described.

R ¹ in the formula (I) and R ⁵ in the formula (II) are preferably an alkyl group, an aryl group or a cyano group, and the alkyl group and the aryl group may further have a monovalent substituent. Here, examples of the substituent which can be introduced into the alkyl group and the aryl group include an alkoxy group, a thioalkoxy group, a cyano group, a halogen atom and the like.

More preferably, R ¹ and R ⁵ are a third butyl group, a phenyl group or an o-methylphenyl group.

R ³ in the formula (I) is more preferably a hydrogen atom, and R ⁴ in the formula (I) and the formula (II) is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. R ⁶ in the formula (II) is more preferably a hydrogen atom.

R ² , R ⁷ and R ⁸ in the general formula (I) and the general formula (II) may each independently be a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an amine methyl sulfonyl group, an amine sulfonyl group or a sulfonyl group. Any one of a mercaptoamine group, a carbonylamino group, a cyano group, an aryl group, and a heteroaryl group preferably has a structure selected from the group consisting of a substituted alkyl group, a PEO (polyethylene oxide) chain, and a PPO ( a polyoxypropylene oxide) chain, an ammonium salt, and a partial structure (partial structure A) of an alkoxycarbonyl group, an amine methyl sulfonyl group, an amine sulfonyl group, a sulfonylamino group, or a carbonyl amine group. It is preferably a sulfonylamino group having a partial structure A.

In the compound represented by the formula (I), a plurality of R ^{2 present} in the molecule may be the same or different from each other, and it is preferably the same in terms of synthesis suitability.

The compound represented by the formula (I) is more preferably a compound represented by the following formula (IV), and the compound represented by the formula (II) is more preferably a compound represented by the following formula (V). Aspect.

In the formula (IV), R ¹ , R ³ and R ⁴ each have the same meanings as R ¹ , R ³ and R ⁴ in the formula (I), and preferred examples are also the same.

R ⁹ and R ¹¹ each independently represent an alkyl group, an aryl group or a heteroaryl group, and R ¹⁰ and R ¹² each independently represent a hydrogen atom, a methyl group or an ethyl group.

R ¹⁰ and R ¹² are each preferably a hydrogen atom.

R ⁹ and R ¹¹ are each preferably a substituted or unsubstituted alkyl group, or have a PEO (polyethylene oxide) chain, a PPO (polypropylene oxide) chain, an ammonium salt, and a polymerizable group. The alkyl, aryl or heteroaryl group having a partial structure is more preferably an alkyl group having 2 to 8 carbon atoms or a substituted alkyl group having a methacryl group at the alkyl chain.

In the general formula ^{(V), R 4, R} 5 and R ⁶ each ^4, the same formula (II) in R R ⁵ and R ⁶ meaning Comparative Example are also the same.

R ¹³ and R ¹⁵ each independently represent an alkyl group, an aryl group or a heteroaryl group, and R ¹⁴ and R ¹⁶ each independently represent a hydrogen atom, a methyl group or an ethyl group.

R ¹⁴ and R ¹⁶ are each preferably a hydrogen atom.

R ¹³ and R ^{15 are} preferably a substituted alkyl group or an alkyl group having a partial structure selected from the group consisting of a PEO (polyethylene oxide) chain, a PPO (polypropylene oxide) chain, an ammonium salt, and a polymerizable group. The group or the heteroaryl group is more preferably an alkyl group having 2 to 8 carbon atoms or a substituted alkyl group having a methacryl group group in the alkyl chain.

Specific examples of the compound represented by the formula (I) or the formula (II) are shown below, but the compound represented by the formula (I) or the formula (II) is not limited to the following specific examples.

Examples of the compound represented by the formula (I) and the compound represented by the formula (IV) which is a preferred embodiment thereof include the following exemplified compounds (B-1) to exemplified compounds (B-9), and An exemplified compound (B-17). Examples of the yellow dye represented by the formula (II) and the yellow dye represented by the formula (V) which is a preferred embodiment thereof include the following exemplified compounds (B-10) and exemplified compounds (B-11). ).

In the case where the green filter of the present invention contains a yellow dye, the mass ratio of the yellow dye to the phthalocyanine compound represented by the formula (1) [the mass of the yellow dye or the enthalpy represented by the formula (1) The content of the cyanine compound is preferably from 0.1 to 1.0, more preferably from 0.2 to 0.9, still more preferably from 0.4 to 0.9, and particularly preferably from 0.5 to 0.8.

<Other colored materials>

The green filter may contain a phthalocyanine compound represented by the formula (1) and a colored material other than the yellow dye to be used as needed.

As the other colored material, a known colored material such as a dye or a pigment can be used.

As the other colored material, for example, a known colored material described in paragraphs 0053 to 0067 of JP-A-2011-164564 can be used.

As the dye, a known dye can be used.

