KR20100075746A - Display device - Google Patents

Abstract

PURPOSE: A display device is provided to reduce the dependence on an observation angle while maintaining color reproduction and implementing high luminance. CONSTITUTION: A display device comprises three color pixel and a color filter(22). The color filter has a maximum value of an optical density under a wavelength of 475 nm~525 nm. The color filter has less than the optical density of 15% under wavelength of 475 nm and the color filter has less than the optical density of 10% under wavelength of 550 nm.

Description

Display {DISPLAY DEVICE}

The present invention relates to a display device. In particular, the present invention relates to a display device having pixels of R, G, and B, and having a device and a color filter which emit light of respective colors.

Recently, electronic displays such as CRT (Cathode Ray Tube) displays, fluorescent display tubes, electroluminescent displays, electroluminescence displays, liquid crystal displays, and the like are used as display panels for various electronic devices including large wall-mounted televisions. As the demand increases, the demand for the improvement of the image quality is increasing.

As a full colorization method, a method of combining a color filter with a white light-emitting backlight represented by a liquid crystal display device is known, but the development of pursuing high quality by using a light emitting device that emits light in three primary colors of blue, green, and red for each pixel Has been done hard.

As a light emitting element used for a pixel, an organic electroluminescence element (organic EL element: Organic Electro-Luminescence devices) is mentioned. The organic EL device has a structure in which a thin organic material layer of one layer to a plurality of layers is sandwiched between a negative electrode and a positive electrode, and holes are injected from the positive electrode and electrons are injected from the negative electrode with respect to the organic material layer, and holes and electrons are recombined in the organic material layer. A light emitting device using light emitted when the light emitting material in the organic material layer is excited by recombination energy at the time and deactivated from the excited state to the ground state. The organic EL device has characteristics such as self-luminous property and high-speed response, and is excellent in visibility, ultra-thin and lightweight, and excellent in high-speed response and moving picture display. Therefore, application to a full-color flat panel display is considered. have. In particular, a two-layer (laminated) organic EL device in which a hole transport organic thin film (hole transport layer) and an electron transport organic thin film (electron transport layer) are stacked (CW Tang and SA VanSlyke, Applied Physics Letters vol. 51, 913) (1987)), the organic EL device has attracted attention as a large area light emitting device capable of emitting light at a low voltage of 10V or less.

The three-color emission method in which an organic EL element that emits light corresponding to three primary colors of color (blue (B), green (G), and red (R)), respectively, is disposed on a substrate. It is preferable also from a viewpoint, and it is a strong one among the full-colorization system of organic EL.

In the three-color emission method, the organic EL element itself can emit light in each color even without using the original color filter. However, for the purpose of preventing the lowering of the contrast as a display due to reflection of external light, a method of combining a color filter adapted to each emission color and a method of employing a microcavity structure have also been proposed (Japanese Patent Laid-Open No. 2003-). See Publication 86358). The wavelength of the light whose intensity is increased in the microcavity structure can be changed by changing the optical path length of the microcavity structure, for example. Therefore, if the optical path length of the microcavity structure is appropriately set for each colored layer of the color filter, the wavelength of the light having the maximum intensity can be matched with the desired wavelength in terms of luminance and color reproduction.

In the full-color display, the improvement of the color reproducibility and the brightness of the conventional display device have a trade-off relationship with each other, and the improvement of the two performances, which are the main performances of these display devices, is improved for a long time. Was being asked. Moreover, especially in a flat panel display, it is calculated | required that image quality does not change in observation from a wide viewing angle.

When the technique which combines the organic electroluminescent element which employ | adopted the microcavity structure with a color filter is used, it becomes possible to make high color reproducibility and high brightness compatible for the said reason. However, an organic EL display device using a microcavity light source has a problem that the image observed from the oblique direction is significantly darker than the image observed from the normal direction. In addition, it is pointed out that the color changes when the image is observed from the normal direction and then observed from the inclined direction, and improvement is required. As for the improvement in the observation direction dependency, an improvement in the structure of the device has been proposed (see Japanese Patent Application Laid-Open No. 2007-27042), and the effect is shown. However, since these methods all lead to complexity of the apparatus and consequently to high cost, further improvement in simple methods has been required.

On the other hand, a color filter material developed for a liquid crystal display can be used for a color filter organic EL display device. Among the three primary colors of the blue (B), green (G), and red (R) pixels, C. I. Pigment Green 36 is frequently used as a pigment used for the green (G) pixel. Although this pigment was considered to be advantageous in terms of improving transmittance by obtaining miniaturization and obtaining high luminance, it was found that the pigment was not at a sufficient level for both high color reproducibility and high luminance in an organic EL display device.

In addition, the three primary color filters are usually formed using photolithography, but since the patterning is required for each color, it is one of the factors that complicate the process and lower the yield.

For this reason, the appearance of the color filter which combines the high color reproducibility and high brightness of an organic electroluminescent display by a simple method was desired.

In addition, attempts to easily improve contrast and color purity by using a filter that absorbs light in an unnecessary wavelength region on the front of the display device have been studied in plasma displays and the like (see Japanese Patent Application Laid-Open No. 2003-157017). This filter is an auxiliary one, and is not a substitute for the photolithography color filter. In particular, the study on the light source of three primary colors has not been conducted until now.

SUMMARY OF THE INVENTION An object of the present invention made in view of the above problems is to provide a display device having a simple configuration and capable of achieving high luminance while maintaining color reproducibility. Further, a new object of the present invention is to provide a display device having a small dependency on the observation direction even when an organic EL element is used.

As a result of intensive research and development, by combining a light emitting element emitting light of each of R, G, and B with a color filter having a specific absorption spectrum, it is possible to realize a display device having high luminance and small observation direction dependence without impairing color reproducibility. It has been found that the present invention has been completed by a simpler method than before.

EMBODIMENT OF THE INVENTION Below, embodiment of this invention is described.

<1> A display device having three colors of pixels and a color filter each consisting of light emitting elements emitting light at R, G, and B, wherein the color filter has a maximum value of optical density in a range of 475 nm to 525 nm, and the optical The ratio of the optical density in wavelength 450nm with respect to the maximum value of density is 15% or less, and the ratio of the optical density in wavelength 550nm with respect to the maximum value of the said optical density is 10% or less.

<2> A display device having three colors of pixels and a color filter each consisting of light emitting elements emitting light of R, G, and B, wherein the color filter has a maximum value of optical density in a range of 550 nm to 620 nm, and the optical A display device in which the ratio of the optical density at the wavelength 500 nm and the wavelength 630 nm to the maximum value of the concentration is all 12% or less.

<3> In <1>, the said color filter further has the maximum value of optical density in the wavelength range of wavelength 550-620 nm, and the ratio of the optical density in wavelength 500nm and wavelength 630nm with respect to the maximum value of the said optical density is all 12% or less display.

<4> The display device according to any one of <1> to <3>, wherein the color filter is a front-mounted filter disposed in front of the display device.

<5> The display device according to any one of <1> to <4>, wherein all of the light emitting elements that emit light of R, G, and B constituting the three colors of pixels are organic electroluminescence elements.

<6> The display device according to <5>, having a microcavity structure.

<7> The color filter according to any one of <1> to <6>, which contains one or more selected from compounds represented by the following general formula (I), (II) and (III). Display.

In said general formula (I), Z <^1> and Z <^2> respectively independently represent the group of the nonmetallic atoms which form the 5-membered or 6-membered nitrogen-containing heterocycle, and the said nitrogen-containing heterocycle contains another heterocyclic ring, aromatic ring, or aliphatic group. The ring may be condensed; R ¹ and R ² each independently represent an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent; L ¹ represents a methine chain composed of an odd number of methines which may have a substituent; a, b and c are each independently 0 or 1; X represents an anion when the cyanine dye moiety is cationic, and a cation when the cyanine dye moiety has an anionic substituent and is anionic;

In General Formula (II), Y ¹ and Y ² each independently represent a group of nonmetallic atoms that form an aliphatic ring or a heterocycle; L ² represents a methine chain composed of an odd number of methines which may have a substituent; X ² represents a hydrogen atom or a cation;

In General Formula (III), Y ³ represents a group of nonmetal atoms forming an aliphatic ring or a heterocycle; L ³ represents a methine chain consisting of one or three methines; Ar represents an aromatic ring.

Also in the form using a three-color light emission type light source, the method of using the color filter formed by three types of patterning using the pigment | dye widely used for liquid crystal display devices is common. However, according to the present invention, it has been found that a combination of one or two types of filters using a three-color light-emitting light source and a pigment having a specific absorption exhibits performance over conventional filters. It was found that high luminance can be obtained by the direction of simplifying the process.

In addition, according to the configuration of the present invention, it was found that the remarkable effect was particularly exerted on the improvement of the observation direction dependence, and it was successful to realize the improvement of the observation direction dependence, which has been a problem in the past, in a simpler method.

Although the reason for exhibiting the said effect by the structure of this invention is not certain, it estimates as follows.

In other words, in the method using a three primary light source, it is considered important to separate wavelengths between colors adjacent to the spectral sensitivity of the human eye in order to secure color reproducibility. Since the wavelength of the highly directional ripple portion amplified by multiple interferences such as microcavity that is the cause of the observation direction is close to the wavelength necessary to secure the color reproducibility, it is sharp to improve luminance without deteriorating color reproduction. By introducing a filter having absorption, it is estimated that luminance improvement and reduction in observation direction dependence can be simultaneously achieved while maintaining color reproducibility.

(Effects of the Invention)

According to the present invention, it is possible to provide an organic EL display device that achieves high luminance without degrading high color reproducibility by a simple configuration. In addition, the present invention can provide a display device with a small dependency on the observation direction even when an organic EL element is used.

Hereinafter, the color filter used for this invention is demonstrated.

The color filter in the conventional liquid crystal display device etc. was for transmitting only the wavelength of the light corresponding to any one of R, G, and B. On the other hand, in the case of a color filter used for a display device using three primary color light emitting elements, all three conventional colors of R, G, and B can be transmitted by only transmitting the light of two or three colors and cutting unnecessary wavelength ranges. The same effect as that of a color filter having a suitable coloring pattern can be achieved.

However, since the spectral sensitivity of the human eye is not clearly separated into R, G, and B, it is necessary to absorb two adjacent colors of the orange color function in the form of broadening the color gamut accurately. In addition, if the absorbed light is excessively absorbed, the brightness is lowered and the image quality is impaired. Therefore, the color filter used in the display device having the three-color light emitting elements has a sharp absorption in a specific wavelength range. It is necessary.

The color filter used for the display element of this invention has the maximum value of optical density in the range of 475 nm-525 nm, and / or the range of 550 nm-620 nm. The former is blue and green, the latter is a wavelength necessary for green and red separation, and is also a desirable wavelength for reducing the dependence of the viewing direction of the display device.

In addition, the color filter according to the present invention has one of the following features in addition to the characteristic of having maximum absorption in the specific wavelength region. Hereinafter, the color filter which has such a characteristic may be called a specific color filter.

(1) In the case where the optical density has a maximum value in the range of 475 nm to 525 nm, the ratio of the optical density at a wavelength of 450 nm to the maximum value of the optical density is 15% or less, and at a wavelength of 550 nm with respect to the maximum value of the optical density. The ratio of the optical density in 10% or less.

(2) When it has the maximum value of optical density in the range of 550 nm-620 nm, the ratio of the optical density in wavelength 500 nm and wavelength 630 nm with respect to the maximum value of the optical density is 12% or less.

The ratio of the optical density prescribed | regulated to said (1) and (2) exceeds the said predetermined value, ie, when the optical density difference of both becomes smaller, since the transmittance | permeability of each color will worsen rather than the conventional one, the said value It is necessary to suppress below.

In the above (1), when the color filter has the maximum value of the optical density in the range of 475 nm to 525 nm, the wavelength region showing the maximum value of the optical density is preferably in the range of 480 nm to 520 nm, in the range of 490 nm to 515 nm. It is particularly desirable to have.

At this time, 15% or less is preferable and, as for the ratio of the optical density in wavelength 450nm with respect to the maximum value of the said optical density, 13% or less is more preferable. 10% or less is preferable, as for the ratio with respect to the maximum value of the said optical density of the optical density in wavelength 550nm, 5% or less is more preferable, 2% or less is especially preferable.

In the above (2), when the color filter has the maximum value of the optical density in the range of 550nm to 620nm, the wavelength region showing the maximum value of the optical density is preferably in the range of 560nm to 610nm, in the range of 570nm to 600nm It is particularly desirable to have. At this time, 12% or less is preferable and, as for the ratio with respect to the said maximum value of the optical density in 500 nm and 630 nm, 10% or less is more preferable.

Thus, in either case, it is preferable to have a sharp peak of the optical density in a specific wavelength region, and the maximum value of the optical density satisfying both the characteristics in (1) and the characteristics in (2) is set in the predetermined region. The color filter which has two can also be used preferably.

In the color filter (henceforth called a filter layer suitably) which concerns on this invention, a color material is used in order to give a desired optical density to a specific absorption wavelength. Although a coloring material may be dye or a pigment, dye is preferable at the point that adjustment is easy.

Although any dye may be used for the above purpose, preferred dyes used for controlling the absorption spectrum include squarylium dyes, azomethine dyes, cyanine dyes, oxonol dyes, azo dyes, arlylidene dyes, xanthene dyes or mero And cyanine dyes.

The above dyes may be used alone or in combination of two or more of the above dyes. Moreover, the dye which has an absorption maximum in both the range whose wavelength is 475 nm-525 nm, and the range which is 550 nm-620 nm can also be used for a filter layer. By using such dye, the color filter which has both the characteristics of said (1) and (2) can be manufactured.

It is particularly preferable to use dyes in the associative state for the purpose of obtaining such sharp absorption.

The associated dyes show sharp absorption spectral peaks because they form so-called J bands. Association of dyes and J bands are described in, for example, Photographic Science and Engineering Vol. 18, No. 323-335 (1974). In the dye in the associated state, the absorption maximum of the dye in the associated state moves to the longer wavelength side than the absorption maximum of the dye in the solution state. Therefore, whether the dye contained in the filter layer is in an associated state or a non-associative state can be easily determined by measuring an absorption maximum.

There are also compounds in the dye which form associations only by dissolving in water. However, generally, gelatin or a salt (for example, barium chloride, ammonium chloride, sodium chloride) is added to the aqueous solution of the dye to form the association. Particular preference is given to a method of adding gelatin to an aqueous solution of a dye.

The association of dyes may be formed as a solid particulate dispersion of the dye. Known dispersers can be used to bring the solid fine particles into a state. Examples of dispersers include ball mills, vibration mills, planetary ball mills, sand mills, colloid mills, jet mills and roller mills. Among them, vertical or horizontal media dispersers such as those described in Japanese Patent Application Laid-open No. 52-92716 and International Patent No. 88/074794 are preferably used.

