JP5786501B2 - Color filter, liquid crystal display element, and method of manufacturing color filter - Google Patents

Description

  The present invention relates to a color filter, a liquid crystal display element, and a method for manufacturing a color filter.

  The liquid crystal display element includes a liquid crystal panel configured by sandwiching liquid crystal between a pair of substrates such as a glass substrate. An alignment film for controlling liquid crystal alignment can be provided on the surface of the substrate sandwiching the liquid crystal. Between the pair of substrates, spherical or rod-like spacers made of glass, alumina, or resin are disposed by spraying or the like, and the thickness of the liquid crystal is maintained at a predetermined value of about 1 μm to 20 μm. The liquid crystal display element causes a change in the alignment of the liquid crystal and functions as a fine shutter for light emitted from a light source such as a backlight or external light. Then, display is performed by partially transmitting or blocking light. The liquid crystal display element has excellent characteristics such as thinness and light weight.

At the beginning of development, liquid crystal display elements were used as display elements for calculators and clocks mainly for character display. Later, by enabling dot matrix display on a large screen, the application was expanded to display devices for notebook computers.
Furthermore, liquid crystal display elements have been used for monitors of PCs (personal computers) because problems such as high definition, colorization, and viewing angle expansion have been overcome. Recently, a wider viewing angle, faster response of liquid crystal, improved display quality, etc. have been realized, and it has come to be used as a display element for large thin televisions.

One of the technologies that enabled the development of such a liquid crystal display element is a colorization technology that enables color display as described above.
A liquid crystal display element usually cannot develop color by itself, and it is difficult to perform color display. Therefore, a technology using a color filter has been developed, and the liquid crystal display element can realize color display.
The colorization technique using a color filter can also be used for an organic EL (Electro Luminescence) element using a white light emitting layer, or for color display such as electronic paper. Furthermore, if a color filter is used, color imaging of a solid-state imaging device such as a CCD (Charge Coupled Device) image sensor or a CMOS (Complementary Metal Oxide Semiconductor) image sensor becomes possible.

The color filter is composed of a transparent substrate such as glass and a minute coloring pattern such as red, green, and blue. The coloring pattern takes a regular shape such as a lattice shape and is arranged on the transparent substrate.
As a color filter manufacturing method, for example, the following is known. On the transparent substrate or a transparent substrate on which a light-shielding layer having a desired pattern is formed, a coloring composition sensitive to an appropriate irradiation beam is applied. As the coloring composition, a pigment-dispersed colored radiation-sensitive composition containing a pigment such as red, green or blue in the colorant can be used. Next, after the coating film is dried, the dried coating film is irradiated with radiation (hereinafter referred to as “exposure”) through a mask and subjected to a development treatment. Then, for example, curing at a high temperature exceeding 200 ° C. such as 230 ° C. is performed to obtain a fixed colored pattern (see, for example, Patent Document 1 or Patent Document 2).

In recent years, the demand for higher image quality and higher brightness for display elements has been increasing, and color filters are also strongly required to contribute to such performance improvements. In order to achieve high contrast of the display element and high definition of the solid-state imaging element, it is effective to use a dye as a colorant (see Patent Documents 3 to 5). Also in color filters, a technique using a dye as a colorant has attracted attention. In a conventional coloring composition containing a dye, a method for forming a coloring pattern is mainly employed, in which a polyfunctional acrylate, an alkoxymethylmelamine resin or the like and a polymerization initiator are combined and cured by heating.
However, a coloring pattern formed using a conventional coloring composition containing a dye has a problem that reliability, particularly heat resistance, is inferior to a coloring pattern using a coloring composition containing a pigment. Therefore, in order to form a colored pattern having excellent characteristics using a coloring composition containing a dye, heating at a lower temperature is required in the curing step.

  In the production of a color filter, after forming a colored pattern, a protective film is formed on the colored pattern before forming an ITO (Indium Tin Oxide) film that forms an electrode. Is possible. This protective film is formed to protect the colored pattern while realizing an ITO electrode with excellent characteristics. Here, in order to form the protective film, a curing step is usually required. When the heating in this curing step has a colored pattern formed using a coloring composition containing a dye in the lower layer, the heating will cause the deterioration. Therefore, there is a demand for lowering the temperature of the curing process for forming the protective film.

  Furthermore, in color filters, a technique for providing columnar spacers has been actively developed recently (see, for example, Patent Document 6). The columnar spacers erected on the color filter are formed using, for example, a photosensitive resin so as to keep a distance between the pair of substrates holding the liquid crystal at a predetermined value. The columnar spacer realizes the control of the thickness of the liquid crystal sandwiched between the substrates with high accuracy. Therefore, this is a technique that replaces the conventional spherical or rod-shaped spacers disposed between the substrates.

  When the columnar spacer is provided in the color filter, the spacer is formed on the ITO electrode which is a transparent electrode of the color filter. That is, after a colored pattern is formed on a substrate, an ITO electrode is formed thereon, and columnar spacers are formed on the ITO electrode using, for example, a photolithography technique. At this time, a curing step is usually required for forming the spacer. And the heating in the hardening process of a columnar spacer may cause deterioration of the coloring pattern of the color filter in the lower layer. In particular, when a coloring pattern is formed from a coloring composition containing a dye, the deterioration becomes a big problem. Accordingly, there is a strong demand for lowering the temperature of the columnar spacer curing process.

  In the liquid crystal display element, as described above, an alignment film for controlling liquid crystal alignment can be provided on the surface of the substrate that holds the liquid crystal. In that case, in the color liquid crystal display element, an alignment film is provided on the ITO electrode on the colored pattern in the color filter. When the color filter has a columnar spacer, the alignment film is formed after the columnar spacer is formed. Conventionally, for example, a liquid crystal aligning agent containing a polyimide or a polymer as a precursor thereof has been used for forming the alignment film. That is, an alignment treatment agent is used, applied onto a substrate constituting a color filter, and heated and cured to obtain an alignment film. Therefore, a curing step is required for forming the alignment film. At this time, the heating in the curing step may cause deterioration when there is a colored pattern formed using a colored composition containing a dye in the lower layer. Therefore, it is required to lower the temperature of the curing process for forming the alignment film, and an alignment film that can cope with curing at a low temperature is required.

  In addition to the function of aligning liquid crystals, the alignment film is required to have a function of suppressing deterioration in display quality of the liquid crystal display element. For example, in order to suppress an afterimage phenomenon that deteriorates the display quality of a liquid crystal, an alignment film that can reduce the charge remaining when a DC voltage is applied is required. Such a function of the alignment film is realized by selecting a material constituting the alignment film and optimizing the structure of the material.

JP-A-2-144502 JP-A-3-53201 JP-A-2005-99584 JP 2007-219466 A JP 2007-316179 A Japanese Patent Laid-Open No. 11-344700

  As described above, although the dye is excellent as a colorant for the color pattern of the color filter, it has a problem in heat resistance. Therefore, a color filter having a colored pattern formed from a conventional colored composition containing a dye has a problem of poor heat resistance. Therefore, the color filter is required to be manufactured by forming a protective film, a columnar spacer (hereinafter, simply referred to as a spacer unless otherwise specified), and an alignment film in addition to a colored pattern by a low-temperature curing process.

  Conventionally, in the manufacture of color filters, for example, the colored pattern, the protective film, the columnar spacer, and the alignment film are cured and formed by a high-temperature heating process exceeding 200 ° C., for example. I came. However, recently, from the viewpoint of energy saving, it has been required to lower the temperature of the heating process in such production. That is, from the viewpoint of realizing energy saving, it is required to lower the temperature of the manufacturing process of the color filter for curing the colored pattern.

However, a conventional color filter obtained by a low temperature curing process may not be able to realize sufficient performance in terms of development resistance and reliability such as voltage holding ratio when applied to a liquid crystal display element. The cause of such a problem is that the coloring reactivity cured at low temperature using the conventional coloring composition, and the curing reactivity of the protective film, spacer and alignment film cured at low temperature are insufficient.
Therefore, there is a need for a highly reliable color filter that uses a coloring composition that can be cured at low temperature and can contain a dye, and further includes a protective film, a spacer, and an alignment film, and can be manufactured by a low-temperature curing process. Yes. In particular, the alignment film is preferably an alignment film that can be formed by curing at a low temperature and has a structure that can reduce residual charges when a DC voltage is applied.

  As described above, a coloring pattern formed of a coloring composition that can be cured at low temperature and containing a dye, a protective film that can be formed by low temperature curing, a spacer that can be formed by low temperature curing, and a direct current charge formed by low temperature curing. Realization of a color filter having an alignment film with little residual is desired. The color filter is excellent in development resistance, heat resistance, solvent resistance, voltage holding ratio, and the like, and it is strongly desired to enable high image quality and high brightness in a liquid crystal display element.

  The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a coloring pattern formed from a coloring composition that can be cured at low temperature and containing a dye in the colorant, a protective film formed by low temperature curing, and a spacer formed by low temperature curing. And a color filter having an alignment film having a structure suitable for low-temperature curing and a reduction in residual of applied DC charge, and a method for manufacturing the color filter.

  Another object of the present invention is to provide a coloring pattern that is formed using a coloring composition that can be cured at low temperature and can contain a dye in the colorant, a protective film formed by low temperature curing, and low temperature curing. An object of the present invention is to provide a liquid crystal display element constituted by using a color filter having a spacer formed and an alignment film having a structure suitable for low temperature curing and reduction of residual applied DC charge.

According to a first aspect of the present invention, there is provided a coloring pattern containing at least one colorant selected from the group consisting of a diketopyrrolopyrrole pigment, a zinc halide phthalocyanine pigment, a triarylmethane dye, and an azo dye. ,
[A] a compound having an epoxy group,
[B] a polymerizable compound having an ethylenically unsaturated bond,
[C] a radiation-sensitive polymerization initiator, and [D] a compound containing at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2). A protective film formed from the radiation sensitive resin composition of 1;
[E] alkali-soluble resin,
[F] a polymerizable compound having an ethylenically unsaturated bond,
[G] a radiation-sensitive polymerization initiator, and [H] a compound containing at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2). A spacer formed from the radiation sensitive resin composition of 2;
A polyamic acid obtained by reacting a tetracarboxylic dianhydride containing 2,3,5-tricarboxycyclopentylacetic dianhydride with a diamine, and a polyimide formed by dehydrating and ring-closing the polyamic acid are selected. The present invention relates to a color filter comprising an alignment film formed from a liquid crystal aligning agent containing at least one [P] polymer.

（式（１）中、Ｒ^１〜Ｒ^６は、それぞれ独立して水素原子、電子吸引性基またはアミノ基である。但し、Ｒ^１〜Ｒ^６のうち少なくとも１つは電子吸引性基であり、かつＲ^１〜Ｒ^６のうち少なくとも１つはアミノ基である。また、上記アミノ基は、水素原子の全部または一部が炭素数１〜６のアルキル基で置換されていてもよい。
式（２）中、Ｒ^７〜Ｒ^１６は、それぞれ独立して水素原子、電子吸引性基またはアミノ基である。但し、Ｒ^７〜Ｒ^１６のうち少なくとも１つはアミノ基である。また、上記アミノ基は、水素原子の全部または一部が炭素数１〜６の炭化水素基で置換されていてもよい。Ａは、単結合、カルボニル基、カルボニルオキシ基、カルボニルメチレン基、スルフィニル基、スルホニル基、メチレン基または炭素数２〜６のアルキレン基である。但し、上記メチレン基およびアルキレン基は、水素原子の全部または一部がシアノ基、ハロゲン原子またはフルオロアルキル基で置換されていてもよい。）

(In formula (1), R ^{1 to} R ⁶ are each independently a hydrogen atom, an electron withdrawing group or an amino group, provided that at least one of R ^{1 to} R ⁶ is an electron withdrawing group. In addition, at least one of R ^{1 to} R ⁶ is an amino group, and all or part of the hydrogen group may be substituted with an alkyl group having 1 to 6 carbon atoms.
In formula (2), R ^{7 to} R ¹⁶ are each independently a hydrogen atom, an electron-withdrawing group, or an amino group. However, at least one of R ^{7 to} R ¹⁶ is an amino group. In the amino group, all or part of the hydrogen atoms may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. A is a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group, or an alkylene group having 2 to 6 carbon atoms. However, in the methylene group and alkylene group, all or part of the hydrogen atoms may be substituted with a cyano group, a halogen atom or a fluoroalkyl group. )

In the first aspect of the present invention, the coloring pattern is:
[I] alkali-soluble resin,
[II] a polymerizable compound having an ethylenically unsaturated bond,
[III] It is preferably formed from a radiation-sensitive polymerization initiator and [IV] a coloring composition containing the coloring agent.

  In the first aspect of the present invention, the coloring composition further includes [V] a compound represented by the above formula (1), a compound represented by the above formula (2), a tertiary amine compound, an amine salt, and a phosphonium salt. It is preferable to contain at least one compound selected from the group consisting of an amidine salt, an amide compound, a thiol compound, a blocked isocyanate compound and an imidazole ring-containing compound.

  In the first aspect of the present invention, the [I] alkali-soluble resin contained in the coloring composition is at least one selected from the group consisting of (I-1) an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. It is preferable that it is a copolymer containing the structural unit formed from (I-2) and the structural unit formed from an epoxy group containing unsaturated compound.

  In the first aspect of the present invention, the compound having an [A] epoxy group contained in the first radiation-sensitive resin composition is preferably a polymer.

  1st aspect of this invention WHEREIN: It is preferable that the compound which has the [A] epoxy group contained in a 1st radiation sensitive resin composition further has a carboxyl group.

  In the first aspect of the present invention, the [E] alkali-soluble resin contained in the second radiation-sensitive resin composition is selected from the group consisting of (E-1) an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. It is preferable that it is a copolymer containing the structural unit formed from the at least 1 type selected, and the structural unit formed from the (E-2) epoxy-group-containing unsaturated compound.

  In the first embodiment of the present invention, the diamine for obtaining the [P] polymer contained in the liquid crystal aligning agent is a diamine represented by the following formula (DA1), formula (DA2) and formula (DA3). It is preferable to include a first diamine having a tertiary nitrogen atom that is at least one selected from the group consisting of:

（式（ＤＡ１）中、Ａ^１１はベンゼン環または窒素含有芳香族複素環であり、Ｚ^１１は、Ａ^１１がベンゼン環である場合は炭素数１〜６の脂肪族基で置換されたジ置換アミノ基であり、Ａ^１１が窒素含有芳香族複素環である場合は水素原子または炭素数１〜６個の脂肪族基で置換されたジ置換アミノ基である。
式（ＤＡ２）中、Ａ^１２は炭素原子を６〜１５個有し、かつベンゼン環を１〜２個有する芳香族基であり、Ａ^１３は炭素数２〜５個のアルキレンまたはビフェニレンであり、Ｚ^１２は、炭素数１〜５のアルキル基またはベンゼン環であり、ｑは０または１の整数である。
式（ＤＡ３）中、Ａ^１４は３級窒素原子で置換された炭素原子数４〜６個のシクロアルキレンであり、Ａ^１５は炭素数２〜５のアルキレンである。）

(In the formula (DA1), A ¹¹ is a benzene ring or a nitrogen-containing aromatic heterocyclic ring, and Z ¹¹ is a di-substituted group substituted with an aliphatic group having 1 to 6 carbon atoms when A ¹¹ is a benzene ring. When it is an amino group and A ¹¹ is a nitrogen-containing aromatic heterocyclic ring, it is a disubstituted amino group substituted with a hydrogen atom or an aliphatic group having 1 to 6 carbon atoms.
In the formula (DA2), A ¹² is an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings, A ¹³ is alkylene or biphenylene having 2 to 5 carbon atoms, Z ¹² is an alkyl group having 1 to 5 carbon atoms or a benzene ring, and q is an integer of 0 or 1.
Wherein ^{(DA3), A 14} is a carbon atom number 4-6 cycloalkylene substituted with a tertiary nitrogen ^{atom, A 15} is alkylene having 2 to 5 carbon atoms. )

  In the first embodiment of the present invention, the first diamine is at least one diamine selected from the group consisting of diamines represented by the following formulas (DA4), (DA5), (DA6) and (DA7). Preferably there is.

（式（ＤＡ４）中、Ａ^２１は窒素含有芳香族複素環である。
式（ＤＡ５）中、Ｚ^２１は３級窒素原子を含む炭素数２〜１２個の脂肪族基である。
式（ＤＡ６）中、Ａ^２２は炭素原子を６〜１５個有し、かつベンゼン環を１〜２個有する芳香族基であり、Ａ^２３は炭素数２〜５個のアルキレンまたはビフェニレンであり、Ｚ^２２は炭素数１〜５個のアルキルまたはベンゼン環であり、ｒは０または１の整数である。
式（ＤＡ７）中、Ａ^２４は上記式（ＤＡ７ａ）または（ＤＡ７ｂ）で表される基であり、Ａ^２５は炭素数２〜５のアルキレンである。）

(In formula (DA4), A ²¹ represents a nitrogen-containing aromatic heterocycle.
In formula (DA5), Z ²¹ represents an aliphatic group having 2 to 12 carbon atoms containing a tertiary nitrogen atom.
In the formula (DA6), A ²² is an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings, A ²³ is alkylene or biphenylene having 2 to 5 carbon atoms, Z ²² is an alkyl or benzene ring having 1 to 5 carbon atoms, and r is an integer of 0 or 1.
Wherein ^{(DA7), A 24} is a group represented by the formula (DA7a) or ^{(DA7b), A 25} is alkylene having 2 to 5 carbon atoms. )

  1st aspect of this invention WHEREIN: It is preferable that the diamine for obtaining the [P] polymer contained in a liquid crystal aligning agent contains the 2nd diamine which has a carboxyl group in a molecule | numerator.

  In the first aspect of the present invention, the second diamine is preferably at least one diamine selected from the group consisting of diamines represented by the following formula (DA8).

（式（ＤＡ８）中、Ａ^３１は炭素数６〜３０の芳香族環を有する有機基であり、ｎ１は１〜４の整数である。）

(In the formula ^{(DA8), A 31} is an organic group having an aromatic ring having 6 to 30 carbon atoms, n1 is an integer from 1 to 4.)

  In the first aspect of the present invention, the second diamine is preferably at least one diamine selected from the group consisting of diamines represented by the following formulas (DA9) to (DA13).

（式（ＤＡ９）中、ｍ１は１〜４の整数である。
式（ＤＡ１０）中、Ａ^３２は単結合、−ＣＨ_２−、−Ｃ_２Ｈ_４−、−Ｃ（ＣＨ_３）_２−、−ＣＦ_２−、−Ｃ（ＣＦ_３）_２−、−Ｏ−、−ＣＯ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−または−Ｎ（ＣＨ_３）ＣＯ−であり、ｍ２およびｍ３はそれぞれ独立に０〜４の整数を示すとともにｍ２＋ｍ３は１〜４の整数を示す。
式（ＤＡ１１）中、ｍ４およびｍ５はそれぞれ独立に１〜５の整数である。
式（ＤＡ１２）中、Ａ^３３は炭素数１〜５の直鎖または分岐のアルキル基であり、ｍ６は１〜５の整数である。
式（ＤＡ１３）中、Ａ^３４は単結合、−ＣＨ_２−、−Ｃ_２Ｈ_４−、−Ｃ（ＣＨ_３）_２−、−ＣＦ_２−、−Ｃ（ＣＦ_３）_２−、−Ｏ−、−ＣＯ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−または−Ｎ（ＣＨ_３）ＣＯ−であり、ｍ７は１〜４の整数である。）

(In Formula (DA9), m1 is an integer of 1-4.
In the formula (DA10), A ³² represents a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) ₂ —, —O—. , —CO—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CON (CH ₃ ) - or -N _(CH 3) a CO-, m2 + m3 with an integer of m2 and m3 are each independently 0 to 4 is an integer of 1-4.
In formula (DA11), m4 and m5 are each independently an integer of 1 to 5.
In the formula (DA12), A ³³ is a linear or branched alkyl group having 1 to 5 carbon atoms, and m6 is an integer of 1 to 5.
Wherein ^{(DA13), A 34} represents a single _{bond, -CH 2 -, - C 2} H 4 -, - C (CH 3) 2 -, - CF 2 -, - C (CF 3) 2 -, - O- , —CO—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CON (CH ₃ ) - or -N _(CH 3) a CO-, m7 is an integer of 1 to 4. )

  In the first aspect of the present invention, the colored pattern is preferably formed at a curing temperature of 200 ° C. or lower.

  In the first aspect of the present invention, the protective film is preferably formed at a curing temperature of 200 ° C. or lower.

  In the first aspect of the present invention, the spacer is preferably formed at a curing temperature of 200 ° C. or lower.

  In the first aspect of the present invention, the alignment film is preferably formed at a heating temperature of 200 ° C. or lower.

  In the first aspect of the present invention, the colored pattern is preferably formed at a curing temperature lower than the curing temperature of the protective film.

  In the first aspect of the present invention, the colored pattern is preferably formed at a curing temperature lower than the curing temperature of the spacer.

  In the first aspect of the present invention, the protective film is preferably formed at a curing temperature lower than the curing temperature of the spacer.

  According to a second aspect of the present invention, there is provided a liquid crystal display element comprising the color filter according to the first aspect of the present invention.

The third aspect of the present invention is:
[1] A coating film of a colored composition containing at least one colorant selected from the group consisting of diketopyrrolopyrrole pigments, halogenated zinc phthalocyanine pigments, triarylmethane dyes and azo dyes on a substrate The process of forming into,
[2] A step of forming a colored pattern on the coating film of the colored composition,
[3] A step of curing the coating film on which the colored pattern is formed at 200 ° C. or lower,
[4] [A] a compound having an epoxy group,
[B] a polymerizable compound having an ethylenically unsaturated bond,
[C] a radiation-sensitive polymerization initiator, and [D] a compound containing at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2). Forming a coating film of the radiation sensitive resin composition of 1 on a substrate;
[5] A step of irradiating at least part of the coating film of the first radiation-sensitive resin composition,
[6] A step of developing the coating film irradiated with radiation in the step [5],
[7] A step of curing the coating film developed in step [6] at 200 ° C. or lower,
[8] [E] Alkali-soluble resin,
[F] a polymerizable compound having an ethylenically unsaturated bond,
[G] a radiation-sensitive polymerization initiator, and [H] a compound containing at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2). Forming a coating film of the radiation sensitive resin composition of 2 on the substrate having the cured coating film of the step [7],
[9] A step of irradiating at least part of the coating film of the second radiation-sensitive resin composition,
[10] A step of developing the coating film irradiated with radiation in step [9],
[11] A step of curing the coating film developed in the step [10] at 200 ° C. or lower to form a spacer, and [12] a tetracarboxylic acid dihydrate containing 2,3,5-tricarboxycyclopentylacetic acid dianhydride. A coating film of a liquid crystal aligning agent containing at least one [P] polymer selected from the group consisting of a polyamic acid obtained by reacting an anhydride with a diamine and a polyimide obtained by dehydrating and ring-closing the polyamic acid. The present invention relates to a method for producing a color filter, comprising a step of forming an alignment film by forming on a substrate having a spacer cured in step [11] and heating the coating film at 200 ° C. or lower.

（式（１）中、Ｒ^１〜Ｒ^６は、それぞれ独立して水素原子、電子吸引性基またはアミノ基である。但し、Ｒ^１〜Ｒ^６のうち少なくとも１つは電子吸引性基であり、かつＲ^１〜Ｒ^６のうち少なくとも１つはアミノ基である。また、上記アミノ基は、水素原子の全部または一部が炭素数１〜６のアルキル基で置換されていてもよい。
式（２）中、Ｒ^７〜Ｒ^１６は、それぞれ独立して水素原子、電子吸引性基またはアミノ基である。但し、Ｒ^７〜Ｒ^１６のうち少なくとも１つはアミノ基である。また、上記アミノ基は、水素原子の全部または一部が炭素数１〜６の炭化水素基で置換されていてもよい。Ａは、単結合、カルボニル基、カルボニルオキシ基、カルボニルメチレン基、スルフィニル基、スルホニル基、メチレン基または炭素数２〜６のアルキレン基である。但し、上記メチレン基およびアルキレン基は、水素原子の全部または一部がシアノ基、ハロゲン原子またはフルオロアルキル基で置換されていてもよい。）

(In formula (1), R ^{1 to} R ⁶ are each independently a hydrogen atom, an electron withdrawing group or an amino group, provided that at least one of R ^{1 to} R ⁶ is an electron withdrawing group. In addition, at least one of R ^{1 to} R ⁶ is an amino group, and all or part of the hydrogen group may be substituted with an alkyl group having 1 to 6 carbon atoms.
In formula (2), R ^{7 to} R ¹⁶ are each independently a hydrogen atom, an electron-withdrawing group, or an amino group. However, at least one of R ^{7 to} R ¹⁶ is an amino group. In the amino group, all or part of the hydrogen atoms may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. A is a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group, or an alkylene group having 2 to 6 carbon atoms. However, in the methylene group and alkylene group, all or part of the hydrogen atoms may be substituted with a cyano group, a halogen atom or a fluoroalkyl group. )

  In the third aspect of the present invention, the coloring composition may further contain [I] an alkali-soluble resin, [II] a polymerizable compound having an ethylenically unsaturated bond, and [III] a radiation-sensitive polymerization initiator. preferable.

  In the third aspect of the present invention, the curing temperature in step [3] is preferably lower than the curing temperature in step [7].

  In the third aspect of the present invention, the curing temperature in step [3] is preferably lower than the curing temperature in step [11].

  In the third aspect of the present invention, the curing temperature in step [7] is preferably lower than the curing temperature in step [11].

  In the third aspect of the present invention, the diamine for obtaining the [P] polymer contained in the liquid crystal aligning agent is a diamine represented by the following formula (DA1), formula (DA2) and formula (DA3). It is preferable to contain the 1st diamine which has a tertiary nitrogen atom which is at least 1 type chosen from the group which consists of.

（式（ＤＡ１）中、Ａ^１１はベンゼン環または窒素含有芳香族複素環であり、Ｚ^１１は、Ａ^１１がベンゼン環である場合は炭素数１〜６個の脂肪族基で置換されたジ置換アミノ基であり、Ａ^１１が窒素含有芳香族複素環である場合は水素原子または炭素数１〜６個の脂肪族基で置換されたジ置換アミノ基である。
式（ＤＡ２）中、Ａ^１２は炭素原子を６〜１５個有し、かつベンゼン環を１〜２個有する芳香族基であり、Ａ^１３は炭素数２〜５個のアルキレンまたはビフェニレンであり、Ｚ^１２は、炭素数１〜５個のアルキル基またはベンゼン環であり、ｑは０または１の整数である。
式（ＤＡ３）中、Ａ^１４は３級窒素原子で置換された炭素原子数４〜６個のシクロアルキレンであり、Ａ^１５は炭素数２〜５個のアルキレンである。）

(In the formula (DA1), A ¹¹ is a benzene ring or a nitrogen-containing aromatic heterocyclic ring, and Z ¹¹ is a disubstituted group having 1 to 6 carbon atoms when A ¹¹ is a benzene ring. A substituted amino group, and when A ¹¹ is a nitrogen-containing aromatic heterocycle, a disubstituted amino group substituted with a hydrogen atom or an aliphatic group having 1 to 6 carbon atoms.
In the formula (DA2), A ¹² is an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings, A ¹³ is alkylene or biphenylene having 2 to 5 carbon atoms, Z ¹² is an alkyl group having 1 to 5 carbon atoms or a benzene ring, and q is an integer of 0 or 1.
Wherein ^{(DA3), A 14} is a carbon atom number 4-6 cycloalkylene substituted with a tertiary nitrogen ^{atom, A 15} is a 2-5 alkylene carbon atoms. )

  3rd aspect of this invention WHEREIN: It is preferable that the diamine for obtaining the [P] polymer contained in a liquid crystal aligning agent contains the 2nd diamine which has a carboxyl group in a molecule | numerator.