It is preferred that the dye be dissolved in an organic solvent in a desired amount, and an appropriate dye can be selected depending on the desired spectral absorption.

The types of dyes include acid dyes, basic dyes, disperse dyes, and reactants with basic compounds by acid dyes, and anti-acid compounds with basic dyes. A dye that is soluble in an organic solvent.

These dyes are required to have a desired spectrum as a color filter, and are dissolved in a solution required to be dissolved in an organic solvent or an alkali-soluble resin to be described later, without causing precipitation or aggregation over time. These dyes can be appropriately selected from C.I. Solvent Colours and the like described in the Colour Index. Further, a dye having a solvent solubility and a suitable spectrum may be selected from known oil-soluble dyes, acid dyes, disperse dyes, reactive dyes, direct dyes, and the like.

<Coloring composition>

Next, a coloring composition suitable for producing a green color filter will be described.

The coloring composition contains the phthalocyanine compound represented by the above formula (1) and an organic solvent (and preferably a yellow dye). The colored composition may further comprise other colored materials.

The green filter can be produced by a method comprising the step of applying the colored composition onto a support (substrate) to form a colored layer.

More specifically, the method may be a known photolithography method or a known dry etching method.

In the case of the photolithography method, in order to impart photosensitivity to the coloring composition, for example, a polymerizable compound and a photopolymerization initiator are contained in the coloring composition. Hereinafter, the coloring composition of this aspect is also referred to as "photosensitive coloring composition".

The preferred range of the content of the phthalocyanine compound represented by the formula (1) in the total solid content of the coloring composition is the same as the content of the phthalocyanine compound represented by the formula (1) in the green filter. The preferred range is the same.

Here, the term "all solid components" means all components other than the organic solvent.

In the case where the coloring composition contains a yellow dye, the mass ratio of the yellow dye to the phthalocyanine compound represented by the formula (1) among all the solid components of the coloring composition [the mass of the yellow dye/the formula (1) The preferred range of the content of the phthalocyanine compound represented by the above is the same as the preferred range of the mass ratio of the green filter.

(polymerizable compound)

The coloring composition (photosensitive coloring composition) contains at least one of polymerizable compounds.

The polymerizable compound is used for the purpose of being activated by an acid or a radical generated by a polymerization initiator by irradiation with radiation, and reacting with an alkali-soluble resin to be described later to cause crosslinking, or by crosslinking. The polymerizable compounds themselves are bonded or polymerized to each other to cause crosslinking, whereby the solubility of the exposed portion in the alkali developing solution is lowered, thereby obtaining a colored pattern (color filter). Further, if necessary, a polymerizable compound is also useful for the purpose of curing the colored pattern after heating the colored pattern.

The polymerizable compound is not particularly limited as long as it is a compound which can be cured by crosslinking or polymerization. The polymerizable compound may, for example, be (a) an epoxy resin; (b) a glycoluril compound or urea substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and a decyloxymethyl group; a compound; (c) a phenol compound substituted with at least one substituent selected from the group consisting of a methylol group, an alkoxymethyl group, and a decyloxymethyl group; (d) a polymerizable monomer compound.

For example, the compounds of the above (a) to (c) can be referred to, for example, paragraphs 0069 to 0084 of JP-A-2006-343598.

The (d) polymerizable monomer compound is preferably a compound having one ethylenically unsaturated group having an addition polymerizable vinyl group and having a boiling point of 100 ° C or higher at normal pressure.

Examples of the (d) polymerizable monomer compound include monofunctional groups such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate. Acrylate or methacrylate; polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol three ( Methyl) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol hexa(meth) acrylate, hexane diol (meth) acrylate, trimethylolpropane tris(propylene oxypropyl) ether And tris(propyleneoxyethyl)isocyanurate, which is added to ethylene oxide or propylene oxide in a polyfunctional alcohol such as glycerin or trimethylolethane, and then (meth)acrylated The urethane amides described in each of the Japanese Patent Publication No. Sho-48-41708, the Japanese Patent Publication No. Sho. Polyester C described in each of the publications of Japanese Patent Publication No. Sho 49-43191, Japanese Patent Publication No. Sho 52-30490 The enoate ester, a reaction product of an epoxy resin and (meth)acrylic acid, or a polyfunctional acrylate or methacrylate such as an epoxy acrylate. Further, as a photocurable monomer, "Japan Adhesive Society", Vol. 20, No. 7, pp. 300-308 And oligomers to introduce compounds.

The polymerizable compound may be used singly or in combination of two or more.

The content of the polymerizable compound in all the solid components of the photosensitive coloring composition is preferably from 1% by mass to 70% by mass, more preferably from 5% by mass to 50% by mass, even more preferably from 7% by mass to 30% by mass.

(polymerization initiator)

The coloring composition (photosensitive coloring composition) contains at least one of photopolymerization initiators.