Dispersion of the dye may be carried out in the presence of a suitable medium (eg, water, alcohol, or solvent). In dispersion, it is preferable to use surfactant for dispersion. As the surfactant for dispersion, an anionic surfactant (for example, those described in Japanese Patent Application Laid-open No. 52-92716 and International Patent No. 88/074794) is preferably used. If necessary, anionic polymers, nonionic surfactants or cationic surfactants may be used.

After dissolving the dye in a suitable solvent, it may be added to the poor solvent to obtain a fine powder. In this case, the surfactant can be used.

In addition, the microcrystal of dye may be precipitated by adjusting the pH of a solution, The microcrystal obtained by precipitation here is also an association of dye.

When the dye in the associated state is fine particles (or microcrystalline), the average particle diameter is preferably 0.01 μm to 10 μm. The average particle diameter of the particle | grains of a dye or a microcrystal is used the average value of 500 measured values extracted from the image | photographed with the scanning electron microscope.

As a dye for preparing a color filter having an absorption maximum in the wavelength region of 475 nm to 525 nm, the ratio of the optical density at 450 nm to the maximum value is 15% or less, and the ratio of the optical concentration at 550 nm is 5% or less. Any dye can be used as long as it is a dye. As long as it satisfy | fills this condition, you may use several dye together.

The dye is preferably a dye having an absorption of 50 nm or less, more preferably 40 nm or less, more preferably 35 nm or less, and most preferably 30 nm or less, at half maximum width (width of a wavelength region exhibiting absorbance at half the absorbance maximum). Do.

Specific examples of the dye species include cyanine dyes, oxonol dyes, arylidene dyes, merocyanine dyes, squarylium dyes, azomethine dyes, azo dyes, and xanthene dyes. Particularly preferred dyes include dyes selected from the group consisting of compounds represented by the following general formula (I), general formula (II) and general formula (III).

In said general formula (I), Z <^1> and Z <^2> respectively independently represent the nonmetallic atom group which forms the 5-membered or 6-membered nitrogen-containing heterocycle.

The heterocyclic ring, aromatic ring, or aliphatic ring may be condensed to the nitrogen-containing heterocycle. Examples of the nitrogen-containing heterocycle and the condensed ring containing Z ¹ and Z ² include oxazole ring, isoxazole ring, benzoxazole ring, naphthooxazole ring, thiazole ring, benzothiazole ring, naphthothiazole ring, indolenin ring, Benzoindollenin ring, imidazole ring, benzoimidazole ring, naphthoimidazole ring, quinoline ring, pyridine ring, pyrrolopyridine ring, furopyrrole ring, indolidine ring, imidazoquinoxaline ring, and quinoxaline ring.

The nitrogen-containing heterocycle is more preferably 5-membered ring than 6-membered ring. Especially, it is more preferable that a benzene ring or a naphthalene ring is condensed to a 5-membered nitrogen-containing heterocyclic ring, and a benzoimidazole ring is most preferable.

The nitrogen-containing heterocycle containing Z ¹ and Z ² and the ring condensed thereon may each have a substituent. Examples of the substituent include an alkyl group (eg, methyl group, ethyl group, propyl group), alkoxy group (eg, methoxy group, ethoxy group), aryloxy group (eg, phenoxy group, p-chlorophenoxy group) Halogen atoms (e.g., Cl, Br, F), alkoxycarbonyl groups (e.g., ethoxycarbonyl groups), halogenated carbon groups (e.g., trifluoromethyl groups), alkylthio groups (e.g., methyl Thio group, ethylthio group, butylthio group), arylthio group (for example, phenylthio group, o-carboxyphenylthio group), cyano group, nitro group, amino group, alkylamino group (for example, methylamino group , Ethylamino group), amide group (for example, acetamide group, propionamide group), acyloxy group (for example, acetoxy group, butyloxy group), hydroxyl group, sulfo group and carboxyl group. The sulfo group and the carboxyl group may be in a salt state.

In general formula (I), R <^1> and R <^2> respectively independently represents the alkyl group which may have a substituent, the alkenyl group which may have a substituent, the aralkyl group which may have a substituent, or the aryl group which may have a substituent.

When R ¹ or R ² represents an alkyl group, the alkyl group preferably has 1 to 20 carbon atoms. The alkyl group may have a substituent. Examples of substituents that can be introduced into the alkyl group include halogen atoms (eg, Cl, Br, F), alkoxycarbonyl groups (eg, methoxycarbonyl groups, ethoxycarbonyl groups), hydroxyl groups, sulfo groups and carboxyl groups. The sulfo group and the carboxyl group may be in a salt state.

When R <^1> or R <^2> represents an alkenyl group, it is preferable that the alkenyl group has 2-10 carbon atoms. Examples of alkenyl groups include 2-pentenyl, vinyl, allyl, 2-butenyl and 1-propenyl groups. The alkenyl group may have a substituent. Examples of the substituent which may be added to the alkenyl group are the same as those of the substituent in the alkyl group.

In the case where R ¹ or R ² represents an aralkyl group, the aralkyl group preferably has 7 to 12 carbon atoms. Examples of aralkyl groups include benzyl groups and phenethyl groups. The aralkyl group may have a substituent. Examples of the substituent include an alkyl group (eg, methyl group, ethyl group, propyl group), alkoxy group (eg, methoxy group, ethoxy group), aryloxy group (eg, phenoxy group, p-chlorophenoxy group), Halogen atoms (e.g., Cl, Br, F), alkoxycarbonyl groups (e.g., ethoxycarbonyl groups), halogenated carbon groups (e.g., trifluoromethyl groups), alkylthio groups (e.g., methyl thi Group, ethylthio group, butylthio group), arylthio group (for example, phenylthio group, o-carboxyphenylthio group), cyano group, nitro group, amino group, alkylamino group (for example, methylamino group, Ethylamino group), amide group (for example, acetamide group, propionamide group), acyloxy group (for example, acetoxy group, butyloxy group), hydroxyl group, sulfo group, and carboxyl group. The sulfo group and the carboxyl group may be in a salt state.

When R ¹ or R ² represents an aryl group, examples of the aryl group include a phenyl group and a naphthyl group. The aryl group may have a substituent. Examples of the substituent of the aryl group are the same as those of the substituent of the aralkyl group.

In general formula (I), L <^1> is the methine chain which consists of an odd number of methines. The number of methines is preferably 1, 3, 5 or 7.

The methine chain may have a substituent. It is preferable that the methine which has a substituent is a methine center (meso position) of a methine chain. Examples of substituents that can be introduced into the methine chain include alkyl groups, aryl groups, alkoxy groups, aryloxy groups, halogen atoms, alkoxycarbonyl groups, halogenated carbon groups, alkylthio groups, arylthio groups, cyano groups, nitro groups, amino groups, alkylamino groups, Amide groups, acyloxy groups, hydroxyl groups, sulfo groups and carboxyl groups are included. Definitions and examples of the alkyl group and the aryl group are as shown in the above R ¹ and R ² .

In general formula (I), a, b, and c are 0 or 1 each independently. It is preferable that a and b are zero. c is 0 when the cyanine dye has an anionic substituent such as sulfo group or carboxyl group to form a salt in the molecule.

In general formula (I), X represents an anion when a cyanine dye part is cationic, and shows a cation when a cyanine dye part has an anionic substituent and is anionic. Examples of the anions include halide ions (Cl ^-, Br ^-, I ^-), p- toluenesulfonate ion, ethyl sulfate _{^{ion, PF 6 -, BF 4 -}} , ClO 4 - and to complex ion represented by the general formula (1) This includes.

In the general formula (1), R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group, an aryl group or a cyano group, or R ⁹ and R ¹⁰ or R ¹¹ and R ¹² are The aromatic ring formed by bonding is shown.

When R <^9> , R <^10> , R <^11> or R <^12> represents an alkyl group, it is preferable that carbon number of the alkyl group is 1-20. The alkyl group may have a substituent. Examples of the substituent include a halogen atom (eg, Cl, Br, F), an alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group), hydroxyl group, sulfo group and carboxyl group. The sulfo group and the carboxyl group may be in a salt state.

Examples of the aryl group in the case where R ⁹ , R ¹⁰ , R ¹¹ or R ¹² represent an aryl group include a phenyl group and a naphthyl group. The aryl group may have a substituent. Examples of the substituent include an alkyl group (eg, methyl group, ethyl group, propyl group), alkoxy group (eg, methoxy group, ethoxy group), aryloxy group (eg, phenoxy group, p-chlorophenoxy group), Halogen atoms (e.g., Cl, Br, F), alkoxycarbonyl groups (e.g., ethoxycarbonyl groups), halogenated carbon groups (e.g., trifluoromethyl groups), alkylthio groups (e.g., methyl thi Group, ethylthio group, butylthio group), arylthio group (for example, phenylthio group, o-carboxyphenylthio group), cyano group, nitro group, amino group, alkylamino group (for example, methylamino group, Ethylamino group), amide group (for example, acetamide group, propionamide group), acyloxy group (for example, acetoxy group, butyryloxy group), hydroxyl group, sulfo group, and carboxyl group. The sulfo group and the carboxyl group may be in a salt state.

Examples of the aromatic ring formed by bonding of R ⁹ and R ¹⁰ or R ¹¹ and R ¹² include a benzene ring and a naphthalene ring. The benzene ring and the naphthalene ring may have a substituent. Examples of the substituent are the same as the examples of the substituents listed in the aryl group.

In General formula (1), although Y <^3> and Y <^4> represent O, S, or NH each independently, S is the most preferable. ^Two or more Y <^3> in General formula (1) may be same or different, and two or more Y <^4> in General formula (1) may be same or different.

In General formula (1), M represents a metal atom. The metal atom is preferably a metal atom from group II to group IV of the periodic table, more preferably a transition metal atom. Examples of transition metal atoms include Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Md and Cd. Especially, Fe, Co, Cu, and Zn are especially preferable.

It is preferable that the cyanine dye represented by the said general formula (I) has at least 1 water-soluble group (strong hydrophilic group enough to make a compound water-soluble). Here, examples of the water-soluble group that the cyanine dye may have include a sulfo group, a carboxyl group, a phosphono group and salts thereof. Examples of counter ions for forming salts include alkali metal ions (e.g., Na, K), ammonium ions, triethylammonium ions, tributylammonium ions, pyridinium ions, tetrabutylammonium ions and the following general formula (2). Onium ions represented by) are included.

In General formula (2), R <^13> and R <^14> is respectively independently an alkyl group, an alkenyl group, an aralkyl group, an aryl group, or a heterocyclic group. Definitions and examples of the alkyl group, alkenyl group, aralkyl group and aryl group are the same as those of R ¹ and R ² in the general formula (I).

Examples of the heterocycle when R ¹³ or R ¹⁴ represents a heterocyclic group include an oxazole ring, a benzoxazole ring, a thiazole ring, a benzothiazole ring, an imidazole ring, a benzoimidazole ring, a pyridine ring, a piperidine ring and a pyrrolidine ring. , Morpholine ring, pyrazole ring, pyrrole ring and coumarin ring.

The heterocyclic group may have a substituent. Examples of the substituent include an alkyl group (eg, methyl group, ethyl group, propyl group), alkoxy group (eg, methoxy group, ethoxy group), aryloxy group (eg, phenoxy group, p-chlorophenoxy group), Halogen atoms (e.g., Cl, Br, F), alkoxycarbonyl groups (e.g., ethoxycarbonyl groups), halogenated carbon groups (e.g., trifluoromethyl groups), alkylthio groups (e.g., methyl thi Group, ethylthio group, butylthio group), arylthio group (for example, phenylthio group, o-carboxyphenylthio group), cyano group, nitro group, amino group, alkylamino group (for example, methylamino group, Ethylamino group), amide group (for example, acetamide group, propionamide group), acyloxy group (for example, acetoxy group, butyryloxy group), hydroxyl group, sulfo group, and carboxyl group. The sulfo group and the carboxyl group may be in a salt state.

In formula (2), R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, an alkoxycarbonyl group, a halogenated carbon group, an alkylthio group, an arylthio group, a cyano group, Nitro group, amino group, alkylamino group, amide group, acyloxy group, hydroxyl group, sulfo group or carboxyl group.

Any two of R ¹³ , R ¹⁴ , R ^15, and R ¹⁶ may combine to form a ring.

In General formula (2), n1 and n2 are 1, 2, 3, or 4 each independently.

In General formula (2), R <^15> when two or more exist may be same or different, and R <^16> when two or more exist may be same or different.

In General formula (2), b is 0.25-3.0. b is determined according to the number of water-soluble groups included in the dye. For example, b is 0.5 if the dye has two sulfo groups. In addition, b is 1.0 when dye has three sulfo groups.

Below, the specific example of the cyanine dye which is represented by General formula (I) and has the absorption spectrum prescribed | regulated in this invention, and can be used suitably for preparation of the color filter in this invention is shown.

Cyanine dyes represented by formula (I) are described in F. M. Harmer, Heterocyclic Compounds-Cyanine Dyes and Related Compounds (John Wiley and Sons), New York, London, 1964; D. M. Sturmer, Heterocyclic Compounds-Special topics in heterocyclic chemistry, chapter 18, section 14, pp. 482-515, John Wiley and Sons, New York, London, 1977; Rod's Chemistry of Carbon Compounds, 2nd Edition, Volume 4 B, Chapter 15, pp. 369–422, Elsevier Science Publising Company Inc., New York, 1977; And Japanese Patent Laid-Open Nos. 6-313939 and 5-88293.

Another example of a dye having a specific absorption spectrum that can be suitably used for the color filter in the present invention is an oxonol dye represented by the general formula (II).

In said general formula (II), Y <^1> and Y <^2> respectively independently represent the nonmetallic atom group which forms an aliphatic ring or a heterocyclic ring. L ² represents a methine chain composed of an odd number of methines which may have a substituent. X ² represents a hydrogen atom or a cation.

In said general formula (II), Y <^1> and Y <^2> respectively independently represent the nonmetallic atom group which forms an aliphatic ring or a heterocyclic ring. As Y ¹ and Y ² , a heterocycle is more preferable than an aliphatic ring.

Examples of aliphatic rings include indandione rings. Examples of heterocycles include 5-parazolone ring, oxazolone ring, barbituric acid ring, pyridone ring, rhodanine ring, pyrazolidinedione ring, pyrazolopyridone ring and meldrumate ring.

Aliphatic rings and heterocycles may have a substituent. Examples of the substituent that can be introduced include an alkyl group (eg, methyl group, ethyl group, propyl group), alkoxy group (eg, methoxy group, ethoxy group), aryl group (eg phenyl group), aryloxy group (eg For example, phenoxy group, p-chlorophenoxy group, halogen atom (for example, Cl, Br, F), alkoxycarbonyl group (for example, ethoxycarbonyl group), halogenated carbon group (for example, trifluoromethyl group ), Alkylthio group (for example, methylthio group, ethylthio group, butylthio group), arylthio group (for example, phenylthio group, o-carboxyphenylthio group), cyano group, nitro group, Amino group, alkylamino group (e.g. methylamino group, ethylamino group), amide group (e.g. acetamide group, propionamide group), acyloxy group (e.g. acetoxy group, butyryloxy group), hydride Roxyl groups, sulfo groups and carboxyl groups are included. The sulfo group and the carboxyl group may be in a salt state.

