JP6539584B2 - Novel compound and composition containing the compound - Google Patents

Description

  The present invention relates to a dye designed to have a desired color and having improved heat resistance and a novel compound suitable for the dye. Furthermore, the present invention relates to a colored photosensitive composition that can be polymerized by energy rays using the dye and a color filter using the colored photosensitive composition.

  Compounds having high intensity absorption for specific light include recording layers of optical recording media such as CD-R, DVD-R, DVD + R, BD-R, liquid crystal display (LCD), plasma display panel (PDP) ), Electroluminescent displays (ELDs), cathode ray tube displays (CRTs), fluorescent display tubes, field emission displays, etc.

Optical filters for image display devices such as liquid crystal display devices (LCDs), plasma display panels (PDPs), electroluminescent displays (ELDs), cathode ray tube displays (CRTs), fluorescent display tubes, field emission displays, etc. Various compounds that absorb light of a wavelength of ̃1100 nm are used as light absorbers.
For these light absorbing agents, it is required that the light absorption be particularly sharp, that is, the half width of λmax be small, and that the function be not lost by light, heat or the like.

Optical filters used mainly in liquid crystal displays (LCDs) include color filters. Although three primary colors of RGB have generally been used for color filters, it is difficult to provide pure RGB hues with a single colorant, and pure RGB hues using a plurality of colorants Efforts have been made to bring them closer to Therefore, color materials such as yellow, orange, and purple are also required instead of RGB.
Organic and / or inorganic pigments have been used as light absorbers for color filters due to their high heat resistance, but since they are pigments, they have the problem of lowering the brightness as a display device. This problem has been solved by increasing the brightness of the However, with the trend toward lower power consumption, development of color filters using dyes has become active.

Furthermore, in recent years, in color filters used in solid-state imaging devices, thinning of a colored pattern is required from the viewpoint of improving image quality, and to thin the film, it is necessary to increase dye concentration in terms of color density. . Further, even when the molar absorption light coefficient of the dye is low, it is necessary to add a large amount of the dye.
However, when the dye concentration is increased, heat resistance is required because color mixing tends to occur between adjacent pixels or between upper and lower layers in a laminated structure when heat treatment (post baking) is performed after film formation.
Moreover, the light absorbing agent used for a color filter also has the problem of the deterioration property by external light, and light resistance is also calculated | required.

Patent Documents 1 to 3 disclose colored resin compositions for color filters containing an organic dye of a specific structure.
However, the compound used for the coloring composition for color filters described in these documents was not satisfactory in the point compatible heat resistance and light resistance.

WO 2012/039286 WO 2012/101946 WO 2012/111400

  Accordingly, an object of the present invention is to provide a coloring composition such as a coloring photosensitive composition using a novel compound which can solve the above problems. Another object of the present invention is to provide an optical filter using the above-mentioned colored photosensitive composition, particularly a color filter suitable for an image display device such as a liquid crystal display panel without lowering the luminance.

  As a result of intensive studies, the present inventor has found that a compound having a specific structure is excellent in heat resistance and light resistance, and the above-mentioned colored photosensitive composition is an optical filter (in particular, a color filter). It has been found that the present invention is suitable for color filters for image display devices such as liquid crystal display panels without lowering the luminance.

  The present invention has been made based on the above findings, and provides a compound represented by the following general formula (1).

（式中、Ａは、ベンゼン環、ナフタレン環又はアントラセン環を表し、これらの環は、ハロゲン原子、シアノ基、水酸基、ニトロ基、炭素原子数１〜１２のアルキル基、アルコキシ基、ハロゲン化アルキル基又はハロゲン化アルコキシ基で置換されていてもよく、
Ｙは、シアノ基又は−ＣＯＯＲ⁴を表し、
Ｒ¹は、水素原子、フェニル基、シアノ基、ニトロ基、ハロゲン原子、炭素原子数１〜１２のアルキル基、炭素原子数１〜１２のアルコキシ基、炭素原子数１〜１２のハロゲン化アルキル基又は炭素原子数１〜１２のハロゲン化アルコキシ基を表し、
Ｒ²及びＲ³は、それぞれ独立に、水素原子、炭素原子数１〜１２のアルキル基、炭素原子数６〜２０のアリール基又は炭素原子数７〜２０のアリールアルキル基を表し、
Ｒ²及びＲ³で表されるアルキル基、アリール基及びアリールアルキル基は、ハロゲン原子又はニトロ基で置換されていてもよく、
Ｒ²及びＲ³で表されるアルキル基及びアリールアルキル基中のメチレン基は、−ＣＯＯ−、−Ｏ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＮＨ−又は−ＣＯＮＨ−で置き換わっていてもよく、
Ｒ⁴は、水素原子、炭素原子数１〜１２のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基又は炭素原子数２〜３５の複素環基を表し、
Ｒ⁴で表されるアルキル基及びアリールアルキル基中のメチレン基は、−ＣＯＯ−、−Ｏ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＮＨ−又は−ＣＯＮＨ−で置き換わっていてもよく、
Ｘは、単結合、窒素原子、−ＮＲ⁵−、酸素原子、硫黄原子、−ＳＯ₂−、−ＳＯ−、リン原子、−ＰＲ⁶−又は下記＜１＞〜＜５＞の何れかの条件を満たす有機基を表し、
Ｒ⁵及びＲ⁶は、それぞれ独立に、水素原子、炭素原子数１〜１２のアルキル基、炭素原子数６〜２０のアリール基又は炭素原子数７〜２０のアリールアルキル基を表し、
ｍ＝２〜６の整数である。）
＜１＞ｍ＝２であり、Ｘが下記式（２）で表される。

(Wherein, A represents a benzene ring, a naphthalene ring or an anthracene ring, and these rings are a halogen atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a halogenated alkyl It may be substituted by a group or a halogenated alkoxy group,
Y represents a cyano group or -COOR ⁴ ;
R ¹ represents a hydrogen atom, a phenyl group, a cyano group, a nitro group, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms Or a halogenated alkoxy group having 1 to 12 carbon atoms,
R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,
The alkyl group, aryl group and arylalkyl group represented by R ² and R ³ may be substituted with a halogen atom or a nitro group,
The methylene group in the alkyl group and arylalkyl group represented by R ² and R ³ may be replaced by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH- ,
R ⁴ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic group having 2 to 35 carbon atoms ,
The methylene group in the alkyl group and arylalkyl group represented by R ⁴ may be replaced by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-,
X is a single bond, a nitrogen atom, -NR ^5- , an oxygen atom, a sulfur atom, -SO _2- , -SO-, a phosphorus atom, -PR ⁶ -or any of the following <1> to <5> Represents an organic group that satisfies
R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,
m is an integer of 2 to 6; )
<1> m = 2 and X is represented by the following formula (2).

（式中、Ｘ¹は、−ＮＲ¹³−、二価の炭素原子数１〜３５の脂肪族炭化水素基、二価の炭素原子数３〜３５の脂環式炭化水素基、二価の炭素原子数６〜３５の芳香環含有炭化水素基、二価の炭素原子数２〜３５の複素環含有基又は下記（２−１）〜（２−３）の何れかで表される基を表し、
Ｘ¹で表される脂肪族炭化水素基は、ハロゲン原子、シアノ基、水酸基、ニトロ基、炭素原子数１〜８のアルキル基、アルコキシ基、ハロゲン化アルキル基又はハロゲン化アルコキシ基で置換されていてもよく、
Ｘ¹で表される脂肪族炭化水素基中のメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＳＯ₂−、−ＮＨ−又はこれらを組み合わせた基で置き換わっていてもよく、
Ｚ¹及びＺ²は、それぞれ独立に、直接結合、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＳＯ−、−ＮＲ¹³−又は−ＰＲ¹⁴−を表し、
Ｒ¹³及びＲ¹⁴は、それぞれ独立に、水素原子、炭素原子数１〜８のアルキル基、炭素原子数６〜２０のアリール基又は炭素原子数７〜２０のアリールアルキル基を表し、
Ｒ¹³及びＲ¹⁴で表されるアルキル基、アリール基及びアリールアルキル基は、ハロゲン原子、水酸基又はニトロ基で置換されていてもよく、
Ｒ¹³及びＲ¹⁴で表されるアルキル基及びアリールアルキル基中のメチレン基は、−ＣＯＯ−、−Ｏ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＮＨ−又は−ＣＯＮＨ−で置き換わっていてもよい。
但し、上記一般式（２）で表される基は炭素原子数１〜３５の範囲内である。）

