JP2002357714A - Hardening type color filter composition for transflective liquid crystal display device, color filter and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simply manufacture a color filter for a transflective color liquid crystal display device with excellent color reproducibility. SOLUTION: A hardening type composition for the color filter for the transflective color liquid crystal display device is a hardening type composition containing a colorant, an alkali soluble resin, a radiation sensitive hardening type compound, a photo-polymerization initiator and a solvent. The residual percentage of its film continuously varies over at least 60 to 70% range within a range of 1 to 1,200 mJ exposure. The photo-polymerization initiator is at least one of compounds selected from a hexaaryl bisimidazole compound, a benzophenone compound, an acetophenone compound, an aclyphosphine compound, a benzoin ether compound, a xanthone compound and a quinone compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition for a color filter capable of easily obtaining a color filter of a transflective color liquid crystal display device having excellent color reproducibility, and a transflective composition using the same. The present invention relates to a type color liquid crystal display device color filter, a method for manufacturing the same, and a liquid crystal display device provided with the color filter.

[0002]

2. Description of the Related Art As is well known, a liquid crystal device does not emit light by itself, but performs display or the like by simply changing the path of light. For this reason, the liquid crystal device must have a configuration in which light is always incident on the panel in some form. In this regard, display devices using other methods, such as an electroluminescence display device and a plasma display, are required. Are very different. Here, in a liquid crystal device, a type in which light incident from a light source or the like provided on the back side of the panel passes through the panel and emits to the observation side is called a transmission type, while external light or the like incident from the observation side is transmitted by the panel. The type that is reflected and emitted to the observation side is called a reflection type.

[0003] With the rapid spread of mobile terminals and the like, reflective liquid crystal panels have attracted attention. However, since these reflective liquid crystal panels reflect external light for display, they are not suitable for use in an environment where external light is strong such as outdoors. While sufficient display performance can be obtained, there is a problem that visibility is extremely reduced in a dark room or at night.

In view of the above, various types of so-called transflective liquid crystal devices have been proposed as a device which can be used both outdoors and indoors by applying a reflective liquid crystal device. This liquid crystal device uses a reflective type as the main device using external light in the same way as a normal reflective type in a bright place, while assisting the transmissive type by turning on a light source provided on the back side of the panel in a dark place. And can be visually recognized at any place. Further, in recent years, color display is required for portable electronic devices and OA devices, and therefore, in many cases, even a transflective liquid crystal device needs to be colored.

[0005] Such a transflective liquid crystal device generally has a structure in which, when a backlight configuration is used, a transmissive portion is provided in a part of a reflective layer, and the transmissive portion is provided in the center of a pixel in a square shape. (For example, see Japanese Patent Application Laid-Open No. 10-31942).
No. 2). However, in the above transflective liquid crystal device, when the color filter layer has the same layer thickness at the time of transmission and at the time of reflection, the degree of light absorption differs between the time of reflection and the time of transmission, and the degree of light absorption differs between the time of transmission and the time of reflection. There was a problem that the hue was different. This is considered to be due to the fact that the light travels back and forth through the color filter layer at the time of reflection, so that the substantial thickness of the color filter layer is twice that at the time of transmission. As a result, for example, if a color filter having a high transmittance for reflection is used in preference to the reflectance,
There is also a problem that the color becomes lighter at the time of transmission.

On the other hand, Japanese Patent Laid-Open No. 2001-75091
In the publication, a color filter layer is formed on a semi-transmissive layer having a concavo-convex structure, and the thickness of the color filter layer on the transmissive portion (concave portion) is made larger than the thickness of the color filter layer on the convex portion having the reflective layer. There is described a technique for obtaining good color reproducibility even in the case of transmitted light by setting the thickness to be large. In this technology, a concave / convex portion is formed on a substrate, a reflective film is formed on a convex portion, and a coating solution for a color filter is applied on a surface having a concave portion as a transmitting portion. In this case, the thickness of the color filter film in the transmission portion in the concave portion can be formed to be relatively large.

[0007]

However, in the transflective liquid crystal display device described above, it is necessary to form irregularities in the lower layer of the color filter to alternately form reflective portions and transmissive portions in a pattern. The manufacturing process becomes complicated, and the unevenness of the color filter layer provided on it depends on the flow characteristics (leveling characteristics) of the color filter coating solution. there were. In addition, since the thickness of the color filter layer is greatly affected by coating conditions other than the characteristics of the liquid, there is a problem that a great deal of study is required to obtain a specific result with good reproducibility.

In order to solve this problem, in forming the color filter layer, the thickness of the color filter layer of the transmission portion is set to be thicker than the thickness of the color filter layer of the reflection portion on the flat reflection surface. Can be considered.
In order to adjust the thickness of the color filter in the reflective portion and the transmissive portion, a method of forming a color filter by separately patterning the reflective portion and the transmissive portion may be considered. In this method, at least two times are performed for each color. A pattern formation process is required, which is very complicated.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems, and to provide a technique capable of easily producing a color filter for a transflective color liquid crystal display device having excellent color reproducibility. It is in. In particular, it is possible to simplify the process by reducing the number of times of exposure and development for separately forming the color filter layer facing the reflection portion and the transmission portion, thereby not only reducing the product cost but also increasing the yield. To provide technology.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a color filter for a transflective liquid crystal display device comprising a curable composition containing a specific photopolymerization initiator and having a specific residual film property. By using for the formation of, it has been found that it is possible to easily adjust the film thickness of the color filter simply by performing the exposure by adjusting the exposure amount corresponding to the transmission portion or the reflection portion, and reached the present invention. is there. That is,
It has been found that the above object of the present invention is achieved by the following constitutions.

(1) A curable composition containing a colorant, an alkali-soluble resin, a radiation-sensitive curable compound, a photopolymerization initiator, and a solvent, and has a thickness of 0.3 to 5.0 μm on a substrate. 1 to the coating film formed by coating and pre-baking
After exposing at an exposure amount of 1200 mJ, the remaining film ratio on the substrate relative to the exposure amount of the coating film when developed with an alkali developer 液 (film thickness after development processing / film thickness after prebaking processing) × 1
00 (%)} changes continuously over a range of at least 60% to 70% in any of the exposure amounts of 1 mJ to 1200 mJ, and the photopolymerization initiator is
(I) hexaarylbisimidazole compounds, (I
At least one selected from the group consisting of I) a benzophenone compound, (III) an acetophenone compound, (IV) an acylphosphine compound, (V) a benzoin ether compound, (VI) a xanthone compound, and (VII) a quinone compound. A curable composition for a color filter of a transflective color liquid crystal display device, characterized by being a compound of the formula:

(2) The transflective composition according to (1), wherein the photopolymerization initiator is a mixture of at least one of (I) a hexaarylbisimidazole-based compound and (II) a benzophenone-based compound. -Type curable composition for color filters of color liquid crystal display devices.

(3) The transflective color liquid crystal display according to the above (1) or (2), wherein the (I) hexaarylbisimidazole compound is a compound represented by the following general formula (Ia). Curable composition for device color filter.