In the case where the colored composition is a negative photosensitive coloring composition, the negative photosensitive coloring composition contains a photopolymerization initiator.

Further, the photopolymerization initiator may be further contained in a positive coloring composition containing a naphthoquinonediazide compound. In this case, the degree of hardening of the pattern can be further promoted after pattern formation.

The photopolymerization initiator is not particularly limited as long as it can initiate a crosslinking reaction or a polymerization reaction of a polymerizable compound by exposure, and is preferably based on characteristics, initiation efficiency, absorption wavelength, availability, and cost. , security and other perspectives to choose. For example, at least one active halogen compound selected from the group consisting of a halogenated methyl oxadiazole compound and a halogenated methyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a horn-order dimer, and a diphenyl group A ketone compound, an acetophenone compound and a derivative thereof, a cyclopentadiene-benzene-iron complex compound, a salt thereof, a quinone compound, and the like.

The photopolymerization initiator can be referred to, for example, the description of paragraphs 0070 to 0079 of JP-A-2004-295116.

The photopolymerization initiator is preferably a quinone compound (hereinafter also referred to as an oxime photopolymerization initiator).

The oxime-based photopolymerization initiator is not particularly limited, and examples thereof include an anthracene compound described in JP-A-2000-80068, WO02/100903A1, and JP-A-2001-233842.

Specific examples thereof include 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-butanedione and 2-(O-benzoguanidinopurine). 1-[4-(phenylthio)phenyl]-1,2-pentanedione, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1 ,2-hexanedione, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-heptanedione, 2-(O-benzylidene fluorenyl)肟)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 2-(O-benzylidene fluorenyl)-1-[4-(methylphenylthio)benzene -1,2-butanedione, 2-(O-benzylidene fluorenyl)-1-[4-(ethylphenylthio)phenyl]-1,2-butanedione, 2-( O-benzylidene hydrazide)-1-[4-(butylphenylthio)phenyl]-1,2-butanedione, 1-(O-ethylindenyl)-1-[9-B -6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-methyl-6-(2 -methylbenzhydryl)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-propyl-6-(2-methylbenzhydrazide -9H-carbazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-ethyl-6-(2-ethylbenzylidene)-9H-indole Zyrid-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-ethyl-6-(2-butylbenzylidene)-9H-indazol-3-yl] Ethylketone, 2-(benzylideneoxyimido)-1-[4-(phenylthio)phenyl]-1-octyl 2-(Ethyloxyimino)-4-(4-chlorophenylthio)-1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole- 3-yl]-1-butanone and the like.

Further, the oxime-based photopolymerization initiator described in paragraphs 0077 to 0168 of JP-A-2009-244692 can also be used.

The content of the photopolymerization initiator in the photosensitive coloring composition is preferably from 0.01% by mass to 50% by mass, more preferably from 1% by mass to 30% by mass, particularly preferably from 1% by mass to 20%, based on the polymerizable compound. quality%.

(Organic solvents)

The coloring composition contains at least one of organic solvents.

The organic solvent can be used regardless of the type as long as it dissolves the phthalocyanine compound represented by the formula (1) (and a yellow dye if necessary).

As the organic solvent, an ester compound, an ether compound, a ketone compound or the like can be used.

As the organic solvent, for example, an organic solvent described in paragraphs 0090 to 0093 of JP-A-2013-160921 can be used.

The organic solvent is preferably: methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyrate Ester, cyclohexyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate and the like.

(surfactant)

The coloring composition may contain at least one of a surfactant.

As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant can be used.

In particular, by containing a fluorine-based surfactant, liquid characteristics (particularly fluidity) at the time of forming a coating liquid can be further improved, and uniformity or province of coating thickness can be further improved. Liquid.

As the surfactant, for example, the surfactant described in paragraphs 0172 to 0175 of JP-A-2011-202025 can be suitably used.

Commercial products of the fluorine-based surfactant include, for example, Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, and Meijiafa. (Megafac) F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F479, Meijiafa ( Megafac) F482, Megafac F554, Megafac F780, Megafac F781 (made by Di Aisheng (DIC)), Fluorad FC430, Vlad ( Fluorad) FC431, Fluorad FC171 (made by Sumitomo 3M (share)), Surflon S-382, Surflon SC-101, Surflon SC- 103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (made by Asahi Glass Co., Ltd.), Solsperse 20000 (manufactured by Zeneca), etc.

(Dispersant)

The coloring composition may contain at least one of dispersing agents.

The dispersing agent is a polymer dispersing agent described in paragraphs 0187 to 0237 of JP-A-2012-162684.