(Wherein, X ¹ represents —NR ¹³ —, a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, divalent carbon Represents an aromatic ring-containing hydrocarbon group having 6 to 35 atoms, a divalent heterocyclic group having 2 to 35 carbon atoms, or a group represented by any of the following (2-1) to (2-3): ,
The aliphatic hydrocarbon group represented by X ¹ is substituted by a halogen atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogenated alkyl group or a halogenated alkoxy group May be
The methylene group in the aliphatic hydrocarbon group represented by X ¹ is —O—, —S—, —CO—, —CO—O—, —O—CO—, —SO ₂ —, —NH— or It may be replaced by a combination of these,
Z ¹ and Z ² are independently a direct bond, -O -, - S -, - SO 2 -, - SO -, - NR 13 - or -PR ¹⁴ - represents,
R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,
The alkyl group, aryl group and arylalkyl group represented by R ¹³ and R ¹⁴ may be substituted with a halogen atom, a hydroxyl group or a nitro group,
The methylene group in the alkyl group and arylalkyl group represented by R ¹³ and R ¹⁴ may be replaced by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH- .
However, the group represented by the above general formula (2) is in the range of 1 to 35 carbon atoms. )

（式中、Ｒ²¹は水素原子、炭素原子数１〜１０のアルキル基若しくはアルコキシ基により置換されてもよいフェニル基、又は炭素原子数３〜１０のシクロアルキル基を表し、
Ｒ²²は炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数２〜１０のアルケニル基又はハロゲン原子を表し、
Ｒ²¹及びＲ²²で表されるアルキル基、アルコキシ基及びアルケニル基は、ハロゲン原子で置換されているか又は無置換であり、
ｄは０〜５の整数である。）

(Wherein, R ²¹ represents a hydrogen atom, a phenyl group which may be substituted by an alkyl group having 1 to 10 carbon atoms or an alkoxy group, or a cycloalkyl group having 3 to 10 carbon atoms,
R ²² represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a halogen atom,
The alkyl group, alkoxy group and alkenyl group represented by R ²¹ and R ²² are substituted or unsubstituted with a halogen atom,
d is an integer of 0 to 5; )

（式中、Ｒ²³及びＲ²⁴は、それぞれ独立に、炭素原子数１〜１０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数６〜２０のアリールオキシ基、炭素原子数６〜２０のアリールチオ基、炭素原子数８〜２０のアリールアルケニル基、炭素原子数７〜２０のアリールアルキル基、炭素原子数２〜２０の複素環含有基又はハロゲン原子を表し、
Ｒ²³及びＲ²⁴で表されるアルキル基、アリール基、アリールオキシ基、アリールチオ基、アリールアルケニル基、アリールアルキル基及び複素環含有基は、ハロゲン原子で置換されているか又は無置換であり、
Ｒ²³及びＲ²⁴で表されるアルキル基及びアリールアルキル基中のメチレン基は、不飽和結合、−Ｏ−又は−Ｓ−で置き換わっていてもよく、
Ｒ²³は、隣接するＲ²³同士で環を形成していてもよく、
ｅは０〜４の数を表し、
ｆは０〜８の数を表し、
ｇは０〜４の数を表し、
ｈは０〜４の数を表し、
ｇとｈの数の合計は２〜４である。）
＜２＞ｍ＝３であり、Ｘが下記式（３）で表される。

(Wherein, R ²³ and R ²⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or 6 carbon atoms To 20 arylthio group, an arylalkenyl group having 8 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or a halogen atom,
The alkyl group, aryl group, aryloxy group, arylthio group, arylalkenyl group, arylalkyl group and heterocycle-containing group represented by R ²³ and R ²⁴ are substituted or unsubstituted with a halogen atom,
The methylene group in the alkyl group and arylalkyl group represented by R ²³ and R ²⁴ may be replaced by an unsaturated bond, -O- or -S-,
R ^{23 s} may form a ring with adjacent R ^{23 s} ,
e represents a number from 0 to 4;
f represents a number from 0 to 8;
g represents a number from 0 to 4;
h represents a number from 0 to 4;
The sum of the numbers of g and h is 2 to 4. )
<2> m = 3, and X is represented by the following formula (3).

（式中、Ｘ²は、Ｒ²⁵で置換された炭素原子、三価の炭素原子数１〜３５の脂肪族炭化水素基、三価の炭素原子数３〜３５の脂環式炭化水素基、三価の炭素原子数６〜３５の芳香環含有炭化水素基又は三価の炭素原子数２〜３５の複素環含有基を表し、
Ｒ²⁵は、水素原子、炭素原子数１〜８のアルキル基、炭素原子数６〜２０のアリール基又は炭素原子数７〜２０のアリールアルキル基を表し、
Ｘ²で表される脂肪族炭化水素基は、ハロゲン原子、シアノ基、水酸基、ニトロ基、炭素原子数１〜８のアルキル基、アルコキシ基、ハロゲン化アルキル基又はハロゲン化アルコキシ基で置換されていてもよく、
Ｘ²で表される脂肪族炭化水素基中のメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＳＯ₂−、−ＮＨ−又はこれらを組み合わせた基で置き換わっていてもよく、
Ｚ¹〜Ｚ³は、それぞれ独立に、上記一般式（２）におけるＺ¹及びＺ²で表される基と同じである。
但し、上記一般式（３）で表わされる基は炭素原子数１〜３５の範囲内である。）
＜３＞ｍ＝４であり、Ｘが下記式（４）で表される。

(Wherein, X ² represents a carbon atom substituted with R ²⁵ , a trivalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, a trivalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, A trivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or a trivalent heterocyclic ring containing group having 2 to 35 carbon atoms,
R ²⁵ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,
The aliphatic hydrocarbon group represented by X ² is substituted by a halogen atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogenated alkyl group or a halogenated alkoxy group May be
The methylene group in the aliphatic hydrocarbon group represented by X ² is —O—, —S—, —CO—, —CO—O—, —O—CO—, —SO ₂ —, —NH— or It may be replaced by a combination of these,
Z ^{1 to} Z ³ are each independently the same as the groups represented by Z ¹ and Z ² in the general formula (2).
However, the group represented by the above general formula (3) is in the range of 1 to 35 carbon atoms. )
It is <3> m = 4 and X is represented by following formula (4).

（式中、Ｘ³は、炭素原子、四価の炭素原子数１〜３５の脂肪族炭化水素基、四価の炭素原子数３〜３５の脂環式炭化水素基、四価の炭素原子数６〜３５の芳香環含有炭化水素基又は四価の炭素原子数２〜３５の複素環含有基を表し、
Ｘ³で表される脂肪族炭化水素基は、ハロゲン原子、シアノ基、水酸基、ニトロ基、炭素原子数１〜８のアルキル基、アルコキシ基、ハロゲン化アルキル基又はハロゲン化アルコキシ基で置換されていてもよく、
Ｘ³で表される脂肪族炭化水素基中のメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＳＯ₂−、−ＮＨ−又はこれらを組み合わせた基で置き換わっていてもよく、
Ｚ¹〜Ｚ⁴は、それぞれ独立に、上記一般式（２）におけるＺ¹及びＺ²で表される基と同じである。
但し、上記一般式（４）で表される基は炭素原子数１〜３５の範囲内である。）
＜４＞ｍ＝５であり、Ｘが下記式（５）で表される。

(Wherein, X ³ represents a carbon atom, a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, a tetravalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, and a tetravalent carbon atom number 6 to 35 aromatic ring-containing hydrocarbon group or a tetravalent heterocyclic group having 2 to 35 carbon atoms,
The aliphatic hydrocarbon group represented by X ³ is substituted by a halogen atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogenated alkyl group or a halogenated alkoxy group May be
The methylene group in the aliphatic hydrocarbon group represented by X ³ is —O—, —S—, —CO—, —CO—O—, —O—CO—, —SO ₂ —, —NH— or It may be replaced by a combination of these,
Z ^{1 to} Z ⁴ are each independently the same as the groups represented by Z ¹ and Z ² in the general formula (2).
However, the group represented by the above general formula (4) is in the range of 1 to 35 carbon atoms. )
<4> m = 5, and X is represented by the following formula (5).