[0014]

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In the formula (Ia), X ¹ and X ² may be the same or different and each represents a hydrogen atom, a chlorine atom or a bromine atom. ｝

(4) The transflective color liquid crystal display device according to the above (1) or (2), wherein the benzophenone compound (II) is a compound represented by the following general formula (II-a): Curable composition.

[0017]

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In formula (II-a), R ^{1 to} R ⁴ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ｝

(5) The (I) hexaarylbisimidazole compound is a compound represented by the above formula (Ia), and the (II) benzophenone compound is a compound represented by the above formula (II-a). The curable composition for a color filter of a transflective color liquid crystal display device according to the above (2), which is a compound represented by the formula (2).

(6) The curable composition for a color filter of a transflective color liquid crystal display device according to the above (1), wherein the (III) acetophenone compound is a compound represented by the following general formula (III-a): .

[0021]

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In the formula (III-a), R ⁵ and R ⁶ may be the same or different and each represents a hydrogen atom or a carbon atom having 1 to 6 carbon atoms.
Represents an alkyl group. ｝

(7) The above (VI) xanthone compound is
The curable composition for a color filter of a transflective color liquid crystal display device according to the above (1), which is a compound represented by the following general formula (VI-a).

[0024]

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In the formula (VI-a), R ¹⁰ and R ¹¹ may be the same or different and each represents a hydrogen atom or a carbon atom having 1 to 6 carbon atoms.
Represents an alkyl group. ｝

(8) A transflective liquid crystal prepared by applying the curable composition according to any one of (1) to (7) on a substrate, prebaking, pattern exposure, alkali development, and postbaking. Color filters for display devices.

(9) The curable composition as described in any of (1) to (7) above is applied to a substrate, prebaked and pattern-exposed, and then alkali-developed with a sodium carbonate-based alkali developing solution, and then post-processed. A method for producing a color filter for a transflective liquid crystal display device, characterized by baking. (10) The method for producing a color filter for a transflective liquid crystal display device according to the above (9), wherein an exposure mask for changing a light amount of a pattern portion for each color is used for pattern exposure.

(11) A transflective liquid crystal display device provided with the color filter according to (8). (12) The transflective liquid crystal display device according to (11), wherein the substrate is an aluminum substrate or a glass substrate.

The curable composition for a color filter of a transflective color liquid crystal display device of the present invention (hereinafter simply referred to as a curable composition) comprises a colorant, an alkali-soluble binder resin, a radiation-sensitive curable compound, a photopolymerization initiator. A curable composition containing an agent and a solvent, wherein 0.3 to 5.0
μm, preferably from 0.5 to 3.0 μm, more preferably from 0.8 to 2.0 μm. After exposure to a coating film formed by pre-baking with an exposure amount of 1 to 1200 mJ / cm ^2. The ratio of the remaining film on the substrate to the amount of exposure of the coating film when developed with an alkali developing solution {(film thickness after development / film thickness after pre-baking) × 100 (%)} is the above-mentioned exposure amount 1 In any of the range of 〜1200 mJ / cm ² , it changes continuously over at least the range of 60% to 70%, and uses the above specific photopolymerization initiator.

In a conventional pattern for forming a curable composition for a color filter, curing of a coating film is promoted in an exposed area, that is, a pattern cannot be formed in a place where a residual film ratio is high and a light exposure amount is low. A curable composition having such a property as to have low adhesion and not to form a pattern has been considered useful in the field of color filters.

However, this time, it has been found that the use of the above-mentioned specific photopolymerization initiator in the curable composition makes it possible to control the amount of the remaining film of the coating film in accordance with the amount of light exposure. The present inventors have found that a transflective color liquid crystal display device having excellent color reproducibility can be easily manufactured by applying the present invention to a color filter, and the present invention has been achieved.

The reason why the residual ratio of the coating film can be controlled in accordance with the amount of exposure by using the above-mentioned photopolymerization initiator is not clear, but it is said that the photopolymerization initiator has conventionally excellent characteristics such as a trihalogen compound. When exposed to light, the photopolymerization initiator generates an acidic gas at the same time as the generation of radicals, kills the generated radicals, drives out oxygen gas that inhibits curing from the inside of the coating film, and allows oxygen from the outside to enter. While pressing has the effect of accelerating the curing of the coating film,
It is presumed that the photopolymerization initiator used in the present invention hardly generates such an acidic gas. That is, when these photopolymerization initiators are used, oxygen that inhibits polymerization is not actively expelled from the film, so that hardening particularly on the coating film surface does not progress easily, whereas oxygen Polymerization curing proceeds from within the film (near the substrate side), which is hardly affected by, and as a result, a cured film is formed corresponding to the exposure amount, and the residual film ratio after development fluctuates according to the exposure amount, It is presumed that a color filter having the above-mentioned residual film characteristics of the present invention can be obtained.

The photopolymerization initiator of the present invention includes (I) a hexaarylbisimidazole compound, (II) a benzophenone compound, (III) an acetophenone compound,
(IV) an acylphosphine compound, (V) a benzoin ether compound, (VI) a xanthone compound, and (VI)
I) At least one compound selected from quinone compounds is used. Two or more of these photopolymerization initiators may be used in combination, and as a result of further investigation, among the photopolymerization initiators, particularly, at least one of (I) hexaarylbisimidazole compounds and (II) It was found that, by using at least one of the benzophenone-based compounds in combination, curing proceeds with a small amount of exposure, and high sensitivity can be achieved.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a specific configuration of the present invention will be described in more detail. In the curable composition of the present invention, the residual film ratio is in a range of at least 60 to 70%, preferably 50 in a range of 1 mJ to 1200 mJ of exposure.
It varies continuously over the range from% to 70%, more preferably from 30% to 70%.

In the curable composition of the present invention, as shown in FIG. 1, the residual film ratio with respect to the exposure amount is at least 6 as shown by a curve A on the graph showing the change in the residual film ratio with respect to the exposure amount.
Since it continuously changes in the range of 0 to 70%, the cured film is formed at a residual film ratio corresponding to the exposure amount in the developing treatment after exposure to the coating film of the curable composition. A cured film having a thickness pattern corresponding to the pattern can be formed. Therefore, when it is necessary to change the film thickness between the transmissive portion and the reflective portion as in the case of a color filter used for a transflective liquid crystal display device, it is possible to form the film by one exposure and one development process. A color filter having such a thickness structure can be formed.

In many conventional color filter constituent compositions, the range of the continuously changing residual film ratio is as narrow as 80 to 95% at most as shown by the curve B in FIG. The film thickness could not be changed with a sufficient width. In particular, when the exposure amount was reduced, film peeling occurred during development (see the broken line portion in FIG. 1). If the curable composition of the present invention is used, a cured film for a color filter remains on the substrate corresponding to the exposure amount in a wide range of the exposure amount, so that pattern exposure is performed. Thickness can be changed.

