KR101858753B1 - Process for forming pixel pattern, color filter and display device - Google Patents

Abstract

Disclosure of the Invention The object of the present invention is to provide a method of forming a pixel pattern for sufficiently expressing excellent color characteristics of a dye or a lake pigment when a dye or a lake pigment is used as a coloring agent.
(1) A process for forming a coating film of a coloring and radiation-sensitive composition containing at least one kind selected from the group consisting of a dye and a rake pigment on a substrate, and (2) Characterized in that the spectral distribution of the radiation has a plurality of peaks in the range of 350 nm to 450 nm and the maximum intensity of the radiation at less than 350 nm is the maximum peak at 350 nm to 450 nm And the strength is 50% or less of the strength.

Description

TECHNICAL FIELD [0001] The present invention relates to a color filter and a display device,

The present invention relates to a method for forming a pixel pattern, a color filter manufactured by the method, and a display element including the color filter.

The color filter transmits light in a specific wavelength range in visible light, and produces colored transmitted light. A liquid crystal display element using a liquid crystal can not be developed by itself, but it can function as a color liquid crystal display element by using a color filter. The color filter is also used for an organic EL (Electro Luminescence) element using a white light emitting layer, and for color display of an electronic paper or the like. In addition, when a color filter is used, color imaging of solid-state image pickup devices such as CCD image sensors and CMOS image sensors becomes possible.

The following are known as a method of manufacturing a color filter. For example, a coloring and radiation-sensitive composition is applied as a coloring composition sensitive to a suitable irradiation line on a transparent substrate or on a transparent substrate on which a light-shielding layer of a desired pattern is formed. Subsequently, the coated film is dried, and the dried film is irradiated with a radiation (hereinafter referred to as "exposure") through a mask and subjected to development processing. Thus, a method of obtaining pixels of each color (see, for example, Patent Documents 1 and 2). A method of obtaining pixels of each color by an ink-jet method using a colored curable resin composition is also known (see, for example, Patent Document 3).

However, it is known that it is effective to use a dye or a lake pigment as a coloring agent (for example, see Patent Documents 4 and 5) in order to realize high luminance and high color purity of a display element or high definition of a solid state image pickup element.

Japanese Patent Application Laid-Open No. 2-144502 Japanese Patent Laid-Open Publication No. 3-53201 Japanese Patent Application Laid-Open No. 2000-310706 Japanese Patent Application Laid-Open No. 2008-304766 Japanese Patent Application Laid-Open No. 2001-081348

However, the coloring and radiation-sensitive composition containing a dye or a lake pigment has a remarkably poor process stability in chromaticity characteristics as compared with a coloring and radiation-sensitive composition containing only a pigment. For this reason, even when a dye or a lake pigment is used as a coloring agent, there is a problem that it is difficult to obtain a color filter having superior chromaticity characteristics to pigments.

The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a method of forming a pixel pattern for sufficiently exhibiting excellent chromaticity characteristics of a dye or a rake pigment when a dye or a rake pigment is used as a coloring agent, a color filter formed by the method, And which is excellent in chromaticity characteristics.

As a result of intensive studies, the present inventors have found that the above problems can be solved by using a specific ultraviolet ray as exposure radiation when forming a pixel pattern.

That is, the present invention provides a process for producing a coloring and radiation-sensitive composition comprising the steps of (1) forming a coating film of a coloring and radiation-sensitive composition containing at least one kind selected from the group consisting of a dye and a rake pigment on a substrate, and (2) Wherein the spectral distribution of the radiation has a plurality of peaks in the range of 350 nm to 450 nm and wherein the maximum intensity of the radiation at less than 350 nm is greater than the maximum peak intensity at 350 nm to 450 nm Is 50% or less of that of the pixel pattern. Hereinafter, the term "radiation having a spectral distribution in a range of 350 nm to 450 nm with a plurality of peaks and having a maximum intensity at a wavelength of less than 350 nm of not more than 50% of a maximum peak intensity at a wavelength of 350 nm to 450 nm" "Is also called.

The present invention also provides a color filter comprising a pixel pattern formed by the above method, and a display element comprising the color filter.

According to the present invention, when a dye or a rake pigment is used as a coloring agent, a color filter in which excellent coloring characteristics of a dye and a rake pigment are sufficiently exhibited can be produced.

1 is a view showing a representative spectral distribution of radiation radiated from an ultra-high pressure mercury lamp.
2 is a view showing the spectral distribution of the radiation obtained by interposing the ultraviolet cut filter 1 on the radiation radiated from the ultra-high pressure mercury lamp.
3 is a diagram showing the spectral distribution of radiation obtained by interposing the ultraviolet cut filter 2 on the radiation radiated from the ultra-high pressure mercury lamp.
4 is a diagram showing the spectral distribution of radiation obtained by interposing the ultraviolet cut filter 3 on the radiation radiated from the ultra-high pressure mercury lamp.