In General Formula (II), L ² is a methine chain composed of an odd number of methines. The number of methines is preferably 3, 5 or 7.

The methine chain may have a substituent. As for the methine which has a substituent, it is preferable that the center (meso position) of a methine chain is methine. Examples of the substituent include alkyl, aryl, alkoxy, aryloxy, halogen, alkoxycarbonyl, halogenated carbon, alkylthio, arylthio, cyano, nitro, amino, alkylamino, amide, acyl Timing, hydroxyl, sulfo and carboxyl groups are included. However, it is preferable that a methine chain is unsubstituted.

In general formula (II), X <^2> represents a hydrogen atom or a cation. Examples of the cation when X ² represents a cation include alkali metal (eg, Na, K) ions, ammonium ions, triethylammonium ions, tributylammonium ions, pyridinium ions, and tetrabutylammonium ions.

Below, the example of the oxonol dye represented by general formula (II) and satisfying the conditions of the said spectrum prescribed | regulated by this invention is shown.

In the following exemplary compounds, the dissociable group is represented in a free form, but may be used in the form of a salt having a counter ion as described in General Formula (I). In particular, those having a structure of a salt having a counter ion represented by General Formula (1) or (2) are particularly preferably used.

The oxonol dye represented by general formula (II) can be synthesize | combined with reference to description of each specification of Unexamined-Japanese-Patent No. 7-230671, European Patent 0778493, and US Patent 5459265.

The dye represented by general formula (III) is mentioned as another example of the dye which has a specific absorption spectrum which can be used suitably for the color filter in this invention.

In general formula (III), Y <^3> is synonymous with Y <^1> and Y <^2> in general formula (II), and its preferable example is also the same. L ³ is a methine chain consisting of one or three methines, and the preferred number of methines is one. The methine chain may have a substituent. Examples of the substituent include alkyl, aryl, alkoxy, aryloxy, halogen, alkoxycarbonyl, halogenated carbon, alkylthio, arylthio, cyano, nitro, amino, alkylamino, amide, acyl Timing, hydroxyl, sulfo and carboxyl groups are included. However, it is preferable that a methine chain is unsubstituted.

Ar is an aromatic ring. Although an aromatic ring may be a hydrocarbon ring or a heterocyclic ring, a hydrocarbon ring is preferable. The most preferable aromatic ring is a benzene ring. An aromatic ring may have a substituent and the preferable substituent is the same as what was listed in description of the substituent of the aliphatic ring and heterocyclic ring of general formula (II).

Below, the preferable example of the dye represented by general formula (III) used preferably for this invention is given.

Specific examples of other preferred dyes include the following dyes (example compounds (IV-1) to (IV-5)) in addition to the dyes having a maximum absorption at 560 nm to 620 nm described in International Patent No. WO00-23829.

Moreover, pigments, such as C. I. pigment violet 19 and copper 23, can also be used preferably.

When using the dye which has such an absorption spectrum for a color filter, only 1 type may be used and it may use it in combination of 2 or more type. The content of the specific dye is preferably in the range of 5 to 70% by mass and more preferably in the range of 8 to 60% by mass in terms of solid content among all components constituting the color filter.

The specific color filter may be used together with a dye having a spectrum which does not correspond to the above-described spectroscopic absorption spectra (prescribes the ratio of the optical density of the specific wavelength at peak wavelengths of 475 nm to 525 nm and 550 nm to 620 nm) for the purpose of suppressing external light reflection. Among these dyes, particularly near-infrared absorbing dyes can be used. Even when such dyes are used in combination, it is necessary to adjust the addition amount because the absorption spectrum of the prepared color filter needs to satisfy the above requirements.

As the near-infrared absorbing dye, cyanine dyes (described in Japanese Patent Application Laid-Open No. 9-96891), metal chelate dyes, aluminum dyes, dimonium dyes, quinone dyes, squarylium dyes (Japanese Patent Laid-Open No. 9-90547, Compounds disclosed in Japanese Patent Application Laid-Open No. 10-204310) and various methine dyes and which do not have the above-described physical properties can be used.

Near-infrared absorbing dyes are also described in colorants (J. Jpn. Soc. Coulor Mater.), 61 [4] 215-226 (1988) and Chemical Industry 43-53 (May 1986, Chemical Industries). Further, other visible light absorbing dyes include triphenylmethane dyes (described in US Patent 2150695 and Japanese Patent Laid-Open No. 5-117536) and fluorescein dyes (for example, fluorescein, dibromofluorescein, Eosin, rhodamine).

Although the specific color filter which concerns on this invention can exhibit the effect of this invention even if it uses it with the structure of one layer containing the dye which has the said specific absorption spectrum, According to the objective, the coloring pattern of arbitrary color among R, G, and B is used. It can also be used as a color filter. In that case, what is necessary is just to contain the dye which has the said specific absorption spectrum with the coloring agent which gives a desired color to a coloring pattern, Preferably a pigment. The manufacturing method of the color filter which has a coloring pattern of multiple colors is explained in full detail below.

When the specific color filter according to the present invention is disposed at a position where light from a light source such as a light emitting element is displayed through the color filter, the arrangement position is arbitrary, and may be embedded in the display device as in the conventional display device, and the front of the display device. May be arranged as a separate member. Hereinafter, the form in which the color filter is arranged in front of the display device will be described.

<Front Mount Type Color Filter>

Although the specific color filter in the display device of the present invention can be produced by photolithography and embedded in the system similarly to the color filter in the conventional liquid crystal display device, it is attached to the display surface like the color correction filter for plasma display. By the method of installing on the front of the display can also be preferably used. This method is described in Japanese Patent Application Laid-Open No. 2003-157017 and the like.

As the polymer binder used for forming the filter layer in the front-mounted color filter, a natural polymer (for example, gelatin, cellulose derivative, arginic acid) or a synthetic polymer (for example, polymethyl methacrylate, polyvinyl butyral, Polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl chloride, styrene-butadiene copolymers, polystyrenes, polycarbonates, water soluble polyamides). Hydrophilic polymers (the above natural polymers, polyvinylbutyral, polyvinylpyrrolidone, polyvinyl alcohol, water-soluble polyamides) are preferred, and gelatin is particularly preferred. It is preferable that it is 5,000-100,000, and, as for the number average molecular weight of a polymer binder, it is more preferable that it is 10,000-100,000.

In addition to the dye and the binder polymer, the filter layer may further contain a fading inhibitor or an ultraviolet absorber. Examples of anti-fading agents that function as stabilizers of pigments include hydroquinone derivatives (US Pat. No. 3,935,016, described in each specification of US Pat. No. 3982944), hydroquinone diether derivatives (US Pat. ), Phenol derivatives (described in Japanese Patent Application Laid-Open No. 54-145530), derivatives of spiroindane or methylenedioxybenzene (described in each of JP 2077455, 2062888, and JP-A 61-90155). ), Derivatives of chromman, spirochroman or coumarane (US Pat. Nos. 3,432,300, 35,73050, 3,574,627, 3,763,373 and Japanese Patent Publication Nos. 52-152225, 53-20327, 53) -17729, described in Japanese Patent Application Laid-Open No. 61-90156), derivatives of hydroquinone monoethers or paraaminophenols (UK Patent 1347556, Japanese Patent Publication No. 2066975 and Japanese Patent Publication No. 54-12337, Japan Patent Each publication of US Pat. No. 55-6321) and bisphenol derivatives (described in US Pat. No. 3700455 and Japanese Patent Publication No. 48-31625).

In addition, in order to improve the stability of the pigment to light or heat, a metal complex (described in US Pat. No. 42,45018 and Japanese Patent Laid-Open No. 60-97353) may be used as a fading inhibitor.

Moreover, in order to improve the light resistance of a pigment, you may use singlet oxygen quencher as a fading inhibitor. Examples of singlet oxygen quencher include a nitroso compound (described in Japanese Patent Application Laid-Open No. 2-300288), a dimonium compound (described in US Patent No. 4656121), and a nickel complex (described in Japanese Patent Application Laid-Open No. 4-146189). And antioxidants (described in European Patent Publication 820057A1).

(Reflective layer)

In the first embodiment of the present invention, an antireflection layer may be further provided on the filter layer to impart an antireflection function to a specific color filter.

As the antireflection function of the antireflection layer, the specular reflectance is preferably 3% or less, and more preferably 1.8% or less.

When forming the antireflection layer, it is essential to form a low refractive index layer. As the low refractive index layer, one having a refractive index lower than that of the transparent support is used. It is preferable that it is 1.20-1.55, and, as for the refractive index of a low refractive index layer, it is more preferable that it is 1.30-1.55.

It is preferable that it is 50 nm-400 nm, and, as for the thickness of a low refractive index layer, it is more preferable that it is 50 nm-200 nm.

The low refractive index layer is made of a fluorine-containing polymer having a low refractive index (Japanese Patent Application Laid-Open No. 57-34526, Japanese Patent Application Laid-Open No. 3-130103, 6-115023, 8-313702, and 7-168004). Gazette), the layer obtained by the sol-gel method (each Gazette of Unexamined-Japanese-Patent No. 5-208811, 6-299091, 7-168003), or the layer containing microparticles | fine-particles (Japanese Patent Publication 60-59250 And Japanese Patent Application Laid-Open No. 5-13021, 6-56478, 7-92306, and 9-288201. In the layer containing the fine particles, voids may be formed in the low refractive index layer between the fine particles or as microvoids in the fine particles. It is preferable that the layer containing microparticles | fine-particles has a porosity of 3-50 volume%, and it is more preferable to have a porosity of 5-35 volume%.

In order to prevent reflection in a wide wavelength region, it is preferable to laminate a layer having a high refractive index (medium-high refractive index layer) in addition to the low refractive index layer.

It is preferable that it is 1.65-2.40, and, as for the refractive index of a high refractive index layer, it is more preferable that it is 1.70-2.20. The refractive index of the medium refractive index layer is adjusted to be the intermediate value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. It is preferable that the refractive index of a medium refractive index layer is 1.50-1.90.

It is preferable that the thickness of a medium and high refractive index layer is 5 nm-100 micrometers, It is more preferable that it is 10 nm-10 micrometers, It is most preferable that it is 30 nm-1 micrometer.

The haze of the medium and high refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less.

The medium and high refractive index layer can be formed using a polymer binder having a relatively high refractive index. Examples of polymers having high refractive index include polystyrenes, styrene copolymers, polycarbonates, melamine resins, phenol resins, epoxy resins, and polyurethanes obtained by reaction of cyclic (alicyclic or aromatic) isocyanates with polyols. Polymers having other cyclic (aromatic, heterocyclic or alicyclic) groups or polymers having a halogen atom other than fluorine as a substituent also have a high refractive index. You may form a polymer by the polymerization reaction of the monomer which introduced the double bond and enabled radical hardening.

In order to obtain a higher refractive index, inorganic fine particles may be dispersed in the polymer binder. It is preferable that the refractive index of an inorganic fine particle is 1.80-2.80.

It is preferable that the inorganic fine particles used for the said medium and high refractive index layer are formed with the oxide or sulfide of a metal. Examples of oxides or sulfides of metals include titanium dioxide (eg, rutile, rutile / anatase blends, anatase, amorphous structures), tin oxide, indium oxide, zinc oxide, zirconium oxide and zinc sulfide. Particular preference is given to titanium oxide, tin oxide and indium oxide. The inorganic fine particles mainly contain oxides or sulfides of these metals, and may further contain other elements. A main component means the component with the most content (weight%) among the components which comprise particle | grains. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S.

Inorganic materials that are film-forming and can be dispersed in a solvent but are themselves liquids, such as alkoxides of various elements, salts of organic acids, coordination compounds (e.g. chelate compounds) in combination with coordinating compounds, active inorganic polymers It is also possible to form a medium and high refractive index layer using.

The antireflection layer can impart an antiglare function (a function of scattering incident light from the surface to prevent infarct around the film from moving to the film surface). For example, the antiglare function can be obtained by forming fine irregularities on the surface of the transparent film, forming an antireflection layer on the surface, or forming an irregularities on the surface by embossing roll after forming the antireflection layer.

Antireflective layers having an antiglare function generally have a haze of 3 to 30%.

(Other layers)

In the specific color filter in the first aspect of the present invention, a hard coat layer, a lubricating layer, an antifouling layer, an antistatic layer, an ultraviolet absorbing layer, or an intermediate layer may be formed.

It is preferable that a hard-coat layer contains the polymer bridge | crosslinked. A hard coat layer can be formed using an acryl-type, urethane type, an epoxy polymer, an oligomer, or a monomer (for example, ultraviolet curable resin). It is also possible to form a hard coat layer from a silica-based material.

A lubricating layer may be formed on the outermost surface of the specific color filter. The lubricating layer has a function of imparting slipperiness to the antireflection film surface to improve scratch resistance. The lubricating layer can be formed using polyorganosiloxane (for example, silicone oil), natural wax, petroleum wax, higher fatty acid metal salt, fluorine-based lubricant or derivatives thereof. It is preferable that the thickness of a lubrication layer is 2 nm-20 nm.

An antifouling layer can be formed using a fluorine-containing polymer. It is preferable that it is 2 nm-100 nm, and, as for the thickness of an antifouling layer, it is more preferable that it is 5 nm-30 nm.

The antireflection layer (medium refractive index layer, high refractive index layer and / or low refractive index layer), filter layer, undercoat layer, hard coat layer, lubricating layer and other layers may be formed by a general coating method, respectively. Examples of the coating method include a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method and an extrusion coating method using a hopper (described in US Patent 2681294 specification). Two or more layers may be formed by simultaneous application. Concurrent coating methods are described in the specifications of US Patents 2761791, 2941898, 3508947, and 3526528, and Harasaki Yuji Co., Ltd., page 253 (published by Asakura Publishing Co., Ltd., 1973). have.

(Compatibility of specific color filter)

The specific color filter is applicable to an image display device such as a liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), or a cathode ray tube display (CRT). In the case of forming the antireflection layer, the surface on which the low refractive index layer is not formed is disposed so as to face the image display surface of the image display apparatus. Particularly significant effects are obtained when the specific color filter according to the present invention is used as a color filter for a display device having an organic EL light emitting element.

In an image display device such as an organic EL display device, a specific color filter is arranged to cover the surface of the display. Certain color filters can be attached directly to the surface of the display. In addition, when the front panel is provided in front of the display, a specific color filter may be attached to the front side (outside) or the rear side (display side) of the front panel.