The residual film ratio can be specifically measured, for example, under the following conditions. The curable composition to be measured is applied on a glass substrate (Corning 1737) in a thickness of 2.0 μm by spin coating, and is applied at 85 ° C. for 2 hours.
A pre-baking process is performed for a minute to form a coating film. The film thickness at this time is referred to as “initial film thickness”. The obtained coating film is exposed with an ultrahigh pressure mercury lamp (20 mV) at an exposure amount in the range of 1 to 1200 mJ / cm ² , and then immersed in an alkali developing solution (aqueous sodium carbonate solution, pH 9.8) at 30 ° C. for 60 seconds. After the development, the substrate is rinsed and dried at 85 ° C. for 60 seconds. The film thickness at this time is defined as the film thickness after the development processing. The coating film thickness can be measured with DEKTAK3 (manufactured by Nihon Vacuum Giken Co., Ltd.), a stylus diameter of 50 μmΦ, and a load of 15 mg. The residual film ratio (%) of the present invention is determined by (film thickness after development processing / initial film thickness) × 100.

The photopolymerization initiator used in the present invention will be described in detail below. (I) A hexaarylbisimidazole-based compound is a compound in which three imidazole rings of a bisimidazole skeleton are each substituted with three aromatic rings, and specifically represented by the following general formula (Ia). Compounds.

[0039]

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In the above formula (Ia), X ¹ and X ² may be the same or different and each represents a hydrogen atom, a chlorine atom or a bromine atom, and preferably represents a hydrogen atom or a chlorine atom. Specific examples include the following compounds.

[0041]

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(II) Benzophenone compounds include:
Benzophenone or a compound represented by the following general formula (II-a) is given.

[0043]

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In the formula (II-a), R ^{1 to} R ⁴ may be the same or different and each represents a hydrogen atom or a carbon atom.
Represents an alkyl group of 1 to 6. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, butyl, and isopropyl. Specific examples include the following compounds.

[0045]

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As the acetophenone compound (III), a compound represented by the following formula (III-a) can be particularly preferably used.

[0047]

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In the formula (III-a), R ⁵ and R ⁶ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, butyl, and isopropyl. (III) Specific examples of the acetophenone-based compound include the following compounds.

[0049]

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Specific examples of the (IV) acylphosphine compound include the following.

[0051]

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As the benzoin ether compound (V), compounds represented by the following formulas (Va) and (Vb) can be particularly preferably used.

[0053]

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In the formula (Va) or (Vb), R ⁷ ,
R ⁸ and R ⁹ may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms. ｝ Specifically, examples of the alkyl group represented by R ⁷ , R ^8, and R ⁹ include methyl, ethyl, butyl, and isopropyl. (V) Specific examples of the benzoin ether-based compound include the following compounds.

[0055]

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As the (VI) xanthone compound, a compound represented by the following general formula (VI-a) can be particularly preferably used.

[0057]

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In the formula (VI-a), R ¹⁰ and R ¹¹ may be the same or different and each represents a hydrogen atom or a carbon atom having 1 to 6 carbon atoms.
Represents an alkyl group. ｝ Specifically, examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹⁰ and R ¹¹ include methyl, ethyl, butyl, and isopropyl. (VI) Specific examples of the xanthone-based compound include the following compounds.

[0059]

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As the quinone compound (VII), a compound represented by the following formula (VII-a) can be particularly preferably used.

[0061]

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In the formula (VII-a), R ¹² and R ¹³ may be the same or different and each represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms. ｝ Specifically, the halogen atom represented by R ¹² and R ¹³ includes a chlorine atom and a bromine atom, and the alkyl group having 1 to 6 carbon atoms includes methyl, ethyl, butyl, and isopropyl. . (VII) Specific examples of the quinone-based compound include the following compounds.

[0063]

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Among the above photopolymerization initiators, it is particularly preferable to use a combination of at least one compound represented by the general formula (I) and at least one compound represented by the general formula (II). preferable.

The use amount of the photopolymerization initiator is not particularly limited, but is preferably 0.1 to the total weight of the photopolymerizable composition.
-20% by weight, more preferably 1-10% by weight.

Next, the radiation-sensitive curable compound used in the curable composition will be described. The radiation-sensitive curable compound preferably comprises at least a polymerizable monomer and the photopolymerization initiator. The polymerizable monomer is preferably a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or more under normal pressure.

Compounds having at least one ethylenically unsaturated group capable of addition polymerization and having a boiling point of at least 100 ° C. at normal pressure include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (Meth) acrylates and other monofunctional acrylates and methacrylates; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) Terol, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane to which ethylene oxide or propylene oxide has been added and then (meth) acrylated, JP-B-48-41708, JP-B-SHO 50
Urethane acrylates as described in JP-A-6034 and JP-A-51-37193;
No. -64183, JP-B-49-43191, JP-B-5
Examples thereof include polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-A-2-30490 and epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid. In addition, Journal of the Adhesion Society of Japan Vol. 20, No. 7, 300-3
Those introduced as photocurable monomers and oligomers on page 08 can also be used.

The following general formula (B-1) or (B
The compound represented by -2) can also be used.

[0069]

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In the formulas (B-1) and (B-2), B is independently-(CH ₂ CH ₂ O)-and-(CH ₂ CH
(CH ₃₎ O) - or a represents a; X each independently represents either an acryloyl group, a methacryloyl group and a hydrogen atom, moreover, in formula (B-1), acryloyl group and methacryloyl group The sum is 5 or 6; in formula (B-2) it is 3 or 4; n
Each independently represents an integer of 0 to 6, and the sum of each n is 3 to 24; m represents each independently an integer of 0 to 6, and the sum of each m is 2 to 16 . ｝

These radiation-polymerizable monomers or oligomers are optional as long as the composition and the composition of the present invention can form a coating film having adhesiveness by irradiation with radiation, as long as the objects and effects of the present invention are not impaired. Can be used in the ratio of The amount used is 5 to 90% by weight, preferably 10 to 50% by weight, based on the total solids of the radiation-sensitive composition.

The alkali-soluble resin that can be used in the curable composition is preferably a linear organic high molecular polymer that is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.
Examples of such a linear organic high molecular polymer include a polymer having a carboxylic acid in a side chain, for example, Japanese Patent Application Laid-Open No. Sho 59-4461.
No. 5, JP-B-54-34327, JP-B-58-125
No. 77, JP-B-54-25957, JP-A-59-53
No. 836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, and a part thereof. There is an acidic cellulose derivative having a carboxylic acid in the side chain, such as an esterified maleic acid copolymer. In addition, those obtained by adding an acid anhydride to a polymer having a hydroxyl group are also useful. In particular, benzyl (meth) acrylate / (meth) acrylic acid copolymer and benzyl (meth) acrylate /
Multicomponent copolymers with (meth) acrylic acid / and other monomers are preferred. In addition, as a water-soluble polymer, 2
-Hydroxyethyl methacrylate, polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol and the like are also useful.