ADVANTAGE OF THE INVENTION According to this invention, the color filter which can be manufactured by low temperature hardening and has high reliability, and its manufacturing method are provided.
Moreover, according to this invention, the liquid crystal display element provided with the color filter which is manufactured by low temperature hardening and has high reliability is provided.

It is typical sectional drawing of the color filter of this Embodiment. It is typical sectional drawing of the liquid crystal display element provided with the color filter of this Embodiment.

Embodiments of the present invention are described below.
In the present invention, “radiation” irradiated upon exposure is a concept including visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams and the like.

<Liquid crystal display element>
The liquid crystal display element of the present embodiment is a color liquid crystal display element having the color filter of the present embodiment. Hereinafter, the structure of the liquid crystal display element of the present embodiment will be described.
The liquid crystal display element of this embodiment has, for example, a structure in which a driving substrate on which a thin film transistor (TFT) is disposed and a substrate that is a color filter of this embodiment are opposed to each other with a liquid crystal layer interposed therebetween. It can be. Alternatively, the liquid crystal display element uses a substrate formed by forming a coloring pattern, a protective film, or a spacer according to the present embodiment, which will be described later, on a driving substrate on which a thin film transistor (TFT) is disposed. It is also possible to have a structure facing a substrate on which an ITO (Indium Tin Oxide) electrode is formed. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.

  FIG. 1 is a schematic cross-sectional view of the color filter of the present embodiment.

  A color filter 10 shown in FIG. 1 is an example of the color filter of the present embodiment. On a transparent substrate 5, a red (R), green (G) and blue (B) colored pattern 6, a black matrix 7, a protective film 8 provided on the colored pattern 6, and a protective film 8 It has a structure in which an ITO electrode 4 provided on top, a spacer 9 provided upright on the ITO electrode 4, and an alignment film 12 provided on the ITO electrode 4 and the spacer 9 are arranged. Note that the color of the coloring pattern 6 is not limited to the above three RGB colors, and it is possible to select other colors or to add four yellow colors to the coloring pattern.

  As will be described later, in the color filter 10 of the present embodiment, the coloring pattern 6 includes a suitable colorant. Specifically, it is formed by applying and patterning a coloring composition containing a preferable colorant such as a dye on a substrate and then curing. Similarly, the protective film 8 is formed by applying and patterning the radiation-sensitive resin composition and then curing. Similarly, the spacer 9 is formed by applying and patterning the radiation-sensitive resin composition and then curing. The alignment film 12 is formed by applying a liquid crystal alignment agent containing a polymer whose suitable structure is selected so that it can be formed by low-temperature heating, and applying and then curing it. In the following description, for the sake of convenience, the radiation-sensitive resin composition for forming the protective film 8 is referred to as a first radiation-sensitive resin composition, and the radiation-sensitive resin composition for forming the spacer 9 is referred to. It will be referred to as a second radiation sensitive resin composition.

  The coloring composition, the first radiation-sensitive resin composition, and the second radiation-sensitive resin composition are all radiation-sensitive resin compositions using similar materials as described later. Is possible. They have the feature that a colored pattern, a protective film 8 and a spacer 9 can be formed by low-temperature curing at 200 ° C. or lower, respectively. As will be described later, also in the alignment treatment agent of the present embodiment, the alignment film 12 can be formed at a low heating temperature such as 200 ° C. or lower.

Therefore, in the color filter 10 of the present embodiment, the colored pattern 6, the protective film 8, the spacer 9, and the alignment film 12 can be formed by low-temperature curing at 200 ° C. or lower. The color filter 10 of the present embodiment can be manufactured by low temperature curing.
In the color filter 10, the protective film 8 is formed after the colored pattern 6 is formed. Since the protective film 8 can be formed by low-temperature curing at 200 ° C. or lower, the colored pattern 6 is not exposed to a high-temperature heating state for forming the protective film after being formed. Similarly, in the color filter 10, the colored pattern 6 is formed, the protective film 8 is formed, and then the spacer 9 is formed. Since the spacer 9 can be formed by low-temperature curing at 200 ° C. or less, the colored pattern 6 is not exposed to a high-temperature heating state for forming the spacer 9 after being formed. Further, in the color filter 10, the alignment film 12 is formed after the colored pattern 6, the protective film 8, and the spacer 9 are formed. Since the alignment film 12 can be formed by low-temperature curing at 200 ° C. or lower, the colored pattern 6 is not exposed to a high-temperature heating state for forming the alignment film 12 after being formed.

  Therefore, in the color filter 10, even when a dye having excellent color characteristics for forming the colored pattern 6 but having a problem in heat resistance is used as a colorant, process deterioration can be reduced. That is, it is possible to select a dye as the colorant of the coloring composition, and it is possible to form the colored pattern 6 having excellent color characteristics from the coloring composition using the dye.

  As described above, the coloring composition, the first radiation-sensitive resin composition, and the second radiation-sensitive resin composition are all radiation-sensitive resin compositions using similar materials. Is possible. And it is used for manufacture of the color filter 10, respectively. Therefore, it is possible to adjust the curing temperature when forming the colored pattern 6 in consideration of the formation of the protective film 8 on the colored pattern 6 during the manufacture of the color filter 10. That is, the colored pattern 6 is formed at a lower curing temperature than the optimum curing temperature for forming the colored pattern 6 alone on the substrate 5. Thereafter, the colored pattern 6 can be heated by curing and heating the protective film 8 formed on the colored pattern 6. Similarly, when the color filter 10 is manufactured, it is possible to adjust the curing temperature when forming the colored pattern 6 in consideration of the formation of the spacer 9 after the colored pattern 6 is formed. That is, the colored pattern 6 is formed at a lower curing temperature than the optimum curing temperature for forming only the colored pattern 6 on the substrate 5. Then, after the ITO electrode 4 is formed, the colored pattern 6 can also be heated by curing and heating the spacers 9 standing on the ITO electrode 4.

  For example, when the optimal curing temperature of the colored pattern 6 and the protective film 8 is 200 ° C. or less, specifically, 180 ° C., the colored pattern 6 is formed on the substrate 5 at a curing temperature of 150 ° C., for example. It is possible to keep it. Next, a protective film 8 is formed by forming a coating film of the first radiation-sensitive resin composition on the colored pattern 6 and curing it at an optimum 180 ° C. In addition, the colored pattern 6 in the lower layer is heated, and the colored pattern 6 in a desired state can be obtained. Further, the colored pattern 6 is formed on the substrate 5 at a curing temperature of 150 ° C., for example, and then the spacer 9 is formed from the second radiation-sensitive resin composition at an optimal curing temperature of 180 ° C. As a result, the colored pattern 6 under the spacer 9 is also heated, and the colored pattern 6 in a desired state can be obtained. In the above case, it becomes possible to select a dye as the colorant of the coloring composition, and the color filter 10 having excellent color characteristics can be provided by the coloring pattern 6 formed from the coloring composition using the dye.

  In consideration of the fact that the spacer 9 is formed after the colored pattern 6 and the protective film 8 are formed at the time of manufacturing the color filter 10, the curing temperature in the formation of the protective film 8 is also set together with the curing temperature in the formation of the colored pattern 6. It is possible to adjust. That is, the colored pattern 6 is formed at a lower curing temperature than the optimum curing temperature for forming only the colored pattern 6 on the substrate 5. Next, the protective film 8 is formed at a lower curing temperature than the optimum curing temperature for forming only the protective film 8. Then, after the ITO electrode 4 is formed, the colored pattern 6 and the protective film 8 can be heated by curing and heating the spacers 9 standing on the ITO electrode 4.

For example, when the optimal curing temperature of the colored pattern 6, the protective film 8, and the spacer 9 is 200 ° C. or less, specifically 180 ° C., the colored pattern 6 is cured on the substrate 5 at, for example, 150 ° C. It can be formed at a temperature. Next, a coating film of the first radiation-sensitive resin composition can be formed on the colored pattern 6 and formed at a curing temperature of 150 ° C., for example. Next, after the ITO electrode 4 is formed on the protective film 8, a coating film of the second radiation-sensitive resin composition is formed on the ITO electrode 4. And the spacer 9 is formed by patterning the coating film and hardening | curing at optimal 180 degreeC. As a result, the colored pattern 6 and the protective film 8 in the lower layer are heated, and the colored pattern 6 and the protective film 8 in a desired state can be obtained. In that case, it is possible to select a dye having heat resistance as a colorant of the coloring composition, and the color filter 10 formed from the coloring composition using the dye provides the color filter 10 having excellent color characteristics. it can.
Next, the liquid crystal display element of this embodiment to which the color filter of this embodiment is applied will be described.

  FIG. 2 is a schematic cross-sectional view of a liquid crystal display element provided with the color filter of the present embodiment.

A liquid crystal display element 1 shown in FIG. 2 is an example of the liquid crystal display element of the present embodiment, and is a color liquid crystal display element of a TN (Twisted Nematic) type liquid crystal mode driven by a TFT. The color liquid crystal display element has a structure in which a driving substrate and a substrate constituting the color filter of the above-described embodiment are opposed to each other through a TN liquid crystal layer.
As shown in FIG. 2, transparent pixel electrodes 3 made of ITO and TFTs (not shown) are arranged in a grid pattern on the side of the transparent substrate 2 in contact with the liquid crystal 13 to form a driving substrate. Yes. Further, on the side of the transparent substrate 5 that is in contact with the liquid crystal 13, the above-described colored pattern 6 manufactured by low-temperature curing is arranged to constitute a color filter 10. Specifically, red, green and blue coloring patterns 6 provided at positions facing the pixel electrodes 3, a black matrix 7, a protective film 8 provided on the coloring patterns 6, and a protective film 8 A color filter 10 having an ITO electrode 4 provided thereon, a spacer 9 erected on the ITO electrode 4, and an alignment film 12 on the substrate 5 is disposed. The ITO electrode 4 constitutes a common electrode in the liquid crystal display element 1.

An alignment film 12 similar to that of the substrate 5 is provided on the substrate 2. Each alignment film 12 is subjected to an alignment process such as a rubbing process, if necessary, to realize uniform alignment of the liquid crystal 13 sandwiched between the substrate 2 and the substrate 5.
In the substrate 2 and the substrate 5, polarizing plates 14 are respectively arranged on the side opposite to the side in contact with the liquid crystal 13. The distance between the substrate 2 and the substrate 5 is usually 2 μm to 10 μm, and these are fixed to each other by a sealing material 16 provided in the peripheral portion.

  In FIG. 2, reference numeral 17 denotes backlight light emitted toward a liquid crystal 13 from a backlight unit (not shown). As the backlight unit, for example, a structure in which a fluorescent tube such as a cold cathode fluorescent lamp (CCFL) and a scattering plate are combined can be used. A backlight unit using a white LED as a light source can also be used. As the white LED, for example, a white LED that obtains white light using a red LED having an independent spectrum, a green LED, and a blue LED, a red LED, a green LED, and a blue LED are combined and white by mixing colors. White LED, blue LED, red LED, and green phosphor that obtain light combine to obtain white light by color mixing White LED, blue LED, red light emitting phosphor, and green light emitting phosphor combine to color A white LED that obtains white light, a blue LED, and a white LED that obtains white light by mixing color with a YAG phosphor, a blue LED, an orange light emitting phosphor, and a green light emitting phosphor are combined to obtain white light by color mixing. White that obtains white light by color mixing by combining white LED, ultraviolet LED, red light emitting phosphor, green light emitting phosphor, and blue light emitting phosphor LED, and the like.

  In addition to the TN type described above, the liquid crystal display element of the present embodiment includes an STN (Super Twisted Nematic) type, an IPS (In-Planes Switching) type, a VA (Vertical Aligned Birefring) type, such as an OCB (Optically Compensated Birefring type). A liquid crystal mode can also be set. In this case, the alignment film for liquid crystal alignment is selected to be optimal for each liquid crystal mode. For example, in the case of a VA liquid crystal display element, a vertical alignment film is used.

Hereinafter, the color filter of this embodiment, which is a main component of the liquid crystal display element of this embodiment, will be described in more detail.
As described above, the color filter of the present embodiment includes a colored pattern, a protective film provided on the colored pattern, a spacer erected on the ITO electrode on the protective film, and an alignment film. The color filter has excellent color characteristics and can be manufactured by low-temperature curing.
The colored pattern can be formed on a suitable substrate using the colored composition, and the protective film can be formed on the colored pattern using the first radiation-sensitive resin composition. The spacer can be formed on the ITO electrode on the protective film using the second radiation-sensitive resin composition. The alignment film can be formed on the ITO electrode using a liquid crystal aligning agent. That is, the color filter of this embodiment can be manufactured using a coloring composition, a 1st radiation sensitive resin composition, a 2nd radiation sensitive resin composition, and a liquid crystal aligning agent.
Below, first, the coloring composition used for the formation of the coloring pattern of the color filter of this Embodiment is demonstrated.

<Coloring composition>
The coloring composition used for manufacturing the color filter of the present embodiment contains [I] an alkali-soluble resin, [II] a polymerizable compound, [III] a polymerization initiator, and [IV] a coloring agent. Furthermore, a [V] compound can be contained. Moreover, you may contain another arbitrary component, unless the effect of this invention is impaired. Hereinafter, each component contained in the coloring composition will be described.

<[I] Alkali-soluble resin>
[I] The alkali-soluble resin is not particularly limited as long as it has a carboxyl group and thus has alkali developability. A copolymer containing at least one structural unit selected from the group consisting of a structural unit having a (meth) acryloyloxy group and a structural unit having an epoxy group is preferable. [I] When the alkali-soluble resin contains the specific structural unit, a cured film having excellent surface curability and deep part curability can be formed.

  [I] The alkali-soluble resin is formed from (I-1) at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter also referred to as “(I-1) compound”). And a structural unit formed from (I-2) an epoxy group-containing unsaturated compound (hereinafter also referred to as “(I-2) compound”). It can be obtained as a copolymer containing.

  [I] The alkali-soluble resin includes, for example, a compound (I-1) that gives a carboxyl group-containing structural unit and a compound (I-2) that gives an epoxy group-containing structural unit in the presence of a polymerization initiator in a solvent. It can be produced by copolymerization. Further, (I-3) a hydroxyl group-containing unsaturated compound that gives a hydroxyl group-containing structural unit (hereinafter also referred to as “(I-3) compound”) may be added to obtain a copolymer. Furthermore, in the production of [I] alkali-soluble resin, together with the compound (I-1), the compound (I-2) and the compound (I-3), the compound (I-4) (the compound (I-1), (I-2) and (I-3) unsaturated compounds that give structural units other than the structural unit derived from the compound) may be further added to form a copolymer. Hereinafter, each compound will be described in detail.

[(I-1) Compound]
(I-1) As the compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated dicarboxylic acid anhydride, poly [carboxylic acid] mono [(meth) acryloyloxyalkyl] ester, Examples thereof include mono (meth) acrylates of polymers having a hydroxyl group, unsaturated polycyclic compounds having a carboxyl group, and anhydrides thereof.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid and the like;
Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like;
Examples of the unsaturated dicarboxylic acid anhydride include, for example, anhydrides of the compounds exemplified as the dicarboxylic acid;
Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] and the like;
Examples of the mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends include, for example, ω-carboxypolycaprolactone mono (meth) acrylate;
Examples of unsaturated polycyclic compounds having a carboxyl group and anhydrides thereof include 5-carboxybicyclo [2.2.1] hept-2-ene and 5,6-dicarboxybicyclo [2.2.1]. Hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5- Carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2. 2.1] hept-2-ene anhydride and the like.

  Among these (I-1) compounds, monocarboxylic acid, dicarboxylic acid anhydride, acrylic acid, methacrylic acid, and maleic anhydride are preferable, and acrylic acid, methacrylic acid, and maleic anhydride are copolymerization-reactive, with respect to an alkaline aqueous solution. It is more preferable from the viewpoint of solubility and availability. These (I-1) compounds may be used alone or in admixture of two or more.

  The proportion of (I-1) compound used is based on the sum of (I-1) compound and (I-2) compound (optional (I-3) compound and (I-4) compound as required). 5 mass% to 30 mass% is preferable, and 10 mass% to 25 mass% is more preferable. (I-1) By using the compound in a proportion of 5% by mass to 30% by mass, [I] a colored composition that optimizes the solubility of the alkali-soluble resin in an alkaline aqueous solution and is excellent in radiation sensitivity is obtained. It is done.

[(I-2) Compound]
The compound (I-2) is an epoxy group-containing unsaturated compound having radical polymerizability. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure).

  Examples of unsaturated compounds having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α-n-butyl acrylic acid. Glycidyl, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6,7-epoxyheptyl O-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate, and the like. Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3, methacrylate 4-Epoxycyclohexyl is preferable from the viewpoint of improving the solvent reactivity such as copolymerization reactivity and coloring pattern.

As an unsaturated compound having an oxetanyl group, for example,
3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -2-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -2 -Acrylic esters such as phenyloxetane;
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -2-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -2 -Methacrylic acid esters such as phenyloxetane and 3- (2-methacryloyloxyethyl) -2,2-difluorooxetane.

Of these (I-2) compounds, glycidyl (meth) acrylate is preferred. These (I-2) compounds may be used alone or in admixture of two or more.
The proportion of (I-2) compound used is based on the sum of (I-1) compound and (I-2) compound (optional (I-3) compound and (I-4) compound as required). 5 mass% to 60 mass% is preferable, and 10 mass% to 50 mass% is more preferable. (I-2) By making the usage-amount of a compound into 5 mass%-60 mass%, the cured film which has the outstanding sclerosis | hardenability etc. can be formed.

[(I-3) Compound]
Examples of (I-3) compounds include (meth) acrylic acid ester having a hydroxyl group, (meth) acrylic acid ester having a phenolic hydroxyl group, and hydroxystyrene.
Examples of the acrylic acid ester having a hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate.
Examples of the methacrylic acid ester having a hydroxyl group include 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate, and the like.

Examples of the acrylic acid ester having a phenolic hydroxyl group include 2-hydroxyethyl acrylate and 4-hydroxyphenyl acrylate. Examples of the methacrylic acid ester having a phenolic hydroxyl group include 2-hydroxyethyl methacrylate and 4-hydroxyphenyl methacrylate.
As hydroxystyrene, o-hydroxystyrene, p-hydroxystyrene, and α-methyl-p-hydroxystyrene are preferable. These (I-3) compounds may be used alone or in admixture of two or more.

  The proportion of (I-3) compound used is based on the total of (I-1) compound, (I-2) compound and (I-3) compound (optional (I-4) compound if necessary). 1% by mass to 30% by mass is preferable, and 5% by mass to 25% by mass is more preferable.

[(I-4) Compound]
The compound (I-4) is not particularly limited as long as it is an unsaturated compound other than the compounds (I-1), (I-2) and (I-3) described above. Examples of the compound (I-4) include methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid chain alkyl ester, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, and unsaturated dicarboxylic acid. Examples thereof include unsaturated compounds having an acid diester, a bicyclo unsaturated compound, a maleimide compound, an unsaturated aromatic compound, a conjugated diene, a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, and other unsaturated compounds.

Examples of the chain alkyl ester of methacrylic acid include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n methacrylate. -Lauryl, tridecyl methacrylate, n-stearyl methacrylate and the like.
Examples of the cyclic alkyl ester of methacrylic acid include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, and tricyclomethacrylate [5.2. 1.0 ^2,6 ] decan-8-yloxyethyl, isobornyl methacrylate and the like.

Examples of the acrylic acid chain alkyl ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, and n-acrylate. -Lauryl, tridecyl acrylate, n-stearyl acrylate and the like.
Examples of the acrylic acid cyclic alkyl ester include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, tricyclo [5.2.1.0 ^{2, 6} ] Decan-8-yloxyethyl acrylate, isobornyl acrylate and the like.

Examples of the methacrylic acid aryl ester include phenyl methacrylate and benzyl methacrylate.
Examples of the acrylic acid aryl ester include phenyl acrylate and benzyl acrylate.
Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate and the like.
Examples of the bicyclo unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2.1]. ] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene and the like.

Examples of maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.
Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene.
Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and the like.
Examples of unsaturated compounds containing a furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-ene. 2-one, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2 -Yl-hex-1-en-3-one, acrylic acid-2-furan-2-yl-1-methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-hepten-3-one Etc.

Examples of the unsaturated compound containing a tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-ene-3- ON, 2-methacrylic acid tetrahydropyran-2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one and the like.
Examples of unsaturated compounds containing a pyran skeleton include 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyran, 4- (1,5-dioxa-6- Oxo-7-octenyl) -6-methyl-2-pyran and the like.
Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

Among these (I-4) compounds, methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, methacrylic acid aryl ester, maleimide compound, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, unsaturated aromatic compound Acrylic acid cyclic alkyl ester is preferred. Among these, styrene, methyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, benzyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, p-methoxy Styrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, 3- (meth) acryloyloxytetrahydrofuran 2-one is more preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution. These (I-4) compounds may be used alone or in admixture of two or more.

  The proportion of (I-4) compound used is 10 based on the sum of (I-1) compound, (I-2) compound and (I-4) compound (and any (I-3) compound). A mass% to 80 mass% is preferable.

<[I] Synthesis Method 1 of Alkali-Soluble Resin>
[I] The alkali-soluble resin is, for example, a compound (I-1) and (I-2) compound (arbitrary (I-3) compound and (I-4) compound in the presence of a polymerization initiator in a solvent. ) Can be copolymerized. According to such a synthesis method, a copolymer containing at least an epoxy group-containing structural unit can be synthesized.

  [I] Solvents used in the polymerization reaction for producing the alkali-soluble resin include, for example, alcohol, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol Examples thereof include monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, ketone and ester.

[I] As the polymerization initiator used in the polymerization reaction for producing the alkali-soluble resin, those generally known as radical polymerization initiators can be used. Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4 Azo compounds such as -methoxy-2,4-dimethylvaleronitrile).
[I] In the polymerization reaction for producing the alkali-soluble resin, a molecular weight modifier can be used to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and thioglycolic acid; Examples thereof include xanthogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide; terpinolene and α-methylstyrene dimer.

[I] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 to 30,000, more preferably 5,000 to 20,000. [I] By making Mw of alkali-soluble resin into the said range, the sensitivity and developability of a coloring composition can be improved. In addition, the Mw and number average molecular weight (Mn) of the polymer in this specification were measured by gel permeation chromatography (GPC) under the following conditions.
Apparatus: GPC-101 (made by Showa Denko)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 combined with mobile phase: tetrahydrofuran Column temperature: 40 ° C.
Flow rate: 1.0 mL / min Sample concentration: 1.0 mass%
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

<[I] Synthesis Method 2 of Alkali-Soluble Resin>
The [I] alkali-soluble resin is, for example, a copolymer (hereinafter also referred to as “specific copolymer”) that can be synthesized by using one or more of the above-mentioned (I-1) compounds, and the above (I- 2) It can be synthesized by reacting with a compound. According to this synthesis method, a copolymer containing at least a structural unit having a (meth) acryloyloxy group can be synthesized.
[I] The structural unit having a (meth) acryloyloxy group contained in the alkali-soluble resin is represented by the following formula (3). This structural unit is obtained by reacting the carboxyl group in the specific copolymer derived from the compound (I-1) with the epoxy group of the compound (I-2) to form an ester bond.

In the formula ^{(3), R 20} and ^{R 21} are each independently a hydrogen atom or a methyl group. c is an integer of 1-6. R ²² is a divalent group represented by the following formula (4-1) or (4-2).

In the above formula ^{(4-1), R 23} is a hydrogen atom or a methyl group. In the above formulas (4-1) and (4-2), * represents a site bonded to an oxygen atom.

For the structural unit represented by the above formula (3), for example, when a compound having a carboxyl group is reacted with a compound such as glycidyl methacrylate or 2-methylglycidyl methacrylate as the compound (I-2), R ²² in the formula (3) becomes the formula (4-1). On the other hand, when a compound such as 3,4-epoxycyclohexylmethyl methacrylate is reacted as the compound (I-2), R ²² in the formula (3) becomes the formula (4-2).

In the synthesis of the specific copolymer, a compound other than the compound (I-1), for example, the above-mentioned (I-3) compound, (I-4) compound or the like may be used as a copolymerization component. These compounds include methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, tricyclomethacrylate [5.2.1.0 ^2,6 from the viewpoint of copolymerization reactivity. Decan-8-yl, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, and 1,3-butadiene are preferred.

  Examples of the copolymerization method of the specific copolymer include a method of polymerizing the compound (I-1) and, if necessary, the compound (I-3) using a radical polymerization initiator in a solvent. It is done. As a radical polymerization initiator, the thing similar to what was illustrated by the term of the above-mentioned [I] alkali-soluble resin is mentioned. The usage-amount of a radical polymerization initiator is 0.1 mass%-50 mass% normally with respect to 100 mass% of polymerizable unsaturated compounds, Preferably it is 0.1 mass%-20 mass%. The specific copolymer may be used for the production of [I] alkali-soluble resin as it is in the polymerization reaction solution, or may be used for the production of [I] alkali-soluble resin after the copolymer is once separated from the solution.

  As Mw of a specific copolymer, 2,000-100,000 are preferable and 5,000-50,000 are more preferable. By setting Mw to 2,000 or more, a sufficient development margin of the colored composition is obtained, and a decrease in the remaining film ratio (ratio in which the patterned thin film remains properly) of the formed coating film is prevented. Can maintain the shape and heat resistance of the resulting pattern well. On the other hand, by setting Mw to 100,000 or less, high sensitivity can be maintained and a good pattern shape can be obtained. Moreover, as molecular weight distribution (Mw / Mn) of a specific copolymer, 5.0 or less are preferable and 3.0 or less are more preferable. By making Mw / Mn 5.0 or less, the shape of the obtained spacer pattern can be kept good. Moreover, the coloring composition containing the specific copolymer having Mw / Mn in the specific range has a high developability and can easily form a predetermined pattern shape without causing a development residue in the development process. it can.

[I] The content of the structural unit derived from the (I-1) compound of the alkali-soluble resin is preferably 5% by mass to 60% by mass, more preferably 7% by mass to 50% by mass, and more preferably 8% by mass to 40%. Mass% is particularly preferred.
[I] The content of structural units derived from compounds such as (I-3) compounds other than (I-1) compounds of alkali-soluble resins and (I-4) compounds is 10% by mass to 90% by mass, It is 20 mass%-80 mass%.

  In the reaction of the specific copolymer with the compound (I-2), an unsaturated compound having an epoxy group is preferably contained in a copolymer solution containing a polymerization inhibitor in the presence of a suitable catalyst as necessary. And stir for a predetermined time under heating. Examples of the catalyst include tetrabutylammonium bromide. Examples of the polymerization inhibitor include p-methoxyphenol. As reaction temperature, 70 to 100 degreeC is preferable. The reaction time is preferably 8 hours to 12 hours.

  (I-2) As a use rate of a compound, 5 mass%-99 mass% are preferable with respect to the carboxyl group originating in the compound (I-1) in a copolymer, and 10 mass%-97 mass% are. More preferred. (I-2) By making the usage-amount of a compound into the said range, the reactivity with a copolymer, the sclerosis | hardenability of a cured film, etc. improve more. (I-2) A compound can be used individually or in mixture of 2 or more types.

<[II] polymerizable compound>
[II] polymerizable compound contained in the colored composition used for the production of the color filter of the present embodiment will be described.
[II] The polymerizable compound is a polymerizable compound having an ethylenically unsaturated bond.
[II] Those that can be used as the polymerizable compound include, for example, ω-carboxypolycaprolactone mono (meth) acrylate, ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol. Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenoxyethanol full orange (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, 2- (2′-vinyloxyethoxy) ethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloyloxyethyl) phosphate, In addition to ethylene oxide-modified dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, etc., a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, and one or more in the molecule And a urethane (meth) acrylate compound obtained by reacting with a compound having 3 to 5 (meth) acryloyloxy groups.