The display device of the present invention is characterized by having elements emitting light in three colors of R, G, and B, such as inorganic or organic EL, and a light emitting element and a light source of any principle can be used. It is preferable that it is a display apparatus. Hereinafter, the organic electroluminescence display used preferably for this invention is demonstrated in detail.

<Organic EL Display and Microcavity Structure>

The organic EL display device used in the present invention can be manufactured by referring to Japanese Patent No. 3944906. It demonstrates using drawing below.

[First embodiment]

Fig. 1 shows a cross-sectional structure of an organic EL display device using an organic EL light emitting element which is a light emitting element according to the first embodiment of the present invention. This display device is used as an ultra-thin organic light emitting color display device or the like. For example, the drive panel 10 and the sealing panel 20 are disposed to face each other, and the front surface is joined by the adhesive layer 30. In the driving panel 10, the organic EL light emitting element 10R for generating red light and the organic EL light emitting element 10G for generating green light on the driving substrate 11 made of an insulating material such as glass, The organic EL light emitting element 10B for generating blue light is provided in a matrix form as a whole as a whole.

The organic EL light emitting elements 10R, 10G, and 10B are each composed of, for example, a first electrode 12 as an anode, an organic layer 13 and a second electrode 14 as a cathode from the driving substrate 11 side. It is laminated in order. In addition, the protective film 15 may be formed on the 2nd electrode 14 as needed.

Since the 1st electrode 12 also functions as a reflection layer, it is preferable at the point which improves luminous efficiency to have a reflectance as high as possible. For example, in the case of using a material having a high extinction coefficient such as metal, a material having as low a real refractive index as possible is used, and the thickness of the stacking direction (hereinafter simply referred to as thickness) is such that light does not transmit, specifically, The ratio is preferably 100 nm or more because the reflectance can be increased. Specifically, the thickness is, for example, about 200 nm, and preferably composed of a single element or an alloy of a metal element having a high work function such as platinum (Pt), gold (Au), or tungsten (W). Moreover, you may add another element to the 1st electrode 12 so that a substantial difference does not arise in an optical constant.

The organic layer 13 has a different structure depending on the color of light emitted by the organic EL light emitting elements 10R, 10G, and 10B. FIG. 2 enlarges and shows the structure of the organic layer 13 in organic electroluminescent element 10R, 10B. The organic layer 13 of the organic EL light emitting elements 10R and 10B has a structure in which a hole transport layer 13A, a light emitting layer 13B, and an electron transport layer 13C are stacked in this order from the first electrode 12 side, respectively. . The hole transport layer 13A is for enhancing the hole injection efficiency to the light emitting layer 13B. In this embodiment, the hole transport layer 13A also serves as the hole injection layer. The light emitting layer 13B generates light by injection of electric current. The electron transport layer 13C is for enhancing the electron injection efficiency to the light emitting layer 13B.

The hole transport layer 13A of the organic EL light emitting element 10R is, for example, about 45 nm in thickness, and is made of bis [(N-naphthyl) -N-phenyl] benzidine (? -NPD). The light emitting layer 13B of the organic EL light emitting element 10R has a thickness of about 50 nm, for example, and is 2,5-bis [4- [N- (4-methoxyphenyl) -N-phenylamino]] styryl It is comprised by benzene-1, 4- dicarbonitrile (BSB). The electron transport layer 13C of the organic light emitting element 10R has, for example, a thickness of about 30 nm and is composed of an 8-quinolinol aluminum complex (Alq3).

The hole transport layer 13A of the organic EL light emitting element 10B has a thickness of about 30 nm, for example, and is composed of α-NPD. The light emitting layer 13B of the organic EL light emitting element 10B has a thickness of about 30 nm, for example, and is composed of 4,4'-bis (2,2'-diphenylvinyl) biphenyl (DPVBi). . The electron transport layer 13C of the organic light emitting element 10B has a thickness of about 30 nm, for example, and is made of Alq3.

3 shows the enlarged configuration of the organic layer 13 in the organic EL light emitting element 10G. The organic layer 13 of the organic EL light emitting element 10G has a structure in which the hole transport layer 13A and the light emitting layer 13B are stacked in this order from the first electrode 12 side. The hole transport layer 13A also serves as a hole injection layer, and the light emitting layer 13B also serves as an electron transport layer.

The hole transport layer 13A of the organic EL light emitting element 10G, for example, has a thickness of about 50 nm and is made of α-NPD. The light emitting layer 13B of the organic EL light emitting element 10G has a thickness of, for example, about 60 nm, and is constituted by mixing 1 volume% of coumarin 6 (C6; Coumarin 6) with Alq3.

The second electrode 14 shown in FIGS. 1-3 has the function as a semi-transmissive reflective layer. That is, the organic EL light emitting elements 10R, 10G, and 10B have a cross section at the light emitting layer 13B side of the first electrode 12 at the first end P1 and a cross section at the light emitting layer 13B side of the second electrode 14. Is a second end P2, the organic layer 13 is a resonator, and has a resonator structure which resonates the light generated in the light emitting layer 13B and draws it out from the second end P2 side. It is preferable to have a resonator structure, since the light generated in the light emitting layer 13B causes multiple interference to act as a kind of narrowband filter, so that the half width of the spectrum of the light to be extracted can be reduced and color purity can be improved.

In addition, external light incident from the sealing panel 20 can also be attenuated by multiple interference, and the organic EL light emitting elements 10R, 10G, and 10B are combined with the color filter 22 (see FIG. 1) described later. Since the reflectance of external light in can be made very small, it is preferable.

The protective film 15 shown in FIG. 1 is, for example, a passivation film made of a transparent dielectric having a thickness of 500 nm or more and 10,000 nm or less. The protective film 15 is made of, for example, silicon oxide (SiO ₂ ), silicon nitride (SiN), or the like.

As shown in FIG. 1, the sealing panel 20 is located on the second electrode 14 side of the driving panel 10 and seals the organic EL light emitting elements 10R, 10G, and 10B together with the adhesive layer 30. The sealing substrate 21 is provided. The sealing substrate 21 is made of a material such as glass that is transparent to light generated by the organic EL light emitting elements 10R, 10G, and 10B. The sealing substrate 21 is provided with, for example, a color filter 22, and extracts the light generated by the organic EL light emitting elements 10R, 10G, and 10B, and the organic EL light emitting elements 10R, 10G, 10B) and the wiring between them are absorbed to improve the contrast.

Although the color filter 22 may be provided in the surface of any side of the sealing substrate 21, it is preferable to be provided in the side of the drive panel 10. As shown in FIG. This is because the color filter 22 may be protected by the adhesive layer 30 without being exposed to the surface. The color filter 22 has the red filter 22R, the green filter 22G, and the blue filter 22B, and is arrange | positioned in order corresponding to organic electroluminescent element 10R, 10G, and 10B.

The red filter 22R, the green filter 22G, and the blue filter 22B are each formed in a rectangular shape without a gap, for example. These red filter 22R, green filter 22G, and blue filter 22B are each comprised by resin which mixed the pigment, and light transmittance in the red, green, or blue wavelength range made into the objective by selecting a pigment. This is adjusted so that the light transmittance in this high and other wavelength range will become low.

4A to 4B and 5A to 5B show the manufacturing method of this display device in the order of steps. First, as shown in Fig. 4A, the first electrode 12 made of the above-described material is formed on the driving substrate 11 made of the above-described material, for example, by direct current sputtering, to the above-described thickness. For example, the substrate is selectively etched using, for example, lithography, and patterned into a predetermined shape. Thereafter, as shown in Fig. 4A, for example, the organic layer 13 (hole transport layer 13A, light emitting layer 13B and / or electron transport layer 13C) made of the above-described thickness and material by evaporation method, for example. And the second electrode 14 are sequentially formed, and the organic light emitting elements 10R, 10G, and 10B as shown in FIGS. 2 and 3 are formed, respectively. Thereafter, the protective film 15 is formed on the second electrode 14 as necessary. As a result, the drive panel 10 is formed.

Fig. 4B shows a color filter having colored patterns of R, G, and B formed by a conventional method. For example, the material of the red filter 22R (in this embodiment, the coloring photosensitive composition mentioned later) is apply | coated by the spin coat method etc. on the sealing substrate 21 which consists of the above-mentioned material, and it applies to a port lithography technique. After patterning, the red filter 22R is formed by firing. Subsequently, similar to the red filter 22R, the blue filter 22B and the green filter 22G are sequentially formed to form the sealing panel 20 having the coloring patterns of R, G, and B shown in Fig. 4B. do.

The order of forming the red filter, the blue filter and the green filter is arbitrarily set.

As mentioned above, it turns out that the process of patterning and baking is repeated by the number of colors in the conventional process. According to the present invention, since the filter of one color can serve as a conventional two-color powder, the number of steps in this portion can be reduced.

After the sealing panel 20 and the drive panel 10 are formed, the adhesive layer 30 is formed on the protective film 15 as shown in Fig. 5A. Thereafter, as shown in FIG. 5B, the driving panel 10 and the sealing panel 20 are bonded through the adhesive layer 30. At this time, it is preferable to arrange | position the surface of the side in which the color filter 22 was formed among the sealing panels 20 facing the drive panel 10. FIG. As mentioned above, the drive panel 10 and the sealing panel 20 are adhere | attached, and the display apparatus shown in FIGS. 1-3 is completed.

In the display device, when a predetermined voltage is applied between the first electrode 12 and the second electrode 14, a current is injected into the light emitting layer 13B, and holes and electrons recombine to emit light mainly at the interface of the light emitting layer 13B. This happens. The light is reflected multiple times between the first electrode 12 and the second electrode 14 to pass through the second electrode 14, the protective layer 15, the color filter 22 and the sealing substrate 21 to be drawn out. do. At this time, external light enters from the sealing substrate 21 side, but external light other than the resonant wavelength is absorbed by the color filter 22 and is caused by multiple interference in the organic EL light emitting elements 10R, 10G, and 10B. Attenuated. On the other hand, external light of the resonant wavelength passes through the color filter 22 and enters the organic EL light emitting elements 10R, 10G, and 10B, and is mainly reflected by the second electrode 14 and the first electrode 12. However, in the present embodiment, the intensity and the intensity of the reflected light of the external light at the side of the first end P1, that is, the side of the first electrode 12 and the second end P2, that is, the second electrode 14 are different. Since the reflectance in the organic EL light emitting elements 10R, 10G, and 10B is 20% or less by adjusting the phases, the reflected light transmitted through the sealing substrate 21 and drawn out is extremely small. Therefore, external light reflection or the reflection of the outer diameter is reduced.

Although 1st Embodiment of this invention was described based on embodiment, this invention is not limited to the said embodiment, A various deformation | transformation is possible. For example, the material and thickness of each layer described in the above embodiments, the film forming method and the film forming conditions are not limited, and may be other materials and thicknesses, or may be other film forming methods and the film forming conditions. In this embodiment, although the microcavity structure suitable for this invention is employ | adopted, even if it is a form which does not use this, implementation is possible.

In the said embodiment, although it has the pixel of three colors of R, G, and B, in this invention, you may have other white pixel which extracts light, without passing through a filter layer.

In addition, although the structure of organic electroluminescent element was mentioned and demonstrated concretely in the said embodiment, it is not necessary to provide all the layers, such as 13 A of hole injection thin films, the protective film 15, and also may provide another layer further. good. For example, the first electrode 12 may have a two-layer structure in which a transparent conductive film is laminated on the dielectric multilayer film or a reflective film such as Al. In this case, the cross section on the light emitting layer side of the reflective film constitutes an end portion of the resonant portion, and the transparent conductive film constitutes a part of the resonant portion.

In addition, in the said embodiment, although the case where the 2nd electrode 14 was comprised by the semi-transmissive reflective layer was demonstrated, the 2nd electrode 14 has the structure where the semi-transmissive reflective layer and the transparent electrode were laminated | stacked in order from the side of a 1st electrode. You may make it. This transparent electrode is for reducing the electrical resistance of a semi-transmissive reflective layer, and is comprised with the electroconductive material which has sufficient light transmittance with respect to the light which arose in the light emitting layer. As a material which comprises a transparent electrode, the compound containing ITO or indium, zinc (Zn), and oxygen is preferable, for example. This is because good conductivity can be obtained even when the film is formed at room temperature. The thickness of a transparent electrode can be 30 nm or more and 1000 nm or less, for example. In this case, the semi-transmissive reflective layer may be formed at one end and the other end may be provided at a position with the transparent electrode interposed therebetween to form a resonator structure having the transparent electrode as the resonator. In the case of providing such a resonator structure, the protective film 15 is preferably made of a material having a refractive index equivalent to that of the material constituting the transparent electrode, so that the protective film 15 can be part of the resonator.

In addition, according to the present invention, the second electrode 14 is constituted by a transparent electrode, and the reflectance of the cross section on the opposite side to the organic layer 13 of the transparent electrode is increased, and the light emitting layer of the first electrode 12 is formed. It is also applicable to the case where the resonator structure having a cross section on the 13B) side as the first end and a cross section on the opposite side to the organic layer of the transparent electrode as the second end is configured. For example, the reflectance at the interface between the protective film 15 or the adhesive layer 30 may be increased, and the interface may be the second end. In addition, without forming the protective film 15 and the adhesive layer 30, the transparent electrode may be brought into contact with the atmospheric layer to increase the reflectance of the interface between the transparent electrode and the atmospheric layer, and the interface may be the second end.

Second Embodiment

Next, the case where light is taken out from the TFT substrate side as 2nd Embodiment is demonstrated.

In the said embodiment, the 1st electrode 12, the organic layer 13, and the 2nd electrode 14 are laminated | stacked on the drive board 11 in order from the drive board 11 side, and the sealing panel 20 is carried out. Although the case where light was taken out from the side was demonstrated, the 2nd electrode 14, the organic layer 13, and the 1st electrode 12 on the drive board 11 were reversed, and the drive board 11 was reversed. The light may be taken out from the side of the driving substrate 11 by being laminated in this order.

For example, in the said embodiment, although the case where the 1st electrode 12 was made into the anode and the 2nd electrode 14 was made into the cathode was demonstrated, the 1st electrode 12 was made into the negative electrode and the 1st electrode with the anode and cathode reversed. The two electrodes 14 may be anodes. In this case, as a material of the second electrode 14, a single or alloy such as gold, silver platinum, copper, etc. having a high work function is suitable, but other materials may be used by forming the hole injection thin film layer 13A. Moreover, you may add another element to the 2nd electrode 14 so that a substantial difference does not arise in an optical constant. In addition, the first electrode 12 is a cathode and the second electrode 14 is an anode, and the second electrode 14, the organic layer 13, and the first electrode 12 are formed on the driving substrate 11. The light may be stacked in order from the driving substrate 11 side to extract light from the driving substrate 11 side.