Hereinafter, the present embodiment will be described in detail.

≪ Pixel pattern formation method and color filter >

A method of forming a pixel pattern according to the present invention includes at least the following steps (1) and (2).

(1) a step of forming, on a substrate, a coating film of a coloring and radiation-sensitive composition containing at least one kind selected from the group consisting of a dye and a rake pigment (hereinafter also referred to as a &

(2) a step of exposing a specific radiation to at least a part of the coating film (hereinafter also referred to as "exposure step &

Hereinafter, each step of (1) and (2) will be described in detail with specific examples.

(1) Coating film formation process

First, a substrate is prepared. As the substrate, for example, a transparent glass substrate such as borosilicate glass, aluminoborosilicate glass, alkali-free glass, quartz glass, synthetic quartz glass, soda lime glass, white sapphire or the like can be used. In addition, it is also possible to use a polymer such as acrylic, polyamide, polyacetal, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, syndiotactic polystyrene, polyphenylene sulfide, polyether ketone, Polyether ether ketone, fluorine resin, polyether nitrile, polycarbonate, modified polyphenylene ether, polycyclohexene, polynorbornene resin, polysulfone, polyethersulfone, polyarylate, polyamideimide, A transparent resin film such as a polyimide or a thermoplastic polyimide may be used. Particularly, alkali-free glass is preferably used because it is a material having a small coefficient of thermal expansion and is excellent in dimensional stability and characteristics in a high-temperature heat treatment.

These substrates may be subjected to appropriate pretreatment such as film formation of a silicon dioxide film by an ion plating method, a sputtering method, a gas phase reaction method, or a vacuum deposition method in addition to a chemical treatment or a plasma treatment with a silane coupling agent as necessary.

Next, a light-shielding layer (black matrix) is formed on the substrate so as to partition a portion for forming a pixel. For example, a metal thin film such as chromium film formed by sputtering or vapor deposition is processed into a desired pattern by photolithography. Alternatively, a radiation-sensitive composition containing a black colorant may be applied on a substrate, and a desired pattern may be formed by photolithography. The thickness of the light-shielding layer including the metal thin film is preferably set to 0.1 to 0.2 mu m. On the other hand, it is preferable that the thickness of the light-shielding film formed using the black radiation sensitive composition is about 1 탆.

Further, the light shielding layer may be unnecessary, and in this case, the step of forming the light shielding layer may be omitted.

Next, a negative-type blue radiation-sensitive composition containing, for example, a blue dye or a lake pigment is applied on the above-mentioned substrate. Subsequently, prebaking is performed to evaporate the solvent to form a coating film.

When the coloring and radiation-sensitive composition is applied to a substrate, a spraying method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, or a bar coating method can be appropriately selected. It is preferable to employ a spin coating method or a slit die coating method in order to obtain a coating film having a uniform film thickness.

Prebaking is usually carried out in combination with reduced pressure drying and heat drying. The reduced-pressure drying is usually carried out until the pressure reaches 50 Pa to 200 Pa. The conditions of heat drying are usually about 1 minute to about 10 minutes at a temperature of from 70 캜 to 110 캜 using a hot plate. The thickness of the coated film to be applied is usually 0.6 to 8 占 퐉, preferably 1.2 to 5 占 퐉, as a film thickness after drying.

As another example of forming a coating film of a color sensitive radiation-sensitive composition on a substrate, there is also a method by an ink jet method disclosed in Japanese Patent Application Laid-Open Nos. 7-318723 and 2000-310706 . In this method, first, a partition wall having a light shielding function is formed on the surface of the substrate. Then, the coloring and radiation-sensitive composition containing, for example, a blue dye or a lake pigment is discharged into the partition wall by an ink jet apparatus. Thereafter, prebaking is performed to evaporate the solvent. The method and conditions of prebaking are the same as those in the first example described above.

In addition, the above-mentioned partition walls function not only to shield the light-shielding function but also to prevent the coloring and radiation-sensitive compositions of the respective colors ejected into the compartment from being mixed. Therefore, the film thickness is thicker than the light-shielding layer (black matrix) used in the first example. The barrier ribs are usually formed using a black radiation sensitive composition.

Further, as a further example of forming a coated film of the colored and radiation-sensitive composition on a substrate, dry film methods disclosed in JP-A-9-5991 can be used. In this method, a coloring and radiation-sensitive composition containing, for example, a blue dye or a rake pigment is applied on a film-like support, and the organic solvent is evaporated by carrying out prebaking, whereby a coloring and radiation- To form a layered dry film. Then, the support on which the coloring and radiation-sensitive composition layer is formed is laminated to a substrate for forming a color filter using a laminator. Thereafter, the layer of the colored and radiation-sensitive composition is transferred to the substrate by peeling the layer from the support. The method of applying the coloring and radiation-sensitive composition onto the support, and the method and conditions of prebaking are the same as those of the first example described above.