（式中、Ｘ⁴は、五価の炭素原子数２〜３５の脂肪族炭化水素基、五価の炭素原子数３〜３５の脂環式炭化水素基、五価の炭素原子数６〜３５の芳香環含有炭化水素基又は五価の炭素原子数２〜３５の複素環含有基を表し、
Ｘ⁴で表される脂肪族炭化水素基は、ハロゲン原子、シアノ基、水酸基、ニトロ基、炭素原子数１〜８のアルキル基、アルコキシ基、ハロゲン化アルキル基又はハロゲン化アルコキシ基で置換されていてもよく、
Ｘ⁴で表される脂肪族炭化水素基中のメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＳＯ₂−、−ＮＨ−又はこれらを組み合わせた基で置き換わっていてもよく、
Ｚ¹〜Ｚ⁵は、それぞれ独立に、上記一般式（２）におけるＺ¹及びＺ²で表される基と同じである。
但し上記一般式（５）で表される基は炭素原子数２〜５０の範囲内である。）
＜５＞ｍ＝６であり、Ｘが下記式（６）で表される。

(Wherein, X ⁴ represents a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a pentavalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, and pentavalent carbon atoms having 6 to 35 carbon atoms) An aromatic ring-containing hydrocarbon group or a pentavalent heterocyclic ring-containing group having 2 to 35 carbon atoms,
The aliphatic hydrocarbon group represented by X ⁴ is substituted by a halogen atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogenated alkyl group or a halogenated alkoxy group May be
The methylene group in the aliphatic hydrocarbon group represented by X ⁴ is —O—, —S—, —CO—, —CO—O—, —O—CO—, —SO ₂ —, —NH— or It may be replaced by a combination of these,
Z ^{1 to} Z ⁵ are each independently the same as the groups represented by Z ¹ and Z ² in the general formula (2).
However, the group represented by the above general formula (5) is in the range of 2 to 50 carbon atoms. )
<5> m = 6, and X is represented by the following formula (6).

（式中、Ｘ⁵は、六価の炭素原子数２〜３５の脂肪族炭化水素基、六価の炭素原子数３〜３５の脂環式炭化水素基、六価の炭素原子数６〜３５の芳香環含有炭化水素基又は六価の炭素原子数２〜３５の複素環含有基を表し、
Ｘ⁵で表される脂肪族炭化水素基は、ハロゲン原子、シアノ基、水酸基、ニトロ基、炭素原子数１〜８のアルキル基、アルコキシ基、ハロゲン化アルキル基又はハロゲン化アルコキシ基で置換されていてもよく、
Ｘ⁵で表される脂肪族炭化水素基中のメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＳＯ₂−、−ＮＨ−又はこれらを組み合わせた基で置き換わっていてもよく、
Ｚ¹〜Ｚ⁶は、それぞれ独立に、上記一般式（２）におけるＺ¹及びＺ²で表される基と同じである。
但し上記一般式（６）で表される基は炭素原子数２〜５０の範囲内である。）

(Wherein, X ⁵ represents a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a hexavalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, and 6 to 35 hexavalent carbon atoms Or an aromatic ring-containing hydrocarbon group or a hexavalent heterocyclic group having 2 to 35 carbon atoms,
The aliphatic hydrocarbon group represented by X ⁵ is substituted by a halogen atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogenated alkyl group or a halogenated alkoxy group May be
The methylene group in the aliphatic hydrocarbon group represented by X ⁵ is —O—, —S—, —CO—, —CO—O—, —O—CO—, —SO ₂ —, —NH— or It may be replaced by a combination of these,
Z ^{1 to} Z ⁶ are each independently the same as the groups represented by Z ¹ and Z ² in the general formula (2).
However, the group represented by the above general formula (6) is in the range of 2 to 50 carbon atoms. )

  The present invention also provides a coloring composition containing the compound represented by the above general formula (1).

  In the present invention, a dye (A) comprising at least one compound represented by the above general formula (1), a polymerizable compound (B) having an ethylenically unsaturated bond having an acid value, photo radical polymerization It is intended to provide a colored photosensitive composition containing an initiator (C) and a monomer (D) having an ethylenically unsaturated bond.

  The present invention also provides a cured product of the above-mentioned colored photosensitive composition and a color filter for a display device, which comprises the cured product.

  The colored photosensitive composition (colored alkaline developable photosensitive composition) of the present invention containing a compound having a specific structure is excellent in heat resistance and light resistance. Moreover, the cured product is suitable for a color filter for display devices.

  Hereinafter, the present invention will be described based on preferred embodiments.

  In the compound represented by the above general formula (1), the m groups may be the same as or different from each other. The value of m is 2 to 6, and preferably 2 to 3 in terms of easiness of synthesis.

In the above general formula (1), a halogen atom which may substitute A, a halogen atom represented by R ¹ , or an alkyl group represented by R ² and R ³ , an aryl group or an arylalkyl group is substituted The halogen atom which may be mentioned includes fluorine, chlorine, bromine and iodine,
As a C1-C12 alkyl group which may substitute A, or a C1-C12 alkyl group represented by R ^{1 to} R ⁶ , methyl, ethyl, propyl, iso-propyl, butyl , Sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl, tert-amyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3- And heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl, tert-octyl, adamantyl and the like.
As a C1-C12 alkoxy group which may substitute A, or a C1-C12 alkoxy group represented by R ¹ , methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, s- Butyloxy, t-butyloxy, isobutyloxy, pentyloxy, isoamyloxy, t-amyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy and the like;
As the halogenated alkyl group having 1 to 12 carbon atoms which may substitute A or the halogenated alkyl group having 1 to 12 carbon atoms represented by R ¹ , the above-mentioned alkyl group having 1 to 12 carbon atoms is exemplified. And those in which at least one hydrogen atom is substituted by the above-mentioned halogen atom, such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, nonafluorobutyl and the like.
As the halogenated alkoxy group having 1 to 12 carbon atoms which may substitute A or the halogenated alkoxy group having 1 to 12 carbon atoms represented by R ¹ , the above-mentioned alkoxy group having 1 to 12 carbon atoms is exemplified. Wherein at least one of the hydrogen atoms is substituted by the above-mentioned halogen atom, such as chloromethyloxy, dichloromethyloxy, trichloromethyloxy, fluoromethyloxy, difluoromethyloxy, trifluoromethyloxy, nonafluorobutyloxy and the like Listed
Examples of the aryl group having 6 to 20 carbon atoms represented by R ^{2 to} R ⁶ include phenyl, naphthyl, anthracenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-iso -Propylphenyl, 4-iso-propylphenyl, 4-butylphenyl, 4-iso-butylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2- Ethylhexyl) phenyl, 4-stearylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl , 2,4-di-tert-butylphenyl, 2,5-di-tert-butyl Phenyl, 2,6-di-tert-butylphenyl, 2,4-di-tert-pentylphenyl, 2,5-di-tert-amylphenyl, 2,5-di-tert-octylphenyl, 2,4- Dicumylphenyl, 4-cyclohexylphenyl, (1,1′-biphenyl) -4-yl, 2,4,5-trimethylphenyl, ferrocenyl and the like;
Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ^{2 to} R ⁶ include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, 2-phenylpropan-2-yl, diphenylmethyl and triphenylmethyl , Styryl, cinnamyl etc.,
The heterocyclic group having 3 to 25 carbon atoms represented by R ⁴ includes pyridyl, pyrimidyl, pyridazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl , Thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidin-1-yl, 2-piperidone-1-yl, 2,4-dioxyl And imidazolidin-3-yl, 2,4-dioxazolidin-3-yl and the like.
The halogen atom, alkyl group, alkoxy group, halogenated alkyl group, halogenated alkoxy group, aryl group and aryl described in the above general formulas (2) to (6) and formulas (2-1) to (2-3) Examples of each alkyl group include the same groups as the groups listed above as examples of the alkyl group, the alkoxy group, the halogenated alkyl group, the halogenated alkoxy group, the aryl group and the arylalkyl group in this paragraph. Among these groups, those having a carbon atom number different from the groups listed in this paragraph include those having a predetermined carbon atom number among the groups listed in this paragraph.

When A is a benzene ring, the substitution position of -NR ² R ³ group and -C (R ¹ ) = C (CN) Y group in A is usually para position, and when A is a naphthalene ring, it is usually 1, 1 When the A is an anthracene ring, it is usually at the 1, 4, 1, 5, 1, 10 or 9, 10 positions.