Commercial products of the dispersant include, for example, the Disperbyk series manufactured by BYK Chemie Co., Ltd. (for example, Disperbyk-161, Disperbyk (Disperbyk) ) -171, Disperbyk-174, Disperbyk-2000, Disperbyk-2001, etc., Eve, manufactured by EFKA EFKA series (eg EFKA 4330, EFKA 4340, etc.), Solsperse series manufactured by Lubrizol, Japan (eg Sol Solsperse 3000, Solsperse 5500, Solsperse 24000, Solsperse 17000, Solsperse 27000, Sol Solsperse 28000, Solsperse 32000, Solsperse 38500, Solsperse 39000, Solsperse 55000, etc. .

(alkali soluble resin)

The coloring composition may contain at least one of alkali-soluble resins.

The alkali-soluble resin is preferably a linear organic high molecular polymer, and is soluble in an organic solvent and can be developed by a weak alkali aqueous solution. Examples of such a linear organic polymer include a polymer having a carboxylic acid in a side chain, for example, Japanese Patent Laid-Open No. 59-44615, Japanese Patent Publication No. Sho 54-34327, and Japanese Patent Publication No. Sho 58-12577 The methacrylic acid copolymer, the acrylic copolymer, and the itaconic acid copolymer described in each of the publications of Japanese Patent Laid-Open Publication No. Sho 59-25957, Japanese Patent Laid-Open No. 59-53836, and Japanese Patent Laid-Open No. 59-71048 , butenoic acid copolymer, A maleic acid copolymer, a partially esterified maleic acid copolymer or the like can be used similarly to an acidic cellulose derivative having a carboxylic acid in a side chain.

As the alkali-soluble resin, for example, the resin described in paragraphs 0049 to 0058 of JP-A-2005-266149 can be suitably used.

(other ingredients)

The coloring composition may contain other components as needed.

Other components include a polymer compound having a hetero ring in a side chain. The polymer compound having a heterocyclic ring in the side chain is, for example, a polymer compound described in paragraphs 0146 to 0175 of JP-A-2012-162684.

Further, for example, when the colored composition is a positive photosensitive coloring composition, the colored composition preferably contains at least one of a naphthoquinonediazide compound as another component.

As the naphthoquinonediazide compound, for example, a compound described in paragraphs 0060 to 0061 of JP-A-2005-266149 can be suitably used.

In addition, examples of the other components include an organic carboxylic acid, a thermal polymerization inhibitor, a filler, a polymer compound other than the above, an adhesion promoter, an antioxidant, an ultraviolet absorber, and a coagulation inhibitor.

Examples of such components include those described in paragraphs 0176 to 0177 of JP-A-2011-202025, and paragraphs 0155 to 0156 of JP-A-2004-295116.

In addition, the coloring composition may contain the Japanese Patent Laid-Open Publication No. 2004-295116 The sensitizer or light stabilizer described in paragraph 0078, and the thermal polymerization inhibitor described in paragraph 0081 of JP-A-2004-295116.

The coloring composition suitable for producing a green color filter has been described above.

The above coloring composition can also be adapted to produce a red color filter or a blue color filter by changing the type (hue) of the colored material contained therein.

<Method of Manufacturing Green Filter>

A preferred method of manufacturing the green filter is a photolithography method.

The method for producing a green filter using the photolithography method is a manufacturing method including a coloring layer step of applying a photosensitive coloring composition described above to a substrate to form a coloring layer, and an exposure step of forming the formed coloring layer. The colored layer (preferably via a mask) is exposed to a pattern; and the step of developing the exposed colored layer to obtain a colored pattern (green filter).

Preferably, the manufacturing method further includes a step of irradiating the colored pattern with ultraviolet rays, and a step of heat-treating the colored pattern irradiated with ultraviolet rays.

For the method of producing the green filter, for example, a known method such as the method described in paragraphs 0210 to 0239 of JP-A-2011-202025 can be appropriately referred to.

In addition to the photolithography method, the green filter can be produced by the following method: the transfer method described in Japanese Laid-Open Patent Publication No. 2009-116078, and the spray described in Japanese Laid-Open Patent Publication No. 2009-134263 A dry etching method or the like described in JP-A-2006-343598.

In addition, the red filter or the blue filter can of course be manufactured in the same manner as the green filter.

<Liquid crystal display device, organic EL display device>

The aspect of the display device of the present invention preferably includes the first light source, the light conversion portion, and an image display panel including the green filter.

Preferably, the image display panel further includes a red filter and a blue filter.

Further, the image display panel is preferably a liquid crystal display panel or an organic EL panel.

That is, the display device of the present invention is preferably a liquid crystal display device or an organic EL display device.

The definition of the liquid crystal display device and the organic EL display device or the details of each display device are described, for example, in "Electronic display devices (sasaki Sasaki, Industrial Research Association, issued in 1990)", "Display devices (Ibuki Shunzhang) , Industrial Books (shares issued in 1989)" and so on. In addition, the liquid crystal display device is described in, for example, "Next-Generation Liquid Crystal Display Technology (Editor Uchida Natsuo, Industrial Research Association, Ltd., 1994)". The liquid crystal display device to which the present invention is applicable is not particularly limited, and can be applied to, for example, a plurality of types of liquid crystal display devices described in the "next-generation liquid crystal display technology".