(2) Exposure process

After the coating film forming process, at least a part of the formed coating film is exposed through a photomask having a predetermined pattern. The present invention is characterized in that the exposure radiation used at this time exhibits specific spectral characteristics. Generally, the radiation irradiated from the ultra-high pressure mercury lamp used when manufacturing the color filter for color liquid crystal display shows the spectroscopic characteristics as shown in Fig. 1, a peak at 436 nm is a g line, a peak at 405 nm is an h line, and a peak at 365 nm is an i line. Radiation emitted from an ultrahigh pressure mercury lamp usually has several peaks at a wavelength of less than 350 nm It contains deep ultraviolet rays. The present inventors have found that the stability of dyes and lake pigments is increased by decreasing the light intensity of less than 350 nm with respect to the exposure radiation exhibiting such spectroscopic characteristics, thereby leading to the present invention.

For a specific radiation, the maximum intensity at less than 350 nm is 50% or less of the maximum peak intensity at 350 nm to 450 nm, but it is preferably 45% or less, more preferably 30% or less, in order to enhance the desired effect.

The specific radiation can be obtained by using a lamp which exhibits the spectroscopic characteristics as described above as the light source, but it can also be obtained by interposing an ultraviolet cut filter in the radiation radiated from the ultrahigh pressure mercury lamp. The ultraviolet shielding filter is not particularly limited as long as it can reduce the light intensity of less than 350 nm to the above-mentioned conditions. For example, the ultraviolet shielding filter UV-35, UV-33 and UV-31 (manufactured by Toshiba Glass) .

The exposure dose of the specific radiation is usually 10 to 10,000 J / m 2, but it is preferably 50 to 5,000 J / m 2, more preferably 100 to 2,000 J / m 2 to enhance the desired effect.

(3) a step of developing the coated film after exposure (hereinafter, also referred to as "developing step") and / or (4) a step of post-baking the coated film are carried out after the above exposure step.

(3) Development process

After the exposure process, the resist film is developed with a developing solution to dissolve and remove the unexposed portion of the coating film. The developing solution is preferably an alkali developer, and examples thereof include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] 5-diazabicyclo- [4.3.0] -5-nonene and the like can be used. A water-soluble organic solvent such as methanol or ethanol or a surfactant may be added in an appropriate amount to the alkali developing solution. After the alkali developing treatment, washing with water is usually carried out.

As the development processing method, for example, a shower development method, a spray development method, a dip (immersion) development method, or a puddle (liquid immersion) development method can be applied. The developing conditions can be, for example, 5 seconds to 300 seconds at room temperature.

Further, when a coating film of a color sensitive radiation-sensitive composition is formed by the ink jet method, a developing step is unnecessary since it is unnecessary.

(4) Step of post-baking the coating film

Post-baking of the patterned coating film after the development process or after the formation of the coating film by the inkjet method and the exposure process is preferable in terms of enhancing the curability. The post-baking conditions may be, for example, from 150 to 250 占 폚 for 20 minutes to 40 minutes in the case of using a hot air furnace.

In this way, a pixel array in which blue pixel patterns containing a blue dye or a lake pigment are arranged in a predetermined arrangement can be formed. Next, the above process is repeated by using a negative-type green-sensitive radiation-sensitive composition to form a green pixel pattern on the same substrate, and further repeating the above process using a negative-type red radiation- Are formed on the same substrate, a pixel array in which pixel patterns of three primary colors of red, green, and blue are arranged in a predetermined arrangement can be formed on a substrate. In the present embodiment, however, the order of forming the pixel patterns of the respective colors on the substrate is not limited to the above example. The order of formation of each color can be appropriately changed.

The film thickness of the pixel pattern formed as described above is usually 0.5 탆 to 5 탆, preferably 1.0 탆 to 3 탆.

In the present invention, the pixel pattern constituting the color filter is not limited to red, green, and blue, and may be a pixel pattern having three primary colors of yellow, magenta, and cyan. In addition to the coloring pattern corresponding to the pixel of the three primary colors, the fourth or fifth coloring pattern may be formed. For example, as disclosed in Japanese Patent Application Laid-Open No. 2005-523465, a fourth pixel (yellow pixel) for widening the coloring range is provided in addition to a coloring pattern corresponding to three primary color pixels of red, green and blue, Or a fifth pixel (cyan pixel) can be arranged.

By providing a protective film on the pixel pattern thus formed, the display characteristics of the display element can be enhanced. As the protective film, an organic film or an organic-inorganic hybrid film formed from a curable composition, or an inorganic film such as a SiNx film and a SiOx film can be given. In the present embodiment, it is preferable to form a protective film using the curable composition.

As a method of forming a protective film by using the curable resin composition, for example, a method disclosed in Japanese Patent Application Laid-Open No. 4-53879 or Japanese Patent Application Laid-Open No. 6-192389 can be adopted .