Further, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macro described in JP-A-7-140654. Monomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer And the like. As the addition amount of the alkali-soluble resin in the curable composition,
It is preferably from 5 to 90% by weight, more preferably from 10 to 60% by weight, based on the total weight of the composition.

As the colorant that can be used in the present invention, various types of conventionally known dyes, inorganic pigments or organic pigments can be used alone or in combination of two or more.

The dye that can be used in the present invention is not particularly limited, and dyes conventionally known for color filters can be used. For example, Japanese Patent Application Laid-Open Nos.
4-91102, JP-A-1-94301,
JP-A-6-11614, JP-B-2592207,
U.S. Pat. No. 4,808,501, U.S. Pat.
No. 20, US Pat. No. 505950, US Pat. No. 5,679,920, JP-A-5-333207, JP-A-6-35183, and JP-A-6-511.
No. 15, JP-A-6-194828 and the like can be used. Chemical structures include pyrazole azo, anilino azo, triphenylmethane,
Anthraquinone, benzylidene, oxonol,
Dyes of pyrazolotriazole azo type, pyridone azo type, cyanine type, phenothiazine type and pyrrolopyrazole azomethine type can be used. In particular, since the curable composition can be cured at a relatively low temperature, even if the dye is inferior in heat resistance compared to the pigment, it may be subjected to a high temperature during post-baking to impart durability to the cured film. Can reduce problems such as decomposition.

The inorganic pigment is a metal compound represented by a metal oxide, a metal complex salt or the like, and specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony or the like. Metal oxides,
And composite oxides of the above metals.

As the organic pigment, CI Pigment Yellow
11, 24, 31, 53, 83, 85, 99, 108, 109, 110, 138, 1
39, 150, 151, 154, 167, 185, CI Pigment Orange
36,38, 43, 71, CI Pigment Red 105, 122, 149, 15
0, 155, 171, 175, 176, 177, 209, 224, 242, 254, C.
I. Pigment Violet 19, 23, 32, 39, CI Pigment B
lue 1, 2, 15, 16, 22, 60, 66, 15: 3, 15: 6, CI Pi
gment Green 7, 36, 37, CI Pigment Brown 25, 28,
CI Pigment Black 1, 7 and carbon black.

These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples are shown below. As the red pigment, an anthraquinone pigment, a perylene pigment alone, or a mixture of at least one of them and a disazo yellow pigment or an isoindoline yellow pigment is used. For example, as anthraquinone pigments, C.I. I. Pigment Red 177 and perylene pigments include C.I. I. Pigment Red 155, and C.I. I. Pigment Yellow 8
3 or C.I. I. Pigment Yellow 139 is good. The weight ratio of the red pigment to the yellow pigment is 100:
5 to 100: 50 is good. In this range,
It is preferable because the light transmittance from 400 nm to 500 nm can be suppressed and the color purity can be increased. Also, the deviation from the NTSC target hue is small, which is preferable. Especially from 100: 10 1
The range of 00:30 is optimal.

As the green pigment, a halogenated phthalocyanine pigment alone or a mixture with a disazo yellow pigment, a quinophthalone yellow dye or an isoindoline yellow pigment is used. I. Pigment Green 7, 3
6, 37 and C.I. I. Pigment Yellow 83, 138,
139 is preferred. The weight ratio of the green pigment to the yellow pigment is preferably from 100: 5 to 100: 100. Within this range, light transmittance from 400 nm to 450 nm can be suppressed and good color purity can be obtained. Also, NTSC
The deviation from the target hue is small, which is preferable. Especially 100:
The range of 5 to 100: 50 is optimal.

As the blue pigment, a phthalocyanine pigment alone or a mixture with a dioxazine purple pigment is used. I. Pigment Blue 15: 6 and C.I.
I. Pigment violet 23 is preferred.
The weight ratio of the blue pigment to the purple pigment is 100: 0 to 100:
50 is preferred. Within this range, the light transmittance from 400 nm to 420 nm can be suppressed, the color purity can be increased, and the deviation from the NTSC target hue is small, which is preferable. Particularly, the range of 100: 0 to 100: 20 is optimal.

Further, a pigment having good dispersibility and dispersion stability can be obtained by using a powdery pigment obtained by finely dispersing the above pigment in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer, an ethyl cellulose resin or the like. Containing photosensitive resin can be obtained.

As the pigment for the black matrix, carbon, titanium oxide, iron oxide, alone or as a mixture is used, and carbon and titanium oxide are preferable. The weight ratio is preferably in the range of 100: 5 to 100: 40. Within this range, the light transmittance of long wavelengths is small and the dispersion stability is good.

A sensitizer may be used in combination with the curable composition of the present invention. Specific examples thereof include 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-
9-fluorenone, 9-anthrone, 2-bromo-9-
Anthrone, 2-ethyl-9-anthrone, 9,10-
Anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,
6-dichloro-9,10-anthraquinone, benzyl,
Dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethylamino) phenyl-p
-Methylstyryl ketone, benzoanthrone, and benzothiazole compounds described in JP-B-51-48516.

Solvents used for preparing the curable composition include esters such as ethyl acetate and acetic acid-n-
Butyl, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methoxy 3 such as methyl acetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, and ethyl 3-oxypropionate;
Alkyl oxypropionates; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2
-Ethyl oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2- Methyl oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate,
Ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate,
Methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .: 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, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Aromatic hydrocarbons, for example, toluene, xylene and the like.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol Acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used.

These solvents may be used alone or
It may be used in combination of more than one kind. The curable composition of the present invention can be prepared by mixing the above main components and other additives used as necessary with a solvent, and mixing and dispersing the mixture using various mixers and dispersers. . A general method for producing the color filter of the present invention using the curable composition is as follows.

The curable composition having the above properties is dissolved in a solvent, and the thickness of the dried composition is firstly 0.3 to 10 μm, preferably 0.5 to 3 μm on a suitable substrate by a spinner or the like.
And left in an oven at 85 ° C. for 2 minutes to obtain a smooth coating film. In order to further improve the adhesiveness between the curable composition and the substrate, after a thin coating with a silane coupling agent or the like in advance on the substrate, a pattern is formed,
Alternatively, a color filter may be formed by using a curable composition to which a small amount of a silane coupling agent or the like is added in advance.

The substrate is not particularly limited, but may be a substrate for electronic parts such as a glass plate, a plastics plate, an aluminum plate, a silicon wafer for an image sensor, a transparent resin plate, a resin film, a cathode ray tube display surface, Light-receiving surface, CC
Wafers with solid-state imaging devices such as D, BBD, CID, and BASIS, contact image sensors using thin-film semiconductors, liquid crystal display surfaces, photoconductors for color electrophotography, substrates for electrochromic (EC) display devices, etc. Is mentioned. Further, it is preferable to perform a high adhesion treatment on the substrate in order to improve the adhesion to the color filter layer. Specifically, a pattern of the curable composition is formed after a thin coating with a silane coupling agent or the like in advance on a substrate, or a color filter is formed by including a silane coupling agent in the curable composition in advance. May be.