Among them, the green color filter of the present invention is particularly effective for a color TFT liquid crystal display device. A liquid crystal display device of a color TFT type is described, for example, in "Color TFT Liquid Crystal Display (Kyoritsu Publishing Co., Ltd., 1996)". Furthermore, the present invention can also be applied to In Plane Switching (IPS), etc. A liquid crystal display device with a wide viewing angle such as a horizontal electric field driving method or a multi-domain vertical alignment (MVA), or a super twisted nematic (STN) or a twisted nematic (Twisted Nematic) , TN), Vertical Alignment (VA), Optically Compensated Splay (OCS), Fringe Field Switching (FFS), and Reflective Optically Compensated Bend (R-OCB) .

In addition, the green filter of the present invention is also available in a bright and high-definition Color-filter On Array (COA) mode.

In the case where a known Cold Cathode Fluorescent Lamp (CCFL) is used as a backlight, the liquid crystal display device including the green filter of the present invention can attain high brightness and high color reproducibility.

However, the liquid crystal display device can obtain extremely high brightness corresponding to an organic EL display device by using red, green, and blue LED light sources (RGB-LEDs), particularly blue LEDs as backlights. Extremely high color reproducibility.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples without departing from the spirit of the invention. In addition, "%" and "parts" are quality standards unless otherwise specified.

<Preparation of phthalocyanine compounds>

The exemplified compound A-1, the exemplified compound A-10, the exemplified compound A-39, the exemplified compound A-40, the exemplified compound A-41, and the exemplified compound A-47 are prepared separately. Exemplary Compound A-48, exemplified compound A-67, exemplified compound A-68, exemplified compound A-77, exemplified compound A-78, exemplified compound A-85, exemplified compound A-86, exemplified compound A-91, exemplified compound A-92 is a phthalocyanine compound represented by the formula (1).

Further, the following compounds C-1, CIPig. Green 58 (CI Pigment Green 58, hereinafter referred to as "PG58"), and CIPig. Green 36 (CI Pigment Green 36, hereinafter also referred to as "PG36") were prepared. ), as a comparative phthalocyanine compound.

[Example 1]

<Preparation of photosensitive coloring composition S1>

The photosensitive coloring composition S1 which is a green composition was prepared by mixing each component of the following composition.

- Composition of photosensitive coloring composition S1 -

. Phthalocyanine compound (exemplified compound A-1) ... 4.8 parts

. Dispersant (Solsperse 5500, manufactured by Lubrizol, Japan)...2.3 parts

. Organic solvent (propylene glycol monomethyl ether acetate)...84.0 parts

. Fluorine-based surfactant (Megafac F554) made by DiCai (DIC)...0.02 parts

. Polymeric compound (dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.))...4.3 parts

. Photopolymerization initiator (OXE-01 (manufactured by BASF)) 1.4 parts

. Yellow dye (the following compound H1, the same compound as the above-exemplified compound B-1)...3.2 parts

<Production of Substrate with Green Filter>

The obtained photosensitive coloring composition S1 was applied to a glass substrate of 10 cm × 10 cm by a spin coater so that the dried film thickness was 2.0 μm (Corning 1737, manufactured by Corning). The thickness was 0.7 mm) and dried to form a coating film on the glass substrate.

Then, the entire surface of the glass substrate on which the coating film was formed was irradiated with ultraviolet rays of 100 mJ/cm ² , developed with an alkali developing solution, and then post-baking in an oven at 230 ° C for 30 minutes. Thereby, the coating film is cured to form a green filter.

From the above, a substrate with a green filter was obtained.

<Measurement of chromaticity value>

(Measurement of chromaticity value in the case of using blue LED and YAG phosphor)

A commercially available liquid crystal display device (manufactured by BenQ Corporation, trade name V2200) was decomposed, and a backlight unit (blue LED + YAG phosphor type) was taken out.

The substrate with a green color filter is disposed on the backlight unit.

Then, the backlight unit is operated such that light generated by the blue LED and the YAG phosphor (white light from the blue LED converted by the YAG phosphor) is transmitted through the green filter. The substrate measures the chromaticity values (x, y, Y) of the green light transmitted through the substrate with the green filter. The chromaticity values (x, y, and Y) were measured using "BM-5" manufactured by Topcon Corporation.

The results are shown in Table 1 below.

(Measurement of chromaticity values in the case of using blue LEDs and quantum dots)

Commercially available liquid crystal display devices (Sony Corporation, trade name KDL46W900A) decompose, remove the backlight unit (blue LED + Color IQ ^TM).