Examples of the curable resin composition used for forming the protective film include thermosetting resin compositions disclosed in JP-A-3-188153 and JP-A-4-53879, 6-192389 or Japanese Patent Application Laid-Open No. 8-183819, Japanese Patent Laid-Open Publication No. 2006-195420, Japanese Patent Laid-Open Publication No. 2008-208342, etc. And a curing composition containing a polyorganosiloxane which is incorporated therein.

According to the pixel pattern forming method of the present invention, it is possible to obtain a pixel pattern in which excellent chromaticity characteristics of a dye or a rake pigment are exhibited without being lost, that is, a color difference (? E * ab) between before and after exposure. Therefore, by using the method of forming a pixel pattern of the present invention, it is possible to obtain a color filter excellent in chromaticity characteristics. The method of forming a pixel pattern of the present invention can be applied to various color filters such as a color filter for a color liquid crystal display element, a color filter for color separation of a solid-state image pickup element, a color filter for an organic EL display element, And is particularly suitable for manufacturing a color filter for a color liquid crystal display device using a large substrate.

Next, the colored and radiation sensitive composition used in the method of forming a pixel pattern of the present invention will be explained. The coloring and radiation-sensitive composition contains at least a colorant, a binder resin, a cross-linking agent and a photopolymerization initiator, which contain at least one kind selected from the group consisting of a dye and a lake pigment. The coloring and radiation-sensitive composition is usually used as a liquid composition by blending a solvent.

Each component will be described below.

The coloring and radiation-sensitive composition used in the method for forming a pixel pattern of the present invention contains at least one kind selected from the group consisting of a dye and a lake pigment as a coloring agent. Examples of the dye include, but are not limited to, azo dyes, anthraquinone dyes, xanthene dyes, triarylmethane dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, Dye and the like. Specifically, the color index (C.I.) name is attached as follows.

C.I. Acid Yellow 11, C.I. Acid Orange 7, C.I. Acid Red 37, C.I. Acid Red 180, C.I. Acid Blue 29, C.I. Solvent Red 89, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Direct Yellow 12, C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reactive Yellow 2, C.I. Reactive Red 17, C.I. Reactive Red 120, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165, C.I. Basic Blue 41, C.I. Basic Red 18, C.I. Mordant red 7, C.I. Azo dyes such as Mordant Yellow 5;

C.I. Bat Blue 4, C.I. Acid Blue 40, C.I. Acid Green 25, C.I. Reactive blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56, C.I. Anthraquinone type dyes such as Disperse Blue 60;

C.I. Basic Red 1, C.I. Basic Red 1: 1, C.I. Basic violet 10, C.I. Xanthene dyes such as Solvent Red 49;

C.I. Basic Blue 7, C.I. Triarylmethane dyes such as Basic Blue 11;

C.I. Phthalocyanine dyes such as Pad Blue 5;

C.I. Basic Blue 3, C.I. Quinone imine dyes such as Basic Blue 9;

C.I. Solvent Yellow 33, C.I. Acid Yellow 3, C.I. Quinoline dyes such as Disperse Yellow 64;

C.I. Acid Yellow 1, C.I. Acid Orange 3, C.I. Nitro-based dyes such as Disperse Yellow 42;

C.I. Methine dyes such as Solvent Yellow 179.

In addition, Japanese Patent Application Laid-Open No. 2010-168531, Japanese Patent Application Laid-Open No. 2010-170073, Japanese Patent Application Laid-Open No. 2010-170074, Japanese Patent Application Laid-Open No. 2010-275531, Japanese Patent Azo dyes described in JP-A-2010-275533 and the like, triarylmethane dyes described in JP-A No. 2007-503477, JP-A No. 10/123071 and JP-A 2007-503477 The xanthene dyes described in claim 3, the Japanese patent publication No. 2010-244027, the Japanese patent publication No. 2010-254964, and the like.

Of these dyes, azo dyes, triarylmethane dyes, xanthene dyes and methine dyes are preferable in that particularly excellent effects can be obtained in the method for forming a pixel pattern of the present invention.

In the present invention, the dyes may be used alone or in combination of two or more.

Further, the lake pigment is a soluble dye, which is made insoluble by the precipitant. Examples of the precipitating agent include barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminum acetate, lead acetate, tannic acid, catanol, tamol, isopoly acid, heteropoly acid (for example, phosphotungstic acid, phosphomolybdic acid , Phosphotungsten-molybdic acid, silico tungsten molybdic acid, silicotungstic acid, silicomolybdic acid). Of these, isopiolic acid and heteropolyacid are preferable as the precipitating agent.

As such a lake pigment, the following color index (C.I.) name is attached.