The color filter with which the display apparatus of this invention is equipped can also be applied to the form which has a well-known color pattern of R, G, B, or the form which has arbitrary color patterns of 1 color-3 colors among them. In this case, it can be set as the specific color filter which concerns on this invention by adding the dye which has the said specific peak to the coloring pattern of 1 color-3 colors predetermined. Hereinafter, the color filter which has a coloring pattern of multiple colors is explained in full detail with the manufacturing method.

The display device of the present invention includes a color filter. If necessary, a color filter further comprising a black matrix may be used for shielding light and preventing reflection.

Each colored pixel can use various pattern shaping | molding methods, such as the photolithographic method, the printing method by inkjet, the reverse printing method, or the nano imprinting method, using the coloring composition colored by each color. Hereinafter, the coloring pattern molding by the port lithography method which is one of the forms of this invention is demonstrated.

In the photolithography method, a colored photosensitive composition is used. A coloring photosensitive composition consists of coloring agents, such as a pigment and dye, alkali-soluble resin, a photopolymerizable compound, a photoinitiator, etc. as a coloring agent.

In addition to the dye of the present invention described above, it is possible to use various dyes for the port lithography method. In addition, addition of a well-known pigment is possible, but it is preferable to process a pigment with various resin beforehand. That is, the pigment is generally dried after synthesis, and dried in various ways, and is usually dried from the water medium and supplied as a powder. However, in order to dry the water, a large latent heat of evaporation is required. Grant. Therefore, it is common for the pigment to form aggregates (secondary particles) in which primary particles are aggregated, and it is not easy to disperse the pigments forming such aggregates in the fine particles. Dispersion becomes easy and is preferable. As resin here, alkali-soluble resin mentioned later is mentioned.

As the method of the dispersion treatment, there is a flashing treatment, a kneading method using a kneader, an extruder, a ball mill, two or three roll mills, or the like. Among them, a flashing treatment or a kneading method using two or three roll mills is suitable for atomization.

The flashing treatment is a method of treating a pigment with a resin by mixing an aqueous dispersion of the pigment with a resin solution dissolved in a solvent which is not miscible with water, extracting the pigment from the water medium into the organic medium. According to this method, since the pigment is not dried, aggregation of the pigment can be prevented and dispersion becomes easy. In addition, in the kneading by the two or three roll mills, a pigment and a resin are coated on the surface of the pigment by mixing the pigment and the resin or a solution of the resin and then kneading the pigment and the resin while applying a high shear force to treat the pigment. Pigment particles aggregated in this process are dispersed from the lower-dimensional aggregates to the primary particles.

Moreover, it can also be used as a processing pigment previously processed with acrylic resin, vinyl chloride-vinyl acetate resin, maleic acid resin, ethyl cellulose resin, nitrocellulose resin. As a form of this process pigment, powder, paste form, pellet form, and paste form in which resin and a pigment are disperse | distributed uniformly are preferable. In addition, it is not preferable that the resin is a gelled non-uniform mass.

Pigments used for the same green, red, and blue pixels as those used in addition to the color filter having the spectrum of the present invention can be arbitrarily selected in consideration of high transmittance and high color reproducibility.

In this invention, it is preferable to use the pigment which was finely refined as needed.

It is preferable to use a method including the step of grinding the organic pigment into a highly viscous liquid composition with a water-soluble organic solvent and a water-soluble inorganic salt.

In the present invention, it is more preferable to use the following method for miniaturization of the organic pigment.

That is, two rolls, three rolls, a ball mill, a trommill, a disper, a kneader, a kneader, a homogenizer, a blender, a shortening of a mixture (liquid composition) of an organic pigment, a water-soluble organic solvent, and a water-soluble inorganic salt. Alternatively, the organic pigment in the mixture is ground by imparting strong shearing force by using a kneader such as a twin screw extruder, and then the mixture is poured into water to form a slurry with a stirrer or the like. Subsequently, the slurry can be filtered, washed with water, the water-soluble organic solvent and the water-soluble inorganic salt are removed, and then dried to obtain the above fined pigment.

As a water-soluble organic solvent used for the said refinement | miniaturization method, methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene Glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether acetate and the like.

In addition, since only a small amount is used, benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate and acetic acid are absorbed by the pigment and are not lost to the waste water. Isopropyl, butyl acetate, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methyl cyclohexane, halogenated hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide , Dimethyl sulfoxide, N-methylpyrrolidone or the like may be used. Moreover, you may mix and use two or more types of solvents as needed.

The use amount of these water-soluble organic solvents is preferably in the range of 50% by mass to 300% by mass with respect to the organic pigment, and more preferably in the range of 100% by mass to 200% by mass.

In the present invention, sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like are used as the water-soluble inorganic salt.

As for the usage-amount of a water-soluble inorganic salt, 1 mass-50 times mass of a pigment are preferable, The more it has a grinding effect, the more preferable quantity is 1 mass-10 times mass from the point of productivity.

Moreover, in order to prevent melt | dissolution of a water-soluble inorganic salt, it is preferable that the moisture in the crushed liquid composition is 1 mass% or less.

In the present invention, when grinding the liquid composition containing the pigment, the water-soluble organic solvent and the water-soluble inorganic salt, a wet grinding device such as a kneader described above may be used. There are no particular limitations on the operating conditions of this wet grinding device, but in order to effectively advance grinding by grinding media (aqueous inorganic salts), the operating conditions when the device is a kneader is preferably 10 rpm to 200 rpm for the blades in the device. In addition, it is preferable that the larger the biaxial rotation ratio is, the larger the grinding effect is. The operating time is preferably 1 hour to 8 hours in accordance with the dry grinding time, and the internal temperature of the apparatus is preferably 50 ° C to 150 ° C. In addition, it is preferable that the water-soluble inorganic salt which is a grinding media has a grinding particle size of 5 µm to 50 µm, a sharp distribution of particle diameters, and a spherical shape.

The water-soluble organic solvent and the water-soluble inorganic salt are dissolved by mixing the above-ground mixture with hot water at 80 ° C., then filtered, washed with water and dried in an oven to obtain a fine organic pigment.

Other methods for obtaining fine organic pigments include dissolving an organic pigment in a good solvent to produce an organic pigment solution, and then mixing the solution with a poor solvent of an organic pigment compatible with the solution to precipitate.

Pigment Dispersion Composition

The pigment thus obtained has the form of a pigment dispersion composition (also called a pigment dispersion) in order to improve the dispersibility of a pigment normally before adjusting a coloring photosensitive composition.

10-60 mass% is preferable with respect to the total solid (mass) of the said composition, and, as for content in the pigment dispersion composition of a pigment, 15-50 mass% is more preferable. When content of a pigment is in the said range, color concentration is enough and it is effective for ensuring the outstanding color characteristic.

The pigment dispersion composition contains at least one kind of dispersant. By containing this dispersing agent, the dispersibility of a pigment can be improved.

As a dispersing agent, a well-known pigment dispersing agent and surfactant can be selected suitably, for example.

Specifically, many kinds of compounds can be used, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW No. 75, which is a (meth) acrylic acid (co) polymer. .90, cationic surfactants such as No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusu Co., Ltd.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene Nonionic surfactants such as oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, etc. W004, W005, W017 (Yusho Co. , Ltd. products), etc .; EFKA-46, EFKA-47, EFKA-47EA, EFKA POLYMER 100, EFKA POLYMER 400, EFKA POLYMER 401, EFKA POLYMER 450 (manufactured by Ciba Japan KK), DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15, DISPERSE AID 9100 from San Nopco Ltd. Polymer dispersant of SOLSPERSE 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc. Various SOLSPERSE dispersants (products of The Lubizol Corporation); ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by ADEKA Corporation) and IONET S-20 (manufactured by Sanyo Chemical Industries Ltd.), Disperbyk 101, 103, 106 , 108, 109, 111, 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (BYK Japan KK Product). In addition, the oligomer or polymer which has a polar group in a molecular terminal or a side chain, such as an acrylic copolymer, is mentioned.

Dispersant 1-100 mass% is preferable with respect to the mass of the pigment mentioned above, and, as for content in a pigment dispersion composition, 3-70 mass% is more preferable.

A pigment derivative is added to a pigment dispersion composition as needed. By adsorbing a pigment derivative having affinity to the dispersant or a polar group introduced thereon onto the surface of the pigment and using this as the adsorption point of the dispersant, the pigment can be dispersed into the colored photosensitive composition by making the pigment into fine particles to prevent reaggregation thereof. It is effective for forming an excellent color filter having high color reproducibility and high luminance.

The pigment derivative is a compound in which an organic pigment is used as a mother skeleton, and an acidic group, a basic group and an aromatic group are introduced into the side chain as a substituent. Specific examples of the organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindolin pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzimidazolone pigments. Can be. Generally, pale yellow aromatic polycyclic compounds, such as naphthalene series, anthraquinone series, triazine series, and quinoline series, which are not called dyes, are also included. As a pigment derivative, Unexamined-Japanese-Patent No. 11-49974, Unexamined-Japanese-Patent No. 11-189732, Unexamined-Japanese-Patent No. 10-245501, Unexamined-Japanese-Patent No. 2006-265528, Japan Unexamined-Japanese-Patent No. 8-295810 What is described in Unexamined-Japanese-Patent No. 11-199796, Unexamined-Japanese-Patent No. 2005-234478, Unexamined-Japanese-Patent No. 2003-240938, Unexamined-Japanese-Patent No. 2001-356210, etc. can be used.

1-30 mass% is preferable with respect to the mass of a pigment, and, as for content in the pigment dispersion composition of a pigment derivative, 3-20 mass% is more preferable. When the content is within the above range, the dispersion can be satisfactorily performed while the viscosity is kept low, and the dispersion stability after dispersion can be improved, and the transmittance is high and excellent color characteristics can be obtained. can do.

The dispersing method is performed by, for example, predispersing a pigment and a dispersant and dispersing it in a homogenizer or the like using a disperser (eg, DISPERMAT made by GETZMANN) using zirconia beads or the like. . As dispersion time, about 3 to 6 hours are suitable.

The colored photosensitive composition comprises the above-mentioned pigment dispersion composition, alkali-soluble resin, a photopolymerizable compound, and a photoinitiator, and may contain the other component as needed. In addition, the detail of a pigment dispersion composition is as above-mentioned. Hereinafter, each component is explained in full detail.

<Alkali Soluble Resin>

As alkali-soluble resin, it is a linear organic high molecular polymer, group which promotes at least 1 alkali solubility in a molecule | numerator (preferably an acryl copolymer or a styrene copolymer as a main chain) (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc.) It can select suitably from alkali-soluble resin which has). Among these, More preferably, it is soluble in an organic solvent and developable by a weak alkali aqueous solution.

For the production of alkali-soluble resin, for example, a method by a known radical polymerization method can be applied. The polymerization conditions such as temperature, pressure, the kind and amount of the radical initiator, the kind of the solvent, and the like when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art and can be determined experimentally.

As said linear organic high polymer, the polymer which has a carboxylic acid in a side chain is preferable. For example, Japanese Patent Publication No. 59-44615, Japanese Patent Publication 54-34327, Japanese Patent Publication 58-12577, Japanese Patent Publication 54-25957, Japanese Patent Publication No. 59-53836, Japan Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and the like as described in the respective publications of Japanese Patent Application Publication No. 59-71048; and The acid cellulose derivative which has a carboxylic acid in a side chain, what added an acid anhydride to the polymer which has a hydroxyl group, etc., Moreover, the high molecular polymer which has a (meth) acryloyl group in a side chain is mentioned as a preferable thing.

Among these, in particular, a benzyl (meth) acrylate / (meth) acrylic acid copolymer or a benzyl (meth) acrylate / (meth) acrylic acid / other monomer composed of other monomers is suitable.

In addition, what copolymerized 2-hydroxyethyl methacrylate etc. can also be mentioned as useful. The said polymer can be mixed and used in arbitrary quantity.

In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer and 2-hydroxy-3-phenoxypropyl described in JP-A-7-140654 Acrylate / polymethylmethacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methylmethacrylate / methacrylic acid copolymer, 2-hydroxy Ethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer; and the like.

About the specific structural unit of alkali-soluble resin, the copolymer of (meth) acrylic acid and the other monomer copolymerizable with this is suitable especially. Here, (meth) acrylic acid is a general term which combined acrylic acid and methacrylic acid, and (meth) acrylate is also a general term of acrylate and methacrylate similarly below.

Examples of the other monomer copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds, and the like. Here, the hydrogen atoms of the alkyl group and the aryl group may be substituted with a substituent.

Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth). Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) Acrylate, cyclohexyl (meth) acrylate, etc. are mentioned.

Moreover, as said vinyl compound, styrene, (alpha) -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene, for example Macromonomer, polymethylmethacrylate macromonomer, CH ₂ = CR ¹¹ R ¹² , CH ₂ = C (R ¹¹ ) (COOR ¹³ ) [wherein R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ¹² represents a C6-C10 aromatic hydrocarbon ring, R <^13> represents a C1-C8 alkyl group or a C6-C12 aralkyl group., Etc. are mentioned.

These copolymerizable other monomers can be used individually by 1 type or in combination of 2 or more types. Preferred copolymerizable other monomers are at least one selected from CH ₂ = CR ¹¹ R ¹² , CH ₂ = C (R ¹¹ ) (COOR ¹³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene, Especially preferred are CH ₂ = CR ¹¹ R ¹² and / or CH ₂ = C (R ¹¹ ) (COOR ¹³ ).

As for content in the coloring photosensitive composition of alkali-soluble resin, 1-15 mass% is preferable with respect to the total solid of the said composition, More preferably, it is 2-12 mass%, Especially preferably, it is 3-10 mass%.

<Photopolymerizable compound>

The coloring photosensitive composition of this invention contains a photopolymerizable compound.

As a photopolymerizable compound, the compound which has at least 1 addition-polymerizable ethylenically unsaturated group, and whose boiling point is 100 degreeC or more at normal pressure is preferable, and the tetrafunctional or more functional acrylate compound is especially preferable.

As a compound which has the said at least 1 addition-polymerizable ethylenically unsaturated group, and whose boiling point is 100 degreeC or more at normal pressure, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth Monofunctional acrylates and methacrylates such as acrylate; Polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Multifunctional such as hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylol ethane (Meth) acrylated addition of ethylene oxide or propylene oxide to alcohol, poly (meth) acrylated of pentaerythritol or dipentaerythritol, Japanese Patent Publication No. 48-41708, Japanese Patent Publication Urethane acrylates described in 50-6034, Japanese Patent Application Laid-Open No. 51-37193, Japanese Patent Publication No. 48-64183, Japan Polyfunctional acrylates and methacrylates, such as the polyester acrylates of Unexamined-Japanese-Patent No. 49-43191, Japanese Unexamined-Japanese-Patent No. 52-30490, and epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid. Can be mentioned.

Moreover, the coloring photosensitive monomer and oligomer described in Journal of the Adhesion Society of Japan Vol.20, No. 7, 300-308 can also be used.

In addition, after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in Japanese Patent Application Laid-open No. Hei 10-62986 with the specific examples as General Formulas (1) and (2), (meth) acrylated Compounds can also be used.