Here, Color IQ ^TM is a quantum dot member manufactured by QD Vision, and a resin in which CdZnSeS nanoparticle as quantum dot G and CdZnSeS nanoparticle as quantum dot R are dispersed is sealed in a glass case. The components of the structure.

The substrate with a green color filter is disposed on the backlight unit.

Then, the operation of the backlight unit, the light (the blue light from the blue LED by Color IQ ^TM converted from white light) generated by the blue LED is transmitted through the substrate and Color IQ with a green filter, measured The chromaticity value (x, y, Y) of light transmitted through the substrate with the green filter. The chromaticity values (x, y, and Y) were measured using "BM-5" manufactured by Topcon Corporation.

The results are shown in Table 1 below.

(calculation of △Y)

Y obtained by measurement of a chromaticity value in the case of using a blue LED and a quantum dot, minus Y obtained by measurement of a chromaticity value in the case of using an LED and a YAG phosphor, Thereby, ΔY is obtained.

The results are shown in Table 1 below.

Here, the larger the Y in the chromaticity value, the higher the luminance of the green light.

Further, the larger the ΔY, the greater the effect of improving the brightness due to the use of quantum dots.

[Example 2 to Example 15]

A substrate with a green filter was produced in the same manner as in Example 1 except that the exemplified compound A-1 was changed to the exemplified compound shown in Table 1 below, and the prepared green filter was used. The substrate was subjected to the same evaluation as in Example 1.

The results are shown in Table 1 below.

[Comparative Example 1]

A substrate with a green filter was produced in the same manner as in Example 1 except that the exemplified compound A-1 was changed to the compound C-1, and the prepared substrate with a green filter was subjected to The same evaluation as in Example 1.

The results are shown in Table 1 below.

[Comparative Example 2]

A substrate with a green filter was produced in the same manner as in Example 1 except that the photosensitive coloring composition S1 was changed to the following comparative photosensitive coloring composition 1 in the same manner as in Example 1. The substrate of the sheet was subjected to the same evaluation as in Example 1.

The results are shown in Table 1 below.

<Preparation of photosensitive coloring composition 1 for comparison>

Propylene glycol monomethyl ether acetate (75 parts), PG58 (17 parts) as a green pigment, and a dispersing agent (Solsperse 5500 manufactured by Lubrizol Co., Ltd.) (8 parts) The mixture was mixed and stirred with a stirrer for 3 hours to prepare a mill base having a solid concentration of 25%. To the paste, 600 parts of 0.5 mm Φ zirconia beads were used, and dispersion treatment was carried out in a bead mill at a peripheral speed of 10 m/s and a residence time of 3 hours to obtain a dispersion ink of PG58.

Then, each component of the following composition was mixed to prepare a comparative photosensitive coloring composition 1 as a green composition. In the comparative photosensitive coloring composition 1, the composition of the colored material was adjusted so as to have the same chromaticity value (x, y) as the chromaticity value (x, y) in the first embodiment.

- Comparison of the composition of photosensitive coloring composition 1 -

. Disperse ink of PG58...27.1 parts

. Dispersant (Solsperse 5500, manufactured by Lubrizol, Japan)...2.3 parts

. Organic solvent (propylene glycol monomethyl ether acetate)...63.9 parts

. Fluorine-based surfactant (Megafac F554) made by DiCai (DIC)...0.02 parts

. Polymeric compound (dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.))...4.3 parts

. Photopolymerization initiator (OXE-01 (manufactured by BASF)) 1.4 parts

. Yellow dye (the compound H1)...1.0 parts

[Comparative Example 2]

A substrate with a green filter was produced in the same manner as in Example 1 except that the photosensitive coloring composition S1 was changed to the following comparative photosensitive coloring composition 2, and the resulting green-colored filter was produced. The substrate of the sheet was subjected to the same evaluation as in Example 1.

The results are shown in Table 1 below.

<Preparation of Comparative Photosensitive Composition 2>

The dispersion ink of PG36 was obtained in the same manner as in the preparation of the dispersion ink of PG58 except that PG58 was changed to PG36 and the residence time was changed to 2 hours in the preparation of the dispersion ink.

Then, each component of the following composition was mixed to prepare a comparative photosensitive coloring composition 2 as a green composition. In the comparative photosensitive coloring composition 2, the composition of the colored material was adjusted so as to have the same chromaticity value (x, y) as the chromaticity value (x, y) in the first embodiment.