Examples of commercially available [II] polymerizable compounds that can be used include:
Aronix (registered trademark) M-400, M-402, M-405, M-450, M-1310, M-1600, M-1960, M-7100, M-8030, M M-8060, M-8100, M-8530, M-8530, M-8560, M-9050, Aronix (registered trademark) TO-756, TO-1450, TO-1382 (above, Toagosei Co., Ltd.) KAYARAD (registered trademark) DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DPCA-120, MAX-3510 (above, Nippon Kayaku Co., Ltd.), Biscote 295, 300, 360, GPT, 3PA, 400 (Osaka Organic Chemical Co., Ltd.), New Frontier (registered trademark) R-1150 (Daiichi Kogyo) as urethane acrylate compound Yakuhin), KAYARAD (registered trademark) DPHA, KAYARAD (registered trademark) DPHA-40H, UX-5000 (Nippon Kayaku), UN-9000H (Negami Kogyo Co., Ltd.), Aronix (registered trademark) M-5300, M -5600, M-5700, M-210, M-220, M-240, M-240, M-270, M-6200, M-305, M-309, M-310, M -315 (above, Toagosei Co., Ltd.), KAYARAD (registered trademark) HDDA, KAYARAD (registered trademark) HX-220, HX-620, R-526, R-167, R-604, R-684 , R-551, R-712, UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX- 101, UX-0937, MU-2100, MU-4001 (Nippon Kayaku Co., Ltd.), Art Resin UN-9000PEP, UN-9200A, UN-7600, UN-333, UN-333, UN-1003, UN -1255, UN-6060PTM, UN-6060P, SH-500B (above, Negami Kogyo Co., Ltd.), Biscote 260, 312 and 335HP (Osaka Organic Chemical Co., Ltd.).

  [II] The polymerizable compounds can be used alone or in admixture of two or more. As a usage-ratio of the [II] polymeric compound in a coloring composition, 10 mass parts-700 mass parts are preferable with respect to 100 mass parts of [I] alkali-soluble resin, and 20 mass parts-600 mass parts are more preferable. [II] By setting the use ratio of the polymerizable compound in the above range, the colored composition can form a colored pattern having sufficient heat resistance, solvent resistance, and voltage holding ratio even at a low exposure amount.

<[III] Polymerization initiator>
The [III] polymerization initiator contained in the coloring composition used for producing the color filter of the present embodiment will be described.
[III] The polymerization initiator is a radiation-sensitive polymerization initiator, and is a component that generates an active species that can initiate polymerization of the polymerizable compound [II] in response to radiation. Examples of such [III] polymerization initiators include O-acyl oxime compounds, acetophenone compounds, biimidazole compounds and the like. These compounds may be used alone or in combination of two or more.

  Examples of the O-acyloxime compound include 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like.

  Among these, 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) is preferred.

Examples of acetophenone compounds include α-aminoketone compounds and α-hydroxyketone compounds.
Examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- ( 4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and the like.
Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one. 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone and the like.

Of these, α-aminoketone compounds are preferred, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-Morpholin-4-yl-phenyl) -butan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one are more preferred.
Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2, 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole or 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 5'-tetraphenyl-1,2'-biimidazole is preferred, of which 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'- Biimidazole is more preferred.

  [III] The use ratio of the polymerization initiator is preferably 1 part by mass to 40 parts by mass and more preferably 5 parts by mass to 30 parts by mass with respect to 100 parts by mass of the alkali-soluble resin [I]. [III] By making the usage-amount of a polymerization initiator into 1 mass part-40 mass parts, the coloring composition can form the coloring pattern and color filter which have high solvent resistance etc., even in the case of a low exposure amount.

<[IV] Colorant>
As described above, high color purity, luminance, contrast, and the like are strongly required for the coloring pattern and the color filter. Therefore, it is necessary to select an [IV] colorant contained in the coloring composition used for manufacturing the color filter of the present embodiment, which is suitable for realizing such characteristics. [IV] As the colorant, for example, any of pigments, dyes and natural pigments can be used. However, the pigments and dyes are preferably selected in consideration of the color pattern and the high color purity and brightness required for the color filter. And the selection of the dye is particularly preferred.

  [IV] Examples of the dye that can be used as the colorant include oil-soluble dyes, acid dyes or derivatives thereof, direct dyes, and modern dyes. Any known dye can be used as long as it is soluble in an organic solvent.

C. I. Examples of oil-soluble dyes include:
C. I. Solvent Yellow 4 (hereinafter, description of “CI Solvent Yellow” is omitted, only the number is described. Other dyes are also described in the same manner), 14, 15, 23, 24, 38, 62, 63, 68, 82, 88, 94, 98, 99, 162, 179;
C. I. Solvent red 45, 49, 125, 130;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56;
C. I. Solvent Blue 35, 37, 59, 67;
C. I. Solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 etc. are mentioned.

C. I. As an acid dye, for example,
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
Varifast yellow 1101, 1109, 1151, 3108, 3120, 3130, 3150, 3170, 4120;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 108, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 249, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324, 335, 340;
C. I. Acid Violet 6B, 7, 9, 17, 19, 49;
C. I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109;
C. I. And dyes such as Acid Black 24.

C. I. Examples of direct dyes include:
C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;
C. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 etc. are mentioned.

C. I. As a modern dye, for example,
C. I. Modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
C. I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 44, 48, 49, 53, 61, 74, 77, 83, 84;
C. I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Modern green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 etc. are mentioned.

  [IV] Regarding the pigment that can be used as the colorant, either an organic pigment or an inorganic pigment can be used. Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyer and Colorists). Specifically, those having the following color index (CI) names are mentioned.

  C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 211;

  C. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 68, C.I. I. Pigment orange 70, C.I. I. Pigment orange 71, C.I. I. Pigment orange 72, C.I. I. Pigment orange 73, C.I. I. Pigment orange 74;

  C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Pigment red 272;

C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment blue 80;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58;
C. I. Pigment brown 23, C.I. I. Pigment brown 25;
C. I. Pigment black 1, C.I. I. Pigment black 7 and the like.

  Next, the chemical structure of the [IV] colorant such as a dye or pigment will be described. Regarding chemical structure, azo, triaryl methane, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, diketopyrrolopyrrole And the like. Of these, triaryl methane, barbituric acid azo, pyrazole azo, anilino azo, pyrazolo triazole azo, pyridone azo, triaryl methane, phthalocyanine, anthraquinone, anthrapyridone and diketopyrrolo Selection of a pyrrole colorant is preferred.

The triarylmethane colorant which is an example of a preferable [IV] colorant exhibits blue and violet color.
Blue and violet colors are C.I. I. Pigment blue, C.I. I. Pigments such as CI pigment violet, C.I. I. Basic blue, C.I. I. Basic dyes such as basic violet, C.I. I. Solvent Blue, C.I. I. Oil-soluble dyes such as solvent violet, C.I. I. Acid Blue, C.I. I. Acid dyes such as Acid Violet, C.I. I. Disperse Blue, C.I. I. Disperse dyes such as disperse violet, C.I. I. Food blue, C.I. I. It belongs to food colorants such as food violet.
Furthermore, these acid dyes (including direct dyes) and basic dyes belong to salt-forming dyes modified with counter ions.

A triphenylmethane colorant, which is an example of a triarylmethane colorant, develops color when an NH ₂ or OH group located in a para position with respect to a central carbon takes a quinone structure by oxidation. Moreover, although it is mainly a basic dye, what introduce | transduced the sulfonic acid group turns into an acidic dye.
Depending on the number of NH ₂ and OH groups, it can be divided into the following three types. Among them, the form of a triaminotriphenylmethane dye is preferable from the viewpoint of producing a good blue color.
a) Diaminotriphenylmethane-based dye b) Triaminotriphenylmethane-based dye c) Rosolic acid-based dye having an OH group Triaminotriphenylmethane-based dye has a clear color tone and is excellent in light resistance. Of these, diphenylnaphthylmethane dye, which is a basic dye, is particularly preferable.

As the triarylmethane colorant, the following five forms of dyes and pigments can be used.
1) Basic dyes of triarylmethane dyes (triarylmethane basic dyes)
2) Salt-forming compound of triarylmethane-based basic dye and organic sulfonic acid, salt-forming compound of triarylmethane-based basic dye and aromatic hydroxycarboxylic acid 3) Acid dye of triarylmethane-based dye 4) Tria Salt-forming compounds of reel methane acid dyes and quaternary ammonium 5) Lake pigments of triarylmethane dyes (especially metal lake pigments of triarylmethane dyes)

These forms include basic triarylmethane dyes, salt formation compounds of triarylmethane basic dyes and organic sulfonic acids, and preparations of triarylmethane basic dyes and aromatic hydroxycarboxylic acids. It is preferable to use a metal lake pigment of a salt compound or a triarylmethane dye.
Triarylmethane dyes have spectral characteristics with high transmittance at 400 nm to 430 nm. However, in spite of having good spectral characteristics, the heat resistance is very poor as in general dyes. Conventionally, it has been considered that the characteristics are not sufficient for use in a color liquid crystal display image display device requiring high reliability. Therefore, it is preferable to use for the color filter of this Embodiment. In addition, the dye can be used as a base, chlorinated, oil-solubilized, or modified with a resin so as to improve the problems of the conventional triarylmethane dyes. Alternatively, the dye can be raked into a pigment.

  Triarylmethane-based dyes and oil-soluble dyes are resistant by mixing with acid groups such as carboxyl groups, rosin esters, and rosin-modified maleic acid resins (also rosin-modified fumaric acid resins). Is improved and preferable. The acid values of these acid group-containing resins, rosin esters, and rosin-modified maleic resins are preferably 20 to 200. Here, the acid value is a value measured by the method of JIS K-0070.

Examples of the triarylmethane basic dye include C.I. I. Basic Blue 1, 5, 7, 26, C.I. I. Basic violet 1, 3 etc. are mentioned. Among them, C.I. I. It is preferable to use Basic Blue 7.
Next, a salt-forming compound of a triarylmethane basic dye and an organic sulfonic acid will be described. The triarylmethane basic dye and the organic sulfonic acid can be reacted with each other by dissolving them in an aqueous solution or an alcohol solution to obtain a salt-forming compound.
As the organic sulfonic acid, a sulfonated product of naphthalene, a sulfonated product of naphthol, or the like can be used.

The sulfonated product of naphthalene is a general term for a compound in which a sulfonic acid group is bonded to a carbon atom of naphthalene, and the sulfonated product of a naphthol is a general term for a compound in which a sulfonic acid group is bonded to a carbon atom of naphthol.
Examples of the sulfonated products of naphthalenes include naphthalene monosulfonic acid having one sulfonic acid group bonded thereto, naphthalene disulfonic acid having two bonded groups, and naphthalene trisulfonic acid having three bonded groups. Specifically, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, 1,3-naphthalenedisulfonic acid, 1,5-naphthalenedisulfonic acid, 1,6-naphthalenedisulfonic acid, 1,7-naphthalenedisulfonic acid, 2 1,6-naphthalene disulfonic acid, 2,7-naphthalene disulfonic acid, 1,3,5-naphthalene trisulfonic acid, 1,3,6-naphthalene trisulfonic acid, 1,3,7-naphthalene trisulfonic acid, etc. .

  Further, the sulfonated product of naphthalenes includes naphthylamine sulfonic acid in addition to the above-mentioned naphthalene sulfonic acid. There are naphthylamine monosulfonic acid with one sulfonic acid group bonded, naphthylamine disulfonic acid with two bonded naphthylamine trisulfonic acids, and naphthylamine trisulfonic acid with three bonded sulfonic acid groups. Specifically, 1,4-naphthylamine sulfonic acid (naphthoic acid), 1,5-naphthylamine sulfonic acid (Lorentzic acid), 1,6-naphthylamine sulfonic acid (6-clebic acid), 1,7-naphthylamine sulfonic acid (7-clebic acid), 1,8-naphthylaminesulfonic acid (peric acid), 2,1-naphthylaminesulfonic acid (tobias acid), 2,5-naphthylaminesulfonic acid, 2,6-naphthylaminesulfonic acid (brenamic acid) 1,3,6-naphthylamine disulfonic acid (Freundic acid), 1,3,7-naphthylamine disulfonic acid, 2,3,6-naphthylamine disulfonic acid (amino R acid), 2,4,6-naphthylamine disulfonic acid ( C acid), 2,5,7-naphthylamine disulfonic acid (amino J acid), 2,6,8-naphthyla Njisuruhon acid (amino G acid), 1,3,6,8-naphthylamine trisulfonic acid (Koch acid) and the like.

  The sulfonated products of naphthols include naphthol monosulfonic acid having one sulfonic acid group bonded thereto, naphthol disulfonic acid having two bonded sulfonic groups, and naphthol trisulfonic acid having three bonded naphthol groups. Specifically, 1-naphthol-2-sulfonic acid, 1-naphthol-4-sulfonic acid (NW acid), 1-naphthol-5-sulfonic acid (L acid), 1-naphthol-8-sulfonic acid, 2 -Naphthol-1-sulfonic acid, 2-naphthol-6-sulfonic acid (Shafer acid), 2-naphthol-8-sulfonic acid (croseiic acid), 1-naphthol-2,4-disulfonic acid, 1-naphthol-3 , 6-Disulfonic acid, 1-naphthol-3,8-disulfonic acid (ε acid), 2-naphthol-3,6-disulfonic acid (R acid), 2-naphthol-3,8-disulfonic acid, 2-naphthol -6,8-disulfonic acid (G acid), 1-naphthol-2,4,7-trisulfonic acid, 1-naphthol-3,6,8-trisulfonic acid (oxycofolic acid), 2-naphthol-3, , And the like 8- trisulfonate.

Of these, naphthalene disulfonic acid and naphthol disulfonic acid having two sulfonic acid groups bonded thereto are preferable. Of these, 1,5-naphthalenedisulfonic acid, 2,7-naphthalenedisulfonic acid, 2-naphthol-3,6-disulfonic acid, and 2-naphthol-3,8-disulfonic acid are preferable.
Furthermore, a salt-forming compound composed of Victoria Pure Blue BO (CI Basic Blue 7) and naphthalenedisulfonic acid, and a salt-forming compound composed of Victoria Pure Blue BO (CI Basic Blue 7) and naphthol disulfonic acid are: Preferred dyes.

When reacting a disulfonated product of naphthalenes or a disulfonated product of naphthols with a triarylmethane basic dye to form the [IV] colorant of this embodiment, 1 mol of disulfone is used per 2 mol of the triarylmethane dye. The compound reacts to form a salt. This is preferable because it neutralizes the charge and the colorant component has an amount twice as much as the molar ratio of the counter ion component, so that the coloring of the dye as a colorant is not impaired. That is, it is preferable to use an organic sulfonic acid having at least two sulfonic acid groups.
A salt-forming compound of a triarylmethane basic dye, an organic sulfonic acid, and (aromatic hydroxycarboxylic acid) can be synthesized by a conventionally known method. A specific method is disclosed in Japanese Patent Laid-Open No. 2003-215850.

Further, a salt-forming compound can be obtained using an aromatic hydroxycarboxylic acid in the same manner as the organic sulfonic acid described above. Among them, 3,5-di-tert-butylsalicylic acid, 3-hydroxy-2-naphthoic acid, and 3-phenylsalicylic acid are preferably used as the aromatic hydroxycarboxylic acid. When an aromatic hydroxycarboxylic acid is used, a salt-forming compound in which the amino group (—NHC ₂ H ₅ ) portion in the triarylmethane dye and the carboxylic acid (—COOH) portion of the aromatic hydroxycarboxylic acid are combined can get. Further, the hydroxyl group (—OH) remains irrespective of the salt formation reaction.
Furthermore, a salt-forming compound composed of Victoria Pure Blue BO (CI Basic Blue 7) and 3,5-di-tert-butylsalicylic acid is a preferred dye.

  As acid dyes for triarylmethane dyes, food blue 101 (CI Acid Blue 1), Acid Pure Blue (CI Acid Blue 3), Lake Blue I (CI Acid Blue 5) Lake Blue II (CI Acid Blue 7) Edible Blue No. 1 (CI Acid Blue 9), C.I. I. Acid Blue 22, C.I. I. Acid Blue 83, C.I. I. Acid Blue 90, C.I. I. Acid Blue 93, C.I. I. Acid Blue 100, C.I. I. Acid Blue 103, C.I. I. Acid Blue 104, C.I. I. It is preferable to use Acid Blue 109.

A salt-forming compound of a triarylmethane acid dye and a quaternary ammonium compound can be synthesized by a conventionally known method.
For example, after the triarylmethane acid dye is dissolved in water, a quaternary ammonium compound is added, and the chlorination treatment may be performed while stirring. Here, a salt-forming compound is obtained in which the sulfonic acid group (—SO ³ H) part in the triarylmethane acid dye and the ammonium group (NH ₄ ⁺ ) part of the quaternary ammonium compound are bonded. As the quaternary ammonium compound, triethylbenzyl chloride or the like is preferably used.

In the present embodiment, a triarylmethane lake pigment can be used as the triarylmethane colorant.
The lake formation in the pigmentation is to obtain an insoluble salt from a soluble dye with a precipitant, and is a state in which the dye component is adsorbed on the precipitant particles while chemically reacting.
Triaminotriphenylmethane-based dyes are improved in weather resistance and heat resistance by forming lakes, and become stable and good colorants.

  Precipitating agents for lake triarylmethane dyes include complex heteropolyacids called barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminum acetate, lead acetate, tannic acid, katanol, tamol, complex acid ( Phosphotungstic acid, phosphomolybdic acid, phosphotungsten / molybdic acid, silicotungsten molybdic acid, silicotungstic acid, silicomolybdic acid). Among these, lake pigments using complex heteropolyacids are preferable because they are clear and have high coloring power, and light resistance is remarkably improved.

Specific examples of triarylmethane pigments include C.I. I. Pigment blue 1, C.I. I. Pigment blue 2, C.I. I. Pigment blue 9, C.I. I. Pigment blue 10, C.I. I. Pigment blue 14, C.I. I. Pigment blue 62, C.I. I. Pigment violet 3, C.I. I. Pigment violet 27, C.I. I. And CI Pigment Violet 39.
More preferable ones are specifically shown.
C. I. Pigment Blue 1.
C. I. Basic Blue 26, C.I. I. Rake Basic Blue 7 with phosphotungsten / molybdic acid.
C. I. Pigment Violet 3.
C. I. Lake basic violet 1 with phosphotungsten / molybdic acid.
C. I. Pigment Violet 39.
C. I. Lake basic violet 3 (crystal violet) with phosphotungsten / molybdic acid.
Among them, C.I. I. It is preferable to use CI Pigment Blue 1.

  Next, barbituric acid azo dyes and pyridone azo dyes, which are examples of preferable [IV] colorants, have, for example, the following structures. However, the barbituric acid azo dyes and pyridone azo dyes used in the present embodiment are not limited to these.

In formula (101), T ¹ and T ² each independently represent an oxygen atom or a sulfur atom.
R ^{101 to} R ¹⁰⁴ are each independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an optionally substituted substituent having 6 to 20 carbon atoms. It represents an aryl group, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, or an acyl group having 2 to 10 carbon atoms which may have a substituent.
R ^{105 to} R ¹¹² are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a carboxyl group, a sulfo group, a sulfamoyl group, or an N-substituted sulfamoyl group. Represents. A hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with a halogen atom.

More specifically, in formula (101), the aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ^{101 to} R ¹⁰⁴ may be linear, branched or cyclic. Carbon number of a C1-C10 aliphatic hydrocarbon group becomes like this. Preferably it is 2-8, More preferably, it is 3-6. Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an ethylhexyl group. (2-ethylhexyl group etc.), cyclopentyl group, cyclohexyl group, cyclohexyl alkyl group and the like.
Moreover, the hydrogen atom contained in a C1-C10 aliphatic hydrocarbon group is a hydroxyl group, a C1-C8 (preferably C1-C4) alkoxyl group, or a C1-C8 (preferably). May be substituted with a thioalkoxyl group having 1 to 4 carbon atoms. Examples of the substituted aliphatic hydrocarbon group include a hydroxyethyl group (such as 2-hydroxyethyl group), an ethoxyethyl group (such as 2-ethoxyethyl group), and an ethylhexyloxypropyl group (3- (2-ethylhexyloxy)). A propyl group) and a methylthiopropyl group (such as a 3-methylthiopropyl group).

The aryl group having 6 to 20 carbon atoms in R ^{101 to} R ¹⁰⁴ may be unsubstituted and has a substituent such as an aliphatic hydrocarbon group, an alkoxyl group, a carboxyl group, a sulfo group, or a group containing an ester bond. You may do it. The carbon number of the aryl group is counted including the carbon number of the substituent, and preferably 6 to 10. Examples of the aryl group include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl group, and a 2-sulfophenyl group. , 3-sulfophenyl group, 4-sulfophenyl group, and ethoxycarbonylphenyl group (4- (COOC ₂ H ₅ ) Ph group (Ph group represents a phenyl group)) and the like.

The alkyl part of the aralkyl group having 7 to 20 carbon atoms in R ^{101 to} R ¹⁰⁴ may be linear, branched or cyclic. The carbon number of the aralkyl group is counted including the carbon number of the substituent, and is preferably 7 to 10. Examples of the aralkyl having 7 to 20 carbon atoms include a benzyl group and a phenethyl group.
The acyl group having 2 to 10 carbon atoms in R ^{101 to} R ¹⁰⁴ may be unsubstituted or may be bonded to a substituent such as an aliphatic hydrocarbon group or an alkoxyl group. The carbon number of the acyl group is counted including the carbon number of the substituent, and the number is preferably 2 to 10. Examples of the acyl group include an acetyl group, a benzoyl group, a methoxybenzoyl group (such as a p-methoxybenzoyl group), and the like.

Aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ¹⁰⁵ to R ^{112 are} the same as those of the case of R 101 ^{to R 104.} The hydrogen atom contained in the aliphatic hydrocarbon group of R ^{105 to} R ¹¹² may be substituted with a halogen atom, and the halogen atom is preferably a fluorine atom. Specific examples of the aliphatic hydrocarbon group substituted with a halogen atom include a trifluoromethyl group.
The number of carbon atoms of the alkoxyl group having 1 to 8 carbon atoms in R ¹⁰⁵ to R ¹¹² is preferably 1-4. Examples of the alkoxyl group include a methoxy group, an ethoxy group, an isopropoxy group, an n-propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.

The N-position-substituted sulfamoyl group in R ^{105 to} R ¹¹² is preferably, for example, an N-position-monosubstituted sulfamoyl group, and represented by —SO ₂ NHR ¹⁴⁰ .
^{R 140} included in the -SO ₂ NHR ¹⁴⁰ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent group, an optionally substituted aryl group having 6 to 20 carbon atoms Represents an aralkyl group having 7 to 20 carbon atoms which may have a substituent or an acyl group having 2 to 10 carbon atoms which may have a substituent.

The C1-C10 aliphatic hydrocarbon group for R ¹⁴⁰ may be linear, branched or cyclic. The carbon number of the aliphatic hydrocarbon group does not include the carbon number of the substituent, and the number is preferably 6 to 10.
Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ¹⁴⁰ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , Methylbutyl group (1,1,3,3-tetramethylbutyl group etc.), methylhexyl group (1-methylhexyl group, 1,5-dimethylhexyl group etc.), ethylhexyl group (2-ethylhexyl group etc.), cyclopentyl Group, cyclohexyl group, methylcyclohexyl group (such as 2-methylcyclohexyl group) and cyclohexylalkyl group.

The aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ¹⁴⁰ contained in —SO ₂ NHR ¹⁴⁰ may be substituted with an alkoxyl group having 1 to 8 carbon atoms (preferably having 1 to 4 carbon atoms); For example, a propoxypropyl group (3- (isopropoxy) propyl group etc.) etc. are mentioned.
The aryl group having 6 to 20 carbon atoms in R ¹⁴⁰ may be unsubstituted or may have a substituent such as an aliphatic hydrocarbon group or a hydroxyl group. The carbon number of the aryl group is counted including the carbon number of the substituent, and preferably 6 to 10. Examples of the aryl group include a phenyl group, a hydroxyphenyl group (such as a 4-hydroxyphenyl group), and a trifluoromethylphenyl group (such as a 4-trifluoromethylphenyl group).

The alkyl part of the aralkyl group having 7 to 20 carbon atoms for R ¹⁴⁰ may be linear or branched. The carbon number of the aralkyl group is usually 7 to 20, preferably 7 to 10. Examples of the aralkyl group include phenylalkyl groups such as a benzyl group, a phenylpropyl group (such as 1-methyl-3-phenylpropyl group), and a phenylbutyl group (such as 3-amino-1-phenylbutyl group).
The acyl group having 2 to 10 carbon atoms in R ¹⁴⁰ may be unsubstituted or a hydrogen atom contained in the acyl group may be substituted with an aliphatic hydrocarbon group or an alkoxyl group. The carbon number of the acyl group is counted including the carbon number of the substituent, and the number is preferably 6 to 10. Examples of the acyl group include an acetyl group, a benzoyl group, an o-toluyl group, an m-toluyl group, a p-toluyl group, and a methoxybenzoyl group (such as a p-methoxybenzoyl group).

  The pyridone azo type which is an example of a preferable [IV] colorant has, for example, the following structure.

  In formula (102), Z is a halogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group, or a carbamoyl group. , A phenyl group having one or two substituents selected from the group consisting of a sulfo group, a sulfamoyl group and an N-substituted sulfamoyl group, or a halogen atom and a carbon number optionally having a substituent At least one selected from the group consisting of 1 to 12 aliphatic hydrocarbon groups, alkoxy groups having 1 to 8 carbon atoms, hydroxyl groups, carboxyl groups, carbamoyl groups, sulfo groups, sulfamoyl groups and N-substituted sulfamoyl groups. A naphthyl group having 1 to 3 substituents is represented.

R ¹²¹ represents a hydrogen atom, a linear, branched or cyclic C 1-10 aliphatic hydrocarbon group, carboxyl group or trifluoromethyl group.
R ¹²² represents a hydrogen atom, a cyano group, a carbamoyl group, an N-position-substituted carbamoyl group, a sulfamoyl group or a sulfo group.
R ¹²³ is a hydrogen atom, an optionally substituted linear, branched or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms, and an optionally substituted carbon atom having 6 to 6 carbon atoms. 30 aryl group, optionally substituted aralkyl group having 7 to 20 carbon atoms, optionally substituted heterocyclic group having 3 to 20 carbon atoms, carbamoyl group, N-substituted carbamoyl Group, an optionally substituted alkyloxycarbonyl group having 2 to 20 carbon atoms, an optionally substituted aryloxycarbonyl group having 7 to 30 carbon atoms, and a substituent. A C2-C20 acyl group, a C1-C30 aliphatic sulfonyl group which may have a substituent or a C6-C30 arylsulfonyl group which may have a substituent. .

  More specifically, in formula (102), the aliphatic hydrocarbon group having 1 to 12 carbon atoms in Z may be linear, branched or cyclic. The carbon number of the aliphatic hydrocarbon group includes all the carbon numbers of the substituents, and the number is usually 1 to 12, preferably 2 to 11. Examples of the aliphatic hydrocarbon group include an n-octyl group, a methylhexyl group (such as 1,5-dimethylhexyl group), an ethylhexyl group (such as 2-ethylhexyl group), a cyclooctyl group, and a methylcyclohexyl group (2, 2). -Dimethylcyclohexyl group) and cyclohexylalkyl group. The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an alkoxyl group having 1 to 8 carbon atoms or a carboxyl group. Examples of the aliphatic hydrocarbon group having a substituent include an alkoxypropyl group (such as 3- (2'-ethylhexyloxy) propyl group) and an 8- (carboxy) octyl group.