Examples of the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by X ¹ in the above general formula (2) include methane, ethane, propane, iso-propane, butane, sec-butane and tert-butane , Iso-butane, hexane, 2-methylhexane, 3-methylhexane, heptane, 2-methylheptane, 3-methylheptane, iso-heptane, tert-heptane, 1-methyloctane, iso-octane, tert-octane, Among these groups, divalent groups in which groups such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2,4-dimethylcyclobutane, 4-methylcyclohexane and the like are substituted with Z ¹ and Z ² are mentioned. methylene groups is, -O -, - S -, - CO -, - COO -, - OCO -, - SO 2 -, - N -Or a combination of these may be replaced, and the combination of these is, for example, -COO-O-, -COO-S-, -O-OCO-, -S-OCO-, -CO. -NH-, -NH-CO-, etc., and among them, -COO-, -O-, -OCO-, -NHCO-, -NH-, -CONH-, -O-CONH-, -NHCO-O- Is preferably replaced by
Examples of the divalent C3-C35 alicyclic hydrocarbon group include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecanyl, 1-adamantyl, 2-adamantyl, noradamantyl, 2-methyladamantyl, norbornyl and isonorbornyl , Perhydronaphthyl, perhydroanthracenyl, bicyclo [1.1.0] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.1.0] pentyl, bicyclo [3.1.0] hexyl , Bicyclo [2.1.1] hexyl, bicyclo [2.2.0] hexyl, bicyclo [4.1.0] heptyl, bicyclo [3.2.0] heptyl, bicyclo [3.1.1] heptyl , Bicyclo [2.2.1] heptyl, bicyclo [5.1.0] octyl, bicyclo [4.2.0] octy , Bicyclo [4.1.1] octyl, bicyclo [3.3.0] octyl, bicyclo [3.2.1] octyl, bicyclo [2.2.2] octyl, spiro [4,4] nonanyl, spiro [4,5] decanyl, decalin, tricyclodecanyl, tetracyclododecanyl, cedrol, cyclododecanyl and the like, divalent groups in which groups such as Z ¹ and Z ² are substituted;
Examples of the divalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms include divalent groups in which groups such as phenylene, naphthylene and biphenyl are substituted with Z ¹ and Z ² ,
Examples of divalent heterocyclic groups having 2 to 35 carbon atoms include groups such as pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexahydrotriazine, furan, tetrahydrofuran, chromane, xanthene, thiophene, and thiolane. And Z ¹ and Z ² substituted divalent groups.
These groups may be further substituted by a halogen atom, a cyano group, a nitro group or an alkoxy group having 1 to 8 carbon atoms.

In the above formula (2-1), examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R ²¹ include cyclopropyl, cyclobutyl, cyclopentyl, cyclobutyl, cyclooctyl and the like, and the number of carbon atoms of these groups And the like, a group substituted with an alkyl group of 1 to 10 or an alkoxy group having 1 to 10 carbon atoms, and the like.
Examples of the alkenyl group having 2 to 10 carbon atoms include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl and the like.
The alkyl group, alkoxy group and alkenyl group in R ²² may be substituted by a halogen atom, and the position of substitution is not limited.

In the above formula (2-3), examples of the aryloxy group having 6 to 20 carbon atoms represented by R ²³ and R ²⁴ include phenyloxy, naphthyloxy, 2-methylphenyloxy, 3-methylphenyloxy, -Methylphenyloxy, 4-vinylphenyldioxy, 3-iso-propylphenyloxy, 4-iso-propylphenyloxy, 4-butylphenyloxy, 4-tert-butylphenyloxy, 4-hexylphenyloxy, 4 -Cyclohexylphenyloxy, 4-octylphenyloxy, 4- (2-ethylhexyl) phenyloxy, 2,3-dimethylphenyloxy, 2,4-dimethylphenyloxy, 2,5-dimethylphenyloxy, 2.6-dimethyl Phenyloxy, 3.4-dimethylphenyloxy, 3.5- Methylphenyloxy, 2,4-di-tert-butylphenyloxy, 2,5-di-tert-butylphenyloxy, 2,6-di-tert-butylphenyloxy, 2.4-di-tert-pentylphenyloxy, 2, Groups such as 5-tert-amylphenyloxy, 4-cyclohexylphenyloxy, 2,4,5-trimethylphenyloxy, ferrocenyloxy and the like, and groups in which these groups are substituted with a halogen atom;
The arylthio group having 6 to 20 carbon atoms, ani Gerare group where the oxygen atom of the aryloxy group having 6 to 20 carbon atoms which may be substituted with the halogen atom is replaced by sulfur atom Bong,
As the arylalkenyl group having 8 to 20 carbon atoms, an oxygen atom of the aryloxy group having 6 to 20 carbon atoms which may be substituted by the above-mentioned halogen atom can be vinyl, allyl, 1-propenyl, isopropenyl, 2- Groups substituted with an alkenyl group such as butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl and the like;
Examples of the heterocyclic group having 2 to 20 carbon atoms include pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexahydrotriazine, furan, tetrahydrofuran, chromane, xanthene, thiophene, thiofuran and the like, and groups thereof Are groups substituted with a halogen atom.

Examples of the trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms represented by X ² in the general formula (3) include the aliphatic hydrocarbon groups exemplified in the description of X ¹ in the general formula (2). And a trivalent group substituted by Z ¹ , Z ² and Z ³ , and the methylene group in these groups is -O-, -S-, -CO-, -CO-O-,- O-CO-, -SO _2- , -NH- or a combination thereof may be replaced, and the group combining these is, for example, -COO-O-, -COO-S-, -O -OCO-, -S-OCO-, -CO-NH-, -NH-CO- and the like, and among them, -COO-, -O-, -OCO-, -NHCO-, -NH-, -CONH -, -O-CONH-, -NHCO-O- which is preferably substituted,
As the trivalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, the alicyclic hydrocarbon group exemplified in the description of X ¹ in the above general formula (2) may be Z ¹ , Z ² and Z ³ And substituted trivalent groups.
As the trivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, the aromatic ring-containing hydrocarbon groups exemplified in the description of X ¹ in the general formula (2) can be Z ¹ , Z ² and Z ³ And substituted trivalent groups.
As the trivalent ring group having a carbon number of 2 to 35, three rings in which the heterocyclic group exemplified in the description of X ¹ in the general formula (2) is substituted with Z ¹ , Z ² and Z ³ Valence groups are mentioned.

The aliphatic hydrocarbon group exemplified in the description of X ¹ in the above general formula (2) as the tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by X ³ in the above general formula (4) And a tetravalent group substituted by Z ¹ , Z ² , Z ³ and Z ⁴ , and the methylene group in these groups is —O—, —S—, —CO—, —COO—, -OCO-, -SO _2- , -NH- or a combination thereof may be substituted, and the group combining these is, for example, -COO-O-, -COO-S-, -O- OCO-, -S-OCO-, -CO-NH-, -NH-CO-, etc., among which -COO-, -O-, -OCO-, -NHCO-, -NH-, -CONH-, Those substituted with -O-CONH- or -NHCO-O- are preferable,
As the alicyclic hydrocarbon group having 4 to 35 carbon atoms, the alicyclic hydrocarbon group exemplified in the description of X ¹ in the above general formula (2) may be Z ¹ , Z ² , Z ³ and A tetravalent group substituted by Z ⁴ is mentioned,
As the tetravalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, the aromatic ring-containing hydrocarbon groups exemplified in the description of X ¹ in the general formula (3) are Z ¹ , Z ² , Z ³ and A tetravalent group substituted by Z ⁴ is mentioned,
As the tetravalent heterocyclic group having 2 to 35 carbon atoms, the heterocyclic group exemplified in the description of X ¹ in the general formula (2) is substituted with Z ¹ , Z ² , Z ³ and Z ⁴ And tetravalent groups that have been mentioned.

As a pentavalent C2-C35 aliphatic hydrocarbon group represented by X ⁴ in the said General formula (5), the aliphatic hydrocarbon group illustrated by description of X ¹ in the said General formula (2) is mentioned. And a pentavalent group substituted by Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ , and the methylene group in these groups is -O-, -S-, -CO-,- CO—O—, —O—CO—, —SO ₂ —, —NH— or a combination thereof may be replaced, and the group combining these is, for example, —COO—O—, —COO -S-, -O-OCO-, -S-OCO-, -CO-NH-, -NH-CO-, etc., among which -COO-, -O-, -OCO-, -NHCO-,- Those substituted with NH-, -CONH-, -O-CONH-, -NHCO-O- are preferred,
Examples of the pentavalent alicyclic hydrocarbon group having 3 to 35 carbon atoms include the alicyclic hydrocarbon groups exemplified in the description of X ¹ in the general formula (2) above, Z ¹ , Z ² , Z ³ , A pentavalent group substituted by Z ⁴ and Z ⁵ ;
As the pentavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, the aromatic ring-containing hydrocarbon group exemplified in the description of X ¹ in the general formula (2) is Z ¹ , Z ² , Z ³ , A pentavalent group substituted by Z ⁴ and Z ⁵ ;
As the pentavalent heterocyclic group having 2 to 35 carbon atoms, the heterocyclic groups exemplified in the description of X ¹ in the general formula (2) are Z ¹ , Z ² , Z ³ , Z ⁴ and Z ^A pentavalent group substituted by ⁵ is mentioned.