Especially, the structure in which dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and these acryloyl groups are via ethylene glycol and a propylene glycol residue is preferable. These oligomer types can also be used.

Furthermore, urethane acrylates and Japanese patents as described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293 and Japanese Patent Publication No. Hei 2-16765. Also suitable are urethane compounds having an ethylene oxide skeleton described in Japanese Patent Application Laid-Open No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418. Furthermore, the use of addition polymerizable compounds having an amino structure or a sulfide structure in the molecules described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-open No. Hei 1-105238 is very sensitive. The photopolymerizable composition excellent in speed can be obtained. Commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Nippon Paper Chemicals), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA- 306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

Moreover, ethylenically unsaturated compounds which have an acidic group are also suitable, As a commercial item, it is TOAGOSEI Co., Ltd., for example. TO-756 which is a carboxyl group-containing trifunctional acrylate of a product, TO-1382 which is a carboxyl group-containing 5-functional acrylate, etc. are mentioned.

A photopolymerizable compound can be used in combination of 2 or more type other than using individually by 1 type.

As for content in the coloring photosensitive composition of a photopolymerizable compound, 3-55 parts are preferable with respect to 100 parts of total solids of the said composition, More preferably, it is 10-50 parts. When content of a photopolymerizable compound exists in the said range, hardening reaction can fully be performed.

<Photopolymerization initiator>

It is preferable that a photoinitiator is contained in the coloring photosensitive composition used for this invention.

As a photoinitiator, for example, the halomethyl oxadiazole described in JP-A-57-6096, JP-A-59-1281, JP-A-53-133428 and the halomethyl-s- Active halogen compounds such as triazine, aromatic carbonyl compounds such as ketal, acetal or benzoin alkyl ethers described in the specifications of US Patent No. 4318791 and European Patent Application Publication No. 888050, and the benzos described in the specification of US Pat. Aromatic ketone compounds such as phenones, (thio) xanthones or acridine compounds described in French Patent Invention No. 2456741, coumarin-based or biimidazole-based compounds described in JP-A-10-62986, Japan Sulfonium organoboron complexes, such as Unexamined-Japanese-Patent No. 8-015521, etc. are mentioned.

Examples of the photopolymerization initiator include acetophenone series, ketal series, benzophenone series, benzoin series, benzoyl series, xanthone series, active halogen compounds (e.g., triazine compounds, halomethyloxadiazole compounds, coumarin compounds), acridine series , Biimidazole type, oxime ester type and the like are preferable.

As said acetophenone photoinitiator, 2, 2- diethoxy acetophenone, p-dimethylamino acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylamino aceto, for example Phenone, 4'-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1, 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholino propane non-1, etc. are mentioned suitably.

As said ketal photoinitiator, benzyl dimethyl ketal, benzyl- (beta)-methoxyethyl acetal, etc. are mentioned suitably, for example.

Examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 '-(bisdimethylamino) benzophenone, 4,4'-(bisdiethylamino) benzophenone, 4,4'-dichlorobenzophenone, and the like. It may be mentioned suitably.

As said benzoin photoinitiator or benzoyl photoinitiator, benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl benzoate, etc. are mentioned suitably, for example.

As said xanthone photoinitiator, diethyl thioxanthone, diisopropyl thioxanthone, monoisopropyl thioxanthone, chloro thioxanthone, etc. are mentioned suitably, for example.

As said active halogen photoinitiator (for example, a triazine compound, an oxadiazole compound, a coumarin compound), it is 2, 4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, for example. , 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1 , 3-butadienyl-s-triazine, 2,4-bis (trichloromethyl) -6-biphenyl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-methyl Biphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di (trichloromethyl) -s-triazine, methoxystyryl-2,6-di (trichloromethyl)- s-triazine, 3,4-dimethoxystyryl-2,6-di (trichloromethyl) -s-triazine, 4-benzoxolane-2,6-di (trichloromethyl) -s-tri Azine, 4- (o-bromo-pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (pN, N- (diethoxy Carbonylamino) -phenyl) -2,6-di (chloromethyl ) -s-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodia Sol, 2-trichloromethyl-5- (naphtho-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3, 4-oxodiazole, 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazine- 2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, etc. are mentioned suitably.

As said acridine photoinitiator, 9-phenyl acridine, 1, 7-bis (9-acridinyl) heptane, etc. are mentioned suitably, for example.

As said biimidazole photoinitiator, 2- (o-chlorophenyl) -4,5-diphenyl imidazolyl dimer and 2- (o-methoxyphenyl) -4,5-diphenyl imida, for example Zolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenyl imidazolyl dimer, etc. are mentioned suitably.

In addition to the above, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6 -Trimethylphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophosphoro-trialkylphenylphosphonium salt, etc. are mentioned.

In the present invention, the photopolymerization initiator is not limited to the above, and other known photopolymerization initiators can also be used. Such photoinitiators include, for example, bisinalpolyketolaldonyl compounds described in US Pat. No. 2,367,660, α-carbonyl compounds described in US Pat. Nos. 2,367,661 and 2,367,670, and US Pat. No. 2,448,828. Acyloinether, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, tris described in US Pat. No. 3,549,367 Combination of allylimidazole dimer / p-aminophenylketone, benzothiazole compound / trihalomethyl-s-triazine compound described in Japanese Patent Publication No. 51-48516, JCS Perkin II (1979) 1653-1660 , JCS Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, Oxime esters described in Japanese Patent Application Laid-Open No. 2000-66385 There may be mentioned compounds and the like.

Moreover, these photoinitiators can also be used together.

As for content in the coloring photosensitive composition of a photoinitiator, 0.1-10.0 mass% is preferable with respect to the total solid of the said composition, More preferably, it is 0.5-5.0 mass%. When content of a photoinitiator is in the said range, a polymerization reaction advances favorably and film formation with favorable strength is attained.

Sensitizing Pigment

It is preferable to add a sensitizing dye to a coloring photosensitive composition as needed. By exposure of the wavelength which this sensitizing dye can absorb, the radical generation reaction of the said polymerization initiator component and the polymerization reaction of the polymeric compound by it are accelerated | stimulated. As such a sensitizing dye, a well-known spectrosensitizing dye or dye, or the dye or pigment which absorbs light and interacts with a photoinitiator is mentioned.

(Spectral sensitizing dye or dye)

Preferred sensitizing dyes or dyes as the sensitizing dyes used in the present invention are polynuclear aromatics (e.g., pyrene, perylene, triphenylene), xanthenes (e.g., fluorescein, eosin, erythrosine, rhoda). Min B, Rose Bengal), Cyanines (e.g., thiacarbocyanine, oxacarbocyanine), Merocyanines (e.g., merocyanine, carbomerocyanine), Thiazines (e.g. For example, thionine, methylene blue, toluidine blue), acridines (for example, acridine orange, chloroflavin, acriflavin), phthalocyanines (for example, phthalocyanine, metal phthalocyanine), porphyrins ( For example, tetraphenylporphyrin, central metal substituted porphyrin), chlorophylls (for example, chlorophyll, chlorophyllin, central metal substituted chlorophyll), metal complex, anthraquinones (for example, anthraquinone), squarylium (For example, squaaryl ), And the like.

Examples of more preferred spectral sensitizing dyes or dyes are illustrated below:

Styryl pigments described in Japanese Patent Application Laid-Open No. 37-13034; Cationic dyes described in Japanese Patent Application Laid-Open No. 62-143044; Quinoxalinium salts described in Japanese Patent Application Laid-Open No. 59-24147; Shin methylene blue compound of Unexamined-Japanese-Patent No. 64-33104; Anthraquinones described in Japanese Patent Application Laid-Open No. 64-56767; Benzoxanthene dyes described in Japanese Patent Application Laid-Open No. 2-1714; Acridines described in Japanese Patent Laid-Open No. 2-226148 and Japanese Patent Laid-Open No. 2-226149; Pyrilium salts of Unexamined-Japanese-Patent No. 40-28499; Cyanines described in Japanese Patent Application Laid-Open No. 46-42363; Benzofuran pigment of Unexamined-Japanese-Patent No. 2-63053; Conjugated ketone dyes of Japanese Patent Application Laid-Open No. 2-85858 and Japanese Patent Laid-Open No. 2-216154; Pigment | dye of Unexamined-Japanese-Patent No. 57-10605; Azocinnamylidene derivatives described in Japanese Patent Application Laid-Open No. 2-30321; Cyanine dyes described in Japanese Patent Application Laid-Open No. 1-287105; Xanthene dyes described in Japanese Patent Application Laid-Open No. 62-31844, Japanese Patent Application Laid-Open No. 62-31848, and Japanese Patent Application Laid-Open No. 62-143043; Aminostyryl ketones disclosed in Japanese Patent Application Laid-Open No. 59-28325; Pigment | dye based on Unexamined-Japanese-Patent No. 2-179643; Merocyanine pigments disclosed in Japanese Patent Application Laid-Open No. 2-244050; Merocyanine pigments disclosed in Japanese Patent Application Laid-Open No. 59-28326; Merocyanine pigments disclosed in Japanese Patent Application Laid-Open No. 59-89303; Merocyanine pigments described in Japanese Patent Application Laid-Open No. 8-129257; The benzopyran pigment | dye of Unexamined-Japanese-Patent No. 8-334897 is mentioned.

(Dye with maximum absorption wavelength in 350 ~ 450nm)

As another preferable form of a sensitizing dye, the pigment | dye which belongs to the following compound groups and has maximum absorption wavelength in 350-450 nm is mentioned.

For example, polynuclear aromatics (e.g. pyrene, perylene, triphenylene), xanthenes (e.g. fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (e.g. Thiacarbocyanine, oxacarbocyanine), merocyanines (e.g. merocyanine, carbomerocyanine), thiazines (e.g. thionine, methylene blue, toluidine blue), Acridines (for example, acridine orange, chloroflavin, acriflavin), anthraquinones (for example anthraquinone), squaryliums (for example, squarylium) are mentioned. .

<Solvent>

Generally, a pigment dispersion composition and a coloring photosensitive composition can be suitably prepared using a solvent with the said component.

Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, and methyl lactate Ethyl lactate, methyl oxyacetic acid, ethyl oxyacetate, oxyacetic acid butyl, methoxyacetic acid, methoxyacetic acid ethyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl, 3-oxypropionate, 3-oxy 3-oxypropionic acid alkyl esters, such as ethyl propionate; Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-methoxy Methyl oxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2-methylpropionic acid Ethyl, 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetic acid, ethyl acetoacetic acid, methyl 2-oxobutanoate, 2- Ethyl oxobutanoic acid and the like; Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; Aromatic hydrocarbons such as toluene, xylene and the like.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxy methyl propionate, 2-heptanone, and cyclohexanone , Ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are suitable.

You may use a solvent in combination of 2 or more type other than using independently.

<Other Ingredients>

In the present invention, the coloring photosensitive composition used in the production of the color filter of the port lithography method includes a chain transfer agent, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, a colorant, a photopolymerization initiator, other fillers, Various additives, such as a high molecular compound other than the said alkali-soluble resin, surfactant, an adhesion promoter, antioxidant, a ultraviolet absorber, an aggregation inhibitor, can be contained.

Chain transfer agent

As a chain transfer agent which can be added to a colored curable composition, N, N- dialkyl amino benzoic acid alkyl esters, such as N, N- dimethylamino benzoic acid ethyl ester, 2- mercapto benzothiazole, 2- mercapto benzo, for example And mercapto compounds having heterocycles such as oxazole and 2-mercaptobenzoimidazole, and aliphatic polyfunctional mercapto compounds.

A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.

Fluorinated Organic Compounds

By containing a fluorine-type organic compound, the liquid characteristic (particularly fluidity) at the time of using a coating liquid can be improved, and the uniformity and liquid saving property of coating thickness can be improved. That is, since the interfacial tension between the substrate and the coating liquid is decreased, the wettability to the substrate is improved, and the coating property to the substrate is improved, so that even when a thin film having a thickness of several micrometers is formed with a small amount of liquid, a uniform thickness with a small thickness unevenness is obtained. This is effective in that a film can be formed.

3-40 mass% is suitable for the fluorine content rate of a fluorine-type organic compound, More preferably, it is 5-30 mass%, Especially preferably, it is 7-25 mass%. If the fluorine content is in the above range, it is effective in terms of coating thickness uniformity and liquid saving property, and the solubility in the composition is also good.

As the fluorine-based surfactant, a compound having a fluoroalkyl group or a fluoroalkylene group in at least one of the terminal, the main chain and the side chain can be suitably used. As a specific commercial item, for example, MEGAFAC F142D, F172, F173, F176, F177, F183, 780, 781, R30, R08, F-472SF, BL20, R-61, Copper R-90 (manufactured by DIC Corporation), FLUORAD FC-135, Copper FC-170C, Copper FC-430, Copper FC-431, Novec FC-4430 (Suhitomo 3M Limited), ASAHI GUARD AG7105, 7000, 950, 7600 SURFLON S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104 , SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), EFTOP EF351, 352, 801, 802 (JEMCO Inc.), and the like.

The fluorine-based organic compound is particularly effective in preventing coating irregularities and thickness irregularities when the coating film is thinned. Moreover, it is effective also in the slit application | coating which is easy to produce liquid liquefaction.

As for the addition amount of a fluorine-type organic compound, 0.001-2.0 mass% is preferable with respect to the total mass of a coloring photosensitive composition, More preferably, it is 0.005-1.0 mass%.

Thermal polymerization initiator

It is also effective to contain a thermal polymerization initiator in a colored photosensitive composition. As a thermal polymerization initiator, various azo compounds and a peroxide compound are mentioned, for example. Examples of the azo compound include azobis compounds, and examples of the peroxide compound include ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy ester, peroxydicarbonate, and the like. Can be.

Thermal polymerization component

It is also effective to contain a thermal-polymerization component in a coloring photosensitive composition. If necessary, an epoxy compound can be added to increase the strength of the coating film. As an example of an epoxy compound, it is a compound which has 2 or more epoxy rings in a molecule | numerator, such as a bisphenol-A compound, a cresol noblock type compound, a biphenyl type compound, and an alicyclic epoxy compound. For example, as a bisphenol A compound, EPOTOHTO YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170, etc. ( Above, manufactured by Tohto Kasei Co., Ltd., DENACOL EX-1101, EX-1102, EX-1103, etc. (from Nagase ChemteX Corporation), PLACCEL GL-61, GL-62, G101, G102 (above, DICEL Chemical Industries, Ltd.), and these similar bisphenol F type compounds and bisphenol S type compounds are also mentioned. In addition, epoxy acrylates such as Ebecryl 3700, 3701, 600 (above, manufactured by DAICEL-CYTEC COMPANY Ltd.) can also be used. As a cresol noblock type compound, EPOTOHTO YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above Tohto Kasei Co., Ltd.), DENACOL EM-125, etc. (above, Nagase ChemteX Corporation product) And 3,5,3 ', 5'-tetramethyl-4,4'-diglycidyl biphenyl, and the like, and bicyclic epoxy compounds include CELLOXIDE 2021, 2081, 2083, 2085, EPOLEAD GT-301, GT-302, GT-401, GT-403, EHPE-3150 (above, manufactured by DICEL Chemical Industries, Ltd.), SANTOHTO ST-3000, ST-4000, ST-5080, ST -5100 etc. (above, Tohto Kasei Co., Ltd. product) etc. are mentioned. 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyl tris (hydroxyethyl) isocyanurate, o Phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and other amine type epoxy resins EPOTOHTO YH-434, YH-434L, and glycidyl ester modified with dimer acid in the skeleton of bisphenol A type epoxy resin can also be used. have.