C.I. Pigment Blue 1, C.I. Pigment Blue 2, C.I. Pigment Blue 3, C.I. Pigment Blue 9, C.I. Pigment Blue 10, C.I. Pigment Blue 14, C.I. Pigment Blue 17: 1, C.I. Pigment Blue 24, C.I. Pigment Blue 24: 1, C.I. Pigment Blue 56, C.I. Pigment Blue 61, C.I. Pigment Blue 62,

C.I. Pigment Violet 1, C.I. Pigment Violet 2, C.I. Pigment Violet 3, C.I. Pigment Violet 3: 1, C.I. Pigment Violet 3: 3, C.I. Pigment Violet 27, C.I. Pigment Violet 39,

C.I. Pigment Green 1, C.I. Pigment Green 4,

C.I. Pigment Red 48: 1, C.I. Pigment Red 48: 2, C.I. Pigment Red 48: 3, C.I. Pigment Red 48: 4, C.I. Pigment Red 48: 5, C.I. Pigment Red 49, C.I. Pigment Red 49: 1, C.I. Pigment Red 49: 2, C.I. Pigment Red 49: 3, C.I. Pigment Red 52: 1, C.I. Pigment Red 52: 2, C.I. Pigment Red 53: 1, C.I. Pigment Red 54, C.I. Pigment Red 57: 1, C.I. Pigment Red 58, C.I. Pigment Red 58: 1, C.I. Pigment Red 58: 2, C.I. Pigment Red 58: 3, C.I. Pigment Red 58: 4, C.I. Pigment Red 60: 1, C.I. Pigment Red 63, C.I. Pigment Red 63: 1, C.I. Pigment Red 63: 2, C.I. Pigment Red 63: 3, C.I. Pigment Red 64: 1, C.I. Pigment Red 68, C.I. Pigment Red 81, C.I. Pigment Red 81: 1, C.I. Pigment Red 200, C.I. Pigment Red 237, C.I. Pigment Red 239, C.I. Pigment Red 247,

C.I. Pigment Yellow 61, C.I. Pigment Yellow 61: 1, C.I. Pigment Yellow 62, C.I. Pigment Yellow 100, C.I. Pigment Yellow 104, C.I. Pigment Yellow 133, C.I. Pigment Yellow 168, C.I. Pigment Yellow 169, C.I. Pigment Yellow 183, C.I. Pigment Yellow 191, C.I. Pigment Yellow 191: 1, C.I. Pigment Yellow 206, C.I. Pigment Yellow 209, C.I. Pigment Yellow 209: 1 and C.I. Pigment Yellow 212.

Of these lake pigments, C.I. Pigment Blue 1, C.I. Pigment Blue 2, C.I. Pigment Blue 3, C.I. Pigment Blue 9, C.I. Pigment Blue 10, C.I. Pigment Blue 14, C.I. Pigment Blue 62, C.I. Pigment Violet 1, C.I. Pigment Violet 2, C.I. Pigment Violet 3, C.I. Pigment Violet 27, C.I. Pigment Violet 39 and the like are preferable in that a particularly excellent effect can be obtained in the method for forming a pixel pattern of the present invention. The triarylmethane lake pigment containing isopoly acid or heteropoly acid as a precipitating agent is also disclosed in, for example, Japanese Patent Laid-Open Publication No. 2011-150195 and Japanese Patent Laid-Open Publication No. 186043/1986.

In the present invention, the lake pigment may be used singly or in a mixture of two or more kinds.

In the present invention, other colorants may be used together with the above-mentioned dyes and lake pigments as colorants. The other colorants are not particularly limited, and the color and the material can be appropriately selected depending on the use of the color filter. Concretely, although organic pigments, inorganic pigments and natural pigments can all be used as colorants, organic pigments are preferably used because they require high color purity, brightness and contrast.

Specific examples of the organic pigments include, by color index (C.I.) name, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Blue 1, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 80, C.I. Pigment Yellow 83, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180, C.I. Pigment Yellow 211, C.I. Pigment Orange 38, C.I. Pigment Violet 23 and the like.

The content of the colorant is usually 5 to 70% by mass, preferably 5 to 60% by mass in the solid content of the coloring and radiation-sensitive composition in that a pixel having high luminance and excellent color purity is formed. The solid content referred to herein is a component other than the solvent described later.

The total content of at least one selected from the group consisting of dyes and lake pigments is preferably 5% by mass or more, more preferably 10% by mass or more, in the total colorant.

The binder resin in the coloring and radiation-sensitive composition is not particularly limited, but preferably contains a polymer having an acidic functional group. Examples of the acidic functional group include a carboxyl group, a phenolic hydroxyl group, an imidic acid group, a sulfo group, a sulfino group or a sulfo group. Of these, a carboxyl group is preferably used.

Examples of the polymer having a carboxyl group include those disclosed in JP-A-5-19467, JP-A-6-230212, JP-A-7-140654, JP-A-7-207211, JP-8-259876, JP-A-09-325494, JP-A-10-31308, JP- Japanese Patent Application Laid-Open Nos. 10-300922, 11-140144, 11-174224, 11-231523, 11- Polymers disclosed in JP-A-258415, JP-A 2000-56118, JP-A 2002-296778, JP-A 2004-101728, and JP-A 2008-181095 .