The aliphatic hydrocarbon group exemplified in the description of X ¹ in the above general formula (2) as the hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by X ⁵ in the above general formula (6) And a hexavalent group substituted by Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ , and the methylene group in these groups is —O—, —S—, —CO -, -COO-, -OCO-, -SO _2- , -NH- or a combination of these may be substituted, and a group combining these is, for example, -COO-O-, -COO- S-, -O-OCO-, -S-OCO-, -CO-NH-, -NH-CO-, etc., among which -COO-, -O-, -OCO-, -NHCO-, -NH -, -CONH-, -O-CONH-, -NHCO-O- which is preferably substituted,
As the alicyclic hydrocarbon group having 3 to 35 carbon atoms which is a hexavalent carbon atom, the alicyclic hydrocarbon group exemplified in the description of X ¹ in the above general formula (2) is Z ¹ , Z ² , Z ³ , A hexavalent group substituted by Z ⁴ , Z ⁵ and Z ⁶ ;
As the hexavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, the aromatic ring-containing hydrocarbon group exemplified in the description of X ¹ in the general formula (2) is Z ¹ , Z ² , Z ³ , A hexavalent group substituted by Z ⁴ , Z ⁵ and Z ⁶ ;
As the hexavalent heterocyclic group having 2 to 35 carbon atoms, the heterocyclic groups exemplified in the description of X ¹ in the general formula (3) are Z ¹ , Z ² , Z ³ , Z ⁴ and Z Examples include hexavalent groups substituted with ⁵ and Z ⁶ .

Among the compounds represented by the above general formula (1), those in which A is a benzene ring; those in which R ¹ is a hydrogen atom; those in which R ² and R ³ are an alkyl group having 1 to 12 carbon atoms; R ⁴ is an alkyl group having 1 to 12 carbon atoms; when m is 2, X is represented by the general formula (2), and X ¹ in the formula (2) is a group selected from the following group 1 Those in which m is 3, X is represented by the general formula (3), and X ² in the formula (3) is a group selected from the following group 2; and when m is 4 A compound represented by the general formula (4), wherein X ³ in the formula (4) is a group selected from group 3; when m is 5, X is represented by the general formula (5); In which X ⁴ is a group selected from the following group 4; when m is 6, X is represented by the general formula (6), and X ⁵ in the formula (6) is selected from the following group 5 What is the basis of the raw material Hands and manufacturing is easy, because of their high heat resistance.

（式中、Ｒ⁵は、上記一般式（１）におけるＲ⁵と同じ基であり、基中に二つ以上ある場合、同じであっても異なっていてもよく、ｐは１〜３の整数を表し、ｑは０〜３の整数を表し、ｒは１〜１９の整数を表す。）

(Wherein, R ⁵ is the same group as R ⁵ in the general formula (1), and when there are two or more in the group, it may be the same or different, and p is an integer of 1 to 3 And q represents an integer of 0 to 3, and r represents an integer of 1 to 19.)

  Specific examples of the compound represented by the above general formula (1) include compounds represented by the following [Formula 15] to [Formula 20B], but the present invention is not limited to these compounds.

  The compound having at least one structure represented by the above general formula (1) of the present invention is used as a dye in a coloring composition such as a coloring photosensitive composition described below, and in a display or an optical lens Optical filter, photosensitive material for silver salt photography, dye, paint, ink, electrophotographic photosensitive member, toner, thermosensitive recording paper, transfer ribbon, optical recording dye, solar cell, organic semiconductor, clinical test reagent, dye for laser treatment, dye It is used for etc.

The method for producing the compound represented by the above general formula (1) is not particularly limited. For example, m = 2, A is a benzene ring, Y is a cyano group, and X is * -Z ¹ -X ¹ -Z ^2- * When it is represented, it can be produced by reacting an aldehyde with malononitrile under basic conditions as in the following reaction formula. Also in the case of m = 3-6, it can manufacture according to this. As a base, anhydrous piperazine etc. can also be used instead of the triethylamine shown below.

（式中、Ｒ¹、Ｒ²及びＲ³は上記一般式（１）と同じであり、Ｚ¹、Ｚ²及びＸ¹は上記一般式（２）と同じである。）

(Wherein, R ¹ , R ² and R ³ are the same as the above general formula (1), and Z ¹ , Z ² and X ¹ are the same as the above general formula (2))

The dye (A) of the present invention may contain at least one compound represented by the above general formula (1), and can be used singly or in combination of two or more. Moreover, it is also possible to use a well-known dye other than the compound represented by the said General formula (1). Examples of known dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, Dyes, such as a phthalocyanine dye and a cyanine dye, etc. are mentioned, You may mix and use these plurality.
Here, the "dye" is used by dissolving it in an organic solvent, and when it is used by dispersing it with a dispersing resin etc., it is called "pigment" described later.

  In the dye (A) of the present invention, the content of the compound represented by the above general formula (1) is preferably 50 to 100% by mass, more preferably 70 to 100% by mass. If the content of the compound represented by the above general formula (1) is less than 50% by mass, the solubility in a solvent may be reduced, or the heat resistance may be reduced.

  Then, the coloring composition of this invention is demonstrated. The coloring composition of the present invention contains the compound represented by the above general formula (1). Among the coloring compositions, the dye (A) containing the compound, a polymerizable compound (B) having an ethylenically unsaturated bond having an acid value, a photo radical polymerization initiator (C), and the above (B) The composition which has a monomer (D) which has an ethylenically unsaturated bond other than a component as an essential component is the coloring photosensitive composition of this invention. The colored photosensitive composition of the present invention will be described below.

  In the colored photosensitive composition, the content of the dye (A) is preferably 0.1 to 20% by mass, and more preferably 0.5 to 15% by mass. When the content of the dye (A) is less than 0.1% by mass, the colorability is insufficient, and when it is 20% by mass, the dye (A) may be precipitated in the colored photosensitive composition.

  As the polymerizable compound having an ethylenically unsaturated bond having the above acid value, (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid , Vinyl acetate, allyl acetate, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypoly Mono (meth) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends such as caprolactone mono (meth) acrylate, hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene malate or 1 carboxyl group and 2 or more (meth) acrylo Unsaturated polybasic acids such as polyfunctional (meth) acrylates having a hydroxyl group; phenol and / or cresol novolac epoxy resin, biphenyl skeleton, novolac epoxy resin having naphthalene skeleton, bisphenol A novolac epoxy compound, dicyclopentadiene novolac Action of unsaturated monobasic acid on epoxy group of epoxy resin such as novolak type epoxy compound such as epoxy type epoxy compound, polyphenylmethane type epoxy resin having polyfunctional epoxy group, epoxy compound represented by the following general formula (7) Resins obtained by reacting with polybasic acid anhydride, hydroxylated polyfunctional acrylates such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate, and succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, etc. Polymers such as polyfunctional acrylate having an acid value which is a reaction product of dibasic acid anhydride.

（式中、Ｘ⁴¹は直接結合、メチレン基、炭素原子数１〜４のアルキリデン基、炭素原子数３〜２０の脂環式炭化水素基、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＳＳ−、−ＳＯ−、−ＣＯ−、−ＯＣＯ−又は上記式（２−１）〜（２−３）で表される基を表し、該アルキリデン基はハロゲン原子で置換されていてもよく、Ｒ⁴¹、Ｒ⁴²、Ｒ⁴³及びＲ⁴⁴は、それぞれ独立に、水素原子、炭素原子数１〜５のアルキル基、炭素原子数１〜８のアルコキシ基、炭素原子数２〜５のアルケニル基又はハロゲン原子を表し、上記アルキル基、アルコキシ基及びアルケニル基はハロゲン原子で置換されていてもよく、ｓは０〜１０の整数である。）

(Wherein, X ⁴¹ represents a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, -O-, -S-, -SO _2- , Represents a group represented by -SS-, -SO-, -CO-, -OCO- or the above formulas (2-1) to (2-3), and the alkylidene group may be substituted with a halogen atom R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each independently represent a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, or an alkenyl group of 2 to 5 carbon atoms Or the above-mentioned alkyl group, alkoxy group and alkenyl group may be substituted by a halogen atom, and s is an integer of 0 to 10.)

  These polymerizable compounds can be used alone or in combination of two or more, and can be used in combination with a polymerizable compound having an ethylenically unsaturated bond having no acid value. When 2 or more types are mixed and used, they may be copolymerized beforehand and you may use as a copolymer.