In order to form an intended image on the coating film, light having the sensitivity of the curable composition (eg, ultraviolet ray, high-pressure mercury lamp, etc.) is passed through a negative mask in at least two stages corresponding to the transmitting portion and the reflecting portion. Irradiation is performed in a pattern such that the exposure amount becomes. At this time, it is preferable to use an exposure mask that changes the light amount of each pattern portion. Further, it is preferable to use an apparatus such as a mask alignment so that a parallel light beam is irradiated on the coating film surface. Next, the irradiated coating film is left as it is or is heated for a short time as needed to promote polymerization, and then exposed to a flowing solution of a developer or a shower to dissolve the uncured portion, By performing the development, an image (color filter) having a remaining film ratio controlled in accordance with the above-described at least two-step exposure amounts, that is, having at least two kinds of film thicknesses is obtained.

The developer used for developing the curable composition is not particularly limited, and a conventionally known developer can be used. Among them, a sodium carbonate-based developer is preferred for achieving the object of the present invention.

When forming two or more color filters, a curable composition containing a colorant corresponding to each color can be used as necessary, that is, according to the following diagram of the color of the filter used. Is repeated by using each of the colors (e.g., R (red), G
(Green), three colors of B (blue), three colors of Y (yellow), M (magenta), C (cyan), and a black matrix, etc.) and two or more types of patterned colored resin layers. Can be obtained.

The color filter of the present invention can be applied to any type of so-called transflective liquid crystal display device having a transmissive portion and a reflective portion. Hereinafter, a specific transflective liquid crystal display device to which the color filter of the present invention can be applied will be described, but the present invention is not limited to this embodiment.

The liquid crystal device of the present invention is a transflective liquid crystal device that performs only reflective display in a bright place, and also uses transmissive display in a dark place. First and second substrates having transparency, a liquid crystal layer sandwiched between the first and second substrates, and a transparent electrode formed on a surface of the first substrate on the liquid crystal layer side; A transflective electrode formed on a surface of the second substrate on the liquid crystal layer side;
A colored layer formed on the upper surface of the transflective electrode.

FIG. 2 is a schematic sectional view showing the structure of a specific liquid crystal device. As shown in FIG. 2, the liquid crystal device has a configuration in which a liquid crystal layer 18 is sealed between two transparent substrates 11 and 21 by a frame-shaped sealing material 19. The liquid crystal layer 18 is a nematic liquid crystal having a predetermined twist angle. Here, a transparent electrode 25 made of ITO (Indium Tin Oxide) or the like is formed on the inner surface of the substrate 21 on the upper side (observation side) in the figure. An alignment film 26 is further formed on the surface of the transparent electrode 25, and rubbing is performed in a predetermined direction.

According to the above-mentioned liquid crystal device, in the transmissive display, light is incident from the second substrate 11 side and transmitted through the transmissive portion 12A of the transflective electrode 12, and then the color filter layer having a large thickness is formed. The light is emitted from the first substrate 21 side through 1A and the liquid crystal layer 18 in order. On the other hand, in the reflection type display, after the light enters from the first substrate 21 side, the light is reflected by the reflection portion 12B of the transflective electrode 12 through the liquid crystal layer 18 and the color filter layer 1B having a small thickness in this order. The light is emitted from the first substrate 21 side by following the path in reverse.

Here, in the liquid crystal device, the transflective electrode 12 is provided with a slit-shaped or square-shaped opening as the transmission portion 12A, and the color corresponding to the position where the opening is provided. The filter is formed thick (1A). Accordingly, in the transmissive display, light is transmitted (passed) through the opening, and is emitted from the first substrate side through the coloring layer and the liquid crystal layer in this order. At this time, since the thick color filter layer 1A is formed corresponding to the position 12A where the opening is provided, the light passing through the opening is colored by the thick color filter layer 1A. . On the other hand, in the reflection type display, coloring is performed by reciprocating through the color filter layer 1B having a small film thickness. As a result, the color reproducibility of the transmissive display and the reflective display is improved. In addition, by forming the transflective electrode 12 on the liquid crystal layer 18 side of the second substrate 11, the distance from the liquid crystal layer can be reduced. Blurring of display can be effectively suppressed.

This will be described in more detail with reference to FIG. In FIG. 2, a transflective electrode 12 made of, for example, aluminum is formed on the inner surface of the lower substrate 11.
Such a transflective film is realized by a configuration in which a transflective electrode 12 is provided with a slit or the like and opened. The transflective electrode 12 has a liquid crystal layer 18 at the reflection portion 12B.
While the light incident from the side (upper side) is reflected and re-introduced into the liquid crystal layer 18, the light incident from the substrate 11 side (lower side) is transmitted and introduced into the liquid crystal layer 18 in the transmission section 12 </ b> A. I have.

On the upper surface of such a transflective electrode 12, the color filter 1 of the present invention is sequentially formed. Here, the color filter 1 is, for example, R
The three colors (red), G (green), and B (blue) are arranged in a predetermined pattern, and a portion 1A having a large film thickness corresponding to a transmission portion and a portion having a small film thickness corresponding to a reflection portion. 1B is set. Here, as the arrangement of the color filters 1, for example, an arrangement of a stripe shape, a mosaic shape, a triangle shape, or the like can be selected and used depending on the application. Further, a flattening film 15 made of an organic film or the like may be formed on the upper surface of the color filter 1 in order to eliminate a step. Then, on the surface of the flattening film 15,
The diffusion film 16 and the alignment film 17 may be formed and rubbed in a predetermined direction.

On the outer surface of the upper substrate 21, a retardation plate 23 and a polarizing plate 24 are arranged in this order when viewed from the substrate 21 side. On the other hand, on the lower side of the liquid crystal panel, that is, outside the lower substrate 11, a retardation plate 13 and a polarizing plate 14 are arranged in this order when viewed from the substrate 11 side. Further, a backlight including a fluorescent tube 32 that emits white light and a light guide plate 31 having an incident end face along the fluorescent tube 32 is disposed below the polarizing plate 14. Among them, the light guide plate 31
Has a rough surface for light scattering on the entire back surface, or
It is a transparent body such as an acrylic resin plate on which a scattering printing layer is formed, receives white light of a fluorescent tube 32 as a light source on its incident end face, and emits substantially uniform light from its surface (upper surface in the figure). It is supposed to. Note that an LED (light emitting diode), EL (electroluminescence), or the like can be used as the backlight.

In the reflective display, external light is transmitted through the polarizing plate 2.
4. After passing through the phase difference plate 23 in order and passing through the liquid crystal layer 18 and the thin portion 1B of the color filter, the light is reflected by the transflective electrode 12B, reversely follows the current path, and is again polarized. The light exits from the plate 24. At this time, passing (bright state) and absorption (dark state) of the polarizing plate 24 and brightness between them can be controlled according to the voltage applied to the liquid crystal layer 18.