-Surfactants-

It is preferable to contain various surfactant in a coloring photosensitive composition from a viewpoint of improving applicability | paintability, and various surfactant of a nonionic surfactant, a cationic surfactant, and an anionic surfactant can be used other than the fluorine-type surfactant mentioned above. Especially, the said fluorine type surfactant or nonionic surfactant is preferable.

Examples of nonionic surfactants include, for example, nonionic interfaces such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters. Active agents are particularly preferred. As a specific example, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether, polyoxyethylene polystyrylated ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene-propylene polystyryl ether and polyoxyethylene nonylphenyl ether; Polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate, polyoxyethylene distearate, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, ethylenediamine polyoxyethylene-polyoxypropylene condensates, etc. And nonionic surfactants, which are Kao Corporation, NOF Corporation, Takemoto Oil & Fat Co., Ltd., ADEKA Corporation, Sanyo Chemical Industries Ltd. What is marketed from etc. can be used suitably. In addition to the above, the above-described dispersant may be used.

In addition to the above, various additives may be added to the colored photosensitive composition. Specific examples of the additive include ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; Aggregation inhibitors such as sodium polyacrylate; Fillers such as glass and alumina; Itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, acid anhydride added to a polymer having hydroxyl group, alcohol soluble nylon, bisphenol A and epichloro Alkali-soluble resins such as phenoxy resins formed from hydrin.

In addition, when promoting the alkali solubility of an unhardened part and further improving developability of a coloring photosensitive composition, you may add organic carboxylic acid, Preferably low molecular weight organic carboxylic acid with a molecular weight of 1000 or less. Specific examples of the organic carboxylic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brasilic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid and camphoric acid; Aromatic mono carboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; Other carboxylic acids such as phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamildeacetic acid, coumalic acid and umbelic acid Can be mentioned.

Thermal polymerization inhibitor

It is preferable to add a thermal polymerization inhibitor to the colored photosensitive composition in addition to the above. Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6 -t-butyl phenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzoimidazole and the like are useful.

<Coloring Photosensitive Composition and Manufacturing Method of Color Filter Using the Same>

A coloring photosensitive composition contains alkali-soluble resin, a photopolymerizable compound, and a photoinitiator (preferably with a solvent) in the said pigment dispersion composition, mixes additives, such as surfactant, as needed, and mixes various mixers and dispersers It can be prepared by going through a mixing dispersion step of mixing and dispersing.

In addition, although the mixing and dispersing step is preferably made of kneading dispersion and subsequent non-dispersion treatment, it is also possible to omit the kneading dispersion.

An example of one of the manufacturing methods of a coloring photosensitive composition is shown below.

A mixture of pigments, water-soluble organic solvents, and water-soluble inorganic salts is kneaded, such as two rolls, three rolls, a ball mill, a trom mill, a disper, a kneader, a kneader, a homogenizer, a blender, a single screw, or a twin screw extruder. After use, the pigment is ground while applying a strong shearing force, and then the mixture is poured into water to form a slurry with a stirrer or the like. Next, the slurry is filtered and washed with water to remove the water-soluble organic solvent and the water-soluble inorganic salt, and then dried to obtain a fine pigment.

Bead dispersion is performed in a pigment, a dispersing agent, and / or a pigment derivative and a solvent. A pigment dispersion composition is obtained by mainly dispersing the beads of glass or zirconia having a particle size of 0.01 to 1 mm using a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, or the like. Moreover, it is also possible to abbreviate | omit the process which refine | miniaturizes a pigment.

Further details on kneading and dispersion are described in T. C. Patton, "Paint Flow and Pigment Dispersion" (published by John Wiley and Sons, 1964) and the like.

And the coloring photosensitive composition of this invention is obtained by adding a photopolymerizable compound, a photoinitiator, alkali-soluble resin, etc. to the pigment dispersion composition obtained as mentioned above.

The colored photosensitive composition is applied directly or through another layer by a coating method such as rotation coating, slit coating, cast coating, roll coating, bar coating, etc. to form a colored photosensitive coating film, and exposed through a predetermined mask pattern. After the exposure, the uncured portion is developed and removed by a developer to form a patterned film made of pixels of each color (three or four colors) to form a color filter.

At this time, as radiation to be used, ultraviolet rays such as g-rays, h-rays, i-rays, and j-rays are particularly preferable. As for the color filter for organic electroluminescent display apparatuses, exposure using mainly the h line | wire and i line | wire is preferable as a proximity exposure machine and a mirror projection exposure machine.

The color filter of the photolithographic method in this invention is formed on board | substrates, such as glass, using the said coloring photosensitive composition, and a coloring photosensitive composition is applied to a board | substrate directly or through another layer, for example by slit application | coating. After forming a coating film, this coating film can be suitably produced by drying, pattern exposure, and performing the image development process using a developing solution sequentially. As a result, the color filter used in the display device of the present invention can be produced with high quality and low cost due to less difficulty in process.

Examples of the substrate include alkali-free glass, soda glass, pyrex (registered trademark) glass, quartz glass, and a transparent conductive film attached thereto, and a plastic substrate. The black matrix which isolate | separates each pixel is normally formed on these board | substrates, or the transparent resin layer is formed in order to promote close contact.

It is preferable that the plastic substrate has a gas barrier layer and / or a solvent-resistant layer on its surface.

In the present invention, a colored layer can also be formed by a photolithography method on a driving substrate on which a thin film transistor (TFT) is arranged.

Although it does not specifically limit as a method of apply | coating a coloring photosensitive composition to a board | substrate, The method of using slit nozzles, such as a slit and spin method and a spinless coating method (henceforth a slit nozzle coating method), is preferable. In the slit nozzle coating method, the slit and spin coating method and the spinless coating method have different conditions depending on the size of the coating substrate, for example, the fifth generation glass substrate (1100 mm x 1250 mm) by the spinless coating method. In the case of coating, the discharge amount of the colored photosensitive composition from the slit nozzle is usually 500 to 2000 microliter / sec, preferably 800 to 1500 microliter / sec, and the coating speed is usually 50 to 300 mm / sec, preferably 100 to 200 mm / Seconds. Solid content of a coloring photosensitive composition is 10 to 20% normally, Preferably it is 13 to 18%. When forming the coating film by the coloring photosensitive composition of this invention on a board | substrate, the thickness (after prebaking process) of the said coating film is generally 0.3 micrometer-5.0 micrometers, Preferably it is 0.5 micrometer-5.0 micrometers, Most preferably, 0.8 micrometer-4.5 micrometers.

Usually, a prebaking process is performed after application | coating. If necessary, vacuum treatment may be performed before prebaking. The conditions of vacuum drying are the degree of vacuum normally 0.1-1.0 torr, Preferably it is about 0.2-0.5 torr.

Prebaking process is 50-140 degreeC using a hotplate or oven, Preferably it is about 70-110 degreeC, and can be performed on 10-300 second conditions. You may use a high frequency process etc. together. High frequency treatment can be used alone.

In the developing treatment, the uncured portion after exposure is eluted in the developing solution so that only the hardened portion remains. Developing temperature is 20-30 degreeC normally, and developing time is 20 to 90 second.

As a developing solution, as long as it melt | dissolves the coating film of the coloring photosensitive coloring photosensitive composition in an uncured part, and does not melt a hardened part, either can be used. Specifically, combinations of various organic solvents and alkaline aqueous solutions can be used.

As said organic solvent, the above-mentioned solvent which can be used when preparing a pigment dispersion composition or a coloring photosensitive composition is mentioned.

As said alkaline aqueous solution, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl The concentration of the alkaline compound such as ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene is 0.001-10% by mass, preferably 0.01 The alkaline aqueous solution melt | dissolved so that it may become -1 mass% is mentioned. A suitable amount of water-soluble organic solvents, such as methanol and ethanol, surfactant, etc. can also be added to alkaline aqueous solution.

The developing method may be any of a dipping method, a shower method, a spray method, and the like, and a swing method, a spin method, an ultrasonic method, or the like may be combined therewith. Before the contact with the developer, the surface to be developed may be wetted with water or the like to prevent development unevenness. It is also possible to develop the substrate by tilting it.

After the development treatment, drying is carried out through a rinse step of washing and removing excess developer, and then heat treatment (post-baking) is performed to complete curing.

Although the rinse step is usually performed with pure water, pure water is used in the final cleaning for liquid saving, and the clean start may be performed using pure water that has been used, washed by tilting the substrate, or combined with ultrasonic irradiation.

After rinsing, liquid saving and drying are performed, and then heat treatment is usually performed at about 200 ° C to 250 ° C. This heat treatment (post-baking) can be carried out continuously or batchwise by using heating means such as a hot plate, a convection oven (hot air circulation dryer), a high frequency heater, or the like so that the coated film after development becomes the above conditions.

By repeatedly performing the above operation for each color in accordance with the desired number of colors, a color filter in which a cured film in which a plurality of colors are colored is formed can be produced.

Conventionally, three colors of R, G, and B have been common, but in the present invention, the number of colors can be 2 or 1, and the series of operations can be reduced or eliminated. Can also contribute.

The display device of the present invention represented by the organic EL display device exhibits an excellent effect of achieving high color reproducibility and high brightness by providing an organic EL light emitting element and a color filter formed by the above method.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the acclaim is exceeded. In addition, "part" is a mass reference | standard unless there is particular notice.

(Comparative Example 1)

An organic EL display device A (display device of Comparative Example 1) is produced by using a color filter made of a pigment widely used in a conventional liquid crystal display device.

Production of Pigment Dispersion

Preparation of dispersion of pigment green 36

Benzyl methacrylate / methacrylic acid copolymer 75 parts

(Copolymerization Composition Ratio 70/30, Weight Average Molecular Weight 30000, Acid Value 40)

Pigment Green 36 125

450 parts of propylene glycol monomethyl ether acetate

Was dispersed in a sand mill for 10 hours.

Adjustment of dispersion of pigment yellow 150

The dispersion of Pigment Yellow 150 was prepared by dispersing the following composition in a sand mill for 15 hours.

Pigment Yellow 150 125

10 parts polyvinylpyrrolidone

(Manufactured by Wako Pure Chemical Industries, Ltd., K30, molecular weight 40,000)

Benzyl methacrylate / methacrylic acid copolymer 65 parts

(Copolymerization Composition Ratio 70/30, Weight Average Molecular Weight 30000, Acid Value 40)

450 parts of 1-methoxy-2-propyl acetate

Preparation of Pigment Dispersion for Red Filter and Blue Filter

In the preparation of the dispersion liquid of Pigment Green 36, Pigment Green 36, Pigment Red 254 / Pigment Red 177 mixed pigment 6/4 (mass ratio), or Pigment Blue 15: 6 / Pigment Violet 23 It changed into the pigment mixed at 9: 1 (mass ratio), respectively, and else the pigment dispersion liquid for red filters and blue filters was prepared like preparation of the dispersion liquid of pigment green 36.

<Preparation of a colored photosensitive composition>

Green photosensitive composition

The green photosensitive composition was prepared by the following compositions.

Pigment dispersion liquid for green filters: 100 parts

As a green pigment dispersion, 100 parts of the pigment dispersion liquid for green filters which mixed the pigment dispersion liquid of Pigment Green 36 and the pigment dispersion liquid of Pigment Yellow 150 in the ratio of 90 to 10 were used.

Alkali Soluble Resin:

50 parts by mass solution of methacrylic acid / methacrylic acid benzyl copolymer ((= 30/70 [molar ratio]), weight average molecular weight: 30,000, solvent: 1-methoxy-2-propyl acetate) 15 parts

Polymerizable compound:

DPHA (manufactured by Nippon Kayaku Co., Ltd.) dipentaerythritol hexaacrylate 6 parts

Photoinitiator:

2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer 2 parts

Sensitizing dye: 1 part of 4,4'-bis (diethylamino) benzophenone

Hydrogen donating compound: 0.5 part of 2-mercaptobenzothiazole

Polymerization inhibitor: 0.001 part of p-methoxyphenol

0.02 parts of fluorine-based surfactant (trade name: manufactured by MEGAFAC R08 DIC Corporation)

Solvent: 128 parts of 1-methoxy-2-propyl acetate

Red and blue photosensitive compositions

Red and blue were completely identical to the preparation of the green photosensitive composition except that 100 parts of the pigment dispersion for the green filter in the preparation of the green photosensitive composition were each changed to 85 parts of the pigment dispersion for the red filter or 45 parts of the pigment dispersion for the blue filter. The photosensitive composition was prepared.

<Production of organic EL display device>

Similarly to the first embodiment of the organic EL device, the color filter 22 was fabricated by R, G and B patterned on the drive panel side of the sealing substrate 21.

The exposure and image development for patterning three types of compositions were performed in three steps.

The said coloring photosensitive composition was used for preparation of a color filter, and the film thickness of each color was 3.1 micrometers for R, G, and B.

Organic EL light emitting elements 10R, 10G, and 10B having the same structure as in the first embodiment were produced, respectively. In that case, the 1st electrode 12 was comprised with the aluminum alloy containing 98 mass% of aluminum, and thickness was 200 nm. The hole injection thin film layer 13A was made of chromium oxide (II) and had a thickness of 4 nm. The organic layer 13 is comprised with the material illustrated by the said embodiment, The total thickness is 125 nm in the organic EL light emitting element 10R, 110 nm in the organic EL light emitting element 10G, and 93 nm in the organic EL light emitting element 10B. (Microcavity was formed). The 2nd electrode 14 was comprised with the same material as the 1st electrode 12, and thickness was 17 nm. The organic EL display device A was produced as mentioned above.

6 is a graph showing the spectral spectrum of the light source of the organic EL light emitting elements 10R, 10G, and 10B. The vertical axis represents light emission intensity (relative value), the horizontal axis represents wavelength, and the solid line graph (series 3) shows the light source spectrum of the green organic EL light emitting device, and the broken line graph (series 2) shows the light source of the red organic EL light emitting device. The graph of the dashed dotted line (series 1) shows the light source spectrum of a blue organic EL light emitting element, respectively.

This comparative example 1 and the display apparatus of each Example and comparative example shown below are equipped with the organic electroluminescent element which has this spectral spectrum.