Examples of the alkoxyl group having 1 to 8 carbon atoms in Z include a methoxy group, an ethoxy group, an isopropoxy group, an n-propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group. It is done.
Examples of the halogen atom in Z include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom.
The N-position-substituted sulfamoyl group in Z is represented by —SO ₂ N (R ¹⁴¹ ) R ¹⁴² . R ¹⁴¹ and R ¹⁴² are each independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 16 carbon atoms, or an optionally substituted substituent having 6 to 20 carbon atoms. An aryl group, an optionally substituted aralkyl group having 7 to 20 carbon atoms, or an optionally substituted acyl group having 2 to 15 carbon atoms (wherein R ¹⁴¹ and R ¹⁴² are They are not hydrogen atoms at the same time).
The aliphatic hydrocarbon group having 1 to 16 carbon atoms may be linear, branched or cyclic, and the aliphatic hydrocarbon group preferably has 6 to 16 carbon atoms.

The aliphatic hydrocarbon group having 1 to 16 carbon atoms in R ¹⁴¹ and R ¹⁴² may be linear, branched or cyclic. The carbon number of the aliphatic hydrocarbon group does not include the carbon number of the substituent, and the number thereof is usually 1 to 16, preferably 6 to 10. Examples of the aliphatic hydrocarbon group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, methylbutyl group (1,1,3, 3-tetramethylbutyl group), methylhexyl group (1,5-dimethylhexyl group etc.), ethylhexyl group (2-ethylhexyl group etc.), cyclopentyl group, cyclohexyl group, methylcyclohexyl group (2-methylcyclohexyl group etc.) And a cyclohexylalkyl group. The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an alkoxyl group having 1 to 8 carbon atoms or a carboxyl group. Examples of the aliphatic hydrocarbon group having a substituent include a propoxypropyl group (such as 3- (isopropoxy) propyl group), a 2- (carboxy) ethyl group, a 3- (carboxy) ethyl group, and a 4-carboxyethyl group. Can be mentioned.

The aryl group having 6 to 20 carbon atoms in R ¹⁴¹ and R ¹⁴² may have a substituent such as an aliphatic hydrocarbon group or a hydroxyl group. Carbon number of an aryl group is counted including carbon number of a substituent, and is 6-20 normally, Preferably it is 6-10. The aryl group includes a phenyl group, a carboxyphenyl group (such as a 2-carboxyphenyl group and a 2,4-carboxyphenyl group), a hydroxyphenyl group (such as a 4-hydroxyphenyl group), and a trifluoromethylphenyl group (4-trifluoro). A methylphenyl group) and a methoxyphenyl group (4-methoxyphenyl group).
The alkyl part of the aralkyl group having 7 to 20 carbon atoms in R ¹⁴¹ and R ¹⁴² may be either linear or branched. The carbon number of the aralkyl group is usually 7 to 20, preferably 7 to 10. Aralkyl includes benzyl group, phenylethyl group (2-phenylethyl group, 2- (4-hydroxyphenyl) ethyl group, etc.), phenylethylene group (2-phenylethylene group, etc.), phenylpropyl group (1-methyl- And phenylalkyl groups such as a 3-phenylpropyl group and a phenylbutyl group (such as a 3-amino-1-phenylbutyl group).

The acyl group having 2 to 15 carbon atoms in R ¹⁴¹ and R ¹⁴² may be unsubstituted or may have a substituent such as an aliphatic hydrocarbon group, an alkoxyl group, or a carboxyl group. Carbon number of an acyl group is counted including carbon number of a substituent, and the number is 2-15 normally, Preferably it is 6-10. Examples of the acyl group include acetyl group, benzoyl group, methoxybenzoyl group (such as p-methoxybenzoyl group), carboxyacetyl group, 2-carboxypropionyl group, 3-carboxypropionyl group, 2-carboxybutyryl group, 3- Examples thereof include a carboxybutyryl group and a 4-carboxybutyryl group.

R ¹²¹ represents a hydrogen atom, a linear, branched or cyclic C 1-10 aliphatic hydrocarbon group, carboxyl group or trifluoromethyl group.
The carbon number of the aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ¹²¹ does not include the carbon number of the substituent. The carbon number is preferably 2 to 8, more preferably 3 to 6. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclopentyl group, and a cyclohexyl group.

R ¹²² represents a hydrogen atom, a cyano group, a carbamoyl group, an N-substituted carbamoyl group, a sulfamoyl group, or a sulfo group.
^Examples of the N-position-substituted carbamoyl group for R ¹²² include —CON (R ¹⁴³ ) R ¹⁴⁴ . R ¹⁴³ and R ¹⁴⁴ are each independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an optionally substituted substituent having 6 to 20 carbon atoms. It represents an aryl group, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, or an acyl group having 2 to 10 carbon atoms which may have a substituent.
The explanation and specific examples of the aliphatic hydrocarbon group, aryl group, aralkyl group and acyl group of R ¹⁴³ and R ¹⁴⁴ are the same as those of R ¹⁴¹ and R ¹⁴² described above. However, the acyl group may have a halogen atom. Examples of the acyl group having a halogen atom include a bromobenzoyl group (such as a p-bromobenzoyl group).

R ¹²³ is a hydrogen atom, an optionally substituted linear, branched or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms, and an optionally substituted carbon atom having 6 to 6 carbon atoms. 30 aryl group, optionally substituted aralkyl group having 7 to 20 carbon atoms, optionally substituted heterocyclic group having 3 to 20 carbon atoms, carbamoyl group, N-substituted carbamoyl Group, an optionally substituted alkyloxycarbonyl group having 2 to 20 carbon atoms, an optionally substituted aryloxycarbonyl group having 7 to 30 carbon atoms, and a substituent. A C2-C20 acyl group, a C1-C30 aliphatic sulfonyl group which may have a substituent, or a C6-C30 arylsulfonyl group which may have a substituent. .
Examples of the aliphatic hydrocarbon group for R ¹²³ include the same groups as the aliphatic hydrocarbon group for R ¹²¹ described above.

The aryl group in R ^123, the number of carbon atoms is usually 6-30, preferably 6-20, more preferably 6-16. Specific examples of the aryl group include a phenyl group, a 4-nitrophenyl group, a 2-nitrophenyl group, a 2-chlorophenyl group, a 2,4-dichlorophenyl group, a 2,4-dimethylphenyl group, and a 2-methylphenyl group. 4-methoxyphenyl group, 2-methoxyphenyl group, 2-methoxycarbonyl-4-nitrophenyl group and the like.
The aralkyl group for R ¹²³ may be linear or branched, and the carbon number is preferably 7 to 10. Specific examples of aralkyl include phenylalkyl groups such as benzyl group, phenylpropyl group (such as 1-methyl-3-phenylpropyl group) and phenylbutyl group (such as 3-amino-1-phenylbutyl group). It is done.

The heterocyclic group having 3 to 20 carbon atoms in the R ^123, which may be saturated or unsaturated, carbon number, preferably from 3 to 20, more preferably 5 to 15. Specific examples of the heterocyclic group include pyrazole group, 1,2,4-triazole group, isothiazole group, benzoisothiazole group, thiazole group, benzothiazole group, oxazole group and 1,2,4-thiadiazole group. Etc. Furthermore, you may have a substituent.
The N-substituted carbamoyl group for R ¹²³ is the same as the N-substituted carbamoyl group described above for R ¹²² .

The alkyloxycarbonyl group for R ¹²³ may be unsubstituted or substituted, or may be cyclic. As carbon number of an alkyloxycarbonyl group, it is 2-20 normally, Preferably it is 2-16, More preferably, it is 2-10. Examples of the alkyloxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group.
The aryloxycarbonyl group for R ¹²³ may be unsubstituted or substituted, and the number of carbon atoms is usually 7 to 30, preferably 7 to 20, and more preferably 7 to 16. It is. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group and a 4-methylphenoxycarbonyl group.

The acyl group in R ¹²³ may be an aliphatic carbonyl group or an arylcarbonyl group, may be saturated or unsaturated, may be cyclic, and further has a substituent. Also good. As carbon number, it is 2-20 normally, Preferably it is 2-15, More preferably, it is 2-10. Examples of the acyl group include acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, and benzoyl group.
The aliphatic sulfonyl group for R ¹²³ may be saturated, unsaturated, or cyclic. As carbon number, it is 1-30 normally, Preferably it is 1-20, More preferably, it is 1-16. Examples of the aliphatic sulfonyl group include a methanesulfonyl group, a butanesulfonyl group, a methoxymethanesulfonyl group, a methoxyethanesulfonyl group, and an ethoxyethanesulfonyl group.

The arylsulfonyl group for R ¹²³ may have a substituent, and the number of carbon atoms is usually 6 to 30, preferably 6 to 20, and more preferably 6 to 18. Examples of the arylsulfonyl group include benzenesulfonyl and toluenesulfonyl groups.

  Next, the diketopyrrolopyrrole system and the phthalocyanine system, which are examples of preferable [IV] colorants, have, for example, the following structures. However, the diketopyrrolopyrrole and phthalocyanine colorants used in the present embodiment are not limited to these.

In formula (103), Y represents an oxygen atom or a sulfur atom. R ¹³¹ and R ¹³² may be the same or different, and are a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group. Or an alkoxycarbonyl group. R ¹³³ and R ¹³⁴ may be the same or different and each represents an alkyl group, a cycloalkyl group, an aralkyl group, or a carbocyclic or heterocyclic aromatic residue.

More specifically, in the formula (103), the alkyl group in R ¹³¹ , R ¹³² , R ¹³³ and R ¹³⁴ may be branched or unbranched, preferably 1 to 18, more preferably Preferably has 1 to 12, particularly preferably 1 to 6 carbon atoms. Specific examples include methyl, ethyl, isopropyl, sec-butyl, tert-butyl, tert-amyl group, octyl, decyl, dodecyl or octadecyl group.

The cycloalkyl group in R ¹³¹ , R ¹³² , R ¹³³ and R ¹³⁴ preferably has 3 to 8, more preferably 3 to 6 carbon atoms, specifically Includes a cyclopentyl group, a cyclohexyl group, and the like. The alkenyl group in R ¹³¹ and R ¹³² preferably has 2 to 8, more preferably 2 to 6 carbon atoms, and specifically includes a vinyl group and an allyl group. Etc. The alkynyl group in R ¹³¹ and R ¹³² preferably has 2 to 8, more preferably 2 to 6 carbon atoms, and specific examples thereof include an ethynyl group. It is done.
The aryl group in R ¹³¹ and R ¹³² preferably has 6 to 10 carbon atoms, and specific examples thereof include a phenyl group and a naphthyl group. Examples of the alkyl group of the alkylcarbamoyl group in R ¹³¹ and R ¹³² include the same alkyl groups as those described above. Examples of the aryl group of the arylcarbamoyl group in R ¹³¹ and R ¹³² include the same aryl groups as those described above. Examples of the alkoxy group of the alkoxycarbonyl group in R ¹³¹ and R ¹³² include those having 1 to 4 carbon atoms, and specific examples include a methoxy group, an ethoxy group, and a butoxy group.

In the formula (103), when R ¹³¹ , R ¹³² , R ¹³³ and R ¹³⁴ represent an aralkyl group, a monocyclic to tricyclic, more preferably monocyclic or bicyclic aryl residue is It is good to contain. Specific examples include benzyl and phenylethyl. In formula (103), when R ¹³³ and R ¹³⁴ represent carbocyclic aromatic residues, monocyclic to tetracyclic, especially monocyclic or bicyclic residues, ie phenyl, diphenylyl or naphthyl are Is preferred.

In the formula (103), when R ¹³³ and R ¹³⁴ represent a heterocyclic aromatic residue, those of monocyclic to tricyclic are preferable. These may be pure heterocyclic and may contain one heterocyclic ring and one or more condensed benzene rings, specifically, for example, pyridyl, pyrimidyl, pyrazinyl, And triazinyl, furanyl, pyrrolyl, thiophenyl, quinolyl, coumarinyl, benzofuranyl, benzoimidazolyl, benzoxazolyl, and the like.
In formula (103), R ¹³¹ and R ¹³² are preferably hydrogen atoms. Further, R ¹³³ and R ¹³⁴ are each preferably an alkyl group having 1 to 4 carbon atoms, a dialkylamino group, a haloalkyl group, or a phenyl group optionally having a halogen atom as a substituent.
Next, the preferred [IV] phthalocyanine colorant, which is an example of the colorant, is preferably a zinc halide phthalocyanine colorant, and has, for example, the following structure.

In Formula (104), X ^{1 to} X ¹⁶ each independently represent a hydrogen atom, a chlorine atom, or a bromine atom.

More specifically, in the formula (104), the number of substituents represented by X ^{1 to} X ¹⁶ is preferably 0 to 6 chlorine atoms, 10 to 16 bromine atoms, and The sum of chlorine and bromine atoms is 10 to 16, more preferably 0 to 3 chlorine atoms, 13 to 16 bromine atoms, and a combination of chlorine and bromine atoms. The sum is 13 to 16, more preferably 1 to 3 chlorine atoms, 13 to 15 bromine atoms, and 14 to 16 sum of chlorine and bromine atoms. is there.

  Next, [IV] Inorganic pigments that can be used for the colorant include, for example, titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron oxide (III)), Examples thereof include cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

Next, the content of [IV] colorant contained in the coloring composition will be described.
[IV] The content of the colorant is preferably 1 part by mass to 400 parts by mass and more preferably 5 parts by mass to 350 parts by mass with respect to 100 parts by mass of the alkali-soluble resin [I]. [IV] By making the content of the colorant in the above range, the alkali developability of the coloring composition, the heat resistance of the pixel, the solvent resistance, the coloring pattern, and the high brightness and high contrast as the color filter are high. Can be achieved in a balanced manner at the level.

<[V] Compound>
The coloring composition used for manufacturing the color filter of the present embodiment can contain a [V] compound. The compound [V] is a compound that functions as a curing agent. Therefore, it may be referred to as [V] curing agent.
[V] The compound is a compound represented by the following formula (1), a compound represented by the following formula (2), a tertiary amine compound, an amine salt, a phosphonium salt, an amidine salt, an amide compound, a thiol compound, or a blocked isocyanate. It is at least one compound selected from the group consisting of a compound and an imidazole ring-containing compound. When the coloring composition contains a [V] compound selected from the specific compound group, low temperature curing of the coloring pattern can be realized. In addition, the storage stability of the colored composition can be improved. Hereinafter, each compound will be described in detail.

[Compounds Represented by Formula (1) and Formula (2)]
[V] The compound is preferably at least one compound selected from the group consisting of compounds represented by the following formula (1) and the following formula (2). By selecting the above-mentioned specific compound having an amino group and an electron-deficient group as the [V] compound, low-temperature curing of the colored pattern can be realized. In addition, the storage stability of the colored composition can be improved. Furthermore, the voltage holding ratio of the liquid crystal display element using the obtained color filter can be further improved.

In said formula (1), R < ¹ > -R < ⁶ > is a hydrogen atom, an electron withdrawing group, or an amino group each independently. However, at least one of R ^{1 to} R ⁶ is an electron withdrawing group, and at least one of R ^{1 to} R ⁶ is an amino group, and the amino group includes all or part of hydrogen atoms. It may be substituted with an alkyl group having 1 to 6 carbon atoms.
In said formula (2), R < ⁷ > -R < ¹⁶ > is a hydrogen atom, an electron withdrawing group, or an amino group each independently. However, at least one of R ^{7 to} R ¹⁶ is an amino group. In the amino group, all or part of the hydrogen atoms may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. And in the case of the [V] compound used for a coloring composition, the amino group may be substituted by the C1-C6 alkyl group. A is a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group, or an alkylene group having 2 to 6 carbon atoms. However, in the methylene group and alkylene group, all or part of the hydrogen atoms may be substituted with a cyano group, a halogen atom or a fluoroalkyl group.

Examples of the electron withdrawing group represented by R ^{1 to} R ^{16 in the} above formula (1) and the above formula (2) include a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, an acyl group, and an alkylsulfonyl group. Group, alkyloxysulfonyl group, dicyanovinyl group, tricyanovinyl group, sulfonyl group and the like. Of these, a nitro group, an alkyloxysulfonyl group, and a trifluoromethyl group are preferable. The group represented by A is preferably a methylene group which may be substituted with a sulfonyl group or a fluoroalkyl group.

As the compounds represented by the above formula (1) and the above formula (2),
2,2-bis (4-aminophenyl) hexafluoropropane, 2,3-bis (4-aminophenyl) succinonitrile, 4,4′-diaminobenzophenone, 4,4′-diaminophenylbenzoate, 4,4 '-Diaminodiphenylsulfone, 1,4-diamino-2-chlorobenzene, 1,4-diamino-2-bromobenzene, 1,4-diamino-2-iodobenzene, 1,4-diamino-2-nitrobenzene, 1, 4-diamino-2-trifluoromethylbenzene, 2,5-diaminobenzonitrile, 2,5-diaminoacetophenone, 2,5-diaminobenzoic acid, 2,2′-dichlorobenzidine, 2,2′-dibromobenzidine, 2,2'-diiodobenzidine, 2,2'-dinitrobenzidine, 2,2'-bis (trifluoromethyl) benzidine , Ethyl 3-aminobenzenesulfonate, 3,5-bistrifluoromethyl-1,2-diaminobenzene, 4-aminonitrobenzene, N, N-dimethyl-4-nitroaniline, and 4,4′-diaminodiphenyl Sulfone, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2′-bis (trifluoromethyl) benzidine, ethyl 3-aminobenzenesulfonate, 3,5-bistrifluoromethyl-1,2- Diaminobenzene, 4-aminonitrobenzene, and N, N-dimethyl-4-nitroaniline are more preferable.

  The compounds represented by the above formula (1) and the above formula (2) can be used alone or in admixture of two or more. As a content rate of the compound represented by the said Formula (1) and the said Formula (2), 0.1 mass part-20 mass parts are preferable with respect to 100 mass parts of [I] alkali-soluble resin, 0.2 More preferred is 10 parts by mass. By making the content rate of the compound represented by the said Formula (1) and the said Formula (2) into the said range, the storage stability and low temperature hardening of a coloring composition can be made compatible at a higher level.

[Tertiary amine compound]
When a highly reactive general primary amine compound or secondary amine compound coexists with an epoxy compound, a curing reaction proceeds due to a nucleophilic attack on the epoxy group of the amine during storage of the composition solution. There is a risk of quality loss. However, when a tertiary amine is used, the storage stability is good even if it is coexistent with an epoxy compound in the composition part due to its relatively low reactivity.
As the tertiary amine compound, at least one selected from the group consisting of compounds represented by the following formula (5) can be used.

In the above formula ^{(5), R} 24 ~R ²⁶ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group or a C7-30 aralkyl group having 6 to 18 carbon atoms. However, R ²⁴ and R ²⁵ may be bonded to each other to form a ring structure together with the nitrogen atom to which they are bonded. In the alkyl group, aryl group and aralkyl group, part or all of the hydrogen atoms may be substituted.

Examples of the alkyl group having 1 to 20 carbon atoms indicated by the R ²⁴ to R ^26, for example, linear or branched methyl group, ethyl group, propyl group, butyl group, a pentyl group, a hexyl group, a heptyl group, Examples include octyl group, nonyl group, decyl group, lauryl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and eicosyl group.
The aryl group having 6 to 18 carbon atoms indicated by the ^R 24 ^{to R 26,} for example, a phenyl group, a naphthyl group, and the like.
Examples of the aralkyl group having 7 to 30 carbon atoms represented by R ^{24 to} R ²⁶ include a benzyl group and a phenethyl group.

  Examples of the tertiary amine compound include N, N-dimethylbenzylamine, triphenylamine, tributylamine, trioctylamine, tridodecylamine, dibutylbenzylamine, trinaphthylamine, N-ethyl-N-methylaniline, N, N-diethylaniline, N-phenyl-N-methylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-4-bromoaniline, N, N-dimethyl-4-methoxyaniline, N-phenylpiperidine N- (4-methoxyphenyl) piperidine, N-phenyl-1,2,3,4-tetrahydroisoquinoline, 6-benzyloxy-N-phenyl-7-methoxy-1,2,3,4-tetrahydroisoquinoline, N, N′-dimethylpiperazine, N, N-dimethylcyclohexylami , 2-dimethylaminomethyl phenol, 2,4,6-tris (dimethylaminomethyl) phenol, and the like.

  Of these tertiary amine compounds, trioctylamine, 2-dimethylaminomethylphenol, N, N-diethylaniline and the like are preferable. The tertiary amine compounds can be used alone or in admixture of two or more. As a content rate of the tertiary amine compound in a coloring composition, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [I] alkali-soluble resin, and 0.5 mass part-5 mass parts are more. preferable. By making the content rate of a tertiary amine compound into the said specific range, the storage stability and low temperature hardening of a coloring composition can be made compatible at a higher level.

[Amine and phosphonium salts]
As amine salt and phosphonium salt, at least 1 sort (s) chosen from the group which consists of a compound represented by following formula (6) can be used.

In the above formula (6), ^{A 1} is a nitrogen atom or a phosphorus atom. R ²⁷ to R ³⁰ each independently represent a hydrogen atom, an alkyl group, an aryl group or a C7-30 aralkyl group having 6 to 18 carbon atoms having 1 to 20 carbon atoms. However, in these groups, some or all of the hydrogen atoms may be substituted. Q ⁻ is a monovalent anion.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ^{27 to} R ³⁰ include, for example, a linear or branched methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, Examples include octyl group, nonyl group, decyl group, lauryl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and eicosyl group.
As a C6-C18 aryl group which said R < ²⁷ > -R < ³⁰ > shows, a phenyl group, a naphthyl group, etc. are mentioned, for example.
Examples of the aralkyl group having 7 to ³⁰ carbon atoms represented by R ^{27 to} R ³⁰ include a benzyl group and a phenethyl group.

Examples of the monovalent anion represented by Q ⁻ include chloride ion, bromide ion, iodide ion, cyanide ion, nitrate ion, nitrite ion, hypochlorite ion, chlorite ion, and chlorate ion. Perchlorate ion, permanganate ion, bicarbonate ion, dihydrogen phosphate ion, hydrogen sulfide ion, thiocyanate ion, carboxylate ion, sulfonate ion, phenoxide ion, tetrafluoroborate ion, tetraarylborate ion, Examples include hexafluoroantimonate ions.

When A ¹ is a nitrogen atom, that is, as an ammonium salt, for example, tetramethylammonium chloride, tetrabutylammonium chloride, dodecyldimethylbenzylammonium chloride, octyltrimethylammonium chloride, decyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetrachloride Decyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzalkonium chloride, benzalkonium bromide, didecyldimethylammonium chloride, dichloride Stearyldimethylammonium is mentioned.

When A ¹ is a phosphorus atom, that is, as a phosphonium salt, for example, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra (p-tolyl) borate, tetraphenylphosphonium tetra (p-ethylphenyl) borate, Tetraphenylphosphonium tetra (p-methoxyphenyl) borate, tetraphenylphosphonium tetra (p-ethoxyphenyl) borate, tetraphenylphosphonium tetra (p-tert-butoxyphenyl) borate, tetraphenylphosphonium tetra (m-tolyl) ) Borate, tetraphenylphosphonium tetra (m-methoxyphenyl) borate, tri (p-tolyl) phenylphosphonium tetra (p-tolyl) borate, tetra (p-to) Ril) phosphonium tetra (p-tolyl) borate, tri (p-methoxyphenyl) phenylphosphonium tetra (p-tolyl) borate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, methyltriphenylphosphonium thiocyanate, p-tolyl Examples include triphenylphosphonium thiocyanate.

  Of these amine salts and phosphonium salts, tetramethylammonium chloride and butyltriphenylphosphonium thiocyanate are preferable. Amine salts and phosphonium salts can be used alone or in admixture of two or more. As a content rate of the amine salt and phosphonium salt in a coloring composition, 0.05 mass part-10 mass parts are preferable with respect to 100 mass parts of [I] alkali-soluble resin, and 0.1 mass part-5 mass parts are. More preferred. By making the content rate of an amine salt and a phosphonium salt into the said specific range, the storage stability and low temperature hardening of a coloring composition can be made compatible at a higher level.

[Amidine salt]
As the amidine salt, at least one selected from the group consisting of salts of compounds represented by the following formula (7) can be used.

In said formula (7), m is an integer of 2-6. However, some or all of the hydrogen atoms of the alkylene group may be substituted with an organic group. Note that the above-mentioned alkylene group refers to both alkylene groups represented by (CH _{2) m} in the alkylene group and wherein in the tetrahydropyrimidine ring (7).

Examples of the organic group that the alkylene group may have as a substituent include:
An alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a t-butyl group, and an n-hexyl group;
Such as hydroxymethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxyisopropyl group, 3-hydroxy-t-butyl group, 6-hydroxyhexyl group, etc. A hydroxyalkyl group having 1 to 6 carbon atoms;
Examples thereof include C2-C12 dialkylamino groups such as dimethylamino group, methylethylamino group, diethylamino group, diisopropylamino group, dibutylamino group, t-butylmethylamino group, and di-n-hexylamino group.

  Examples of the compound represented by the above formula (7) include 1,5-diazabicyclo [4,3,0] -nonene-5 (DBN), 1,5-diazabicyclo [4,4,0] -decene-5, 1,8-diazabicyclo [5,4,0] -undecene-7 (DBU), 5-hydroxypropyl-1,8-diazabicyclo [5,4,0] -undecene-7, 5-dibutylamino-1,8 -Diazabicyclo [5,4,0] -undecene-7 and the like. Of these, DBN and DBU are preferred.

Examples of the acid for the compound represented by the above formula (7) to form a salt include organic acids and inorganic acids.
Examples of the organic acid include carboxylic acid, monoalkyl carbonic acid, aromatic hydroxy compound, sulfonic acid and the like.
Of these acids, carboxylic acids, aromatic hydroxy compounds and sulfonic acids are preferred, saturated fatty acids, aromatic hydroxy compounds and sulfonic acids are more preferred, sulfonic acids which are strong acids are particularly preferred, toluenesulfonic acid, methanesulfonic acid, Octylbenzenesulfonic acid is most preferred. The amidine salt is preferably a salt of DBU and toluenesulfonic acid, a salt of DBU and octylbenzenesulfonic acid, a salt of DBN and toluenesulfonic acid, or a salt of DBN and octylbenzenesulfonic acid.

  Amidine salts can be used alone or in admixture of two or more. As content rate of the amidine salt in a coloring composition, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [I] alkali-soluble resin, and 0.5 mass part-5 mass parts are more preferable. By setting the content ratio of the amidine salt within the above specific range, both the storage stability and the low temperature curing of the colored composition can be achieved at a higher level.

[Amide compound]
As the amide compound, at least one selected from the group consisting of compounds having an amide group represented by the following formulas (8) to (10) can be used.

In the formula ^{(8), R 31} and ^{R 32} are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclohexyl group, a phenyl group, a naphthyl group, a vinyl group or a 2-pyridyl group. However, the alkyl group having 1 to 12 carbon atoms, the phenyl group, and the naphthyl group may be substituted with an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, or an acetyl group.

In said formula (9), ^R33 and ^R34 are respectively independently a hydrogen atom, a C1-C12 alkyl group, or a cyclohexyl group. A ² is a methylene group, an alkylene group having 2 to 12 carbon atoms, a phenylene group, a naphthylene group, or a vinylene group. However, the methylene group, the alkylene group having 2 to 12 carbon atoms, the phenylene group, and the naphthylene group may be substituted with an alkyl group having 1 to 6 carbon atoms and a halogen atom.
In said formula (10), R ^<35> and R ^<36> are respectively independently a hydrogen atom, a C1-C12 alkyl group, or a cyclohexyl group. A ³ is a methylene group, an alkylene group having 2 to 12 carbon atoms, a phenylene group, a naphthylene group, or a vinylene group. However, the methylene group, the alkylene group having 2 to 12 carbon atoms, the phenylene group, and the naphthylene group may be substituted with an alkyl group having 1 to 6 carbon atoms and a halogen atom.