In the transmissive display, the light from the backlight is transmitted through the polarizing plate 14 and the phase difference plate 13 in order to be in a predetermined polarization state, and the transflective electrode 12A
Through the filter, and the portion 1 where the thickness of the color filter is large.
A, after being introduced into the liquid crystal layer 18, through the retardation plate 23,
The light exits from the polarizing plate 24. At this time, the passing (bright state) and absorption (dark state) of the polarizing plate 24 and the intermediate brightness can be controlled according to the voltage applied to the liquid crystal layer 18.

According to such a liquid crystal device, light is transmitted through the color filter portion 1B having a small film thickness in the reflection type display and the color filter portion 1A having the large film thickness in the transmission type display. An improvement in reproducibility can be achieved. A preferable thickness ratio of the color filter portion 1A having a large thickness to the color filter portion 1B having a small thickness is in a range of 1.5 to 5.0.

In this liquid crystal device, since light from the backlight passes through the transflective electrode, a bright display using a transmissive display can be performed even in a dark place, while a bright display can be obtained. In some places, bright display by reflective display is possible, and power consumption is reduced by turning off the backlight. In addition, a front light may be provided on the upper surface of the upper substrate 21 instead of the backlight, and a mechanism for taking in external light may be provided below the lower substrate 11. In this configuration, in a bright place, a transmissive display is mainly performed, while in a dark place, a reflective display is mainly performed.

Further, in the liquid crystal device, although not shown, a protective film may be formed between the color filter layer (colored layer) 1 and the transflective electrode 12.

As a driving method of the liquid crystal device, various methods such as an active matrix method can be applied in addition to a passive matrix method. The switching elements in these embodiments include TFD (Thin Fil).
Various elements such as an mDiode element and a TFT (ThinFilm Transistor) element can be applied.

Further, the liquid crystal device may further have a second transparent electrode on the upper surface of the colored layer. Thus, since the second transparent electrode exists in the opening provided in the transflective electrode, an electric field is also applied to the opening.
For this reason, the liquid crystal molecules located in the opening are aligned without being caused by the leaked electric field from the edge of the opening, so that light having no optical rotation is prevented from passing through the opening, thereby improving the display quality. It will be improved. Further, the opening can be formed without depending on the formation area of the pixel or the dot.

Further, the light-shielding layer 3 (black matrix) may be formed on the portion of the substrate 11 where the color filter 1 is not formed. The light-shielding layer 3 is provided to eliminate light leakage from a non-display portion in the liquid crystal device and prevent a decrease in contrast. The formation of the light shielding layer 3 is effective in terms of increasing the contrast and preventing deterioration of the switching element. Further, in an active matrix type liquid crystal device in which a switching element is connected to a pixel electrode, the light shielding layer 3 also has a role of preventing deterioration of the switching element due to a light leakage current. The light-shielding layer 3 is formed separately from the color filter 1 using a metal having a high light-shielding property such as chrome, a color resist in which a black pigment is dispersed, or the like.
By superposing the color filters 1 of (red), G (green) and B (blue), the color filters 4 can be formed by themselves.

In the above description, three colors of R (red), G (green), and B (blue) are used as the color filter 1.
The present invention is not limited to this, and for example, three colors of Y (yellow), M (magenta), and C (cyan) may be used. Here, the transflective electrode 12 has been described as not being patterned in particular. However, it should be noted that the transflective electrode 12 may or may not be patterned into a predetermined shape as described later. .

The liquid crystal device of the present invention can be used as various display devices capable of bright and high-quality display in a dark place or in a bright place, and further, can be used as a display unit of various electronic devices. is there. Examples of electronic devices in which such a liquid crystal device is used include a liquid crystal television, a viewfinder type or a monitor direct-view type video tape recorder,
Examples include a car navigation device, a calculator, a PDA (personal information terminal), a pager, a word processor, a workstation, a videophone, a POS terminal, and a device equipped with a touch panel.

[0110]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these examples. In the following examples, “parts” means “parts by mass” unless otherwise specified.

Examples 1 and 2 and Comparative Example 1 <Preparation of Red Pigment Dispersion> The following composition was mixed, and the resulting mixture was dispersed with beads having an average particle diameter of 0.3 mm using a bead disperser. Thus, a pigment dispersion was prepared.

(Red Pigment Composition) Benzyl methacrylate / methacrylic acid copolymer (80/20 wt%) 12 parts CI Pigment Red 254, 18 parts Dispersant 2 parts Propylene glycol monomethyl ether acetate 68 parts

<Preparation of Coating Film> Each of the following compositions was applied to a glass substrate for a color filter by spin coating.
1. Pre-bake on a hot plate at 00 ° C for 2 minutes.
A coating of 0 μm was obtained.

Curable composition (CR); Comparative example 1R Red pigment dispersion 13.3 parts Dipentaerythritol hexaacrylate 9.6 parts Photopolymerization initiator (1) 1.1 parts Both benzyl methacrylate / methacrylic acid Polymer (80 / 20wt%) 9.5 parts Propylene glycol monomethyl ether acetate 66.5 parts

Curable Composition (1R); Example 1R The above red pigment dispersion 13.3 parts Dipentaerythritol hexaacrylate 9.6 parts The above photopolymerization initiator (I-1) 1.1 parts Benzyl methacrylate / methacrylic Acid copolymer (80 / 20wt%) 9.5 parts Propylene glycol monomethyl ether acetate 66.5 parts

Curable Composition (2R); Example 2R The above red pigment dispersion 13.3 parts Dipentaerythritol hexaacrylate 9.6 parts The above photopolymerization initiator (I-1) 0.6 part The above photopolymerization initiation Agent (II-2) 0.5 part Benzyl methacrylate / methacrylic acid copolymer (80/20 wt%) 9.5 parts Propylene glycol monomethyl ether acetate 66.5 parts

[0117]

Embedded image

Then, using an ultra-high pressure mercury lamp of 2.5 Kw, passing through a mask, 50, 100, 600, 1200 m
An exposure dose of J / cm ² was applied. Pixels were formed by developing with a 10% dilution of a developer CD (manufactured by Fuji Film Arch Co., Ltd.) at 30 ° C. for 40 seconds. The results of the residual film ratio shown in Table 1 were obtained.

[0119]

[Table 1]

<Preparation of Green Pigment Dispersion> A pigment dispersion was prepared by mixing the following compositions and dispersing the resulting mixture using beads having an average particle diameter of 0.3 mm using a bead disperser.

(Green Pigment Composition) Benzyl methacrylate / methacrylic acid copolymer (80/20 wt%) 12 parts C.I. Pigment Green 36, 18 parts Dispersant 2 parts Propylene glycol monomethyl ether acetate 68 parts

<Preparation of Coating Film> Each of the following compositions was applied to a glass substrate for a color filter by spin coating.
1. Pre-bake on a hot plate at 00 ° C for 2 minutes.
A coating of 0 μm was obtained.