  Examples of the polymerizable compound having an ethylenically unsaturated bond not having an acid value include (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, glycidyl (meth) acrylic acid, The following compound No. A1-No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate ( (Meth) acrylate isooctyl, (meth) acrylate isononyl, (meth) acrylate stearyl, (meth) acrylate lauryl, (meth) acrylate methoxyethyl, (meth) acrylate dimethylaminomethyl, (meth) acrylate dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meth ) Ethyl hexyl acrylate, (meth) acrylic acid Phenoxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethane tri ( Meta) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol Unsaturated monobasic acids such as tra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloyl ethyl] isocyanurate, polyester (meth) acrylate oligomers and the like Polyhydric alcohol or ester of polyhydric phenol; Metal salt of unsaturated polybasic acid such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrofuran Phthalic anhydride-anhydrous Acid anhydride of unsaturated polybasic acid such as leic acid adduct, dodecenyl succinic anhydride, methyl hymic acid anhydride; (meth) acrylamide, methylene bis (meth) acrylamide, diethylene triamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyhydric amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanation Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylene Unsaturated aromatic compounds such as 2-phenol, vinyl sulfonic acid, 4-vinyl benzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allylamine, N-vinyl pyrrolidone, vinyl Unsaturated amine compounds such as piperidine; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; unsaturated imides such as maleimide, N-phenyl maleimide, N-cyclohexyl maleimide; And indenes such as 1-methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, polymethyl (meth) acrylate, poly-n- Macromonomers having a mono (meth) acryloyl group at the end of polymer molecular chain such as chill (meth) acrylate and polysiloxane; (meth) acrylonitrile, other vinyl such as ethylene, propylene, butylene, vinyl chloride and vinyl acetate Compounds, and macromonomers such as polymethyl methacrylate macromonomer and polystyrene macromonomer, monomethacrylate of tricyclodecane skeleton, N-phenylmaleimide, methacryloyloxymethyl-3-ethyl oxetane, etc., and (meth) acrylic acid Polymers and copolymers of (meth) acrylic acid obtained by reacting an isocyanate compound having an unsaturated bond such as Karenz MOI manufactured by Showa Denko KK and AOI with these, vinyl chloride, vinylidene chloride, divinyl succ Nath, Allyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl urethane compound of hydroxyl group-containing vinyl monomer and polyisocyanate compound, hydroxyl group-containing vinyl monomer And vinyl epoxy compounds of polyepoxy compounds, and reaction products of hydroxyl group-containing polyfunctional acrylates such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate with polyfunctional isocyanates such as tolylene diisocyanate and hexamethylene diisocyanate.

  In order to adjust the acid value to improve the developability of the photosensitive composition, a monofunctional or polyfunctional epoxy compound can be used together with the polymerizable compound having an ethylenically unsaturated bond having the acid value. It is preferable that the acid value of solid content is the range of 5-120 mgKOH / g, and the using amount of the monofunctional or polyfunctional epoxy compound is the above-mentioned acid. It is preferable to select to satisfy the price.

  Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidyl ether , Propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl Ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monoxide, 1,2-epoxy-4-vinyl Examples include cyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide and the like.

It is preferable to use one or more selected from the group consisting of bisphenol type epoxy compounds and glycidyl ethers as the above-mentioned polyfunctional epoxy compound, since a colored alkaline developable photosensitive composition having better properties can be obtained. As the bisphenol epoxy compound, in addition to the epoxy compound represented by the above general formula (7), for example, a bisphenol epoxy compound such as a hydrogenated bisphenol epoxy compound can also be used. Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, , 10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-tri (g Glycidyl oxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1- tetra (glycidyloxymethyl) include methane.
In addition, novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds, etc .; 3,4-epoxy-6-methyl; Alicyclic epoxy such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane and the like Compounds; Glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, dimer acid glycidyl ester; tetraglycidyl diamino acid Glycidyl amines such as phenylmethane, triglycidyl-p-aminophenol, N, N-diglycidyl aniline, etc .; Heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin, triglycidyl isocyanurate; Dioxide compounds such as cyclopentadiene dioxide; naphthalene type epoxy compounds, triphenylmethane type epoxy compounds, dicyclopentadiene type epoxy compounds and the like can also be used.

  In the colored photosensitive composition, the content of the polymerizable compound (B) having an ethylenically unsaturated bond having an acid value in the colored photosensitive composition is preferably 0.1 to 90% by mass, and more preferably Is 1 to 80% by mass. When the content of the polymerizable compound (B) is less than 0.1%, the development characteristics are insufficient, and when it exceeds 90%, the strength of the cured film may be insufficient.

  The above photo radical polymerization initiator may be any compound as long as it can start radical polymerization by receiving light irradiation. For example, ketones such as acetophenone compounds, benzyl compounds, benzophenone compounds, thioxanthone compounds and the like Preferred examples of the compound include compounds and oxime compounds.

  Examples of acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2 -Methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tertiarybutyl dichloroacetophenone, p-tertiarybutyl trichloroacetophenone, p-azidobenzal Acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1, benzoin , Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane- 1-ON etc. are mentioned.

  Examples of the benzyl compounds include benzyl and anisyl.

  Examples of benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and the like. .

  As oxime compounds, 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), methanone, (2-methylphenyl) [6-nitro-9- [3- (trimethylsilyl) propyl] -9H-carbazole-3- Yl]-, 1-O-acetyloxime), methanone, (9-ethyl-6-nitro-9H-carbazol-3-yl) (2-methylphenyl), O-acetyloxime, methanone, (9-ethyl- 6-nitro-9H-carbazol-3-yl) [2-methyl-4- (4-morpholinyl) phenyl), O-acetyloxime, methanone, (3,5-dinitropheny ) (9-ethyl-6-nitro-9H-carbazol-3-yl) (2-methylphenyl), O-acetyloxime, methanone, (9-ethyl-6-nitro-9H-carbazol-3-yl) ( 3-Nitrophenyl), O-acetyloxime, 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris [2- (acetyloxy) -3 -[3-[(1E) -1-[(acetyloxy) iminoethyl] -6-nitro-9H-carbazol-9-yl] propyl]-, 1,2-butanedione, 1- [4- (phenylthio) phenyl ], 2- (O-acetyloxime), 1,2-butanedione, 1- [4-[[4- (2-hydroxyethoxy) phenyl] thio] phenyl]-, 2- (O-acetyloxime), 1,2-butanedione, , 1 ′-(Thiodi-4,1-phenylene) bis-, 2,2-bis (O-acetyloxime), 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- [2 O- (4-methyl benzoyl) oxime] etc. are mentioned.

  As a thioxanthone type-compound, thioxanthone, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-chloro thioxanthone, 2-isopropyl thioxanthone, 2,4- diethyl thioxanthone etc. are mentioned.

  Other photoradical polymerization initiators include 2,4,6-trimethyl benzoyl diphenyl phosphene oxide, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pyr-1-yl)] titanium Etc.

  These photo radical polymerization initiators may be used alone or in combination of two or more depending on the desired performance.

  In the colored photosensitive composition, the content of the photo radical polymerization initiator (C) in the colored photosensitive composition is preferably 0.1 to 30% by mass, and more preferably 0.5 to 10% by mass. When the content of the photopolymerization initiator (C) is less than 0.1% by mass, curing by exposure may be insufficient, and when it is more than 30% by mass, the initiator (C) in the resin composition May precipitate out.

  In the colored photosensitive composition of the present invention, as the monomer (D) having an ethylenically unsaturated bond, a polymerizable compound having an ethylenically unsaturated bond not having the above-mentioned acid value can be used. The content of the monomer (D) having an ethylenically unsaturated bond is preferably 10 to 1000% by mass, more preferably 20 to 100% by mass with respect to 100% by mass of the polymerizable compound having an ethylenically unsaturated bond having an acid value. It is 800 mass%.

An inorganic pigment or an organic pigment can be further added to the colored photosensitive composition, and examples thereof include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, and phthalocyanine compounds, Isoindolinone compounds, isoindoline compounds, quinacridone compounds, anthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acids; azo dyes, cyanines Metal complex compounds of dyes; lake pigments; carbon black obtained by furnace method, channel method, thermal method, or acetylene black, ketjen black or LA Carbon blacks such as black gold; those prepared by coating the above carbon black with an epoxy resin, those obtained by dispersing the carbon black in a solvent beforehand with a resin and adsorbing a resin of 20 to 200 mg / g, the above carbon black Treated with an acid or alkaline surface, those with an average particle diameter of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, CO in volatiles at 950 ° C., total oxygen amount calculated from CO ₂ is surface area of carbon black 100 m ² as per at 9mg above; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon airgel, fullerene; aniline black, pigment black 7, titanium black; hydrophobic resin, Chrome oxide green, Miroli Rue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate group blue, bitumen, ultramarine, cerulian blue, pyridinium, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III) Inorganic content or organic pigments such as cadmium red, synthetic iron black, and amber can be used. These pigments may be used alone or in combination of two or more.

  Commercially available pigments can also be used as the above-mentioned inorganic pigment or organic pigment, and for example, pigment red 1, 2, 3, 9, 10, 14, 17, 22, 22, 31, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; pigment oranges 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; pigment yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 3, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 154, 154, 154, 154, 154, 154, 166, 168, 175, 180, 185; pigment green 7, 10, 36; pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50 and the like.