The acid value of the binder resin is preferably 10 to 200 KOH / mg, more preferably 30 to 270 KOH / mg, and still more preferably 50 to 250 KOH / mg. Here, "acid value" means the number of mg of KOH required to neutralize 1 g of the solid content of the binder resin. In the present invention, the binder resins may be used alone or in combination of two or more.

The crosslinking agent in the coloring and radiation-sensitive composition is not particularly limited as long as it is a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenic unsaturated group, an oxiranyl group, an oxetanyl group and an N-alkoxymethylamino group.

As the crosslinking agent in the present invention, a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethyl amino groups is preferably used.

Particularly preferred crosslinking agents include, for example, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate and succinic anhydride , Compounds obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride, compounds obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride, compounds obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride, compounds obtained by reaction of caprolactone (Alkoxymethyl) melamine or N, N, N ', N'-tetra (alkoxymethyl) benzoguanamine, and the like, .

In the present invention, the crosslinking agents may be used alone or in combination of two or more.

The photopolymerization initiator in the coloring and radiation-sensitive composition is a compound capable of generating an active species capable of initiating the curing reaction of the crosslinking agent described above by exposure to a specific radiation.

Preferred examples of the photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, an O-acyloxime compound, an onium salt compound, a benzoin compound, an? -diketone compound, a polynuclear quinone compound, a diazo compound or an imidosulfonate compound.

In the present invention, the photopolymerization initiator may be used in combination with a known sensitizer or a hydrogen donor. The photopolymerization initiator may be used alone or in admixture of two or more.

The solvent in the coloring and radiation-sensitive composition can be appropriately selected and used as long as it disperses or dissolves each component constituting the coloring and radiation-sensitive composition, does not react with these components, and has appropriate volatility.

Examples of suitable solvents in the present invention include propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether , Diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate Methyl 3-methoxybutyl propionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, propionic acid n -Butyl, ethyl butyrate, i-propyl butyrate, n-butyl butyrate or ethyl pyruvate.

In the present invention, the solvents may be used alone or in admixture of two or more.

The coloring and radiation-sensitive composition may further contain other components. Examples of other components include a urethane-based dispersant, a polyethyleneimine-based dispersant, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene alkyl phenyl ether-based dispersant, a polyethylene glycol diester-based dispersant, a sorbitan fatty acid ester- Dispersing agents such as a dispersant and an acrylic dispersant; Surfactants such as fluorine-based surfactants and silicone-based surfactants; Vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3- Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like, and the like.

<Display element>

The display element of the present invention comprises a color filter manufactured by the above-described method. Specific examples of the display element include a color liquid crystal display element, an organic EL display element, or an electronic paper.

The color liquid crystal display device having the color filter manufactured by the method of the present invention can be applied to a liquid crystal display device having a driving substrate on which a thin film transistor (TFT) The liquid crystal layer can be opposed to the liquid crystal layer. Alternatively, the color liquid crystal display element may be formed by forming a substrate on which a color filter of the present embodiment is formed and an ITO (indium tin oxide: tin-doped indium oxide) electrode on the surface of a driving substrate on which a thin film transistor A structure in which one substrate faces the liquid crystal layer is also possible. The latter structure can remarkably improve the aperture ratio and has an advantage that a bright and high-definition liquid crystal display element can be obtained.

The color liquid crystal display element includes a backlight unit. As the backlight unit, for example, a structure in which a fluorescent tube such as a cold cathode fluorescent lamp (CCFL) or the like and a scattering plate are combined can be used. Further, a backlight unit using a white LED as a light source may also be used. Examples of white LEDs include white LEDs that combine red LEDs, green LEDs, and blue LEDs to obtain white light by mixing colors, white LEDs that combine blue LEDs, red LEDs, and green phosphors to obtain white light by mixing colors, A white LED for obtaining a white light by mixing a red light emitting phosphor and a green light emitting phosphor and a white LED for obtaining white light by mixing a blue LED and a YAG based phosphor, a blue LED, an orange light emitting phosphor and a green light emitting phosphor A white LED for obtaining white light by mixing white light, an ultraviolet LED and a white LED for obtaining a white light by mixing a red light emitting phosphor, a green light emitting phosphor and a blue light emitting phosphor in combination, and the like.

The color liquid crystal display device having the color filter manufactured by the method of the present invention may be applied to a color liquid crystal display device such as TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (In- And an OCB (Optically Compensated Birefringence) type liquid crystal mode.

An organic EL display device having a color filter manufactured by the method of the present invention can adopt a suitable structure, and includes a structure disclosed in, for example, Japanese Patent Laid-Open No. 11-307242.

An electronic paper having a color filter manufactured by the method of the present invention can adopt a suitable structure, and for example, there is a structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169.