Curable Composition (CG); Comparative Example 1G The above green pigment dispersion 13.3 parts Dipentaerythritol hexaacrylate 9.6 parts The above photopolymerization initiator (1) 1.1 parts Benzyl methacrylate / methacrylic acid Polymer (80 / 20wt%) 9.5 parts Propylene glycol monomethyl ether acetate 66.5 parts

Curable Composition (1G); Example 1G The above green pigment dispersion 13.3 parts Dipentaerythritol hexaacrylate 9.6 parts The above photopolymerization initiator (I-1) 1.1 parts Benzyl methacrylate / methacrylic Acid copolymer (80 / 20wt%) 9.5 parts Propylene glycol monomethyl ether acetate 66.5 parts

Curable Composition (2G); Example 2G The above green pigment dispersion 13.3 parts Dipentaerythritol hexaacrylate 9.6 parts The above photopolymerization initiator (I-1) 0.6 part The above photopolymerization initiation Agent (II-2) 0.5 part Benzyl methacrylate / methacrylic acid copolymer (80/20 wt%) 9.5 parts Propylene glycol monomethyl ether acetate 66.5 parts

Then, using an ultra-high pressure mercury lamp of 2.5 Kw and passing through a mask, 50, 100, 600, 1200 m
An exposure dose of J / cm ² was applied. Pixels were formed by developing with a 10% dilution of a developer CD (manufactured by Fuji Film Arch Co., Ltd.) at 30 ° C. for 40 seconds. The results of the residual film ratio shown in Table 2 were obtained.

[0127]

[Table 2]

<Preparation of Blue Pigment Dispersion> A pigment dispersion was prepared by mixing the following compositions and dispersing the resulting mixture with beads using an average particle diameter of 0.3 mm beads.

(Blue pigment composition) Benzyl methacrylate / methacrylic acid copolymer (80/20 wt%) 12 parts C.I. Pigment Blue 15: 6, 18 parts Dispersant 2 parts Propylene glycol monomethyl ether acetate 68 parts

<Preparation of Coating Film> Each of the following compositions was applied to a glass substrate for a color filter by spin coating.
1. Pre-bake on a hot plate at 00 ° C for 2 minutes.
A coating of 0 μm was obtained.

Curable composition (CB); Comparative Example 1B The above blue pigment dispersion 13.3 parts Dipentaerythritol hexaacrylate 9.6 parts The above photopolymerization initiator (1) 1.1 parts Benzyl methacrylate / methacrylic acid Polymer (80 / 20wt%) 9.5 parts Propylene glycol monomethyl ether acetate 66.5 parts

Curable Composition (1B); Example 1B The above blue pigment dispersion 13.3 parts Dipentaerythritol hexaacrylate 9.6 parts The above photopolymerization initiator (I-1) 1.1 parts Benzyl methacrylate / methacrylic Acid copolymer (80 / 20wt%) 9.5 parts Propylene glycol monomethyl ether acetate 66.5 parts

Curable Composition (2B); Example 2B The above blue pigment dispersion 13.3 parts Dipentaerythritol hexaacrylate 9.6 parts The above photopolymerization initiator (I-1) 0.6 parts The above photopolymerization initiation Agent (II-2) 0.5 part Benzyl methacrylate / methacrylic acid copolymer (80/20 wt%) 9.5 parts Propylene glycol monomethyl ether acetate 66.5 parts

Then, using an ultra-high pressure mercury lamp of 2.5 Kw, passing through a mask, 50, 100, 600, 1200 m
An exposure dose of J / cm ² was applied. Pixels were formed by developing with a 10% dilution of a developer CD (manufactured by Fuji Film Arch Co., Ltd.) at 30 ° C. for 40 seconds. The results of the residual film ratio shown in Table 3 were obtained.

[0135]

[Table 3]

Example 3 and Comparative Example 2 A yellow pigment dispersion was prepared by mixing the following components, dispersing the mixture with beads having an average particle diameter of 0.3 mm using a bead disperser.

(Yellow pigment composition) Benzyl methacrylate / methacrylic acid copolymer (80/20 wt%) 12 parts C.I. Pigment Yellow 139, 18 parts Dispersant 2 parts Propylene glycol monomethyl ether acetate 68 parts

Next, a red curable composition (3R), a green curable composition (3G) and a blue curable composition (3B) having the following compositions were prepared.

(Red curable composition (3R)) The red pigment dispersion 16.9 parts The yellow pigment dispersion 1.0 parts Dipentaerythritol hexaacrylate 9.6 parts The photopolymerization initiator (I-1) 0.6 part The photopolymerization initiator (II-1) 0.5 part Benzyl methacrylate / methacrylic acid copolymer (80/20 wt%) 4.9 parts Propylene glycol monomethyl ether acetate 66.5 parts

(Green curable composition (3G)) The green pigment dispersion 10.8 parts The yellow pigment dispersion 2.5 parts Dipentaerythritol hexaacrylate 9.6 parts The photopolymerization initiator (I-1) 0.6 part The photopolymerization initiator (II-1) 0.5 part Benzyl methacrylate / methacrylic acid copolymer (80/20 wt%) 9.5 parts Propylene glycol monomethyl ether acetate 66.5 parts

(Blue curable composition (3B)) The above blue pigment dispersion 14.6 parts Dipentaerythritol hexaacrylate 9.6 parts The above photopolymerization initiator (I-1) 0.6 parts The above photopolymerization initiator (II-1) 0.5 part Benzyl methacrylate / methacrylic acid copolymer (80/20 wt%) 8.2 parts Propylene glycol monomethyl ether acetate 66.5 parts

As Comparative Example 2, the above curable composition (3
R), (3G) and (3B)
-1) Instead of 0.6 part and 0.5 part of photopolymerization initiator (II-1), 1.1 parts of photopolymerization initiator (1) used in Comparative Example 1 were used.
Red curable composition (CCR), Green curable composition (CCG)
And a blue curable composition (CCB).

<Preparation of the Color Filter of the Present Invention> The red curable composition (3R) was placed on a glass substrate according to a general procedure of a color filter production method of a photolithography method.
Was coated in a thickness of 0 .mu.m, 200 mJ / cm ² with respect to the color filter substrate portion corresponding to the reflective film facing portion, exposure of 1000 mJ / cm ² with respect to the color filter substrate part corresponding to the coating removal portion facing portion , Development, rinsing, and post-baking, and the thickness of the reflective film facing portion (1B) is set to 0.
A red pattern having a thickness of 8 μm and a thickness of the film-removed portion facing portion (1A) of 1.6 μm was obtained. Similarly, patterning was performed using the green curable composition (3G) and the blue curable composition (3B), thereby producing a color filter (1).

<Preparation of Comparative Color Filter> A comparative red curable composition (CCR) was placed on a glass substrate in an amount of 0.9%.
It is applied with a thickness of μm, uniformly exposed at an exposure amount of 200 mJ / cm ² , developed, rinsed, and post-baked, and the film thickness of the reflective film facing portion (1B) and the film removing portion facing portion (1A) is reduced. In each case, a red pattern having a thickness of 0.8 μm was obtained. Similarly, patterning was performed using the green curable composition (CCG) and the blue curable composition (CCB) to prepare a color filter (C).