  The above-mentioned colored photosensitive composition is dissolved or dispersed in an organic solvent as necessary, and the obtained coating solution is known by spin coater, roll coater, bar coater, die coater, curtain coater, various printing, immersion, etc. By means, it can be coated on a supporting substrate such as soda glass, quartz glass, semiconductor substrate, metal, paper, plastic and the like, and can be irradiated with light and cured.

  As the organic solvent, a solvent which can dissolve or disperse each of the above components as needed, such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone Ketones, etc .; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, acetic acid Ester solvents such as isopropyl, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate and texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; meta Alcohol solvents such as alcohol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol 1-monomethyl ether 2-acetate ( PGMEA), ether ether solvents such as dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, etc .; BTX solvents such as benzene, toluene, xylene etc .; aliphatics such as hexane, heptane, octane, cyclohexane etc. Hydrocarbon solvents; terpene hydrocarbon oils such as turpentine oil, D-limonene, pinene, etc .; mineral spirit, swazor # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (E. Paraffin solvents such as Son Chemical Co., Ltd .; halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1,2-dichloroethane; halogenated aromatic ring-containing hydrocarbons such as chlorobenzene Solvents: carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water, etc. The solvent of can be used as one or more mixed solvents. Among these, ketones, ether ester solvents and the like, particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone and the like are preferable because they have good compatibility between the resist and the photopolymerization initiator in the photosensitive composition.

  The colored photosensitive composition may further contain an inorganic compound. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; layered clay minerals, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenide, aluminum silicate, calcium silicate, aluminum silicate, aluminum hydroxide, platinum, gold, silver, copper Etc.

  In the case of using a pigment and / or an inorganic compound in the above-mentioned colored photosensitive composition, a dispersant can be added. Any dispersant may be used as the dispersant, as long as it can disperse and stabilize a coloring material and an inorganic compound, and a commercially available dispersant, such as BYK series manufactured by Bick Chemie Co., Ltd., can be used, and polyester having a basic functional group Polymer dispersant made of polyether, polyurethane, having nitrogen atom as basic functional group, functional group having nitrogen atom is amine, and / or its quaternary salt, and has an amine value of 1 to 100 mg KOH / g Is preferably used.

  In the above-mentioned colored photosensitive composition, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine, etc .; plasticizer; adhesion promoter; filler; Leveling agents; Surface conditioners; Antioxidants such as phenolic antioxidants, phosphite antioxidants, thioether antioxidants, etc .; UV absorbers; dispersion aids; aggregation inhibitors; catalysts; Cross-linking agents; conventional additives such as thickeners can be added.

  Moreover, the characteristic of the hardened | cured material of the said coloring photosensitive composition can also be improved by using another organic polymer with the polymeric compound which has an ethylenically unsaturated bond which has the said acid value. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene-(meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate Copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated Polyester, phenol resin, phenoxy resin, polyamide imide resin, polyamic acid resin, epoxy resin, etc. may be mentioned. Among these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, epoxy resin Masui.

  The colored photosensitive composition may further contain a thermal radical polymerization initiator, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, melamine and the like in combination.

  Examples of the thermal radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, Azo initiators such as 1′-azobis (1-acetoxy-1-phenylethane); benzoyl peroxide, di-t-butyl benzoyl peroxide, t-butyl peroxypivalate, di (4-t-butylcyclohexyl) 2. Peroxide initiators such as peroxydicarbonate, and persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate. These may be used alone or in combination of two or more.

  A sulfur atom-containing compound is generally used as the chain transfer agent and the sensitizer. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- ( 2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3- 3- Mercapto compounds such as mercapto propionates, Disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acids, iodoacetic acids, iodopropionic acids, 2-iodoethanol, 2-iodoethanesulfonic acid, iodos such as 3-iodopropanesulfonic acid Alkylated compounds, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, tris hydroxyethyl tris thiopropionate, compound No. 1 below. C1, Aliphatic polyfunctional thiol compounds such as trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate; Kalens MT BD1, PE1, NR1 manufactured by Showa Denko K. K.

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates, and higher amines Cationic surfactants such as halides and quaternary ammonium salts, polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, nonionic surfactants such as fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

  As the above-mentioned silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among them, KBE-9007, KBM-502, KBE-403, etc., silane cup having isocyanate group, methacryloyl group, epoxy group Ring agents are preferably used.

Examples of the melamine compound, (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, all or part of the (poly) active methylol groups of the nitrogen compound such as methylol urea (CH ₂ OH groups) Mention may be made of compounds in which (at least two) are alkyletherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group or a butyl group, which may be identical to or different from each other. Moreover, the methylol group which is not alkyletherified may be self-condensing within one molecule, or may be condensed between two molecules to form an oligomer component as a result. Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used. Among these, alkyletherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable.

  In the above-mentioned colored photosensitive composition, a dye (A), a polymerizable compound (B) having an ethylenic unsaturated bond having an acid value, a photoradical polymerization initiator (C) and a monomer having an ethylenic unsaturated bond (D The content of the optional components (but excluding the organic solvent) other than the above is not limited as appropriate depending on the purpose of use, but preferably, the polymerizable compound (B) 100 having an ethylenically unsaturated bond having an acid value is used. It is 500 mass parts or less in total with respect to mass parts.

  Moreover, as a light source of the active light used when hardening the said coloring photosensitive composition, what light-emits the light of wavelength 300-450 nm can be used, For example, super-high pressure mercury, mercury vapor arc, a carbon arc , A xenon arc or the like can be used.

  Furthermore, by using a laser beam as an exposure light source, a laser direct writing method of directly forming an image from digital information of a computer or the like without using a mask improves not only productivity but also resolution and positional accuracy. It is useful because it can also be used, and light with a wavelength of 340 to 430 nm is suitably used as the laser light, but the visible to infrared region such as argon ion laser, helium neon laser, YAG laser, and semiconductor laser Are also used. When using these lasers, sensitizing dyes that absorb the relevant region of visible to infrared are added.

  The above-mentioned colored photosensitive composition (or the cured product thereof) may be a photocurable coating or varnish, a photocurable adhesive, a printed circuit board, or a liquid crystal display of color display such as a color television, a PC monitor, a portable information terminal or a digital camera. Color filter for panel, color filter for CCD image sensor, electrode material for plasma display panel, powder coating, printing ink, printing plate, adhesive, dental composition, resin for stereolithography, gel coat, photoresist for electronics , Structures for electroplating resists, etching resists, both liquid and dry films, solder resists, for manufacturing color filters for various display applications, or in the manufacturing process of plasma display panels, electroluminescent displays, and LCDs Resists for sealing, compositions for sealing electrical and electronic components, Dar resist, magnetic recording material, micro mechanical parts, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, stencils for screen printing, for producing three-dimensional objects by stereolithography Materials, holographic recording materials, image recording materials, microelectronics, bleaching materials, bleaching materials for image recording materials, bleaching materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, UV and It can be used for various applications such as photoresist materials for visible laser direct imaging systems, photoresist materials used to form dielectric layers in successive lamination of printed circuit boards, and protective films, and the applications are not particularly limited. .

  The colored photosensitive composition is used for the purpose of forming pixels of a color filter, and is particularly useful as a photosensitive composition for forming a color filter for a display device for an image display device such as a liquid crystal display panel.

  The color filter for a display device comprises the steps of (1) forming a coating film of the colored photosensitive composition on a substrate, and (2) irradiating the coating film with active light through a mask having a predetermined pattern shape. It is preferably formed by the steps of: (3) developing the film after exposure with a developer; and (4) heating the film after development. Moreover, the said coloring photosensitive composition is useful also as a coloring photosensitive composition of the inkjet system without a development process.

  EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples and the like, but the present invention is not limited to these examples and the like.

Examples 1-1 and 1-2 Compound No. 1 1 and No. 1 Aldehyde (4 mmol), malononitrile (8 mmol), anhydrous piperazine (0.03 g) and dimethylacetamide (5 g) were put into a reaction vessel and dissolved, and the mixture was stirred at 80 ° C. for 5 hours. 7 g of ethanol was added dropwise for crystallization, and the obtained solid was filtered, washed with ethanol, concentrated, purified by silica gel column chromatography (developing solution: toluene), and dried to obtain a yellow solid. It was confirmed by ¹ H-NMR and IR that the obtained yellow solid is the desired product. The absorption wavelength characteristics were also measured. The results are shown in [Table 1] and [Table 2].

Examples 1-3 and 1-4 Compound No. 1 3 and No. Synthesis of 4 Aldehyde (4 mmol), ethyl cyanoacetate (8 mmol), anhydrous piperazine (0.03 g) and dimethylacetamide (5 g) were put into a reaction vessel and dissolved, and the mixture was stirred at 50 ° C. for 5 hours. Crystallization was performed by dropwise addition of 7 g of ethanol, and the obtained solid was filtered and washed with ethanol to obtain a yellow solid. It was confirmed by ¹ H-NMR and IR that the obtained yellow solid is the desired product. The absorption wavelength characteristics were also measured. The results are shown in [Table 1] and [Table 2].