Although the present embodiment has been described above, the present invention is not limited to the above-described embodiments, and various modifications may be made without departing from the scope of the present invention.

[Example]

Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to the following examples.

[Preparation of Pigment Dye Mixture, etc.]

Production Example 1

As a colorant, C.I. Pigment Green 58 / C.I. 15 mass parts of solvent yellow 179 = 60/40 (by mass ratio), 10 parts by mass of BYK-LPN21116 (manufactured by BYK) as a dispersant (nonvolatile component = 40 mass%) and propylene glycol monomethyl ether acetate Were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dye mixture (A1).

Production Example 2

As a colorant, C.I. Pigment Blue 15: 6 / C.I. 10 parts by mass (nonvolatile component = 40% by mass) of BYK-LPN21116 (manufactured by BYK) as a dispersing agent, 15 parts by mass of a mixture of Basic Blue 7 = 60/40 (mass ratio) and propylene glycol monomethyl ether acetate Were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dye mixture (A2).

Production Example 3

As a colorant, C.I. 15 parts by mass of a yellow pigment (barbituric acid azo dye) = 70/30 (mass ratio) represented by Pigment Green 58 and 10 parts by mass of BYK-LPN21116 (manufactured by BYK) as a dispersing agent Non-volatile component = 40% by mass), and 75 parts by mass of propylene glycol monomethyl ether acetate as a solvent were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dye mixture (A3).

Production Example 4

As a colorant, C.I. Pigment Green 58 / C.I. 15 mass parts of Pigment Yellow 150 = 60/40 (by mass ratio), 10 parts by mass of BYK-LPN21116 (manufactured by BYK) as a dispersant (nonvolatile component = 40 mass%) and propylene glycol monomethyl ether Acetate were mixed and dispersed in a bead mill for 12 hours to prepare a pigment dispersion (A4).

Production Example 5

As a colorant, C.I. Pigment Blue 15: 6 / xanthene dye C.I. 10 parts by mass (nonvolatile component = 40% by mass) of BYK-LPN21116 (manufactured by BYK) as a dispersant, 15 parts by mass of a mixture of propylene glycol monomethyl ether acetate Were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dye mixture (A5).

Production Example 6

As a colorant, C.I. Pigment Blue 15: 6 15 parts by weight of a triarylmethane lake pigment (wherein x = 1 to 2) = 60/40 (mass ratio) mixture represented by the following formula: BYK-LPN21116 (BYK ) (Nonvolatile component = 40% by mass) and 75 parts by mass of propylene glycol monomethyl ether acetate as a solvent were mixed and dispersed with a bead mill for 12 hours to prepare a pigment dispersion (A6).

[Synthesis of binder resin]

Synthesis Example 1

A cooling tube and a stirrer, 2 parts by mass of 2,2'-azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate were charged. Then, 15 parts by mass of methacrylic acid, 50 parts by mass of N-phenylmaleimide 20 mass parts of benzyl methacrylate, 55 mass parts of styrene, and 3 mass parts of 2,4-diphenyl-4-methyl-1-pentene (trade name: , And the mixture was purged with nitrogen. Thereafter, the mixture was gently stirred, the temperature of the reaction solution was raised to 80 DEG C, and this temperature was maintained for 5 hours to polymerize to obtain a resin solution (solid content concentration = 33 mass%). The resin thus obtained had Mw = 16,000 and Mn = 7,000. This resin solution is referred to as "binder resin solution (B1) ".

Synthesis Example 2

44 parts by mass of p-vinylbenzyl glycidyl ether, 40 parts by mass of N-phenylmaleimide and 16 parts by mass of benzyl methacrylate were dissolved in 300 parts by mass of propylene glycol monomethyl ether acetate, Further, 8 parts by mass of 2,2'-azobisisobutyronitrile and 8 parts by mass of 2,4-diphenyl-4-methyl-1-pentene were charged and replaced with nitrogen. Thereafter, the reaction solution was heated to 80 캜 while bubbling with nitrogen while gently stirring, and the polymerization was carried out at this temperature for 5 hours.

Then, 17 parts by mass of methacrylic acid, 0.5 parts by mass of p-methoxyphenol and 4.4 parts by mass of tetrabutylammonium bromide were added to this reaction solution, and the reaction was carried out at a temperature of 120 ° C for 9 hours. After 18.5 parts by mass of succinic anhydride was added and the reaction was carried out at a temperature of 100 ° C for 6 hours, the reaction solution was rinsed twice with the temperature maintained at 85 ° C and concentrated under reduced pressure to obtain a binder resin solution = 33 mass%). The resulting binder resin had Mw = 7,800 and Mn = 5,000. This binder resin solution is referred to as "binder resin solution (B2) ".