The amide compound represented by the above formula (8) is a compound having one amide bond in the molecule. Specific examples thereof include acetamide, N-methylacetamide, N-ethylacetamide, phthalamic acid, acrylamide, benzamide, naphthamide, nicotinamide, and isonicotinamide.
Of these, acetamide, N-methylacetamide, and phthalamic acid are preferred from the viewpoints of improving storage stability at room temperature, heat resistance of the resulting colored pattern, voltage holding ratio, and the like.

The compounds represented by the above formulas (9) and (10) are compounds having two amide bonds in the molecule. Specific examples thereof include, for example, phthalamide, isophthalamide, terephthalamide, malonamide, succinamide, N, N′-diacetyl-p-phenylenediamine, N, N′-diacetyl-hexamethylenediamine, N, N′-diacetyl- And dodecylmethylenediamine.
Among these, from the viewpoint that both storage stability and low temperature curing can be achieved at a high level, isophthalamide, adipine amide, N, N′-diacetyl-p-phenylenediamine, and N, N′-diacetyl-hexamethylenediamine are used. preferable.

  An amide compound can be used individually or in mixture of 2 or more types. As a content rate of the amide compound in a coloring composition, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [I] alkali-soluble resin, and 0.5 mass part-5 mass parts are more preferable. By making the content rate of an amide compound into the said specific range, the storage stability and low temperature hardening of a coloring composition can be made compatible at a higher level.

[Thiol compound]
The thiol compound is a compound having two or more mercapto groups in one molecule. The thiol compound is not particularly limited as long as it has two or more mercapto groups in one molecule, but at least one selected from the group consisting of compounds represented by the following formula (11) may be used. it can.

In formula (11), R ³⁷ is a methylene group or an alkylene group having 2 to 10 carbon atoms. However, in these groups, some or all of the hydrogen atoms may be substituted with alkyl groups. Y ¹ is a single bond, —CO— or O—CO— ^* . However, bond binds to ^{R 37} marked with *. n is an integer of 2-10. A ⁴ is an n-valent hydrocarbon group having 2 to 70 carbon atoms which may have one or more ether bonds, or a group represented by the following formula (12) when n is 3.

In said formula (12), R < ³⁸ > -R < ⁴⁰ > is a methylene group or a C2-C6 alkylene group each independently. “*” Represents a bond.

  As the compound represented by the above formula (11), typically, an esterified product of mercaptocarboxylic acid and a polyhydric alcohol can be used. Examples of the mercaptocarboxylic acid constituting the esterified product include thioglycolic acid, 3-mercaptopropionic acid, 3-mercaptobutanoic acid, and 3-mercaptopentanoic acid. Examples of the polyhydric alcohol constituting the esterified product include ethylene glycol, propylene glycol, trimethylolpropane, pentaerythritol, tetraethylene glycol, dipentaerythritol, 1,4-butanediol, pentaerythritol and the like.

  Examples of the compound represented by the formula (11) include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate). Dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), Pentaerythritol tetrakis (3-mercaptopentylate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione preferable.

  As the compound having two or more mercapto groups in one molecule of the thiol compound, compounds represented by the following formulas (13) to (15) can also be used.

In the above formula ^{(13), R 41} is an alkylene group of methylene group or 2-20 carbon atoms. ^R42 is a methylene group or a linear or branched alkylene group having 2 to 6 carbon atoms. k is an integer of 1-20.
In the above formula (14), R ^{43 to} R ⁴⁶ are each independently a hydrogen atom, a hydroxyl group or a group represented by the following formula (15). However, at least one of R ^{43 to} R ⁴⁶ is a group represented by the following formula (15).

In the above formula ^{(15), R 47} is a methylene group or a linear or branched alkylene group having 2 to 6 carbon atoms.

  A thiol compound can be used individually or in mixture of 2 or more types. As a content rate of the thiol compound in a coloring composition, 1 mass part-20 mass parts are preferable with respect to 100 mass parts of [I] alkali-soluble resin, and 5 mass parts-15 mass parts are more preferable. By making the content rate of a thiol compound into the said specific range, the storage stability and low temperature hardening of a coloring composition can be made compatible at a higher level.

[Block isocyanate compounds]
A block polyisocyanate compound is a compound in which an isocyanate group is reacted with an active hydrogen group-containing compound (blocking agent) to make it inert at room temperature, and when this is heated, the blocking agent dissociates and the isocyanate group is regenerated. It has something. When the colored composition contains the block polyisocyanate, an isocyanate-hydroxyl crosslinking reaction proceeds as an effective crosslinking agent, and the storage stability and low-temperature curing of the colored composition can be achieved at a high level.
The block polyisocyanate compound is obtained by a known reaction between a polyisocyanate derived from an aliphatic or alicyclic diisocyanate and a compound having an active hydrogen (blocking agent).

  Examples of the diisocyanate include tetramethylene diisocyanate, pentane diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethyl-1,6-diisocyanatohexane, 2,4,4-trimethyl-1,6-di- Isocyanatohexane, lysine diisocyanate, isophorone diisocyanate (IPDI), 1,3-bis (isocyanatomethyl) cyclohexane, 4,4-dicyclohexylmethane diisocyanate, norbornene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, tolidine diisocyanate, xylidine isocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate Sulfonates, 1,6-hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl diisocyanate.

As a commercial item, for example,
As an isocyanate group blocked with an oxime of methyl ethyl ketone, Duranate (registered trademark) TPA-B80E, TPA-B80X, E402-B80T, MF-B60XN, MF-B60X, MF-B80M (above, Asahi Kasei Kogyo Co., Ltd.);
As an isocyanate group blocked with active methylene, Duranate (registered trademark) MF-K60X (Asahi Kasei Kogyo Co., Ltd.);
Examples of the block body of an isocyanate compound having a (meth) acryloyl group include Karenz (registered trademark) MOI-BP and Karenz (registered trademark) MOI-BM (shown above, Showa Denko KK). Among these, when using DURANATE (registered trademark) E402-B80T and MF-K60X, high flexibility is expressed, and by using it in a mixed system with others, its hardness can be freely controlled. This is preferable because it is possible.

Examples of the polyisocyanate derived from diisocyanate include isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, and allophanate type polyisocyanate. From the viewpoint of curability, isocyanurate type polyisocyanate is preferable.
Examples of the blocking agent include alcohol compounds, phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds, imidazole compounds, pyrazole compounds, urea compounds, oxime compounds, Examples include amine compounds, imine compounds, pyridine compounds, and the like.

Examples of the alcohol compound include methanol, ethanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, cyclohexanol and the like;
Examples of phenolic compounds include phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, hydroxybenzoic acid ester and the like;
Examples of active methylene compounds include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone and the like;
Examples of mercaptan compounds include butyl mercaptan and dodecyl mercaptan;
Examples of acid amide compounds include acetanilide, acetic acid amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, and the like;
Examples of the acid imide compound include succinimide and maleic imide;
Examples of the imidazole compound include imidazole and 2-methylimidazole;
Examples of the pyrazole compound include 3-methylpyrazole, 3,5-dimethylpyrazole, 3,5-ethylpyrazole and the like;
Examples of urea compounds include urea, thiourea, ethylene urea, and the like;
Examples of oxime compounds include formaldoxime, acetoaldoxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime and the like;
Examples of amine compounds include diphenylamine, aniline, carbazole and the like;
Examples of the imine compound include ethyleneimine and polyethyleneimine;
Examples of the pyridine compound include 2-hydroxypyridine and 2-hydroxyquinoline.

  A block polyisocyanate compound can be used individually or in mixture of 2 or more types. As a content rate of the block polyisocyanate compound in a coloring composition, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [I] alkali-soluble resin, and 0.5 mass part-5 mass parts are more. preferable. By making the content rate of a block polyisocyanate compound into the said range, the storage stability and low temperature hardening of a coloring composition can be made compatible at a higher level.

[Imidazole ring-containing compound]
As the imidazole ring-containing compound, at least one selected from the group consisting of compounds represented by the following formula (16) can be used.

In the above formula (16), A ⁵ , A ⁶ , A ⁷ and R ⁴⁸ are each independently a hydrogen atom or a linear, branched or cyclic group having 1 to 20 carbon atoms which may have a substituent. It is a hydrocarbon group. A ⁶ and A ⁷ may be connected to each other to form a ring.

Examples of the linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms represented by A ⁵ , A ⁶ , A ⁷ and R ⁴⁸ include:
Methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group N-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group An alkyl group having 1 to 20 carbon atoms such as n-octadecyl group, n-nonadecyl group, n-eicosyl group;
A cycloalkyl group having 3 to 20 carbon atoms such as a cyclopentyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group;
Aryl groups having 6 to 20 carbon atoms such as phenyl group, toluyl group, benzyl group, methylbenzyl group, xylyl group, mesityl group, naphthyl group, anthryl group;
Examples thereof include a bridged alicyclic hydrocarbon group having 6 to 20 carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclododecyl group, an adamantyl group, a methyladamantyl group, an ethyladamantyl group, and a butyladamantyl group.

The hydrocarbon group may be substituted. Specific examples of the substituent include
Hydroxyl group;
Carboxyl group;
Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl A hydroxyalkyl group having 1 to 4 carbon atoms such as a 4-hydroxybutyl group;
C1-C4 alkoxyl such as methoxyl group, ethoxyl group, n-propoxyl group, i-propoxyl group, n-butoxyl group, 2-methylpropoxyl group, 1-methylpropoxyl group, t-butoxyl group, etc. Group;
A cyano group;
A cyanoalkyl group having 2 to 5 carbon atoms such as a cyanomethyl group, a 2-cyanoethyl group, a 3-cyanopropyl group, a 4-cyanobutyl group;
An alkoxycarbonyl group having 2 to 5 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, or a t-butoxycarbonyl group;
An alkoxycarbonylalkoxyl group having 3 to 6 carbon atoms such as a methoxycarbonylmethoxyl group, an ethoxycarbonylmethoxyl group, a t-butoxycarbonylmethoxyl group;
Halogen atoms such as fluorine and chlorine;
Examples thereof include fluoroalkyl groups such as a fluoromethyl group, a trifluoromethyl group, and a pentafluoroethyl group.

Preferred examples of the ring formed by connecting A ⁶ and A ⁷ to each other include an aromatic ring and a saturated or unsaturated nitrogen-containing heterocyclic ring having 2 to 20 carbon atoms. Examples of the imidazole ring-containing compound in the case where the ring formed by connecting A ⁶ and A ⁷ to each other is a benzene ring include compounds represented by the following formula (17).

In the above formula ^{(17), R 48} and ^{A 5} is as defined in the above formula (16). R ^{49 to} R ⁵² are each independently a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. As the hydrocarbon group represented by R ⁴⁹ to R ^52, it may be the same as the hydrocarbon group in the above formula (16).

  As the imidazole ring-containing compound, 2-phenylbenzimidazole, 2-methylimidazole, and 2-methylbenzimidazole are preferable. An imidazole ring containing compound can be used individually or in mixture of 2 or more types. As a content rate of an imidazole ring containing compound, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [I] alkali-soluble resin, and 0.5 mass part-5 mass parts are more preferable. By making the content rate of an imidazole ring containing compound into the said specific range, the storage stability and low temperature hardening of a coloring composition can be made compatible at a higher level.

<Other optional components>
The colored composition used in the production of the color filter of the present embodiment includes the above [I] alkali-soluble resin, [II] polymerizable compound, [III] polymerization initiator, [IV] colorant, and [V] compound. In addition to (curing agent), other optional components such as a surfactant, a storage stabilizer, an adhesion aid, and a heat resistance improver can be contained as necessary within the range not impairing the effects of the present invention. Each of these optional components may be used alone or in combination of two or more. Hereinafter, each component will be described in detail.

[Surfactant]
Surfactant can be used in order to improve the film-forming property of a coloring composition more. Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and other surfactants.

As the fluorosurfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of the terminal, main chain and side chain is preferable.
Commercially available fluorosurfactants include, for example, Footent (registered trademark) FT-100, -110, -140A, -150, -250, -251, -300, and -310. , -400S, Footent (registered trademark) FTX-218, -251 (above, Neos).

  Commercially available silicone surfactants include, for example, Tore Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (above, Toray Dow Corning Silicone).

  As the usage-amount of surfactant, 1.0 mass part or less is preferable with respect to 100 mass parts of [I] alkali-soluble resin, and 0.7 mass part or less is more preferable. When the usage-amount of surfactant exceeds 1.0 mass part, it will become easy to produce a film | membrane nonuniformity.

[Storage stabilizer]
Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitronitroso compounds, and more specifically, 4-methoxyphenol, N-nitroso-N-phenylhydroxylamine aluminum. Etc.

  As the usage-amount of a storage stabilizer, 3.0 mass parts or less are preferable with respect to 100 mass parts of [I] alkali-soluble resin, and 1.0 mass part or less is more preferable. When the amount of the storage stabilizer exceeds 3.0 parts by mass, the sensitivity may decrease and the pattern shape may deteriorate.

[Adhesion aid]
Adhesion aids can be used to further improve the adhesion between the resulting colored pattern and the color filter and the substrate. As the adhesion assistant, a functional silane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, or an oxiranyl group is preferable. For example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltri Examples include methoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. .

  As the usage-amount of an adhesion assistant, 20 mass parts or less are preferable with respect to 100 mass parts of [I] alkali-soluble resin, and 15 mass parts or less are more preferable. When the usage-amount of an adhesion assistant exceeds 20 mass parts, there exists a tendency for it to become easy to produce the image development remainder.

<Method for preparing colored composition>
The colored composition used in the production of the color filter of the present embodiment includes [I] alkali-soluble resin, [II] polymerizable compound, [III] polymerization initiator, [IV] colorant, and [V] compound (curing agent). , And other optional components that are added as necessary. This colored composition is preferably used in the form of a solution after being dissolved in a suitable solvent.
As a solvent used for the preparation of the coloring composition, a solvent that uniformly dissolves essential components and optional components and does not react with each component is used. As such a solvent, the thing similar to what was illustrated as a solvent which can be used in order to manufacture the above-mentioned [I] alkali-soluble resin is mentioned.

  Among such solvents, from the viewpoint of the solubility of each component, the reactivity with each component, the ease of film formation, and the like, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n- Propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol Non-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether (Poly) alkylene glycol monoalkyl ethers such as

  Acetic acid ethylene glycol monomethyl ether, acetic acid ethylene glycol monoethyl ether, acetic acid ethylene glycol mono-n-propyl ether, acetic acid ethylene glycol mono-n-butyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether, acetic acid diethylene glycol mono-n-propyl Acetic acid (poly) alkylene glycol monoalkyl ethers such as ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate ;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexane-2-one;
Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, N-butyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl hydroxyacetate, ethyl ethoxyacetate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, Ethyl 2-hydroxy-2-methylpropionate, 2 Hydroxy-3-methyl-butyric acid methyl, other esters such as ethyl 2-oxo acid;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like.

  Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, propylene glycol monoethyl 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, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate Le acetate i- butyl, formic acid n- amyl acetate, i- amyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate are preferred. The solvent can be used alone or in combination of two or more.

  Furthermore, together with the above solvents, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, maleic acid A high boiling point solvent such as diethyl, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate may be used in combination. The said high boiling point solvent can use single or 2 types or more.

  Although it is not limited as content of a solvent, The quantity from which the total density | concentration of each component remove | excluding the solvent of a coloring composition from viewpoints of the applicability | paintability of a coloring composition obtained, stability, etc. will be 5 mass%-50 mass%. Is preferable, and the amount of 10% by mass to 40% by mass is more preferable. When the colored composition is prepared in a solution state, the solid content concentration (components other than the solvent in the composition solution) can be set to any concentration (for example, 5 mass% to 50% by mass). The more preferable solid content concentration varies depending on the method of forming the coating film on the substrate, which will be described later. The composition solution thus prepared can be used after being filtered using a Millipore filter or the like having a pore diameter of about 0.5 μm.

  The colored composition by the above components and preparation method can form a colored pattern by low-temperature curing. Specifically, a colored pattern having good reliability such as solvent resistance can be obtained at a curing temperature of 200 ° C. or lower, and even at a curing temperature of 180 ° C. or lower. And the color filter of this Embodiment can be provided by low-temperature hardening.

  Next, the color filter of this Embodiment has a protective film provided on the coloring pattern. This protective film is formed using the first radiation-sensitive resin composition on the colored pattern. Below, the 1st radiation sensitive resin composition used for formation of the protective film of the color filter of this Embodiment is demonstrated.

<First radiation sensitive resin composition>
The 1st radiation sensitive resin composition used for formation of the protective film of the color filter of this embodiment contains a [A] compound, a [B] polymeric compound, a [C] polymerization initiator, and a [D] compound. Furthermore, you may contain an arbitrary component. The first radiation-sensitive resin composition can easily form a fine and elaborate pattern by exposure and development utilizing radiation sensitivity, and realizes low-temperature curing. In addition, it has storage stability and sufficient resolution and radiation sensitivity. Hereinafter, each component will be described in detail.

<[A] Compound>
The [A] compound contained in the first radiation-sensitive resin composition is a compound having an epoxy group. Examples of the compound [A] include compounds having two or more 3,4-epoxycyclohexyl groups in one molecule.

  Examples of the compound having two or more 3,4-epoxycyclohexyl groups in one molecule include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxy Cyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-ethylene glycol) (Epoxycyclohexylmethyl) ether , Ethylenebis (3,4-epoxycyclohexane carboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane carboxylate and the like.

As other [A] compounds, for example,
Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, Diglycidyl ethers of bisphenol compounds such as brominated bisphenol F diglycidyl ether and brominated bisphenol S diglycidyl ether;
Polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether Glycidyl ether;
Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;
Phenol novolac type epoxy resin;
Cresol novolac type epoxy resin;
Polyphenol type epoxy resin;
Cycloaliphatic epoxy resin;
Diglycidyl esters of aliphatic long-chain dibasic acids;
Glycidyl esters of higher fatty acids;
Examples include epoxidized soybean oil and epoxidized linseed oil.

As these commercial products, for example,
As bisphenol A type epoxy resin, Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (Japan Epoxy Resin Co., Ltd.) and the like;
As bisphenol F type epoxy resin, Epicoat 807 (Japan Epoxy Resin Co., Ltd.) and the like;
As a phenol novolac type epoxy resin, Epicoat 152, 154, 157S65 (above, Japan Epoxy Resin Co., Ltd.), EPPN (registered trademark) 201, 202 (above, Nippon Kayaku Co., Ltd.), etc .;
As cresol novolac type epoxy resin, EOCN (registered trademark) 102, 103S, 104S, 1020, 1025, 1027 (above, Nippon Kayaku Co., Ltd.), Epicoat 180S75 (Japan Epoxy Resin Co., Ltd.), etc .;
As polyphenol type epoxy resin, Epicoat 1032H60, XY-4000 (above, Japan Epoxy Resin Co., Ltd.) and the like;
Cyclic aliphatic epoxy resins include CY-175, 177, 179, Araldite CY-182, 192, 184 (above, Ciba Specialty Chemicals), ERL-4234, 4299, 4221, 4206 (above, U.C.C.), Shodyne 509 (Showa Denko), Epicron 200, 400 (above, Dainippon Ink), Epicoat 871, 872 (above, Japan Epoxy Resin), ED -5661, 5562 (above, Celanese Coating), etc .;
Examples of the aliphatic polyglycidyl ether include Epolite 100MF (Kyoeisha Chemical Company), Epiol (registered trademark) TMP (Nippon Yushi Co., Ltd.) and the like.
Of these, phenol novolac type epoxy resins and polyphenol type epoxy resins are preferred.

  [A] The compound exemplified above and the [A] compound, which is a copolymer having a carboxyl group described later, are both contained in the first radiation-sensitive composition. A] The amount of the compound used is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and more preferably 2 parts by mass to 100 parts by mass of the compound [A] which is a copolymer having a carboxyl group described later. A range of 15 parts by mass is particularly preferable.

  [A] The compound is preferably a polymer, and more preferably the polymer further has a carboxyl group. The [A] compound is more preferably a copolymer having a carboxyl group. When the compound [A] has a structure having a carboxyl group, the first radiation-sensitive resin composition can form a cured film that is superior in heat resistance, light resistance, chemical resistance, transmittance, flatness, and the like.

  As the compound [A], a structural unit formed from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a structural unit formed from an epoxy group-containing unsaturated compound Copolymers containing can be used. In that case, as [A] compound, the copolymer similar to [I] alkali-soluble resin contained in the coloring composition used for color filter manufacture of this Embodiment mentioned above can be used. For example, at least one ((I-1) compound) selected from the group consisting of the above-mentioned (I-1) unsaturated carboxylic acid and unsaturated carboxylic anhydride, and (I-2) epoxy group-containing unsaturated An alkali-soluble alkali-soluble resin obtained by copolymerizing a compound ((I-2) compound) can be used.

<[B] Polymerizable compound>
[B] The polymerizable compound is a polymerizable compound having an ethylenically unsaturated bond. [B] As the polymerizable compound, the same compound as the [II] polymerizable compound contained in the coloring composition used for producing the color filter of the present embodiment described above can be used.

  [B] The polymerizable compounds can be used alone or in admixture of two or more. The content ratio of the [B] polymerizable compound in the first radiation-sensitive resin composition is 20 parts by mass to 200 parts by mass with respect to 100 parts by mass of the [A] compound that is a copolymer having a carboxyl group. Preferably, 40 parts by mass to 160 parts by mass is more preferable. [B] By making the content rate of a polymeric compound into the said range, the 1st radiation sensitive resin composition can form the cured film which was excellent in adhesiveness and sufficient hardness also in the low exposure amount, and was excellent. A protective film can be provided.

<[C] Polymerization initiator>
[C] The polymerization initiator is a radiation-sensitive polymerization initiator, and is a component that generates an active species capable of initiating a polymerization reaction in response to radiation. The same compound as the [III] polymerization initiator contained in the coloring composition used for manufacturing the color filter of the present embodiment described above can be used.

  [C] The polymerization initiators can be used alone or in admixture of two or more. The content ratio of the [C] polymerization initiator in the first radiation-sensitive resin composition is 1 part by mass to 40 parts by mass with respect to 100 parts by mass of the [A] compound that is a copolymer having a carboxyl group. Preferably, 5 to 30 parts by mass is more preferable. [C] By making the content rate of a polymerization initiator into 1 mass part-40 mass parts, the 1st radiation sensitive resin composition forms the cured film which has high hardness and adhesiveness even in the case of a low exposure amount. And an excellent protective film can be provided.

<[D] Compound>
The 1st radiation sensitive resin composition used for formation of the protective film of the color filter of this embodiment contains 1st radiation sensitivity by containing the [D] compound which has an amino group and an electron withdrawing group. The cured film can be accelerated by curing at a low temperature of the resin composition. In addition, the storage stability is also realized, and the voltage holding ratio of the liquid crystal display element including the obtained color filter having the protective film can be maintained at a high level.

[D] The compound is at least one compound selected from the group consisting of compounds represented by the above formula (1) and the above formula (2). Details of the structures of the compounds represented by the formula (1) and the formula (2) were explained when the [V] compound contained in the above-mentioned coloring composition was explained. Therefore, at least one of R ^{7 to} R ¹⁶ is an amino group, and all or part of the hydrogen atoms of the amino group may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. In the case of the [D] compound used in the radiation sensitive resin composition, all or part of the hydrogen atoms may be substituted with an alkylene group having 2 to 6 carbon atoms.

[D] As a compound,
2,2-bis (4-aminophenyl) hexafluoropropane, 2,3-bis (4-aminophenyl) succinonitrile, 4,4′-diaminobenzophenone, 4,4′-diaminophenylbenzoate, 4,4 '-Diaminodiphenylsulfone, 1,4-diamino-2-chlorobenzene, 1,4-diamino-2-bromobenzene, 1,4-diamino-2-iodobenzene, 1,4-diamino-2-nitrobenzene, 1, 4-diamino-2-trifluoromethylbenzene, 2,5-diaminobenzonitrile, 2,5-diaminoacetophenone, 2,5-diaminobenzoic acid, 2,2′-dichlorobenzidine, 2,2′-dibromobenzidine, 2,2'-diiodobenzidine, 2,2'-dinitrobenzidine, 2,2'-bis (trifluoromethyl) benzidine , Ethyl 3-aminobenzenesulfonate, 3,5-bistrifluoromethyl-1,2-diaminobenzene, 4-aminonitrobenzene, N, N-dimethyl-4-nitroaniline, and 4,4′-diaminodiphenyl Sulfone, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2′-bis (trifluoromethyl) benzidine, ethyl 3-aminobenzenesulfonate, 3,5-bistrifluoromethyl-1,2- Diaminobenzene, 4-aminonitrobenzene, and N, N-dimethyl-4-nitroaniline are more preferable.

  The content ratio of the [D] compound in the first radiation-sensitive resin composition is 0.1 to 20 parts by mass with respect to 100 parts by mass of the [A] compound that is a copolymer having a carboxyl group. Preferably, 0.2 mass part-10 mass parts are more preferable. [D] By making the content rate of a compound into 0.1 mass part-10 mass parts, hardening acceleration | stimulation of the protective film formed from a 1st radiation sensitive resin composition is realizable. In addition, the storage stability of the first radiation-sensitive resin composition can be improved, and further, the voltage holding ratio of the liquid crystal display element including the obtained color filter having the protective film can be maintained at a high level.

<Other optional components>
The first radiation-sensitive resin composition used for forming the protective film of the color filter of this embodiment includes the above-described [A] compound, [B] polymerizable compound, [C] polymerization initiator, and [D]. [J-1] Adhesive aid, [J-2] Surfactant, [J-3] Storage stabilizer, and [J-4] Heat resistance as required, in addition to the compound, within a range not impairing the intended effect An optional component such as a property improver can be contained. Each of these optional components may be used alone or in combination of two or more. Hereinafter, it explains in full detail in order.

[[J-1] Adhesion aid]
[J-1] The adhesion assistant can be used to further improve the adhesion between the obtained protective film and the substrate. As such [J-1] adhesion assistant, the same compound as the adhesion assistant which is the other arbitrary component of the coloring composition mentioned above can be used.
[J-1] The amount of the adhesion aid used is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less with respect to 100 parts by mass of the compound [A] which is a copolymer having a carboxyl group. [J-1] When the amount of the adhesion assistant used exceeds 20 parts by mass, there is a tendency that undeveloped development tends to occur.

[[J-2] Surfactant]
[J-2] The surfactant can be used to further improve the film-forming property of the first radiation-sensitive resin composition. [J-2] Surfactants include, for example, fluorine-based surfactants, silicone-based surfactants, and other surfactants, and surfactants that are other optional components of the above-described coloring composition. The same can be used.
[J-2] The amount of the surfactant used is preferably 1.0 part by mass or less, and 0.8 part by mass or less with respect to 100 parts by mass of the compound [A] which is a copolymer having a carboxyl group. More preferred. [J-2] When the amount of the surfactant used exceeds 1.0 part by mass, film unevenness is likely to occur.

[[J-3] Storage stabilizer]
[J-3] As the storage stabilizer, the same storage stabilizers as other optional components of the above-described coloring composition can be used. For example, sulfur, quinones, hydroquinones, polyoxy compounds, amines And nitronitroso compounds, and more specifically, 4-methoxyphenol, N-nitroso-N-phenylhydroxylamine aluminum and the like.

  [J-3] The amount of the storage stabilizer used is preferably 3.0 parts by mass or less and more preferably 1.0 part by mass or less with respect to 100 parts by mass of the compound [A] which is a copolymer having a carboxyl group. preferable. [J-3] When the amount of the storage stabilizer exceeds 3.0 parts by mass, the sensitivity of the first radiation-sensitive resin composition may be reduced and the pattern shape may be deteriorated.