Example 1-5 Compound No. 1 Aldehyde (4 mmol), malononitrile (12 mmol), anhydrous piperazine (0.04 g) and dimethylacetamide (5 g) were put into a reaction vessel and dissolved, and the mixture was stirred at 50 ° C. for 3 hours. Crystallization was performed by dropwise addition of 7 g of ethanol, and the obtained solid was filtered and washed with ethanol to obtain a yellow solid. It was confirmed by ¹ H-NMR and IR that the obtained yellow solid is the desired product. The absorption wavelength characteristics were also measured. The results are shown in [Table 1] and [Table 2].

Evaluation Example 1-1 to 1-5 Absorption wavelength characteristic evaluation The compound No. 1 obtained above was obtained. 1 to No. 5 and the above-mentioned comparative compound Nos. The absorption wavelength characteristics of 1 and 2 were evaluated with CHCl ₃ solution. The results are shown in [Table 3].

  From the results of the above [Table 3], it is clear that the dye (A) of the present invention containing the compound represented by the above general formula (1) has an appropriate absorption wavelength.

[Examples 2-1 to 2-5] Colored photosensitive composition No. 1 1 to No. Preparation of <Step 1> Photosensitive Composition No. 5 Preparation of 1 39.7 g of SPC-1000 (manufactured by Showa Denko KK) as component (B) and 9.2 g of A-9300-1-CL (manufactured by Shin-Nakamura Chemical Co., Ltd.) as component (D), (C) 0.8g of Irgacure OXE-01 (manufactured by BASF) as a component, 28.0g of PGMEA as a solvent, and 2.31g of FZ 2122 (manufactured by Toray Dow Corning) as another component are mixed until insoluble matter disappears Photosensitive composition No. 1; I got one.

<Step 2> Dye solution No. 1 to No. Preparation of Compound No. 5 obtained above as component (A). 1 to No. 1.90 g of dimethylacetamide was added to 0.10 g of each of 5 and stirred to dissolve.

<Step 3> Colored photosensitive composition No. 1 1 to No. Preparation of Photosensitive Composition No. 5 obtained in Step 1 No. 1 of 5.0 g and dye solution No. 1 obtained in step 2 1 to No. 5 and 1.0 g of each of them are mixed, and the colored photosensitive composition No. 1 of the present invention is mixed. 1 to No. I got 5 respectively.

Comparative Examples 2-1 and 2-2 Comparative Colored Photosensitive Composition No. 1 1 and No. 1 Preparation of Compound No. 2 of component (A) in step 2 of Example 2-1. Comparative compound No. 1 1 and No. 1 Comparative Coloring Photosensitive Composition No. 2 was changed in the same manner as in Example 2-1 except that it was changed to No. 2. 1 and No. 1 I got two.

Evaluation Examples 2-1 to 2-5 and Comparative Evaluation Examples 2-1 and 2-2 Evaluation of Heat Resistance by Firing The above-obtained colored photosensitive composition No. 1 was obtained. 1 to No. 5 and Comparative Colored Photosensitive Composition No. 5 1 and No. 1 Each 2 was applied to a glass substrate under the condition of 410 rpm × 7 sec and dried on a hot plate (90 ° C., 90 sec). The obtained coating film was exposed to light (150 mJ / cm ² ) using an extra-high pressure mercury lamp. The coated film after exposure was fired at 230 ° C. for 30 minutes. The absorbance of the coating before baking (after exposure) and the absorbance of the coating after baking at the maximum absorption wavelength (λmax) of the compound (dye) used were measured, and the absorbance of the coating before baking (after exposure) was 100 The ratio of the absorbance of the coating film after firing was evaluated as the relative intensity. The heat resistance is higher as the absorbance of the coating film after firing is closer to 100. The results are shown in [Table 4].

  From the above results, it is clear that the colored photosensitive composition of the present invention has high heat resistance.

[Evaluation Examples 3-1 to 3-5 and Comparative Evaluation Examples 3-1 and 3-2] Evaluation of Light Resistance The colored photosensitive composition No. 1 obtained as described above. 1 to No. 5 and Comparative Colored Photosensitive Composition No. 5 1 and No. 1 Each 2 was applied to a glass substrate under the condition of 410 rpm × 7 sec and dried on a hot plate (90 ° C., 90 sec). The obtained coating film was exposed to light (150 mJ / cm ² ) using an extra-high pressure mercury lamp. The coated film after exposure was subjected to a light resistance test for 12 hours using a Suga Test Instruments Xenon Light Resistance Tester Table Sun XT-1500L. The absorbance of the coating before the light resistance test at the maximum absorption wavelength (λmax) of the compound (dye) used and the absorbance of the coating after the light resistance test were measured, and the absorbance of the coating before the light resistance test was 100. The ratio of the absorbance of the coating after the light resistance test was evaluated as the relative intensity. In addition, it shows that light resistance is so high that the light absorbency of the coating film after a light resistance test is close to 100. The evaluation results are shown in [Table 5].

  From the above results, it is clear that the colored photosensitive composition of the present invention has high light resistance.

  From the above results, it is clear that the dye using the novel compound of the present invention has absorption in an appropriate wavelength range, and the heat resistance and light resistance of the photosensitive composition using the dye and the cured product thereof are high. It is clear. Thus, the novel compound and the colored photosensitive composition of the present invention are useful for color filters for display devices and liquid crystal display panels using the same.

Claims (5)

The compound which is represented by following General formula (1), or is at least 1 sort (s) among the compound shown to the following group A, the following group B, the following group C, and the following group D.

(Wherein, A represents a benzene ring, and this ring is a halogen atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a halogenated alkyl group or a halogenated alkoxy group) It may be substituted,
Y represents a cyano group or -COOR ⁴ ;
R ¹ represents a hydrogen atom,
R ² and R ³ each independently represent an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,
The alkyl group, aryl group and arylalkyl group represented by R ² and R ³ may be substituted with a halogen atom or a nitro group,
The methylene group in the alkyl group and arylalkyl group represented by R ² and R ³ may be replaced by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH- ,
R ⁴ represents an alkyl group having 1 to 12 carbon atoms,
The methylene group in the alkyl group represented by R ⁴ may be replaced by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-,
X represents an organic group satisfying the following condition <1> or <2>,
m is an integer of 2 to 3. )
<1> m = 2 and X is represented by the following formula (2).

(Wherein, X ¹ represents a divalent aliphatic hydrocarbon group obtained by removing two hydrogen atoms from a hydrocarbon compound selected from the following group α , a divalent aromatic hydrocarbon group having 6 to 35 carbon atoms Or a group selected from group 1 below,
The group α is ethane, propane, iso-propane, butane, sec-butane, tert-butane, iso-butane, hexane, 2-methylhexane, 3-methylhexane, heptane, 2-methylheptane, 3-methylheptane , iso- heptane, tert- heptane, 1-methyl-octane, iso- octane, tert- octane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, consists cycloheptane, 2,4-dimethyl-cyclobutane and 4-methylcyclohexanol down ,
The divalent aliphatic hydrocarbon group obtained by removing two hydrogen atoms from the hydrocarbon compound selected from the group α is a cyano group, a nitro group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogenated alkyl group Or may be substituted with a halogenated alkoxy group,
A methylene group in a divalent aliphatic hydrocarbon group obtained by removing two hydrogen atoms from a hydrocarbon compound selected from the above group α is replaced by a group combining -CO-, -CO-O- or a combination thereof Well,
Z ¹ and Z ² each independently represent a direct bond, -O-, -S-, -SO ₂ -or -SO-,
However, the group represented by the above general formula (2) is in the range of 1 to 35 carbon atoms. )

(In the formula, p represents an integer of 1 to 3; q represents an integer of 0 to 3; r 1 represents an integer of 2 to 4 or 6 to 19; r 2 represents an integer of 1 to 9 )
<2> m = 3, and X is represented by the following formula (3).

(Wherein, X ² represents a trivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms,
Z ^{1 to} Z ³ are each independently the same as the groups represented by Z ¹ and Z ² in the general formula (2).
However, the group represented by the above general formula (3) is in the range of 1 to 35 carbon atoms. )

  A coloring composition comprising the compound according to claim 1. A dye (A) comprising at least one compound according to claim 1;
Polymerizable compound (B) having an ethylenically unsaturated bond having an acid value,
Colored photosensitive composition containing a radical photopolymerization initiator (C) and a monomer (D) having an ethylenically unsaturated bond.   A cured product of the colored photosensitive composition according to claim 3.   The color filter for display devices which uses the hardened | cured material of Claim 4.