Using these color filters, the chromaticity and color reproducibility of the transmission part of the color filters were measured, and the results shown in Table 4 were obtained.

[0146]

[Table 4]

Here, the color reproducibility means the NTSC chromaticity (R: x = 0.67, y = 0.33,
G: x = 0.21, y = 0.71, B: x = 0.14,
The area of the chromaticity triangle of red (R), green (G), and blue (B) is expressed as a percentage when the area of the chromaticity triangle of y = 0.88) is set to 100. The reproducibility (%) is determined by (the area of the chromaticity triangle of RGB / the area of the chromaticity triangle of the NTSC dye) × 100. It can be seen from the invention that the color reproducibility of the filter is excellent.

Examples 4 to 8 In the same manner as in the green curable composition (1G) prepared in Example 1, each of the green curable compositions (4G) to (8G) having the composition shown in Table 5 below. Was prepared and applied and developed on a glass substrate in the same manner as in Example 1 to form each pixel. The results of the residual film ratio shown in Table 6 were obtained.

[0149]

[Table 5]

[0150]

[Table 6]

By using these photopolymerization initiators, a color filter for transflective liquid crystal display having excellent color reproducibility can be easily obtained in the same manner as in Example 3.

[0152]

By using the curable composition of the present invention, a transflective color liquid crystal display device having excellent color reproducibility can be easily obtained. In particular, according to the present invention, the number of times of exposure and development for separately creating a color filter layer opposed to a reflective portion and a transmissive portion is reduced, thereby simplifying the process. And the above transflective color liquid crystal display device can be obtained.

[Brief description of the drawings]

FIG. 1 is a graph for explaining characteristics of a curable composition of the present invention.

FIG. 2 is a schematic sectional view showing a part of the configuration of a transflective color liquid crystal display device of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 color filter layer 3 light-shielding layer (black matrix) 11 transparent substrate 12 semi-transmissive reflective electrode 12A transmitting part 12B reflecting part 13 retardation plate 14 polarizing plate 15 flattening film 16 diffusion layer 17 alignment film 18 liquid crystal layer 19 sealing material 21 transparent Substrate 23 Retardation plate 24 Polarizing plate 25 Transparent electrode 26 Alignment film 31 Light guide plate 32 Fluorescent tube

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 291/00 C08F 291/00 4J011 G02F 1/1333 500 G02F 1/1333 500 4J026 1/1335 505 1/1335 505 G03F 7/028 G03F 7/028 7/26 501 7/26 501 F term (reference) 2H025 AA04 AB13 AC01 AD01 BC13 BC42 CA03 CA09 CA22 CA35 CB08 CB42 CC11 FA17 2H048 BA45 BA48 BB12 BB14 BB43 2H090 JB02 FB02 2104 FC10 FC22 FC23 GA01 LA12 LA15 2H096 AA28 BA05 EA02 GA08 4J011 PA07 PA22 PA63 PA67 PA69 PA70 PA74 PA90 PB25 PB40 PC02 PC08 QA03 QA04 QA13 QA22 QA23 QA24 QA33 QA39 QA46 QB14 QB16 QB19 RA10 SA02 RA02 SA02 RA02 SA02 RA02 SA02 RA02 SA22 SA24 SA28 SA29 SA32 SA34 SA38 SA61 SA63 SA64 SA82 TA03 TA07 TA09 TA10 UA01 UA06 VA01 W A01 4J026 AA43 AA44 AA53 AA76 AC36 BA27 BA28 BA29 BA30 BA50 DB06 DB11 DB36 GA06

Claims (12)

[Claims] 1. A curable composition containing a colorant, an alkali-soluble resin, a radiation-sensitive curable compound, a photopolymerization initiator and a solvent, which is applied on a substrate in a thickness of 0.3 to 5.0 μm. , 1 to 12 on the coating film formed by pre-baking
After exposing with an exposure amount of 00 mJ, the remaining film ratio on the substrate relative to the exposure amount of the coating film when developed with an alkali developing solution / (film thickness after development / film thickness after pre-baking) × 100
(%) Varies continuously in at least the range of 60% to 70% in any range of the exposure amount of 1 mJ to 1200 mJ, and the photopolymerization initiator comprises (I)
Hexaarylbisimidazole compounds, (II) benzophenone compounds, (III) acetophenone compounds, (IV) acylphosphine compounds, (V) benzoin ether compounds, (VI) xanthone compounds, and (VII) quinone compounds A curable composition for a color filter of a transflective color liquid crystal display device, which is at least one compound selected from compounds. 2. The method according to claim 1, wherein the photopolymerization initiator comprises at least one of (I) a hexaarylbisimidazole compound and (I)
2. The curable composition for a color filter of a transflective color liquid crystal display device according to claim 1, which is a mixture of at least one type of a benzophenone compound. 3. The transflective color liquid crystal display device according to claim 1, wherein the (I) hexaarylbisimidazole compound is a compound represented by the following general formula (Ia). Curable composition. Embedded image 中 In the formula (Ia), X ¹ and X ² may be the same or different and each represents a hydrogen atom, a chlorine atom or a bromine atom. ｝ 4. The curable composition for a color filter of a transflective color liquid crystal display device according to claim 1, wherein the benzophenone compound (II) is a compound represented by the following general formula (II-a). . Embedded image 中 In the formula (II-a), R ^{1 to} R ⁴ may be the same or different,
Each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ｝ 5. The (I) hexaarylbisimidazole compound is a compound represented by the general formula (Ia) according to claim 3, and the (II) benzophenone compound is a compound represented by the general formula (4). The curable composition for a color filter of a transflective color liquid crystal display device according to claim 2, which is a compound represented by the formula (II-a). 6. The curable composition for a color filter of a transflective color liquid crystal display device according to claim 1, wherein the acetophenone compound (III) is a compound represented by the following general formula (III-a). Embedded image 中 In the formula (III-a), R ⁵ and R ⁶ may be the same or different and each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ｝ 7. The curable composition for a color filter of a transflective color liquid crystal display device according to claim 1, wherein the (VI) xanthone-based compound is a compound represented by the following general formula (VI-a). Embedded image 中 In the formula (VI-a), R ¹⁰ and R ¹¹ may be the same or different and each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ｝ 8. A color for a transflective liquid crystal display device prepared by applying the curable composition according to claim 1 on a substrate, prebaking, pattern exposure, alkali development, and postbaking. filter. 9. After applying the curable composition according to any one of claims 1 to 7 on a substrate, pre-baking and pattern exposure, alkali-developing with a sodium carbonate-based alkali developing solution,
A method of manufacturing a color filter for a transflective liquid crystal display device, characterized by post-baking. 10. The method of manufacturing a color filter for a transflective liquid crystal display device according to claim 9, wherein an exposure mask for changing the light amount of the pattern portion for each color is used for the pattern exposure. 11. A transflective liquid crystal display device comprising the color filter according to claim 8. 12. The transflective liquid crystal display device according to claim 11, wherein the substrate is an aluminum substrate or a glass substrate.