[[J-4] Heat resistance improver]
The 1st radiation sensitive resin composition can contain a [J-4] heat resistance improvement agent similarly to the coloring composition mentioned above. [J-4] As the heat resistance improver, the same heat resistance improver as other optional components of the coloring composition can be used.
[J-4] The amount of the heat resistance improver used is preferably 50 parts by mass or less and more preferably 30 parts by mass or less with respect to 100 parts by mass of the compound [A] which is a copolymer having a carboxyl group. [J-4] If the blending amount of the heat resistance improver exceeds 50 parts by mass, the sensitivity of the first radiation-sensitive resin composition may be reduced, and the pattern shape may be deteriorated.

<Preparation of first radiation-sensitive resin composition>
In addition to the [A] compound, the [B] polymerizable compound, the [C] polymerization initiator, and the [D] compound, the first radiation-sensitive resin composition that forms the protective film of the color filter of this embodiment, It is prepared by mixing arbitrary components at a predetermined ratio as required as long as the desired effect is not impaired. This first radiation-sensitive resin composition is preferably used in a solution state after being dissolved in an appropriate solvent.

  As a solvent used for the preparation of the first radiation sensitive resin composition, [A] compound, [B] polymerizable compound, [C] polymerization initiator, [D] compound and optional components are uniformly dissolved or dispersed. And what does not react with each component is used. As such a solvent, what was illustrated as a solvent used for preparation of the coloring composition of the color filter of this embodiment mentioned above is mentioned. A solvent can be used individually or in mixture of 2 or more types.

  When a high boiling point solvent is used in combination as the solvent for the first radiation-sensitive resin composition, the amount used is preferably 50% by mass or less, more preferably 40% by mass or less, based on the total amount of solvent, 30 A mass% or less is particularly preferred. When the amount of the high-boiling solvent used is 50% by mass or less, the film thickness uniformity, sensitivity, and residual film ratio of the coating film are good.

  When the first radiation-sensitive resin composition is prepared in a solution state, the solid content concentration (components other than the solvent in the composition solution) can be any concentration depending on the purpose of use, the desired film thickness, etc. (For example, 5 mass%-50 mass%) can be set. A more preferable solid content concentration varies depending on a method of forming a coating film on a substrate, but this will be described later. The composition solution thus prepared can be used after being filtered using a Millipore filter or the like having a pore size of about 0.5 μm.

  The 1st radiation sensitive resin composition by the above component and preparation method can form a protective film by low temperature hardening. Specifically, a protective film having good reliability can be obtained even at a curing temperature of 200 ° C. or lower, and even at a curing temperature of 180 ° C. or lower. And the color filter of this Embodiment can be provided by low-temperature hardening.

  Next, the color filter of this embodiment has an ITO electrode on the protective film. The ITO electrode is formed by forming an ITO film on the protective film using a known method such as a sputtering method. In addition, the transparent electrode on the coloring pattern can be configured by using a transparent material having high transmittance and conductivity with respect to visible light in addition to ITO. For example, IZO (Indium Zinc Oxide), ZnO (zinc oxide), or the like can be used.

  Next, the color filter of the present embodiment has columnar spacers that are erected on the ITO electrode on the protective film. This spacer is formed using the second radiation-sensitive resin composition. Below, the 2nd radiation sensitive resin composition used for formation of the spacer of the color filter of this Embodiment is demonstrated.

<Second radiation sensitive resin composition>
The second radiation sensitive resin composition used for forming the spacer of the color filter of this embodiment contains an [E] compound, a [F] polymerizable compound, a [G] polymerization initiator, and a [H] compound. Furthermore, you may contain an arbitrary component. The second radiation-sensitive resin composition can easily form a fine and elaborate pattern by exposure and development utilizing radiation sensitivity, and realizes low-temperature curing. In addition, it has storage stability and sufficient resolution and radiation sensitivity. Hereinafter, each component will be described in detail.

<[E] compound>
As the [E] compound contained in the second radiation-sensitive resin composition, it is preferable to select an alkali-soluble resin in consideration of the patterning of the spacer of the color filter of the present embodiment. The alkali-soluble resin is not particularly limited as long as it has a carboxyl group and thus has alkali developability. And alkali-soluble resin can contain the compound which has an epoxy group.
Examples of the compound having an epoxy group include compounds having two or more oxiranyl groups, oxetanyl groups, glycidyl groups, and 3,4-epoxycyclohexyl groups in one molecule.

Examples of the compound having two or more 3,4-epoxycyclohexyl groups in one molecule include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxy Cyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-ethylene glycol) Epoxycyclohexylmethyl) ether, ether Renbisu (3,4-epoxycyclohexane carboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane carboxylate and the like.
Examples of the compound having two or more oxetanyl groups (1,3-epoxy structure) in one molecule include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis {[1- Ethyl (3-oxetanyl)] methyl} ether, bis (3-ethyl-3-oxetanylmethyl) ether, and the like.

As an epoxy compound which can be contained in the other [E] compound, as a compound having a glycidyl group, for example,
Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, Diglycidyl ethers of bisphenol compounds such as brominated bisphenol F diglycidyl ether and brominated bisphenol S diglycidyl ether;
Polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether Glycidyl ether;
Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;
Phenol novolac type epoxy resin;
Cresol novolac type epoxy resin;
Polyphenol type epoxy resin;
Cycloaliphatic epoxy resin;
Diglycidyl esters of aliphatic long-chain dibasic acids;
Glycidyl esters of higher fatty acids;
Examples include epoxidized soybean oil and epoxidized linseed oil.

As these commercial products, for example,
As bisphenol A type epoxy resin, Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (Japan Epoxy Resin Co., Ltd.) and the like;
As bisphenol F type epoxy resin, Epicoat 807 (Japan Epoxy Resin Co., Ltd.) and the like;
As a phenol novolac type epoxy resin, Epicoat 152, 154, 157S65 (above, Japan Epoxy Resin Co., Ltd.), EPPN (registered trademark) 201, 202 (above, Nippon Kayaku Co., Ltd.), etc .;
As cresol novolac type epoxy resin, EOCN (registered trademark) 102, 103S, 104S, 1020, 1025, 1027 (above, Nippon Kayaku Co., Ltd.), Epicoat 180S75 (Japan Epoxy Resin Co., Ltd.) and the like;
As polyphenol type epoxy resin, Epicoat 1032H60, XY-4000 (above, Japan Epoxy Resin Co., Ltd.) and the like;
Cyclic aliphatic epoxy resins include CY-175, 177, 179, Araldite CY-182, 192, 184 (above, Ciba Specialty Chemicals), ERL-4234, 4299, 4221, 4206 (above, U.C.C.), Shodyne 509 (Showa Denko), Epicron 200, 400 (above, Dainippon Ink), Epicoat 871, 872 (above, Japan Epoxy Resin), ED -5661, 5562 (above, Celanese Coating), etc .;
Examples of the aliphatic polyglycidyl ether include Epolite 100MF (Kyoeisha Chemical Company), Epiol (registered trademark) TMP (Nippon Yushi Co., Ltd.) and the like.
Of these, phenol novolac type epoxy resins and polyphenol type epoxy resins are preferred.

  The alkali-soluble resin that is the [E] compound contained in the second radiation-sensitive resin composition is (E-1) at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides ( Alkali-soluble, which is a copolymer comprising a structural unit formed from (E-1) compound) and a structural unit formed from (E-2) an epoxy group-containing unsaturated compound ((E-2) compound) Resin can be used. And the copolymer similar to [I] alkali-soluble resin contained in the coloring composition used for color filter manufacture of this Embodiment mentioned above can be used. For example, as the compound (E-1), at least one selected from the group consisting of the above-mentioned (I-1) unsaturated carboxylic acid and unsaturated carboxylic acid anhydride ((I-1) compound) is used. -2) An epoxy group-containing unsaturated compound ((I-2) compound) can be used as the compound. And as alkali-soluble resin which is a [E] compound, alkali-soluble resin which is a copolymer containing the structural unit formed from (I-1) compound, and the structural unit formed from (I-2) compound Can be used.

<[F] polymerizable compound>
[F] The polymerizable compound is a polymerizable compound having an ethylenically unsaturated bond. And as [F] polymeric compound, the compound similar to [II] polymeric compound contained in the coloring composition used for the color filter manufacture of this Embodiment mentioned above can be used.
[F] A polymeric compound can be used individually or in mixture of 2 or more types. As a content rate of the [F] polymeric compound in a 2nd radiation sensitive resin composition, 20 mass parts-200 mass parts are preferable with respect to 100 mass parts of [E] compounds, and 40 mass parts-160 mass parts. Is more preferable. [F] By making the content rate of a polymeric compound into the said range, the 2nd radiation sensitive resin composition can form the cured film which was excellent in adhesiveness and had sufficient hardness also in the low exposure amount, and was excellent. Spacers can be provided.

<[G] Polymerization initiator>
[G] The polymerization initiator is a radiation-sensitive polymerization initiator. [G] As the polymerization initiator, the same compound as the [III] polymerization initiator contained in the coloring composition used for producing the color filter of the present embodiment described above can be used.

  [G] The polymerization initiators can be used alone or in admixture of two or more. As a content rate of the [G] polymerization initiator in a 2nd radiation sensitive resin composition, 1 mass part-40 mass parts are preferable with respect to 100 mass parts of [E] compounds, and 5 mass parts-30 mass parts. Is more preferable. [G] By setting the content ratio of the polymerization initiator to 1 part by mass to 40 parts by mass, the second radiation-sensitive resin composition is a cured film having high hardness and adhesiveness even in the case of a low exposure amount. And an excellent spacer can be formed.

<[H] Compound>
The 2nd radiation sensitive resin composition used for formation of the spacer of the color filter of this embodiment contains the [H] compound which has an amino group and an electron withdrawing group, and is 2nd radiation sensitive resin. Curing acceleration of the cured film in the low temperature curing of the composition can be realized. In addition, storage stability is also realized, and the voltage holding ratio of the liquid crystal display element including the obtained color filter having the spacer can be held at a high level.

The [H] compound is at least one compound selected from the group consisting of compounds represented by the above formula (1) and the above formula (2). Details of the structures of the compounds represented by the formula (1) and the formula (2) were explained when the [V] compound contained in the above-mentioned coloring composition was explained. Therefore, at least one of R ^{7 to} R ¹⁶ is an amino group, and all or part of the hydrogen atoms of the amino group may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. In the case of the [H] compound used in the radiation-sensitive resin composition, all or part of the hydrogen atom may be substituted with an alkylene group having 2 to 6 carbon atoms.

As the [H] compound,
2,2-bis (4-aminophenyl) hexafluoropropane, 2,3-bis (4-aminophenyl) succinonitrile, 4,4′-diaminobenzophenone, 4,4′-diaminophenylbenzoate, 4,4 '-Diaminodiphenylsulfone, 1,4-diamino-2-chlorobenzene, 1,4-diamino-2-bromobenzene, 1,4-diamino-2-iodobenzene, 1,4-diamino-2-nitrobenzene, 1, 4-diamino-2-trifluoromethylbenzene, 2,5-diaminobenzonitrile, 2,5-diaminoacetophenone, 2,5-diaminobenzoic acid, 2,2′-dichlorobenzidine, 2,2′-dibromobenzidine, 2,2'-diiodobenzidine, 2,2'-dinitrobenzidine, 2,2'-bis (trifluoromethyl) benzidine , Ethyl 3-aminobenzenesulfonate, 3,5-bistrifluoromethyl-1,2-diaminobenzene, 4-aminonitrobenzene, N, N-dimethyl-4-nitroaniline, and 4,4′-diaminodiphenyl Sulfone, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2′-bis (trifluoromethyl) benzidine, ethyl 3-aminobenzenesulfonate, 3,5-bistrifluoromethyl-1,2- Diaminobenzene, 4-aminonitrobenzene, and N, N-dimethyl-4-nitroaniline are more preferable.

  As a content rate of the [H] compound in the 2nd radiation sensitive resin composition, 0.1 mass part-20 mass parts are preferable with respect to 100 mass parts of [E] compounds, and 0.2 mass part-10 mass parts. Part by mass is more preferable. By making the content rate of a [H] compound into 0.1 mass part-10 mass parts, hardening promotion of the spacer formed from a 2nd radiation sensitive resin composition is realizable. In addition, the storage stability of the second radiation-sensitive resin composition can be improved, and further, the voltage holding ratio of the liquid crystal display element including the color filter having the obtained spacer can be maintained at a high level.

<Other optional components>
The second radiation-sensitive resin composition used for forming the spacer of the color filter of this embodiment includes the above-mentioned [E] compound, [F] polymerizable compound, [G] polymerization initiator, and [H] compound. [K-1] Adhesive aid, [K-2] Surfactant, [K-3] Storage stabilizer and [K-4] Heat resistance as required, as long as the desired effects are not impaired. It can contain optional components such as improvers. Each of these optional components may be used alone or in combination of two or more. Hereinafter, it explains in full detail in order.

[[K-1] Adhesion aid]
[K-1] The adhesion assistant can be used to further improve the adhesion between the obtained spacer and the substrate. As such [K-1] adhesion assistant, the same compound as the adhesion assistant which is the other arbitrary component of the coloring composition mentioned above can be used.
[K-1] The use amount of the adhesion assistant is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less with respect to 100 parts by mass of the [E] compound. [K-1] When the amount of the adhesion assistant used exceeds 20 parts by mass, there is a tendency that development residue is likely to occur.

[[K-2] Surfactant]
[K-2] The surfactant can be used to further improve the film-forming property of the second radiation-sensitive resin composition. [K-2] Surfactants include, for example, fluorine-based surfactants, silicone-based surfactants, and other surfactants, and surfactants that are other optional components of the colored composition described above. The same can be used.
[K-2] The amount of the surfactant used is preferably 1.0 part by mass or less and more preferably 0.8 part by mass or less with respect to 100 parts by mass of the [E] compound. [K-2] When the amount of the surfactant used exceeds 1.0 part by mass, film unevenness tends to occur.

[[K-3] Storage stabilizer]
[K-3] As the storage stabilizer, the same storage stabilizers as other optional components of the above-described coloring composition can be used. For example, sulfur, quinones, hydroquinones, polyoxy compounds, amines And nitronitroso compounds, and more specifically, 4-methoxyphenol, N-nitroso-N-phenylhydroxylamine aluminum and the like.
[K-3] The amount of the storage stabilizer used is preferably 3.0 parts by mass or less and more preferably 1.0 part by mass or less with respect to 100 parts by mass of the [E] compound. [K-3] When the blending amount of the storage stabilizer exceeds 3.0 parts by mass, the sensitivity of the second radiation-sensitive resin composition may decrease and the pattern shape may deteriorate.

[[K-4] heat resistance improver]
The 2nd radiation sensitive resin composition can contain a [K-4] heat resistance improvement agent similarly to the coloring composition mentioned above. [K-4] As the heat resistance improver, the same heat resistance stabilizer as other optional components of the coloring composition can be used.
[K-4] The use amount of the heat resistance improver is preferably 50 parts by mass or less and more preferably 30 parts by mass or less with respect to 100 parts by mass of the [E] compound. [K-4] If the blending amount of the heat resistance improver exceeds 50 parts by mass, the sensitivity of the second radiation-sensitive resin composition may be reduced, and the pattern shape may be deteriorated.

<Preparation of second radiation-sensitive resin composition>
In addition to the [E] compound, the [F] polymerizable compound, the [G] polymerization initiator, and the [H] compound, the second radiation-sensitive resin composition that forms the spacer of the color filter of the present embodiment includes: It is prepared by mixing arbitrary components at a predetermined ratio as needed within a range not impairing the effect of the period. This second radiation sensitive resin composition is preferably used in a solution state after being dissolved in an appropriate solvent.

As a solvent used for the preparation of the second radiation sensitive resin composition, [E] compound, [F] polymerizable compound, [G] polymerization initiator, [H] compound and optional components are uniformly dissolved or dispersed. And what does not react with each component is used. As such a solvent, what was illustrated as a solvent used for preparation of the coloring composition of the color filter of this embodiment mentioned above is mentioned. A solvent can be used individually or in mixture of 2 or more types.
When a high boiling point solvent is used in combination as the solvent for the second radiation-sensitive resin composition, the amount used is preferably 50% by mass or less, more preferably 40% by mass or less, and more preferably 30% by mass. A mass% or less is particularly preferred. When the amount of the high-boiling solvent used is 50% by mass or less, the film thickness uniformity, sensitivity, and residual film ratio of the coating film are good.

  When the second radiation-sensitive resin composition is prepared in a solution state, the solid content concentration (components other than the solvent in the composition solution) can be any concentration depending on the purpose of use, the desired film thickness, etc. (For example, 5 mass%-50 mass%) can be set. A more preferable solid content concentration varies depending on a method of forming a coating film on a substrate, but this will be described later. The composition solution thus prepared can be used after being filtered using a Millipore filter or the like having a pore size of about 0.5 μm.

  The 2nd radiation sensitive resin composition by the above component and preparation method can form a spacer by low temperature hardening. Specifically, a spacer having good reliability can be obtained even at a curing temperature of 200 ° C. or lower, and even at a curing temperature of 180 ° C. or lower. And the color filter of this Embodiment can be provided by low-temperature hardening.

  In the color filter of this embodiment, an alignment film for liquid crystal alignment can be provided on the surface on the liquid crystal layer side when the liquid crystal display element is formed, as described above. This alignment film can be formed using a liquid crystal aligning agent at a heating temperature of 200 ° C. or less. Next, particularly the main components of the liquid crystal aligning agent that forms the alignment film of the color filter of the present embodiment will be described.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of this embodiment that forms the alignment film of the color filter of this embodiment includes a tetracarboxylic dianhydride containing 2,3,5-tricarboxycyclopentylacetic acid dianhydride, and a diamine component. And at least one [P] polymer selected from the group consisting of polyimides obtained by dehydrating and ring-closing the polyamic acid. The diamine component can contain multiple types of diamines. For example, the 1st diamine and 2nd diamine which are mentioned later can be included. And the liquid crystal aligning agent of this Embodiment can contain [N] other components, unless the effect of this invention is impaired.

In the liquid crystal aligning agent of the present embodiment, the contained [P] polymer is obtained using tetracarboxylic dianhydride including 2,3,5-tricarboxycyclopentylacetic acid dianhydride. Therefore, for example, the alignment film can be formed at a low curing temperature such as 200 ° C. or lower. Moreover, the [P] polymer which this liquid crystal aligning agent contains is a polymer obtained using the diamine containing the 1st diamine explained in full detail behind. Therefore, in a liquid crystal display element having an alignment film formed using this liquid crystal aligning agent, the residual charge can be reduced when a DC voltage is applied. Moreover, the [P] polymer which this liquid crystal aligning agent contains can contain the 2nd diamine explained in full detail later with a 1st diamine as a diamine to be used. In the [P] polymer, the second diamine component can electrostatically interact with the first diamine component to further enhance the above-described effects. Therefore, when the [P] polymer contained in this liquid crystal aligning agent is a polymer obtained using a diamine containing the first diamine and the second diamine, the alignment formed using this liquid crystal aligning agent In a liquid crystal display element having a film, the residual charge can be reduced when a DC voltage is applied.
Hereinafter, the component which comprises a [P] polymer is demonstrated.

<Tetracarboxylic dianhydride>
The tetracarboxylic dianhydride used for synthesizing the polyamic acid which is a [P] polymer that can be contained in the liquid crystal aligning agent of the present embodiment is 2,3,5-tricarboxycyclopentylacetic acid dianhydride. Including.

  As the tetracarboxylic dianhydride, only 2,3,5-tricarboxycyclopentylacetic acid dianhydride may be used alone or in combination with other tetracarboxylic dianhydrides. In that case, as other tetracarboxylic dianhydrides, for example, alicyclic tetracarboxylic dianhydrides other than 2,3,5-tricarboxycyclopentylacetic acid dianhydride, aliphatic tetracarboxylic dianhydrides and Aromatic tetracarboxylic dianhydrides can be mentioned.

Specific examples of the alicyclic tetracarboxylic dianhydride other than the above-mentioned 2,3,5-tricarboxycyclopentylacetic acid dianhydride include, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3 3a, 4,5,9b-Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] Octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 5- (2,5-dioxotetrahydro-3-furanyl)- 3-methyl-3-cyclohexene- , 2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3 .0] octane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.02,6] undecane-3,5,8,10-tetraone, and the like;
Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride and the like, and the tetracarboxylic dianhydride described in Japanese Patent Application No. 2009-157556 can be used.

  The tetracarboxylic dianhydride used for synthesizing the polyamic acid which is a [P] polymer that can be contained in the liquid crystal aligning agent of the present embodiment is 2,3,5-tricarboxycyclopentylacetic acid dianhydride. , It is preferable to contain 50 mol% or more with respect to all tetracarboxylic dianhydrides, and more preferably 80 mol% or more. By doing so, it is possible to form an alignment film at a low curing temperature such as 200 ° C. or lower using the liquid crystal aligning agent of the present embodiment.

<Diamine component>
The diamine component used for synthesizing the polyamic acid that is a [P] polymer that can be contained in the liquid crystal aligning agent of the present embodiment can be a diamine containing a first diamine. The liquid crystal aligning agent of this Embodiment contains the [P] polymer obtained using the 1st diamine, and the liquid crystal display element of this Embodiment is the alignment film formed using this liquid crystal aligning agent. Therefore, the voltage holding ratio is high, and the remaining charge can be reduced even when a DC voltage is applied. And the diamine used in order to synthesize | combine the polyamic acid which is a [P] polymer which can be contained in the liquid crystal aligning agent of this Embodiment can contain multiple types of diamine. That is, the diamine contains a first diamine and a second diamine, and can be used for the synthesis of a polyamic acid that is a [P] polymer. In that case, the liquid crystal aligning agent of this Embodiment contains the [P] polymer obtained using the 1st diamine and the 2nd diamine, and the liquid crystal display element of this Embodiment is this liquid crystal aligning agent. Therefore, even if a DC voltage is applied, the remaining electric charge can be further reduced.

[First diamine]
The 1st diamine used in order to synthesize | combine the polyamic acid which is a [P] polymer which can be contained in the liquid crystal aligning agent of this Embodiment is following formula (DA1), following formula (DA2), and following formula (DA3). ), A diamine having a tertiary nitrogen atom, which is at least one diamine selected from the group consisting of:
Here, in this embodiment, the tertiary nitrogen atom means a nitrogen atom in which three bonds of the nitrogen atom are bonded to an atom other than a hydrogen atom, preferably a carbon atom.

In formulas (DA1) to (DA3), A ¹¹ is a benzene ring or a nitrogen-containing aromatic heterocycle, A ¹² is an aromatic having 6 to 15 carbon atoms and 1 to 2 benzene rings. A ¹³ is an alkylene or biphenylene having 2 to 5 carbon atoms, A ¹⁴ is a cycloalkylene having 4 to 6 carbon atoms substituted with a tertiary nitrogen atom, and A ¹⁵ is 2 carbon atoms. ~ 5 alkylenes. Z ¹¹ is a disubstituted amino group substituted with an aliphatic group having 1 to 6 carbon atoms when A ¹¹ is a benzene ring, and hydrogen when A ¹¹ is a nitrogen-containing aromatic heterocyclic ring. A disubstituted amino group substituted with an atom or an aliphatic group having 1 to 6 carbon atoms, Z ¹² is an alkyl group having 1 to 5 carbon atoms or a benzene ring, and q is an integer of 0 or 1 is there.

    Of the diamines represented by formulas (DA1) to (DA3), preferred diamines include the following formulas (DA4) to (DA7).

In formula (DA4) to formula (DA7), A ²¹ is a nitrogen-containing aromatic heterocyclic ring, A ²² is an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings. , ^{a 23} is alkylene or biphenylene 2-5 carbon ^{atoms, a 24} is a group represented by the formula (DA7a) or ^{(DA7b), a 25} is alkylene having 2 to 5 carbon atoms. Z ²¹ is an aliphatic group having 2 to 12 carbon atoms containing a tertiary nitrogen atom, Z ²² is an alkyl or benzene ring having 1 to 5 carbon atoms, and r is an integer of 0 or 1. .

A ²¹ in the above formula (DA4) is a nitrogen-containing aromatic heterocyclic ring, specifically, a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, Carbazole ring, purine ring, thiadiazole ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thioline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring Oxadiazole ring and acridine ring.

A ²² in the formula (DA6) is preferably a benzene ring or a structure represented by the following formula (DA6a).

In the formula (DA6a), A ³⁰ is a bonding group selected from a single bond, —O—, —NH—, methylene, and an amide group.
In this embodiment mode, only one kind of the first diamine can be used, or a plurality of kinds can be used in combination.

[Secondary diamine]
The 2nd diamine used in order to synthesize | combine the polyamic acid which is a [P] polymer which can be contained in the liquid crystal aligning agent of this Embodiment is a diamine which has a carboxyl group in a molecule | numerator. Preferably, the second diamine is a diamine having 1 to 4 carboxyl groups in the molecule. The structure of the second diamine compound is not particularly limited, but is preferably a diamine represented by the following formula (DA8).

Wherein ^{(DA8), A 31} is an organic group having an aromatic ring having 6 to 30 carbon atoms, n1 is an integer of 1 to 4.
As preferable structures of the diamine represented by the formula (DA8), the structures of the following formulas (DA9) to (DA13) can be given.

In formula (DA9), m1 is an integer of 1-4. In the formula (DA10), A ³² represents a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) ₂ —, —O—. , —CO—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CON (CH ₃ ) - or -N _(CH 3) a CO-, m2 + m3 with an integer of m2 and m3 are each independently 0 to 4 is an integer of 1-4. In formula (DA11), m4 and m5 are each independently an integer of 1 to 5. In the formula (DA12), A ³³ is a linear or branched alkyl group having 1 to 5 carbon atoms, and m6 is an integer of 1 to 5. Wherein ^{(DA13), A 34} represents a single _{bond, -CH 2 -, - C 2} H 4 -, - C (CH 3) 2 -, - CF 2 -, - C (CF 3) 2 -, - O- , —CO—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CON (CH ₃ ) - or -N _(CH 3) a CO-, m7 is an integer of 1 to 4.

  The diamine component used for synthesizing the polyamic acid which is a [P] polymer that can be contained in the liquid crystal aligning agent of the present embodiment is the present invention in addition to the first diamine and the second diamine described above. As long as the effect is not impaired, other diamine compounds other than the first diamine and the second diamine can be used in combination as the diamine. The content of the other diamine compound is preferably from 0.01 mol to 10 mol, and more preferably from 0.1 mol to 5 mol, relative to 1 mol of the first diamine.

  In the diamine component used for synthesizing the polyamic acid that is a [P] polymer that can be contained in the liquid crystal aligning agent of the present embodiment, the higher the content of the first diamine, the more the liquid crystal aligning agent is used. In the liquid crystal display element of this embodiment having the formed alignment film, the voltage holding ratio is high, and the remaining charge can be reduced even when a DC voltage is applied. When the second diamine is used in combination, the second diamine has an effect of enhancing the effect of the first diamine. The content of the second diamine in the diamine component is preferably 0.01 mol to 99 mol with respect to 1 mol of the first diamine. More preferably, it is 0.1 mol to 50 mol, more preferably 0.5 mol to 20 mol, and most preferably 0.5 mol to 10 mol with respect to 1 mol of the first diamine. .

<Synthesis of polyamic acid>
The ratio of the tetracarboxylic dianhydride and the diamine used for the synthesis reaction of the polyamic acid, which is a [P] polymer that can be contained in the liquid crystal aligning agent of the present embodiment, is 1 equivalent of the amino group of the diamine. The ratio of the tetracarboxylic dianhydride acid anhydride group is preferably 0.2 to 2 equivalents, and more preferably 0.3 to 1.2 equivalents.
The polyamic acid synthesis reaction is preferably performed in an organic solvent, preferably at −20 ° C. to 150 ° C., more preferably at 0 ° C. to 100 ° C., preferably 0.1 hour to 120 hours, more preferably 0.5 hour. It takes ~ 48 hours.