(Example 1)

<Production of Pigment Dispersion>

150 parts of compound (II-7) represented by formula (II)

10 parts polyvinylpyrrolidone

(Manufactured by Wako Pure Chemical Industries, Ltd., K30, molecular weight 40,000)

Benzyl methacrylate / methacrylic acid copolymer 65 parts

(Copolymerization Composition Ratio 70/30, Weight Average Molecular Weight 30000, Acid Value 40)

450 parts of 1-methoxy-2-propyl acetate

Each said component was mixed at 80 degreeC and 10 atmospheres, and the pigment dispersion B was produced.

<Preparation of a colored photosensitive composition and preparation of an organic electroluminescent apparatus>

In the preparation of the green photosensitive resin composition in the preparation of the organic EL display device A, Pigment Green 36 and Pigment Yellow 150 are all changed to compound (II-7) represented by the general formula (II) so as to be changed to the same weight. A photosensitive composition B was produced in the same manner as in the green photosensitive composition in preparation of the organic EL device A, except that the dye dispersion B was introduced.

An organic EL display device B (display device of Example 1) was produced in the same manner as the organic EL display device A except that the photosensitive composition B was changed to a blue and green photosensitive composition in the preparation of the organic EL display device A. At this time, B (blue) and G (green) filters have a common composition. Therefore, the three-color filter of R, G, and B became a two-color filter of R filter and BG common filter, and patterning was made into two steps.

(Example 2)

<Production of Pigment Dispersion>

In the preparation of the dye dispersion B, the dye dispersion C was produced in the same manner as in Example 1 except that the compound (II-7) represented by the general formula (II) was used and the above-described example compound (IV-1) was used in an equal weight.

<Preparation of a colored photosensitive composition and preparation of an organic electroluminescent apparatus>

Pigment dispersion liquid so that both Pigment Green 36 and Pigment Yellow 150 may be changed to compound (IV-1) in an amount of 1/2 of the weight in the preparation of the green photosensitive resin composition in the preparation of the organic EL display device A Except having introduced C, it carried out similarly to the green photosensitive composition in preparation of organic electroluminescent apparatus A, and produced the photosensitive composition C.

An organic EL display device C (display device of Example 2) was fabricated in the same manner as the organic EL display device A except that the photosensitive composition C was changed to the red and green photosensitive compositions in the preparation of the organic EL display device A. did.

At this time, since the filters of R and G have a common composition, the three-color filters of R, G, and B became two-color filters of the B filter and the RG common filter, so that the patterning could be performed in two stages.

(Example 3)

In the preparation of the dye dispersion B, the pigments were prepared in the same manner except that the amount of one third of the compound (II-7) represented by the general formula (II) was changed to the same compound (IV-1) by the same weight. Dispersion D was produced.

<Preparation of a colored photosensitive composition and preparation of an organic electroluminescent apparatus>

In the preparation of the photosensitive resin composition B in the preparation of the organic EL display device B, the photosensitive composition D was produced in the same manner as in the photosensitive composition B, except that the dye dispersion D was introduced so that the dye content was the same. .

In addition, the organic EL display device D (Example 3) was prepared in the same manner as the organic EL display device A except that the photosensitive resin composition D was used for the entire surface, instead of being replaced with the patterned R, G, and B filters in the production of the organic EL display device A. Display device).

At this time, the filters stacked on each of the light emitting elements of R, G, and B are common and have one type, so patterning could be performed in only one step for making the filter into the required shape.

(Comparative Example 2)

<Production of Organic EL Device>

In fabricating the organic EL display device A, the thickness of the organic layer 13 is the same as that of the organic EL light emitting devices 10R, 10G, and 10B, except that the thickness of the organic layer 13 is 135 nm (no microcavity is formed). Organic EL display device E was manufactured in exactly the same way.

(Example 4)

<Production of Organic EL Device>

In the fabrication of the organic EL device D, the thickness of the organic layer 13 is the same as that of the organic EL display device D except that the organic EL light emitting elements 10R, 10G, and 10B have the same thickness of 135 nm (without forming a microcavity). In the same manner, an organic EL display device F was manufactured.

(Example 5)

<Production of front display type filter>

Formation of Undercoat Layer

After both sides of the 100-micrometer-thick transparent polyethylene terephthalate film were corona-discharge-treated, the undercoat layer was formed by apply | coating the latex which consists of styrene butadiene copolymer on one side so as to be 130 nm thick.

Formation of a second undercoat layer

On the undercoat layer, a gelatin aqueous solution containing acetic acid and glutaraldehyde was applied to have a thickness of 50 nm to form a second undercoat layer.

Formation of Low Refractive Index Layer

To 2.50 g of a reactive fluoropolymer (JN-7219, manufactured by JSR Corporation), 1.3 g of t-butanol was added, stirred at room temperature for 10 minutes, and filtered through a polypropylene filter having a pore diameter of 1 μm. The obtained coating liquid for low refractive index layer was applied to a surface on the side opposite to the undercoat surface of the transparent support using a bar coater so as to have a dry film thickness of 110 nm, and dried at 120 ° C. for 30 minutes to cure to form a low refractive index layer. .

Formation of Filter Layer

0.4g of compound (II-7) represented by general formula (II) and 0.2g of said exemplary compound (IV-1) were melt | dissolved in 180g of 10 weight% aqueous solution of gelatin, and it stirred at 40 degreeC for 30 minutes. The solution was filtered through a polypropylene filter having a pore diameter of 2 µm to prepare a filter layer coating liquid.

The coating liquid for filter layers was apply | coated so that a dry film thickness might be set to 3.3 micrometers on the 2nd undercoat layer, it dried at 120 degreeC for 10 minutes, the filter layer was formed, and the specific color filter was produced.

<Production of Organic EL Device>

In manufacture of the organic electroluminescent apparatus A, the thing which did not produce the color filter 22 in 1st Embodiment of the said organic electroluminescent apparatus was produced.

The display device front-mounted filter (surface on the side where the low refractive index layer was not formed) prepared as described above was bonded with an adhesive to be referred to as organic EL device G.

(Example 6)

Except having changed into the exemplary compound (II-7) used in preparation of organic electroluminescent apparatus G, and using compound (I-7) represented by General formula (I) by equal weight, it carried out similarly to organic electroluminescent apparatus G, The organic EL device H was produced.

Table 1 shows each component used for the adjustment of the display device produced in the above embodiment. As a spectroscopic absorption characteristic of the filter layer, the values measured by a spectrophotometer (Hitachi Ltd., Spectrophotometer U-3500) before assembling into the display device are shown in Table 1 as well.

<Evaluation of organic EL display device>

Color gamut, transmittance

The chromaticity and luminance of each organic EL display device are provided with a chromatic luminance meter (TOPCON TECHNOHOUSE CORPORATION, BM-5) in the normal direction with respect to the display device to determine chromaticity (x value, y value) and luminance (cd / m ² ). Measured.

(Color reproduction station)

The CIE chromaticity value at the time of displaying each color of R, G, and B was measured, and the reproduction range in the figure of CIE chromaticity was shown by NTSC ratio.

NTSC is an abbreviation of National Television System Committee, and NTSC is one of the standards of color television broadcasting. NTSC ratio shows the color reproduction range on the xy chromaticity diagram of a CIE standard as an area ratio with respect to NTSC standard.

Transmittance

For each of R, G, and B, the ratio (%) of the luminance after color filter installation to the measured luminance without color filter was taken as the transmittance, and the average value of three colors was taken as a reference for the transmittance of the display device.

These results are shown in Table 2.

Observation direction dependence

The difference in color taste seen at an angle of 45 degrees with respect to the normal direction and the normal direction when gray was displayed was evaluated by ten panelists, five stages of evaluation were performed, and the average point was shown in Table 2.

(Evaluation standard)

5: No difference at all.

4: A little difference can be recognized.

3: Recognize the difference.

2: The difference is big.

1: A completely different color.

From the results of the display devices A and B shown in Table 2, the spectral characteristics of the color filter produced by using the dye used in the conventional liquid crystal display device were low in transmittance, and the observation direction dependence was very deteriorated. On the other hand, the display devices B, C, and D of the embodiment using the color filter having the spectral characteristics of the present invention have a small number of patterning, and thus have a high transmittance without deteriorating the color gamut even with a simple configuration obtained by a simplified process. It turns out that it is realizable and it improves also about observation direction dependence. Among them, the display device D of Example 3, which combines the two types of properties specified in the present invention by using two kinds of dyes in combination, has particularly high performance, and the observation direction dependence is largely no problem, and the number of patterning is reduced. It can be seen that the process can be more simplified.

The results of Example 4 show that even in the case of a light source that does not use a microcavity as in the display device F, high transmittance and color reproducibility can be obtained according to the present invention.

Further, from the results of the fifth embodiment, it can be seen that the excellent effect of the present invention can be similarly exhibited even when arranged in the form of a front-mounted filter without the built-in color filter like the display device G.

(Example 7)

On the display device manufactured in the second embodiment of the organic EL device, that is, on the driving substrate 11, the second electrode 14, the organic layer 13, and the first electrode 12 are placed on the driving substrate 11 side. When the color filter used in the display device D of Example 3 was assembled into the display device configured to be laminated in order from the driving substrate 11 and to take out light from the driving substrate 11 side, the same effect as in Example 3 was achieved. I could confirm it. From this, it can be seen that the specific color filter according to the present invention exhibits the excellent effect of the present invention also in the display device having the second embodiment as in the first embodiment.

1 is a cross-sectional structure of a display device using an organic EL light emitting element according to the first embodiment of the present invention.

2 is an enlarged view of the configuration of the organic layer 13 in the organic EL light emitting elements 10R and 10B.

3 is an enlarged view of the configuration of the organic layer 13 in the organic EL light emitting element 10G.

Fig. 4A shows a schematic cross-sectional view of a drive panel in a step of a method of manufacturing a conventional organic EL display device, and Fig. 4B shows a schematic cross-sectional view of a sealing panel.

Fig. 5A is a schematic sectional view of a state in which an adhesive layer is applied to a drive panel in a step of a method of manufacturing an organic EL display device, and Fig. 5B is a view showing bonding of the drive panel and the sealing panel shown in Fig. 5A. It is a schematic sectional drawing which shows one form.

6 is a graph showing spectral spectra of light sources of the organic EL light emitting elements 10R, 10G, and 10B used in the examples.

Claims (11)

A display device comprising three colors of pixels and a color filter each consisting of light emitting elements emitting light of R, G, and B: The said color filter has the maximum value of the optical density in the range of wavelength 475nm-525 nm, The ratio of the optical density in wavelength 450nm with respect to the maximum value of the said optical density is 15% or less, and the wavelength 550 nm with respect to the maximum value of the said optical density. The ratio of the optical density in the display device is 10% or less. A display device comprising three colors of pixels and a color filter each consisting of light emitting elements emitting light of R, G, and B: The color filter has a maximum value of the optical density in the range of 550 nm to 620 nm, and the ratio of the optical density at the wavelength 500 nm and the wavelength 630 nm to the maximum value of the optical density is all 12% or less. The method of claim 1, The color filter has a maximum value of optical density even in a wavelength range of 550 to 620 nm, and the ratio of the optical density at a wavelength of 500 nm and a wavelength of 630 nm to the maximum value of the optical density is all 12% or less. The method of claim 1, The color filter is a display device, characterized in that the front-mounted filter disposed on the front of the display device. The method of claim 1, A light emitting device which emits light of R, G, and B constituting the three colors of pixels is an organic electroluminescence device. The method of claim 5, A display device having a microcavity structure. 7. The method according to any one of claims 1 to 6, And said color filter contains at least one selected from the compounds represented by the following general formulas (I), (II) and (III).

[In General Formula (I), Z <^1> and Z <^2> respectively independently represent the group of the nonmetallic atom which forms the 5-membered or 6-membered nitrogen-containing heterocycle, and the said nitrogen-containing heterocycle contains another heterocyclic ring, an aromatic ring, or Aliphatic rings may be condensed to form condensed rings; R ¹ and R ² each independently represent an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent; L ¹ represents a methine chain composed of an odd number of methines which may have a substituent; a, b and c are each independently 0 or 1; X represents an anion when the cyanine dye moiety is cationic, and a cation when the cyanine dye moiety has an anionic substituent and is anionic.]

[In the general formula (II), Y ¹ and Y ² each independently represent a group of nonmetal atoms forming an aliphatic ring or a heterocycle; L ² represents a methine chain composed of an odd number of methines which may have a substituent; X ² represents a hydrogen atom or a cation.]

[In the general formula (III), Y ³ represents a nonmetallic atom group that forms an aliphatic ring or a heterocycle; L ³ represents a methine chain consisting of one or three methines; Ar represents an aromatic ring.] The method of claim 7, wherein In said general formula (I), the said nitrogen-containing heterocyclic ring or its condensed ring is an oxazole ring, an isoxazole ring, a benzoxazole ring, a naphthooxazole ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, an indolenin ring, and a benzo Indolenin ring, imidazole ring, benzoimidazole ring, naphthoimidazole ring, quinoline ring, pyridine ring, pyrrolopyridine ring, furopyrrole ring, indolidine ring, imidazoquinoxaline ring or quinoxaline ring; The carbon number of the alkyl group represented by R ¹ or R ² is 1 to 20, the carbon number of the alkenyl group represented by R ¹ or R ² is 2 to 10, and the carbon number of the aralkyl group represented by R ¹ or R ² is 7 to Twelve and the aryl group represented by R ¹ or R ² is a phenyl group or a naphthyl group; The number of methine in the methine chain is 1, 3, 5 or 7, characterized in that the display device. The method of claim 7, wherein In the general formula (I), a and b are zero. The method of claim 7, wherein In the general formula (I), the anion represented by X is a halide ion, p-toluene sulfonic acid ion, ethyl sulfate ion, PF ₆ ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ or a complex ion represented by the following general formula (1): Display device characterized in that.

[In the formula (1), R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group, an aryl group or a cyano group, or R ⁹ and R ¹⁰ are each R ¹¹ and R ^12. Represents an aromatic ring formed by bonding; Y ³ and Y ⁴ each independently represent O, S or NH, and a plurality of Y ^{3 's} may be the same or different, and a plurality of Y ^{4' s} may be the same or different; M represents a metal atom.] The method of claim 7, wherein In the general formula (1), X is a compound represented by the following general formula (2).

[In Formula (2), R <^13> and R <^14> is respectively independently an alkyl group, an alkenyl group, an aralkyl group, an aryl group, or a heterocyclic group; R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, an alkoxycarbonyl group, a halogenated carbon group, an alkylthio group, an arylthio group, a cyano group, a nitro group, an amino group, an alkylamino group, An amide group, acyloxy group, hydroxyl group, sulfo group or carboxyl group; n1 and n2 are each independently 1, 2, 3 or 4; b is 0.25 to 3.0.]

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