- Comparison of the composition of the photosensitive coloring composition 2 -

. Disperse ink of PG36...27.6 parts

. Dispersant (Solsperse 5500, manufactured by Lubrizol, Japan)...2.8 parts

. Organic solvent (propylene glycol monomethyl ether acetate)...63.5 parts

. Fluorine-based surfactant (Megafac F554) made by DiCai (DIC)...0.02 parts

. Polymeric compound (dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.))...4.3 parts

. Photopolymerization initiator (OXE-01 (manufactured by BASF)) 1.4 parts

. Yellow dye (the compound H1)...0.4 parts

As shown in Table 1, in Examples 1 to 15, in which a green filter containing a phthalocyanine compound represented by the general formula (1) was used, Comparative Example 1 to Comparative Example 3 using a comparative phthalocyanine compound were used. In comparison, ΔY is large, and the effect of improving the brightness of green light by using a blue LED and a quantum dot is remarkable.

2 shows the transmittance spectra of the substrates with green filters in Example 1 and Comparative Example 2.

In addition, in FIG. 2, the luminescence spectrum of the light generated by the two types of backlight units used other than Example 1 is shown in combination.

Here, the luminescence spectrum of light generated by the two kinds of backlight units refers in detail to the spectrum of white light converted from the blue light of the blue LED by the YAG phosphor (in FIG. 2, "blue" The spectrum of white light converted by quantum dots (LED + YAG phosphor) and the blue light from the blue LED ("blue LED + quantum dot" in Fig. 2).

Although not shown in FIG. 2, the vertical axis of the light emission spectrum of the light is intensity.

In FIG. 2, the transmittance spectrum of the substrate with a green filter is measured using a spectrophotometer "MCPD-3700" manufactured by Otsuka Electronics Co., Ltd., and the measurement wavelength range is 200 nm to 800 nm.

In addition, in FIG. 2, the luminescence spectrum of the light generated by the backlight unit is a spectroradiometer "SR-3" manufactured by Topcon, and the spectroradiometer is supplied from the spectrometer to the sample (light conversion section: The distance from the quantum dot member or the YAG phosphor is 70 mm, the measurement angle is 0.2 degrees, and the measurement mode is "automatic". The measurement was carried out by setting the measurement wavelength range to 380 nm to 780 nm.

As shown in FIG. 2, it was confirmed that the green color filter (the coloring agent is exemplified as the compound A-1 and the compound H1) of the first embodiment is compared with the green color filter of the second comparative example (the coloring agent is PG58 and the compound H1). The transmittance of the green light in the "blue LED + quantum dot" (500 nm to 560 nm) is high.

This is considered to be the cause of the high luminance of the green light of Example 1.

As will be described in more detail with reference to Fig. 2, in the light emission spectrum of "blue LED + quantum dot", the maximum value of the peak of green light exists in the vicinity of the wavelength of 530 nm, and the full width at half maximum of the peak of the green light is about 30 nm. On the other hand, in the light emission spectrum of the "blue LED + YAG phosphor", the peak of the green light region is wide, the maximum value of the peak exists near the wavelength of 560 nm, and the full width at half maximum of the peak is 100 nm or more.

Further, the transmittance spectrum of Example 1 has a maximum value in the vicinity of a wavelength of 500 nm, and the full width at half maximum of the peak including the maximum value is about 100 nm. Further, the transmittance of the transmittance spectrum of Example 1 in the range of 500 nm to 530 nm was 90% or more. On the other hand, the transmittance spectrum of Comparative Example 1 has a maximum value around the wavelength of 520 nm, and the full width at half maximum of the peak including the maximum value is about 100 nm. Further, the transmittance of the transmittance spectrum of Comparative Example 2 in the range of 500 nm to 530 nm was less than 90%.

As described above, the transmittance spectrum of Example 1 using the phthalocyanine compound represented by the general formula (1) has a maximum value of transmittance on the short-wavelength side as compared with the transmittance spectrum of Comparative Example 2 using PG58. Moreover, the green wavelength region as a whole The transmittance is increased. Further, as described above, the peak of the green light in the light emission spectrum of the "blue LED + quantum dot" is on the short wavelength side as compared with the peak of the green light in the light emission spectrum of the "blue LED + YAG phosphor". It has a very large value and a sharp (semi-high width and small width) peak.

From the above reasons, it is considered that the effect of improving the luminance of the green light by the quantum dots is remarkably obtained in the first embodiment as compared with the comparative example 2.

From the above results, it is understood that the phthalocyanine compound represented by the general formula (1) is changed from the conventional "blue LED + YAG phosphor" to the "blue LED + quantum dot" as compared with the existing pigment phthalocyanine. The brightness increase rate is high.

In general, the spectral characteristics of a phthalocyanine pigment are determined mainly by a central metal or a crystal structure, and are not largely changed by the influence of a modifying group such as a substituent or a pigment derivative in a surface treatment.

On the other hand, the phthalocyanine compound (dye) represented by the formula (1) is a compound having extremely characteristic spectral characteristics different from those of the conventional phthalocyanine pigment. Further, it is understood that the phthalocyanine compound represented by the formula (1) is extremely useful as a colored material for quantum dot backlighting.