Here, examples of the organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, and the like. Examples include aprotic polar solvents; phenolic solvents such as m-cresol, xylenol, phenol, and halogenated phenol. The amount of the organic solvent used (a) is such that the total amount (b) of tetracarboxylic dianhydride and diamine is 0.1% to 50% by weight with respect to the total amount (a + b) of the reaction solution. It is preferable that
As described above, a reaction solution obtained by dissolving polyamic acid is obtained.

  This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid was purified. You may use for preparation of a liquid crystal aligning agent. When polyamic acid is dehydrated and cyclized into a polyimide, the above reaction solution may be directly subjected to dehydration and cyclization reaction, or may be subjected to dehydration and cyclization reaction after isolating the polyamic acid contained in the reaction solution. Alternatively, the isolated polyamic acid may be purified and then subjected to a dehydration ring closure reaction. Isolation and purification of the polyamic acid can be performed according to a known method.

<Synthesis of polyimide>
The polyimide, which is a [P] polymer that can be contained in the liquid crystal aligning agent of the present embodiment, can be obtained by dehydrating and ring-closing and imidizing the polyamic acid synthesized as described above. Even if the polyimide which is a [P] polymer which can be contained in the liquid crystal aligning agent of this Embodiment is a completely imidized thing which carried out the dehydration ring closure of all the amic acid structures which the polyamic acid which is the precursor had. Alternatively, it may be a partially imidized product in which only a part of the amic acid structure is dehydrated and closed and the amic acid structure and the imide ring structure coexist. The polyimide in the present embodiment preferably has an imidization ratio of 30% or more, and more preferably 40% to 90%. This imidation ratio represents the ratio of the number of imide ring structures to the total of the number of polyimide amic acid structures and the number of imide ring structures in percentage.

  The polyamic acid is preferably dehydrated and closed by heating the polyamic acid, or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, and heating if necessary. . Of these, the latter method is preferred.

  In the above-described method of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used. It is preferable that the usage-amount of a dehydrating agent shall be 0.01 mol-20 mol with respect to 1 mol of the amic acid structure of a polyamic acid. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, triethylamine can be used. It is preferable that the usage-amount of a dehydration ring closure catalyst shall be 0.01 mol-10 mol with respect to 1 mol of dehydrating agents to be used. Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 ° C to 180 ° C, more preferably 10 ° C to 150 ° C. The reaction time is preferably 1.0 hour to 120 hours, more preferably 2.0 hours to 30 hours.

  In this way, a reaction solution containing polyimide which is a [P] polymer that can be contained in the liquid crystal aligning agent of the present embodiment is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution. It may be used for the preparation of a liquid crystal aligning agent or may be used for the preparation of a liquid crystal aligning agent after purifying the isolated polyimide. These purification operations can be performed according to known methods.

<[N] other ingredients>
The liquid crystal aligning agent that forms the alignment film of the color filter of the present embodiment contains a [P] polymer, and may contain [N] other components as long as the effects of the present invention are not impaired. it can. [N] Examples of other components include polymers other than the above-mentioned [P] polymer, curing agents, curing catalysts, curing accelerators, epoxy compounds, functional silane compounds, surfactants, photosensitizers, and the like. Can be mentioned.

<Solvent>
In the liquid crystal aligning agent forming the alignment film of the color filter of the present embodiment, the above-mentioned [P] polymer and [N] other components optionally blended as necessary are preferably in an organic solvent. Dissolved and contained.
Examples of the organic solvent that can be used for the liquid crystal aligning agent that forms the alignment film of the color filter of the present embodiment include the solvents exemplified as those used in the polyamic acid synthesis reaction. In addition, an organic solvent believed to be a poor solvent for conventional polyamic acid and polyimide can be appropriately selected and used in combination. Preferred examples of such an organic solvent include, for example, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl. -2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol -I-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether Diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, cyclohexanone, diacetone alcohol, Examples thereof include ethyl carbitol, ethoxyethyl propionate, butyl cellosolve acetate, carbitol acetate, and propylene carbonate. These can be used alone or in admixture of two or more.

  The solid content concentration of the liquid crystal aligning agent that forms the alignment film of the color filter of the present embodiment (the ratio of the total weight of the components excluding the organic solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is the viscosity, Although it is appropriately selected in consideration of volatility and the like, it is preferably in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent that forms the alignment film of the color filter of the present embodiment is applied to the substrate surface, and a coating film that becomes the liquid crystal alignment film is formed by removing the organic solvent. If the concentration is less than 1% by weight, the film thickness of this coating film may be too small to obtain a good alignment film. On the other hand, if the solid content concentration exceeds 10% by weight, The film thickness of the film may be excessive, and it may be difficult to obtain a good alignment film as well, and the viscosity of the liquid crystal aligning agent may increase, resulting in poor coating characteristics.

  The particularly preferable range of the solid content concentration varies depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, when the spinner method is used, the range of 1.5 wt% to 4.5 wt% is particularly preferable. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3% by weight to 9% by weight, and thereby the solution viscosity is in the range of 12 mPa · s to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 mPa · s to 15 mPa · s.

<Coloring pattern, protective film, spacer, alignment film, color filter and production method thereof>
In the production of the color filter of the present embodiment, a step for forming a colored pattern from the above-described colored composition, a step for forming a protective film from the above-mentioned first radiation-sensitive resin composition, A process for forming a spacer from the second radiation-sensitive resin composition described above and a process for forming an alignment film from the liquid crystal aligning agent described above are included as main manufacturing processes. Hereinafter, a coloring pattern, a protective film, a spacer, an alignment film, a color filter, and a manufacturing method thereof will be described.

The manufacturing method of the color filter of the present embodiment includes at least the following steps [1] to [12] in the following order.
[1] A step of forming a coating film of a colored composition on a substrate (hereinafter sometimes referred to as “[1] step”).
[2] A step of forming a colored pattern on the coating film of the colored composition (hereinafter sometimes referred to as “[2] step”).
[3] A step of curing the coating film on which the colored pattern is formed at 200 ° C. or lower (hereinafter sometimes referred to as “[3] step”).
[4] A step of forming a coating film of the first radiation-sensitive resin composition on the substrate after the step [3] (hereinafter sometimes referred to as “[4] step”).
[5] A step of irradiating at least a part of the coating film of the first radiation-sensitive resin composition on the substrate (hereinafter sometimes referred to as “[5] step”).
[6] A step of developing the coating film irradiated with radiation (hereinafter sometimes referred to as “[6] step”).
[7] A step of curing the developed coating film at 200 ° C. or lower (hereinafter sometimes referred to as “[7] step”).
[8] A step of forming a coating film of the second radiation-sensitive resin composition on a substrate having a coating film cured in the step [7] (hereinafter, referred to as “[8] step”). )
[9] A step of irradiating at least a part of the coating film of the second radiation-sensitive resin composition formed in the step [8] (hereinafter sometimes referred to as “[9] step”).
[10] A step of developing the coating film irradiated with radiation (hereinafter sometimes referred to as “[10] step”).
[11] A step of curing the developed coating film at 200 ° C. or lower to form a spacer (hereinafter sometimes referred to as “[11] step”).
[12] A step of forming a coating film of a liquid crystal aligning agent on a substrate having a spacer cured in the step [11], and heating the coating film at 200 ° C. or lower to form an alignment film (hereinafter referred to as “[12] Sometimes referred to as a "process".)

  By the color filter manufacturing method of the present embodiment as described above, a colored pattern is formed on the substrate using the above-described colored composition, a protective film is formed using the above-described first radiation-sensitive resin composition, A spacer can be formed using the second radiation-sensitive resin composition described above, and an alignment film can be formed using the liquid crystal aligning agent described above. As a result, a color filter having good heat resistance, chemical resistance, voltage holding ratio, and the like can be formed. In that case, low-temperature curing can be realized, and heating temperatures of 200 ° C. or less are possible in the [3] step, the [7] step, the [11] step, and the [12] step, respectively. Therefore, a dye having a problem in heat resistance can be used as a colorant in the above-described coloring composition. Therefore, a color filter having excellent color characteristics can be manufactured. And the color filter manufactured in this way becomes a suitable color filter even when low temperature hardening is desired from a viewpoint of energy saving. Hereinafter, each process is explained in full detail.

[[1] Step]
In this step, a coating film of the above-described coloring composition is formed on the substrate.
A light-shielding layer (black matrix) is formed on the surface of the substrate so as to partition a portion where pixels are formed as necessary. Next, for example, after applying a colored composition containing a red [IV] colorant on the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. As another method for forming a colored pattern on a substrate, a method of obtaining pixels of each color by an ink jet method disclosed in Japanese Patent Laid-Open Nos. 7-318723 and 2000-310706 can be employed. In this method, first, a partition that also serves as a light shielding function is formed on the surface of the substrate. Next, after a coloring composition containing, for example, a red colorant is discharged into the formed partition wall by an ink jet apparatus, pre-baking is performed to evaporate the solvent. Next, this coating film is exposed as necessary to form a red pixel pattern. In addition, since the said partition fulfill | performs not only the light-shielding function but the function for the coloring composition of each color discharged in the division not to mix colors, a film thickness is thick compared with said black matrix.

  Examples of the substrate material include glass such as soda lime glass and non-alkali glass, silicon, polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, aromatic polyamide, polyamideimide, and polyimide. In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

Examples of the method for applying the coloring composition to the substrate include a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, and a bar coating method. Of these, spin coating and slit die coating are preferred.
Pre-baking is usually performed by combining vacuum drying and heat drying. The drying under reduced pressure is usually performed until the pressure reaches 50 Pa to 200 Pa. Moreover, as conditions of heat drying, it is about 70 minutes-110 degreeC normally for 1 minute-10 minutes.
The film thickness after drying is usually 0.6 μm to 8.0 μm, preferably 1.2 μm to 5.0 μm.

[[2] Process]
In the step [2], the coating film formed in the step [1] is exposed through a photomask, developed using an alkali developer, and the unexposed portion of the coating film is dissolved and removed, thereby red pixels. A pixel array in which patterns are arranged in a predetermined arrangement is formed, and a colored pattern can be obtained.

Next, the green and blue pixel arrays are sequentially formed on the same substrate by repeating the above-described steps [1] and [2] using the green or blue coloring compositions. Thereby, a color filter in which a pixel array of the three primary colors of red, green and blue is arranged on the substrate is obtained. However, in this embodiment, the order of forming the pixels of each color and the number of colors are not limited to those described above.
The black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithography method. However, a black composition containing a black colorant is used. Thus, it can be formed in the same manner as in the case of forming the pixel.

Examples of radiation sources include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, and the like, argon ion lasers, YAG lasers, XeCl excimer lasers, nitrogen A laser light source such as a laser may be used. Radiation with a wavelength in the range of 190 nm to 450 nm is preferred. Exposure of ^{radiation, 10J / m 2 ~10,000J / m} 2 is preferred.

Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [ 4.3.0] -5-Nonene is preferred.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development. As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development condition is preferably 5 seconds to 300 seconds at room temperature.

[[3] Process]
[2] After the colored pattern is formed in the step, the colored pattern can be cured by curing (also referred to as post-baking), and the formation of the colored pattern can be completed. The heating condition for post baking is 200 ° C. or lower. The heating time for post baking is 10 minutes to 60 minutes. In the present embodiment, a good colored pattern such as solvent resistance can be obtained even when the post-baking temperature is low. Specifically, even when the post-bake temperature is 200 ° C. or lower, or even 180 ° C. or lower, a color filter having sufficient solvent resistance can be obtained. The film thickness of the pixel is usually 0.5 μm to 5.0 μm, and preferably 1.0 μm to 3.0 μm. In order to increase the hardness or the like to a level that is actually required commercially, a curing step at a temperature exceeding 120 ° C. is usually required. And hardening in higher temperature is preferable within the range of 180 degrees C or less.

[[4] Process]
[3] After forming a colored pattern in the step, a coating film of the first radiation-sensitive resin composition is formed on the colored pattern on the substrate on which the colored pattern is formed.
When a coating film is formed by a coating method, the coating surface is preferably heated (prebaked) after the first radiation-sensitive resin composition solution is coated on the substrate on which the colored pattern is formed. A film can be formed. As solid content concentration of the composition solution used for a coating method, 5 mass%-50 mass% are preferable, 10 mass%-40 mass% are more preferable, 15 mass%-35 mass% are especially preferable. Examples of the coating method of the first radiation-sensitive resin composition solution include a spray method, a roll coating method, a spin coating method (also referred to as a spin coating method or a spinner method), a slit coating method (slit die coating method), An appropriate method such as a bar coating method or an ink jet coating method can be employed. Of these, spin coating or slit coating is preferred.

  The prebaking conditions vary depending on the type of each component, the blending ratio, and the like, but are preferably 70 ° C. to 120 ° C. and about 1 to 15 minutes. The film thickness after pre-baking of the coating film is preferably 0.5 μm to 10 μm, and more preferably about 1.0 μm to 7.0 μm.

[[5] Step]
Next, radiation is applied to at least a part of the formed coating film. At this time, when irradiating only a part of the coating film, for example, a method of irradiating through a photomask having a predetermined pattern can be used.
Examples of radiation used for irradiation include visible light, ultraviolet light, and far ultraviolet light. Of these, radiation having a wavelength in the range of 250 nm to 550 nm is preferable, and radiation containing ultraviolet light of 365 nm is more preferable.

Radiation dose (exposure dose), as a value measured by a luminometer intensity at a wavelength 365nm of the radiation emitted (OAI model 356, Optical Associates Ltd. ^{Inc.), 100J / m 2 ~5,000J} / m 2 is Preferably, 200 J / m ^{2 to} 3,000 J / m ² is more preferable.
The first radiation-sensitive resin composition used for forming the protective film of the color filter of the present embodiment has a higher radiation sensitivity than a conventionally known protective film-forming composition. Therefore, even when the radiation irradiation amount is 700 J / m ² or less, and even 600 J / m ² or less, it is possible to obtain a protective film having a desired film thickness, good shape, excellent adhesion and high hardness. Have.

[[6] Step]
Next, by developing the coated film after irradiation, unnecessary portions are removed to form a predetermined pattern.
Examples of the developer used for the development include aqueous solutions of alkaline compounds such as inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate, and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Can be used. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol can be added to the aqueous solution of the alkaline compound. Furthermore, it is possible to use the surfactant alone or in addition to the above-mentioned water-soluble organic solvent and an appropriate amount.

  As a developing method, any of a liquid piling method, a dipping method, a shower method and the like may be used, and the developing time is preferably about 10 seconds to 180 seconds at room temperature. Following the development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, and then a desired pattern is obtained by air drying with compressed air or compressed nitrogen.

[[7] Process]
Next, the obtained patterned coating film is cured (also referred to as post-baking) with an appropriate heating device such as a hot plate or an oven to obtain a protective film as a cured film. The curing temperature is preferably 200 ° C. or lower. And even if it is 180 degrees C or less, the protective film of sufficient characteristics is obtained. Specifically, 100 ° C. to 200 ° C. is preferable, and 150 ° C. to 180 ° C. is more preferable when trying to achieve both low temperature curing and reliability performance at a high level. The curing time is preferably, for example, 5 minutes to 30 minutes on a hot plate and 30 minutes to 180 minutes in an oven. Since the 1st radiation sensitive resin composition contains a [D] compound as mentioned above, it can implement | achieve such low-temperature hardening in this way. In addition, it provides storage stability and has sufficient resolution and radiation sensitivity.

  Therefore, when forming a protective film, the first radiation-sensitive resin composition is suitably used as a protective film forming material used in combination with a coloring pattern using a dye that is desirably cured at low temperature.

  The manufacture of the color filter of the present embodiment includes a step of forming an ITO electrode on the protective film after the step [7] of forming the protective film. The ITO electrode can be formed by forming an ITO film using a sputtering method. In the case where a patterned ITO electrode is required, the formed ITO film can be formed by patterning by photolithography.

[[8] Process]
[7] A protective film is formed in the step, and then an ITO electrode is formed on the protective film, and then a second radiation sensitive material is formed on the ITO electrode on the substrate on which the protective film is formed. A coating film of the resin composition is formed.

  When a coating film is formed by a coating method, after applying a solution of the second radiation sensitive resin composition on a substrate on which a colored pattern or the like is formed, preferably by heating (pre-baking) the coating surface, A coating film can be formed. As solid content concentration of the composition solution used for a coating method, 5 mass%-50 mass% are preferable, 10 mass%-40 mass% are more preferable, 15 mass%-35 mass% are especially preferable. Examples of the coating method of the second radiation-sensitive resin composition solution include a spray method, a roll coating method, a spin coating method (also referred to as a spin coating method or a spinner method), a slit coating method (slit die coating method), An appropriate method such as a bar coating method or an ink jet coating method can be employed. Of these, spin coating or slit coating is preferred.

  The prebaking conditions described above vary depending on the type of each component, the blending ratio, and the like, but are preferably 70 ° C to 120 ° C, and are about 1 minute to 15 minutes. The film thickness after pre-baking of the coating film is preferably 0.5 μm to 10 μm, and more preferably about 1.0 μm to 7.0 μm.

[[9] Process]
Next, radiation is applied to at least a part of the coating film formed in the step [8]. At this time, in order to form a spacer at a desired position, a part of the coating film is irradiated with radiation. For example, the irradiation can be performed through a photomask having a predetermined pattern.
Examples of radiation used for irradiation include visible light, ultraviolet light, and far ultraviolet light. Of these, radiation having a wavelength in the range of 250 nm to 550 nm is preferable, and radiation containing ultraviolet light of 365 nm is more preferable.

Radiation dose (exposure dose), as a value measured by a luminometer intensity at a wavelength 365nm of the radiation emitted (OAI model 356, Optical Associates Ltd. ^{Inc.), 100J / m 2 ~5,000J} / m 2 is Preferably, 200 J / m ^{2 to} 3,000 J / m ² is more preferable.
The 2nd radiation sensitive resin composition used for spacer formation of the color filter of this embodiment has high radiation sensitivity compared with the conventionally known spacer formation composition. Therefore, even if the radiation dose is 700 J / m ² or less, and even 600 J / m ² or less, a spacer can be obtained as a cured film having a desired film thickness, good shape, excellent adhesion, and high hardness. Have advantages.

[[10] Step]
Next, by developing the coating film after irradiation, unnecessary portions are removed to form a predetermined spacer pattern.
Examples of the developer used for the development include aqueous solutions of alkaline compounds such as inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate, and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Can be used. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol can be added to the aqueous solution of the alkaline compound. Furthermore, it is possible to use the surfactant alone or in addition to the above-mentioned water-soluble organic solvent and an appropriate amount.

  As a developing method, any of a liquid piling method, a dipping method, a shower method and the like may be used, and the developing time is preferably about 10 seconds to 180 seconds at room temperature. Subsequent to the development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, followed by air drying with compressed air or compressed nitrogen, thereby obtaining a desired spacer pattern.

[[11] Step]
Next, the obtained patterned coating film is cured (also referred to as post-baking) with an appropriate heating device such as a hot plate or an oven, whereby a spacer is obtained as a cured film. The curing temperature is preferably 200 ° C. or lower. A spacer having sufficient characteristics can be obtained even at 180 ° C. or lower. Specifically, 100 ° C. to 200 ° C. is preferable, and 150 ° C. to 180 ° C. is more preferable when trying to achieve both low temperature curing and reliability performance at a high level. The curing time is preferably, for example, 5 minutes to 30 minutes on a hot plate and 30 minutes to 180 minutes in an oven. Since the second radiation-sensitive resin composition contains the [H] compound as described above, such low low-temperature curing can be realized. In addition, it provides storage stability and has sufficient resolution and radiation sensitivity.

Accordingly, the radiation-sensitive resin composition is suitably used as a material for forming a spacer used in combination with a coloring pattern using a dye that is desirably cured at low temperature.
According to the above manufacturing method, a color pattern, a protective film, and a spacer can be manufactured, and the color filter of this Embodiment can be manufactured. As described above, the coloring pattern of the color filter of the present embodiment is formed by applying and patterning a coloring composition on a suitable substrate and then curing. Similarly, the protective film is formed by applying and patterning the first radiation-sensitive resin composition, followed by curing. Similarly, the spacer is formed by applying and patterning the second radiation-sensitive resin composition and then curing. The colored composition, the first radiation sensitive resin composition, and the second radiation sensitive resin composition are all radiation sensitive resin compositions using similar materials as described above. Can do. And each can form a coloring pattern, a protective film, and a spacer by low temperature hardening below 200 degreeC.

Therefore, in the color filter of the present embodiment, a colored pattern, a protective film, and a spacer can be formed by low-temperature curing at 200 ° C. or lower. The color filter of the present embodiment can be manufactured by low temperature curing.
In the color filter of this embodiment, the protective film is formed after the colored pattern is formed. Since the protective film can be formed by low-temperature curing at 200 ° C. or lower, the colored pattern is not exposed to a high-temperature heating state for forming the protective film after the formation. Similarly, in the color filter of this embodiment, the spacer is formed after the colored pattern is formed. Since the spacer can be formed by low-temperature curing at 200 ° C. or lower, the colored pattern is not exposed to a high-temperature heating state for forming the spacer after the formation. Therefore, even if a dye having excellent color characteristics but having a problem in heat resistance is used as a colorant, process deterioration can be reduced.

  Further, as described above, the coloring composition, the first radiation-sensitive resin composition, and the second radiation-sensitive resin composition are all radiation-sensitive resin compositions using similar materials. Is possible. Therefore, at the time of forming the colored pattern at the time of manufacturing the color filter of the present embodiment, it is possible to adjust the curing temperature in consideration of the subsequent protective film formation and spacer formation. That is, the colored pattern is formed at a lower curing temperature than the optimum curing temperature for forming the colored pattern alone on the substrate. Thereafter, it is possible to heat the colored pattern by curing heating of the protective film formed on the colored pattern or curing heating of the spacer.

  For example, when the optimum curing temperature of the coloring pattern, the protective film, and the spacer is 200 ° C. or less, specifically 180 ° C., the coloring pattern can be formed at a curing temperature of 150 ° C., for example. . Next, a coating film of the first radiation-sensitive resin composition is formed on the colored pattern and cured at an optimal 180 ° C. to form a protective film. As a result, the colored pattern formed in the lower layer is also heated, and it is possible to obtain the color filter of the present embodiment including the desired colored pattern and the protective film. Further, for example, a coloring pattern and a protective film are formed at a curing temperature of 150 ° C., and then a spacer is formed from the coating film of the second radiation-sensitive resin composition at an optimal curing temperature of 180 ° C. Is possible. As a result, the previously formed colored pattern and protective film are also heated, and it is possible to obtain the color filter of the present embodiment including the desired colored pattern, protective film, and spacer. .

[[12] Step]
Next, in the color filter manufacturing method of the present embodiment, as described above, there is a step of forming a [12] alignment film after the [11] step, and the color filter of the present embodiment has a liquid crystal alignment. It is possible to have an alignment film having a function.

  [12] In the step, the liquid crystal aligning agent described above is used. And the liquid crystal aligning agent mentioned above on the board | substrate which formed the coloring pattern, the protective film, and the spacer by the above-mentioned [1] process-[11] process, for example, a roll coater method, a spinner method, a printing method, an inkjet Apply by an appropriate application method such as a method. Next, the substrate coated with the liquid crystal aligning agent is pre-baked and then post-baked to form a coating film. As prebaking conditions, it is 0.1 minute-5 minutes at 40 to 120 degreeC, for example. The post-bake conditions are preferably 120 ° C. to 200 ° C., more preferably 150 ° C. to 200 ° C., further preferably 150 ° C. to 180 ° C., preferably 5 minutes to 200 minutes, more preferably 10 minutes to 100 minutes. is there. The film thickness of the coating film after post-baking is preferably 0.001 μm to 1 μm, more preferably 0.005 μm to 0.5 μm.

  The solid content concentration of the liquid crystal aligning agent used when applying the liquid crystal aligning agent on the substrate is appropriately selected in consideration of viscosity, volatility, etc. as described above. It is in the range of 10% by weight.

  When the liquid crystal aligning agent contains polyimide as the [P] polymer, the post-baked liquid crystal aligning agent coating film may be used as an alignment film as it is, for example, for vertical alignment. If necessary, the coating film is subjected to alignment treatment such as light irradiation or rubbing treatment, and an alignment film can be formed.

When performing alignment treatment by light irradiation on the above-mentioned post-baked coating film, liquid crystal alignment capability is imparted by irradiating the coating film with linearly polarized light, partially polarized radiation, or non-polarized radiation. . Such treatment corresponds to a conventional alignment treatment method such as rubbing treatment, and can be performed more easily. Here, as the radiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used. In particular, the radiation is preferably ultraviolet rays containing light having a wavelength of 300 nm to 400 nm. When the radiation used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction to give a pretilt angle, or a combination of these. You may go. When irradiating non-polarized radiation, the direction of irradiation needs to be an oblique direction.
The irradiation dose of radiation, preferably less than 1 J / ^{m 2} or more 10,000 J / ^{m 2,} more preferably ^{10J / m 2 ~3,000J / m 2} .

When performing orientation treatment by rubbing treatment on the above-described post-baked coating film, for example, rubbing the coating film surface in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, cotton (rubbing treatment) It is possible to form an alignment film having liquid crystal alignment ability.
As described above, in the color filter manufacturing method of the present embodiment, it is possible to form an alignment film at a heating temperature of 200 ° C. or lower and further at a heating temperature of 180 ° C. or lower using the liquid crystal aligning agent described above. is there. Therefore, it is possible to avoid that the colored pattern of the color filter formed in the above-described steps [1] to [3] is exposed to a high temperature state in the [12] step of forming the alignment film.

  Hereinafter, although an embodiment of the present invention is explained in full detail based on an example, the present invention is not limitedly interpreted by this example.

<Formation and evaluation of colored pattern>
Example 1
[[I] Synthesis of alkali-soluble resin (IA)]
A flask equipped with a condenser and a stirrer was charged with 5 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether. Subsequently, 18 parts by mass of methacrylic acid as the compound (I-1), 14 parts by mass of 2-methylglycidyl methacrylate and 20 parts by mass of glycidyl methacrylate as the compound (I-2), and 10 parts by mass of styrene as the compound (I-4) After charging 23 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate and 15 parts by mass of methyl methacrylate and replacing with nitrogen, the temperature of the solution was adjusted to 70 with gentle stirring. By raising the temperature to 0 ° C. and polymerizing while maintaining this temperature for 5 hours, a solution containing an alkali-soluble resin (IA) as a copolymer was obtained. The solid content concentration of the obtained polymer solution was 31.5%, and the Mw of the alkali-soluble resin (IA) as a copolymer was 10,100.

Example 2
[[I] Synthesis of alkali-soluble resin (IB)]
A flask equipped with a condenser and a stirrer was charged with 4 parts by weight of AIBN and 300 parts by weight of diethylene glycol methyl ethyl ether. Then, 32 parts by mass of benzyl methacrylate and 35 parts by mass of methyl methacrylate were added, and 2.7 parts by mass of α-methylstyrene dimer was added, and the temperature of the solution was raised to 80 ° C. while gently stirring. After maintaining for 4 hours, the temperature was raised to 100 ° C., and this temperature was maintained for 1 hour for polymerization to obtain a solution containing a copolymer. The resulting polymer solution had a solid content concentration of 24.9% and Mw of 12,500. Then, 1.1 parts by mass of tetrabutylammonium bromide and 0.05 parts by mass of 4-methoxyphenol as a polymerization inhibitor were added to the solution containing the copolymer, and the mixture was stirred at 90 ° C. for 30 minutes in an air atmosphere. (I-2) 16 parts by mass of glycidyl methacrylate was added as a compound and reacted at 90 ° C. for 10 hours to obtain an alkali-soluble resin (IB) as a copolymer. The obtained polymer solution had a solid content concentration of 29.0% and Mw of 14,200.