Example 1

[Preparation of coloring and radiation-sensitive composition]

18 parts by mass (solid content concentration = 33% by mass) of the binder resin solution (B1) as the binder resin and 100 parts by mass of the pigment dye mixture solution (KAARAD MAX-3510 manufactured by Nippon Kayaku Kabushiki Kaisha, , 8 parts by mass of a mixture of pentaerythritol hexaacrylate and dipentaerythritol pentaacrylate), 4 parts by mass of Kayalad DPCA-60 (caprolactone-modified dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Kagaku Co., Ltd., 1 part by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one as an initiator and 1 part by mass of ethanone, 1- [ -Carbazol-3-yl] -, 1- (O-acetyloxime), 0.2 part by mass of Megafac F-554 manufactured by DIC Corporation as a fluorine surfactant, and propylene glycol monomethyl ether acetate To prepare a green radiation-sensitive composition having a solid content concentration of 15 mass% The.

[Formation of Pixel Pattern and Evaluation of Color Stability]

The green radiation sensitive composition thus obtained was coated on a glass substrate using a slit die coater and prebaked on a hot plate at 90 DEG C for 4 minutes to form a coating film having a thickness of 2 mu m.

Subsequently, the coated substrate was cooled to room temperature and irradiated with ultraviolet ray cut filter 1 (UV-31 (manufactured by Toshiba Kagas Co., Ltd.)) to radiation radiated from ultra-high pressure mercury lamp, And the coating film was exposed through a striped photomask at an exposure dose of 2,000 J / m &lt; 2 &gt;. Subsequently, a developer containing 0.04 mass% potassium hydroxide aqueous solution at 23 캜 was ejected to the obtained substrate at a developing pressure of 1 kgf / cm 2 (nozzle diameter: 1 mm) to perform showering for 1 minute. Thereafter, this substrate was cleaned with ultra-pure water and air-dried to form a green stripe-shaped pixel pattern on the substrate.

The spectral characteristics of the coated film and the formed pixel pattern before exposure were measured using a color analyzer (MCPD2000 manufactured by OTSUKA DENKI CO., LTD.) To obtain a color difference (DELTA E * ab). The evaluation results are shown in Table 1 below.

Examples 2 to 11, Comparative Examples 1 to 5, and Reference Examples 1 to 2

Each coloring and radiation sensitive composition was prepared in the same manner as in Example 1, except that the kind and content of each component in Example 1 were changed as shown in Table 1. Subsequently, a pixel pattern was formed in the same manner as in Example 1, except that the obtained coloring and radiation-sensitive composition was used and exposure radiation was selected as shown in Table 1, and color stability was evaluated. The evaluation results are shown in Table 1. 3 is obtained by interposing an ultraviolet cut filter 2 (UV-33 (manufactured by Toshiba Garasu)) to the radiation radiated from the ultrahigh pressure mercury lamp, and the radiation showing the spectral characteristics of Fig. (UV-35, manufactured by Toshiba Kagas Co., Ltd.) to the radiation emitted from the ultraviolet ray shielding filter 3.

In Table 1, the respective components are as follows.

C1: caprolactone-modified dipentaerythritol hexaacrylate (trade name: Kayalad DPCA-60, manufactured by Nippon Kayaku Kabushiki Kaisha)

C2: a mixture of dipentaerythritol pentaacrylate and monoesters of succinic acid, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name TO-1382, manufactured by Toagosei Co., Ltd.)

C3: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name KAYARAD MAX-3510, manufactured by Nippon Kayaku Kabushiki Kaisha)

C4: ethylene oxide oligomer-modified dipentaerythritol hexaacrylate (trade name: KAYARAD DPEA-12, manufactured by Nippon Kayaku Kabushiki Kaisha)

D1: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Irgacure 369 available from Ciba Specialty Chemicals)

D2: ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O- acetyloxime) Cure OXE02)

D3: 2-Mercaptobenzothiazole

D4: 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Hodogaya Chemical Co., CIM)

D5: 2,4-Diethylthioxanthone (trade name: CAYACURE DETX-S, manufactured by Nippon Kayaku Kabushiki Kaisha)

D6: 4,4'-bis (diethylamino) benzophenone

D7: manufactured by Adeka &quot; NCI930 &quot;

Claims (3)

(1) a step of forming on a substrate a coating film of a coloring and radiation-sensitive composition containing a coloring agent containing at least one kind selected from the group consisting of dyes of green, blue, yellow or cyan and a lake pigment, and 2) irradiating at least a part of the coating film with radiation,
Wherein the content of the colorant is 5 to 70% by mass in the solid content of the coloring and radiation-sensitive composition,
Characterized in that the spectral distribution of the radiation has a plurality of peaks in the range of 350 nm to 450 nm and the maximum intensity of the radiation at less than 350 nm is not more than 50% of the maximum peak intensity at 350 nm to 450 nm. Green, blue, yellow or cyan. A color filter comprising a pixel pattern formed by the method according to claim 1. A display device comprising the color filter according to claim 2.

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