The disclosure of Japanese Patent Application No. 2013-205347, filed on Sep. 30, 2013, is hereby incorporated by reference. All documents, patent applications, and technical specifications described in the specification are incorporated by reference to the same extent as the respective disclosures of In this manual.

100‧‧‧Liquid crystal display device

10B‧‧‧Blue filter

10G‧‧‧Green Filter

10R‧‧‧Red Filter

12‧‧‧Transmissive substrate

14‧‧‧Substrate with color filter

20‧‧‧Liquid layer

22‧‧‧ Alignment substrate

30‧‧‧LCD panel

40‧‧‧Blue LED (primary light source)

42‧‧‧Light conversion member (light conversion unit)

46‧‧‧Light guiding members

R, G, B‧‧· Quantum dots

Claims (14)

A display device comprising: a primary light source that emits primary light; a light conversion portion that includes a quantum dot that absorbs at least a portion of the primary light to emit green light; and a green filter that transmits the green light, and Containing a phthalocyanine compound represented by the following formula (1), In the general formula (1), a plurality of X atoms independently represent a halogen atom; and a plurality of R ¹ each independently represent a group represented by the following formula (2) or (3); A plurality of R each independently represent a hydrogen atom or a monovalent substituent; M represents Cu, Zn, V(=O), Mg, Ni, Ti(=O), Sn, or Si; and a plurality of a are independently represented An integer of 0 to 4, and a plurality of n each independently represent an integer of 0 to 4, and a plurality of r independently represent an integer of 0 to 4; wherein at least one of the plurality of a is 1 or more, and at least one of the plurality of n 1 is 1 or more; the sum of multiple a, multiple n and multiple r is 16] [In the general formula (2) and the general formula (3), the presence of b of R ² independently represents a monovalent substituent selected from the group consisting of the following general formulae (4) to (6); R ³ represents a monovalent substituent; b represents an integer of 1 to 5, and c represents an integer of 0 to 4; wherein, in the general formula (2), the total of b and c does not exceed 5; Y represents -O-, -S-, -SO ₂ -, or -NR ⁸ -; R ⁸ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent] [In the formula (4), R ⁴ represents a hydrogen atom, an alkyl group which may have a substituent, an oxyalkyl group which may have a substituent, an aryl group which may have a substituent, an alkylamine group which may have a substituent, and a dialkylamino group having a substituent, an arylamine group which may have a substituent, a diarylamine group which may have a substituent, or an alkylarylamine group which may have a substituent; in the formula (5) d represents an integer of 0 to 2, and when d is 0 or 1, R ⁵ represents an alkyl group which may have a substituent, or an aryl group which may have a substituent, and in the case where d is 2, R ⁵ represents An alkyl group which may have a substituent, an aryl group which may have a substituent, a dialkylamino group which may have a substituent, a diarylamine group which may have a substituent, or an alkylarylamine group which may have a substituent In the formula (6), R ⁶ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, and a substituent which may have a substituent An alkylsulfonyl group, an arylsulfonyl group which may have a substituent, R ⁷ represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic group which may have a substituent base]. The display device of claim 1, wherein the primary light is blue light. The display device of claim 2, wherein the primary light source comprises a blue light emitting diode. The display device according to claim 1 or 2, wherein the light conversion portion further comprises an inorganic phosphor that absorbs a part of the primary light and emits red light, and transmits the first time by transmitting The primary light is converted to white light by a portion of the light. The display device according to claim 4, wherein the inorganic phosphor is a quantum dot. The display device according to claim 1 or 2, wherein the luminescence spectrum of the green light has a maximum value in a wavelength range of 500 nm to 550 nm. The display device according to claim 6, wherein the green light has a full width at half maximum of 20 nm to 80 nm. The display device according to claim 1 or 2, wherein the transmission spectrum of the green filter has a peak having a maximum value in a wavelength range of 460 nm to 550 nm. The display device according to claim 8, wherein the half-height of the peak in the transmission spectrum of the green filter is from 80 nm to 200 nm. The display device according to claim 8, wherein a transmittance in a wavelength range of 500 nm to 530 nm is 90% or more in a transmission spectrum of the green filter. The display device according to claim 1 or 2, wherein the green filter further contains a yellow dye. The display device according to claim 1 or 2, wherein the quantum dot comprises a component selected from the group consisting of a group II-VI compound, a group III-V compound, a group IV-VI compound, and a group IV compound. At least one type of semiconductor nanoparticle in the group. The display device according to claim 1 or 2, wherein the quantum dot comprises a layer selected from the group consisting of CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, At least one semiconductor nanoparticle of a group consisting of PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe, Si, Ge, SiC, and SiGe. The display device according to claim 1 or 2, comprising: the primary light source; the light conversion portion; and a liquid crystal display panel or an organic electroluminescence display panel, including the green filter .