Example 3
[Preparation of colored composition]
With respect to 90 parts by mass of the alkali-soluble resin (IA) which is the copolymer obtained in Example 1, [II] ethylene oxide-modified dipentaerythritol hexaacrylate (II-1) and a polyfunctional acrylate compound as a polymerizable compound 100 parts by mass of the mixture (KAYARAD (registered trademark) DPHA-40H, Nippon Kayaku Co., Ltd.) (II-2) (mixture ratio ((II-1) / (II-2)) = 4) ] 25-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure (registered trademark) 907, Ciba Specialty Chemicals) (III-1) as a polymerization initiator 100 parts by mass of a red colorant (IV-1) composed of a red dye as a [IV] colorant, and pentaerythritol as a [V] compound 6 of a mixture of rutetrakis (3-mercaptopropionate) (V-1) and ethyl 3-aminobenzenesulfonate (V-2) (mixing ratio ((V-1) / (V-2) = 5)) 10 parts by mass of the alkali-soluble resin (IB) obtained in Example 2 as another part of the alkali-soluble resin was mixed in. Next, cyclohexanone was used as the solvent, and the solid content concentration of the colored composition was 30% by mass. After adding the solvent as described above, a red colored composition was prepared by filtering through a Millipore filter having a pore size of 0.5 μm.

  [IV] A green colored composition was prepared in the same manner as above except that the green colorant (IV-2) comprising a green dye was used as the colorant. Moreover, the blue coloring composition was prepared like the above except having used the blue coloring agent (IV-3) which consists of a blue dye as a [IV] coloring agent.

Example 4
[Formation of colored pattern]
The red coloring composition obtained in Example 3 was applied using a spin coater on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed on the surface. Next, prebaking was performed for 2 minutes on a hot plate at 90 ° C. to form a coating film having a film thickness of 2.5 μm after prebaking. After cooling these substrates to room temperature, a high-pressure mercury lamp is used, and the coating film is irradiated with radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 1,000 (J / m ² ) through a photomask. Exposed. Thereafter, a developing solution (0.04 mass% potassium hydroxide aqueous solution at 23 ° C.) is discharged onto these substrates at a developing pressure of 1 (kgf / cm ² ) (nozzle diameter of 1 mm) to perform shower development and the substrates. A colored pattern of 200 μm × 200 μm was formed thereon. Further, post-baking was performed at 180 ° C. for 30 minutes to form a red colored pattern.

  A green coloring pattern was formed in the same manner as described above except that the green coloring composition obtained in Example 3 was used as the coloring composition. Moreover, the blue coloring pattern was formed like the above except having used the blue coloring composition obtained in Example 3 as a coloring composition.

Example 5
[Evaluation of coloring pattern]
The following evaluation was performed about the manufactured coloring pattern.

Evaluation of development resistance In the formation of the coloring patterns of the respective colors, the following formula: Film thickness ratio before and after development = (film thickness after development / film thickness before development) × 100
The value of was calculated. Each of the colored patterns of the above colors has a film thickness ratio of 95% or more before and after development, and has been found to have good development resistance.

Evaluation of heat resistance The colored pattern of each color was further heated at 180 ° C. for 30 minutes. Then, the color change ΔEab ^* before and after additional heating was determined. All the colored patterns of the above colors had ΔEab ^* of less than 3, indicating that they had good heat resistance.

Evaluation of solvent resistance About the said coloring pattern, it immersed in N-methylpyrrolidone of 60 degreeC with the board | substrate for 30 minutes. Then, when the coloring pattern of each color on a board | substrate was observed, all confirmed that the coloring pattern was hold | maintained after immersion and the N-methylpyrrolidone after immersion was not colored at all. It was found that any of the above colored patterns has good solvent resistance.

<Formation and evaluation of protective film>
Example 6
[Synthesis of [A] Compound]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 16 parts by weight of methacrylic acid, 16 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 38 parts by weight of methyl methacrylate, 10 parts by weight of styrene, and 20 parts by weight of glycidyl methacrylate were charged. After nitrogen substitution, the temperature of the solution was raised to 70 ° C. while gently stirring, and polymerization was carried out while maintaining this temperature for 4 hours to obtain a solution containing the copolymer (A-1) ( Solid content concentration = 34.4% by mass, Mw = 8,000, Mw / Mn = 2.3). In addition, solid content concentration means the ratio of the copolymer mass which occupies for the total mass of a copolymer solution.

Example 7
[Preparation of radiation-sensitive resin composition]
[B] 100 parts by mass of dipentaerythritol hexaacrylate (B-1) as a polymerizable compound with respect to 100 parts by mass of the copolymer (A-1) obtained in Example 6 as the compound [A] C] Etanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure® OXE02, Ciba as a polymerization initiator・ Specialty Chemicals Co., Ltd. (C-1) (5 parts by mass) and 4,4′-diaminodiphenylsulfone (D-1) as a [D] compound were mixed, and [J-1] as an adhesion aid γ-glycidoxypropyltrimethoxysilane 5 parts by mass, [J-2] surfactant (FTX-218, Neos) 0.5 part by mass, [J-3] 4-methoxyphene as a storage stabilizer The mixture was mixed with 0.5 parts by mass of propylene glycol monomethyl ether acetate so that the solid concentration was 30% by mass, and then filtered through a Millipore filter having a pore size of 0.5 μm. A resin composition was prepared.

Example 8
[Formation of protective film]
After coating the radiation-sensitive resin composition solution prepared in Example 7 on an alkali-free glass substrate with a spinner, pre-baking on a hot plate at 100 ° C. for 2 minutes forms a coating film having a thickness of 4.0 μm. did. Subsequently, the obtained coating film was irradiated with radiation using a high-pressure mercury lamp at an exposure amount of 700 J / m ² . Then, a protective film was formed by post-baking in an oven at a curing temperature of 180 ° C. and a curing time of 30 minutes.

Example 9
[Evaluation of protective film]
Evaluation of Storage Stability A protective film was formed from the radiation-sensitive resin composition solution of Example 7 immediately after preparation by the formation method of Example 8, and the film thickness was measured (in the following formula, “film thickness immediately after preparation” "). Moreover, after preparing by the formation method of Example 7, the radiation sensitive resin composition solution was preserve | saved at 25 degreeC for 5 days, and the film thickness of the protective film formed similarly after 5 days was measured (in a following formula, " Called the film thickness after 5 days). The film thickness increase rate (%) was calculated from the following formula.
Film thickness increase rate (%) = (film thickness after 5 days−film thickness immediately after preparation) / (film thickness immediately after preparation) × 100
The film thickness increase rate was 3% or less, and the storage stability was judged to be good.

Evaluation of light resistance The protective film by the formation method of Example 8 was further irradiated with 800,000 J / m ² at an illuminance of 130 mW with a UV irradiation apparatus (UVX-02516S1JS01, Ushio Inc.), and the amount of film reduction was examined. . The amount of film loss was 2% or less, and light resistance was judged to be good.

Evaluation of heat resistance The protective film formed by the formation method of Example 8 was further heated in an oven at 230 ° C. for 20 minutes, and the film thickness before and after this heating was measured using a stylus-type film thickness measuring machine (Alphastep IQ, KLA Tencor). ). And the remaining film rate (film thickness after a process / film thickness before a process x100) was computed, and this remaining film rate was made into heat resistance. The residual film ratio was 99%, and the heat resistance was judged to be good.

Evaluation of chemical resistance About the protective film by the formation method of Example 8, it was immersed in alignment film peeling liquid Chemiclean (registered trademark) TS-204 (Sanyo Kasei Kogyo Co., Ltd.) heated to 60 ° C. for 15 minutes, and then washed with water. Further, it was dried in an oven at 120 ° C. for 15 minutes. The film thickness before and after this treatment was measured with a stylus-type film thickness measuring device (Alphastep IQ, KLA Tencor), and the remaining film ratio (film thickness after treatment / film thickness before treatment × 100) was calculated. The rate was chemical resistance. The residual film ratio was 99%, and the chemical resistance was judged to be good.

<Spacer formation and evaluation>
Example 10
[Spacer formation]
As an example of forming the spacer, an example in which only the spacer is formed on the substrate will be described. The radiation sensitive resin composition used in the formation of the protective film prepared in Example 7 was used as the radiation sensitive resin composition for forming the spacer.
On the alkali-free glass substrate, the radiation sensitive resin composition solution prepared in Example 7 was applied using a spin coater. Next, a film having a thickness of 6.0 μm was formed by pre-baking on a hot plate at 100 ° C. for 2 minutes. Subsequently, the obtained coating film was irradiated with radiation using a high-pressure mercury lamp at an exposure amount of 700 J / m ² . Thereafter, a developing solution (0.04 mass% potassium hydroxide aqueous solution at 23 ° C.) is discharged onto the substrate at a developing pressure of 1 (kgf / cm ² ) (nozzle diameter of 1 mm) to perform shower development on the substrate. A spacer pattern was formed. Next, spacers were formed on the substrate by post-baking in an oven at a curing temperature of 180 ° C. and a curing time of 30 minutes. And it confirmed that the spacer was formed on the board | substrate with the desired position and shape (resolution).

Example 11
[Evaluation of spacer]
About the spacer obtained in Example 10, the cross-sectional shape was observed with the scanning electron microscope. All of the formed spacers had good pattern edges and forward taper.
Next, on the spacer formed on the substrate in Example 10, AL3046 (manufactured by JSR Co., Ltd.) was applied as a liquid crystal alignment film by a liquid crystal alignment film coating printer, and dried at 180 ° C. for 1 hour. An orientation film having a dry film thickness of 0.05 μm was formed. The coating film was rubbed with a rubbing machine having a roll around which a nylon cloth was wound under conditions of a roll rotation speed of 500 rpm and a stage moving speed of 1 cm / sec. At this time, no scraping or peeling occurred in the spacer.

<Preparation of liquid crystal aligning agent>
Example 12
[Synthesis of polyimide]
2,3,5-tricarboxycyclopentylacetic acid dianhydride (1.0 mol) as tetracarboxylic dianhydride, N-methyl-4,4′-diaminodiphenylamine (0.5 mol) and 3,5 as diamine -Diaminobenzoic acid (0.5 mol) was dissolved in 800 g of N-methyl-2-pyrrolidone (NMP) and reacted at 60 ° C for 6 hours. A small amount of the resulting polyamic acid solution was taken, NMP was added, and the viscosity was measured with a solution having a solid content concentration of 10%. As a result, it was 60 mPa · s. Next, 1800 g of NMP was added to the obtained polyamic acid solution, 80 g of pyridine and 100 g of acetic anhydride were added, and dehydration ring closure was performed at 110 ° C. for 4 hours. After the imidization reaction, the solvent in the system was replaced with new NMP (pyridine and acetic anhydride used for the imidization reaction were removed from the system in this operation), and polyimide (PI) with an imidation ratio of about 80% (PI A solution containing about 15% by weight of -1) was obtained.

Example 13
[Preparation of liquid crystal aligning agent]
Using the polyimide (PI-1) solution obtained in Example 12, NMP and butyl cellosolve (BC) were added thereto, and the mixture was sufficiently stirred, and a solid content concentration of NMP: BC = 70: 30 was 5% by weight. It was. A liquid crystal aligning agent was prepared by filtering this solution using a filter having a pore diameter of 1 μm.

<Manufacture of color filters>
Example 14
A color filter was produced using the colored compositions (red colored composition, green colored composition and blue colored composition) described in Example 3. First, the red coloring composition was applied to a glass substrate on which a black matrix pattern was formed by a slit die coater, and prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film. Thereafter, the intensity ratio of ghi lines (wavelengths of 436 nm, 405 nm, and 365 nm = 2.7: 2.5: 4.8) using an exposure machine Canon PLA (registered trademark) 501F (Canon) through a predetermined pattern mask. ) At an exposure dose of 1,000 J / m ^{2 in} terms of i-line, developed with 0.05% aqueous potassium hydroxide solution, rinsed with ultrapure water for 60 seconds, and further in an oven at 180 ° C. Was heated for 30 minutes to form a red stripe pattern (pattern width 100 μm) having a thickness of 2.0 μm.

  Subsequently, the same operation was performed to form a green stripe pattern using the green coloring composition. Further, a blue stripe pattern was formed using the blue coloring composition, and a stripe color filter (stripe width 100 μm) of three colors of red, green, and blue was formed. The above-mentioned formed post-baking temperature of 180 ° C. and the colored pattern of three colors of red, green, and blue formed under the conditions of 30 minutes does not cause problems such as chipping of the pattern due to insufficient curing and peeling from the substrate, A three-color stripe pattern could be formed.

Next, the radiation-sensitive resin composition described in Example 7 was applied on the obtained three-color stripe pattern with a slit die coater. Next, pre-baking is performed on a hot plate at 90 ° C. for 5 minutes to form a coating film. Then, the obtained coating film is irradiated with a high-pressure mercury lamp at an exposure amount of 700 J / m ² , and further in an oven. A heat treatment was performed at 180 ° C. for 60 minutes to form a protective film having a thickness of 2.0 μm from the upper surface of the three-color stripe pattern. As described above, a substrate having a protective film formed on the colored pattern was manufactured.

  About the board | substrate with which the protective film was formed on the obtained coloring pattern, the unevenness | corrugation (flatness) of the surface of a protective film was measured with the contact-type film thickness measuring apparatus (alpha) -step (Tencor Japan) (measurement length 2). , 000 μm, measuring range 2,000 μm square, number of measuring points n = 5). That is, the measurement direction is two directions of the stripe line minor axis direction of red, green and blue directions and the stripe axis major axis direction of red, red, green, green, blue and blue, and n = 5 for each direction. Measured (total n number is 10). An average value of 10 times of height difference (nm) between the highest part and the lowest part for each measurement was obtained. The average value at this time was 220 nm. Even after the formation of the protective film, the coloring pattern did not shrink or expand, and the surface of the protective film had no irregularities, indicating good flatness.

  Next, for the substrate on which the protective film was formed on the obtained colored pattern, an ITO film was formed on the protective film using a sputtering method to form an ITO electrode.

Next, the radiation sensitive resin composition prepared in Example 7 was coated on the ITO electrode with a slit die coater. Next, a film having a thickness of 6.0 μm was formed by pre-baking on a hot plate at 100 ° C. for 2 minutes. Subsequently, the obtained coating film was irradiated with radiation using a high-pressure mercury lamp at an exposure amount of 700 J / m ² . Thereafter, a developing solution (0.04 mass% potassium hydroxide aqueous solution at 23 ° C.) is discharged onto the substrate at a developing pressure of 1 (kgf / cm ² ) (nozzle diameter of 1 mm) to perform shower development on the substrate. A spacer pattern was formed. Subsequently, post-baking was performed in an oven at a curing temperature of 180 ° C. and a curing time of 30 minutes. Thus, a spacer was formed on the ITO electrode. The spacer is formed in a region corresponding to the formation region of the black matrix on the ITO electrode.

Next, an alignment film is formed on the substrate on which the spacer is formed to manufacture a color filter.
First, the liquid crystal aligning agent obtained in Example 13 was applied onto a substrate on which a spacer was formed using a spinner. Next, after pre-baking for 1 minute on a hot plate at 80 ° C., it was heated at 180 ° C. for 1 hour in an oven in which the inside was replaced with nitrogen to form a coating film having a thickness of 80 nm. The coating film was subjected to the rubbing treatment described above to perform an orientation treatment, and a color filter having an orientation film was produced.
As described above, the color filter of this example was manufactured. The manufactured color filter of this example had excellent color characteristics.

<Application of color filters to liquid crystal display elements>
Example 15
[Manufacture of color liquid crystal display elements]
A liquid crystal display element was manufactured using the color filter obtained in Example 14. The manufactured liquid crystal display element is a color liquid crystal display element, and has the same structure as the liquid crystal display element shown in FIG. The liquid crystal display element of this example showed high uniformity in the gap between the substrates sandwiching the liquid crystal. And it showed excellent electrical characteristics, display characteristics and reliability performance.

  The color filter of the present invention can be produced by low-temperature curing, has high reliability, and is excellent in color characteristics. Therefore, the color filter of the present invention can be suitably used as a color filter for a flexible liquid crystal display using a resin substrate or a color filter for a large liquid crystal television requiring high image quality.

DESCRIPTION OF SYMBOLS 1 Liquid crystal display element 2, 5 Board | substrate 3 Pixel electrode 4 ITO electrode 6 Coloring pattern 7 Black matrix 8 Protective film 9 Spacer 10 Color filter 12 Orientation film 13 Liquid crystal 14 Polarizing plate 16 Sealing material 17 Backlight

Claims (20)

A coloring pattern containing at least one colorant selected from the group consisting of diketopyrrolopyrrole pigments, halogenated zinc phthalocyanine pigments, triarylmethane dyes and azo dyes;
[A] a compound having an epoxy group,
[B] a polymerizable compound having an ethylenically unsaturated bond,
[C] a radiation-sensitive polymerization initiator, and [D] a compound containing at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2). A protective film formed from the radiation sensitive resin composition of 1;
[E] alkali-soluble resin,
[F] a polymerizable compound having an ethylenically unsaturated bond,
[G] a radiation-sensitive polymerization initiator, and [H] a compound containing at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2). A spacer formed from the radiation sensitive resin composition of 2;
A polyamic acid obtained by reacting a tetracarboxylic dianhydride including 2,3,5-tricarboxycyclopentylacetic acid dianhydride with a diamine, and a polyimide formed by dehydrating and ring-closing the polyamic acid are selected. A color filter comprising an alignment film formed from a liquid crystal aligning agent containing at least one [P] polymer.

(In formula (1), R ^{1 to} R ⁶ are each independently a hydrogen atom, an electron withdrawing group or an amino group, provided that at least one of R ^{1 to} R ⁶ is an electron withdrawing group. In addition, at least one of R ^{1 to} R ⁶ is an amino group, and all or part of the hydrogen group may be substituted with an alkyl group having 1 to 6 carbon atoms.
In formula (2), R ^{7 to} R ¹⁶ are each independently a hydrogen atom, an electron-withdrawing group, or an amino group. However, at least one of R ^{7 to} R ¹⁶ is an amino group. In the amino group, all or part of the hydrogen atoms may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. A represents a single bond, a mosquito Ruboniruokishi group, carbonyl methylene group, a sulfinyl group, a sulfonyl group, a methylene group or an alkylene group having 2 to 6 carbon atoms. However, in the methylene group and alkylene group, all or part of the hydrogen atoms may be substituted with a cyano group, a halogen atom or a fluoroalkyl group. ) The coloring pattern is
[I] alkali-soluble resin,
[II] a polymerizable compound having an ethylenically unsaturated bond,
The color filter according to claim 1, wherein the color filter is formed from [III] a radiation-sensitive polymerization initiator and [IV] a coloring composition containing the coloring agent. The colored composition further characterized in that it contains at least one compound selected from the compounds or Ranaru group represented by [V] the compound represented by formula (1) and the formula (2) The color filter according to claim 2.   The [I] alkali-soluble resin contained in the colored composition is (I-1) a structural unit formed from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, The color filter according to claim 2 or 3, which is a copolymer comprising (I-2) a structural unit formed from an epoxy group-containing unsaturated compound.   The color filter according to any one of claims 1 to 4, wherein the compound having an [A] epoxy group contained in the first radiation-sensitive resin composition is a polymer.   The color filter according to claim 1, wherein the compound having an [A] epoxy group contained in the first radiation-sensitive resin composition further has a carboxyl group.   The [E] alkali-soluble resin contained in the second radiation-sensitive resin composition is formed from at least one selected from the group consisting of (E-1) an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. The color according to any one of claims 1 to 6, which is a copolymer comprising a structural unit formed from (E-2) a structural unit formed from an epoxy group-containing unsaturated compound. filter. The diamine for obtaining the [P] polymer contained in the liquid crystal aligning agent is at least selected from the group consisting of diamines represented by the following formula (DA1), formula (DA2) and formula (DA3). The color filter according to claim 1, comprising a first diamine having a tertiary nitrogen atom which is one kind.

(In the formula (DA1), A ¹¹ is a benzene ring or a nitrogen-containing aromatic heterocyclic ring, and Z ¹¹ is a di-substituted group substituted with an aliphatic group having 1 to 6 carbon atoms when A ¹¹ is a benzene ring. When it is an amino group and A ¹¹ is a nitrogen-containing aromatic heterocyclic ring, it is a disubstituted amino group substituted with a hydrogen atom or an aliphatic group having 1 to 6 carbon atoms.
In the formula (DA2), A ¹² is an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings, A ¹³ is alkylene or biphenylene having 2 to 5 carbon atoms, Z ¹² is an alkyl group having 1 to 5 carbon atoms or a benzene ring, and q is an integer of 0 or 1.
Wherein ^{(DA3), A 14} is a carbon atom number 4-6 cycloalkylene substituted with a tertiary nitrogen ^{atom, A 15} is alkylene having 2 to 5 carbon atoms. ) The first diamine is at least one diamine selected from the group consisting of diamines represented by the following formulas (DA4), (DA5), (DA6), and (DA7). The color filter according to 8.

(In formula (DA4), A ²¹ represents a nitrogen-containing aromatic heterocycle.
In formula (DA5), Z ²¹ represents an aliphatic group having 2 to 12 carbon atoms containing a tertiary nitrogen atom.
In the formula (DA6), A ²² is an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings, A ²³ is alkylene or biphenylene having 2 to 5 carbon atoms, Z ²² is an alkyl or benzene ring having 1 to 5 carbon atoms, and r is an integer of 0 or 1.
Wherein ^{(DA7), A 24} is a group represented by the formula (DA7a) or ^{(DA7b), A 25} is alkylene having 2 to 5 carbon atoms. )   The color filter according to claim 8 or 9, wherein the diamine for obtaining the [P] polymer contained in the liquid crystal aligning agent includes a second diamine having a carboxyl group in the molecule. . 11. The color filter according to claim 10, wherein the second diamine is at least one diamine selected from the group consisting of diamines represented by the following formula (DA8).

(In the formula ^{(DA8), A 31} is an organic group having an aromatic ring having 6 to 30 carbon atoms, n1 is an integer from 1 to 4.) The color according to claim 10 or 11, wherein the second diamine is at least one diamine selected from the group consisting of diamines represented by the following formulas (DA9) to (DA13). filter.

(In Formula (DA9), m1 is an integer of 1-4.
In the formula (DA10), A ³² represents a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) ₂ —, —O—. , —CO—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CON (CH ₃ ) - or -N _(CH 3) a CO-, m2 + m3 with an integer of m2 and m3 are each independently 0 to 4 is an integer of 1-4.
In formula (DA11), m4 and m5 are each independently an integer of 1 to 5.
In the formula (DA12), A ³³ is a linear or branched alkyl group having 1 to 5 carbon atoms, and m6 is an integer of 1 to 5.
Wherein ^{(DA13), A 34} represents a single _{bond, -CH 2 -, - C 2} H 4 -, - C (CH 3) 2 -, - CF 2 -, - C (CF 3) 2 -, - O- , —CO—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CON (CH ₃ ) - or -N _(CH 3) a CO-, m7 is an integer of 1 to 4.
) A liquid crystal display element comprising the color filter according to claim 1. [1] A coating film of a colored composition containing at least one colorant selected from the group consisting of diketopyrrolopyrrole pigments, halogenated zinc phthalocyanine pigments, triarylmethane dyes and azo dyes on a substrate The process of forming into,
[2] A step of forming a colored pattern on the coating film of the colored composition,
[3] A step of curing the coating film on which the colored pattern is formed at 200 ° C. or lower,
[4] [A] a compound having an epoxy group,
[B] a polymerizable compound having an ethylenically unsaturated bond,
[C] a radiation sensitive polymerization initiator, and
[D] Coating film of first radiation-sensitive resin composition containing at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2) Forming on the substrate,
[5] A step of irradiating at least a part of the coating film of the first radiation-sensitive resin composition,
[6] A step of developing the coating film irradiated with radiation in the step [5],
[7] A step of curing the coating film developed in the step [6] at 200 ° C. or lower,
[8] [E] Alkali-soluble resin,
[F] a polymerizable compound having an ethylenically unsaturated bond,
[G] a radiation-sensitive polymerization initiator, and
[H] Coating film of second radiation-sensitive resin composition containing at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2) Forming on the substrate having the cured coating film of step [7],
[9] A step of irradiating at least part of the coating film of the second radiation-sensitive resin composition,
[10] A step of developing the coating film irradiated with radiation in the step [9],
[11] A step of curing the coating film developed in step [10] at 200 ° C. or lower to form a spacer, and
[12] A polyamic acid obtained by reacting a tetracarboxylic dianhydride containing 2,3,5-tricarboxycyclopentylacetic acid dianhydride with a diamine, and a group consisting of polyimides obtained by dehydrating and ring-closing the polyamic acid. A coating film of a liquid crystal aligning agent containing at least one selected [P] polymer is formed on a substrate having a spacer cured in step [11], and the coating film is heated at 200 ° C. or less to align. Process for forming a film
A method for producing a color filter, comprising:

(In formula (1), R ¹ ~ R ⁶ Are each independently a hydrogen atom, an electron-withdrawing group or an amino group. However, R ¹ ~ R ⁶ At least one of which is an electron-withdrawing group and R ¹ ~ R ⁶ At least one of them is an amino group. In the amino group, all or part of the hydrogen atoms may be substituted with an alkyl group having 1 to 6 carbon atoms.
  In formula (2), R ⁷ ~ R ¹⁶ Are each independently a hydrogen atom, an electron-withdrawing group or an amino group. However, R ⁷ ~ R ¹⁶ At least one of them is an amino group. In the amino group, all or part of the hydrogen atoms may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. A is a single bond, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group, or an alkylene group having 2 to 6 carbon atoms. However, in the methylene group and alkylene group, all or part of the hydrogen atoms may be substituted with a cyano group, a halogen atom or a fluoroalkyl group. ) The colored composition further contains [I] an alkali-soluble resin, [II] a polymerizable compound having an ethylenically unsaturated bond, and [III] a radiation-sensitive polymerization initiator. Manufacturing method of color filter. The method for producing a color filter according to claim 14 or 15, wherein the curing temperature in the step [3] is lower than the curing temperature in the step [7]. The method for producing a color filter according to any one of claims 14 to 16, wherein the curing temperature in the step [3] is lower than the curing temperature in the step [11]. The method for producing a color filter according to any one of claims 14 to 17, wherein the curing temperature in the step [7] is lower than the curing temperature in the step [11]. The diamine for obtaining the [P] polymer contained in the liquid crystal aligning agent is at least selected from the group consisting of diamines represented by the following formula (DA1), formula (DA2) and formula (DA3). The method for producing a color filter according to any one of claims 14 to 18, comprising a first diamine having a tertiary nitrogen atom which is one kind.

(In the formula (DA1), A ¹¹ Is a benzene ring or a nitrogen-containing aromatic heterocycle, and Z ¹¹ A ¹¹ Is a di-substituted amino group substituted with an aliphatic group having 1 to 6 carbon atoms, ¹¹ When is a nitrogen-containing aromatic heterocyclic ring, it is a disubstituted amino group substituted with a hydrogen atom or an aliphatic group having 1 to 6 carbon atoms.
  In formula (DA2), A ¹² Is an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings; ¹³ Is alkylene or biphenylene having 2 to 5 carbon atoms, and Z ¹² Is an alkyl group having 1 to 5 carbon atoms or a benzene ring, and q is an integer of 0 or 1.
  In formula (DA3), A ¹⁴ Is a cycloalkylene having 4 to 6 carbon atoms substituted with a tertiary nitrogen atom, and A ¹⁵ Is alkylene having 2 to 5 carbon atoms. ) The said diamine for obtaining the [P] polymer contained in the said liquid crystal aligning agent contains the 2nd diamine which has a carboxyl group in a molecule | numerator, The manufacture of the color filter of Claim 19 characterized by the above-mentioned. Method.

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