JP6027753B2 - Colored alkali-developable photosensitive composition - Google Patents

Description

  The present invention relates to a colored alkali-developable photosensitive composition containing a cyanine compound having a specific structure and a polymerizable compound, and a color filter using the colored alkali-developable 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 devices (LCD), plasma display panels (PDP). ), An electroluminescence display (ELD), a cathode ray tube display (CRT), a fluorescent display tube, and an optical display element such as a field emission display.

In an optical filter for an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), a cathode ray tube display device (CRT), a fluorescent display tube, a field emission display, etc., 300 Various compounds that absorb light having a wavelength of ˜1100 nm are used as light absorbers.
These light absorbers are required to have particularly steep light absorption, that is, having a small half-value width of λmax and not to lose its function due to light, heat, or the like.

An optical filter mainly used for a liquid crystal display (LCD) includes a color filter. In general, three primary colors of RGB have been used for a color filter, but it is difficult to have a pure RGB hue with a single color material, and a pure RGB hue using a plurality of color materials. Efforts have been made to get closer to. Therefore, color materials such as yellow, orange and purple are required instead of RGB.
Organic and / or inorganic pigments have been used as light absorbers for color filters due to their high heat resistance. However, since they are pigments, there is a problem in that the luminance of a display device is lowered. This problem has been solved by increasing the brightness of the. However, with the trend toward lower power consumption, development of color filters using materials with high heat resistance has become active. As such a material having high heat resistance, Patent Documents 1 and 2 disclose dyes using a compound having a specific structure. Patent Documents 3 to 5 disclose colored alkali-developable photosensitive compositions containing a photopolymerizable monomer and a dye.
However, the dyes and colored alkali-developable resin compositions described in these documents are not satisfactory in terms of heat resistance.

International Patent Application Publication No. WO 1986/04694 JP-A-08-109335 Japanese Patent Laid-Open No. 08-227153 JP 2004-029518 A JP 2004-295116 A

  Accordingly, an object of the present invention is to provide a colored alkali-developable photosensitive composition having excellent heat resistance. Another object of the present invention is to provide an optical filter using the colored alkali-developable photosensitive composition, particularly a color filter suitable for an image display device such as a liquid crystal display panel without reducing the luminance. is there.

  As a result of extensive studies, the present inventor has found that a colored alkali-developable photosensitive composition containing a cyanine compound and a polymerizable compound having a specific structure is excellent in heat resistance. The present inventors have found that the developable photosensitive composition is suitable for a color filter for an image display device such as a liquid crystal display panel without reducing the luminance of an optical filter (particularly a color filter), and has reached the present invention.

The present invention provides at least one cyanine compound (A) represented by the following general formula (IA), an alkali-developable resin (B) having an ethylenically unsaturated bond represented by the following general formula (II), and 2- Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one or 1,2-propanedione, 1- [4-[[4- (2-hydroxyethoxy) phenyl] thio] phenyl A colored alkali-developable photosensitive composition containing a photopolymerization initiator (C) that is any one of 2- (O-acetyloxime) is provided.

（式中、環Ａ及び環Ａ’は、それぞれ独立に、Ｒ³若しくはＲ^3'で置換されてもよいベンゼン環又は無置換のナフタレン環を表し、
Ｒ³及びＲ^3'は、それぞれ独立に、ハロゲン原子又はシアノ基を表し、
ｒ及びｒ’は、それぞれ独立に０又は１を表し、
Ａｎ^q-はビス（トリフルオロメタンスルホニル）イミド酸塩を表し、
Ｘ及びＸ’は、それぞれ独立に、−ＣＲ⁵¹Ｒ⁵² −を表し、
Ｒ ⁵¹ 及びＲ ⁵² は、それぞれ独立に、水素原子、水酸基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数１〜８のアルキル基を表し、該アリール基、該アリールアルキル基及び該アルキル基は、水酸基、ハロゲン原子、ニトロ基、シアノ基、−ＳＯ ₃ Ｈ、カルボキシル基、アミノ基、アミド基又はフェロセニル基で置換されていてもよく、
Ｚ¹¹、Ｚ¹²及びＺ¹³は水素原子を表し、
Ｙ及びＹ’は、それぞれ独立に、ハロゲン原子で置換されてもよい炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数１〜８のアルキル基を表し、上記Ｙ及びＹ’におけるアリールアルキル基及びアルキル基中のメチレン基は、−Ｏ―、−ＣＯ−、−ＣＯＯ―、−ＯＣＯ−、−ＣＯＮＨ−、―ＮＨＣＯ−、又は２重結合で中断されていてもよい。）

（式中、Ｘ¹¹は水素原子又はメチル基を表し、
Ｙ¹¹は、下記一般式（１）で表される二価の結合基であり、
Ｒ¹¹は、炭素原子数１〜２０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、上記Ｒ¹¹におけるアルキル基、アリール基及びアリールアルキル基は、ハロゲン原子又は水酸基で置換されていてもよく、上記Ｒ¹¹におけ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、−Ｏ―、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−又はこれらの基を複数組み合わせた基で中断されていてもよく、
Ｒ¹²、Ｒ¹³及びＲ¹⁴は、それぞれ独立に、水素原子又はメチル基であり、
０．１≦ｔ≦０．６５、０．３≦ｍ≦０．８、０≦ｎ≦０．２であり、ｔ＋ｍ＋ｎ＝１である。）

（式中、Ｘ¹は、二価の炭素原子数１〜３５の鎖状炭化水素基又は二価の炭素原子数３〜３５の脂環式炭化水素で表される基を表し、
Ｚ ¹ 及びＺ²は、直接結合を表す。
但し、上記一般式（１）で表される基の炭素原子数は１〜３５の範囲内である。）

(Wherein, ring A and ring A ′ each independently represent a benzene ring or an unsubstituted naphthalene ring which may be substituted with R ³ or R ^{3 ′} ;
R ³ and R ^{3 ′} each independently represent a halogen atom or a cyano group ,
r and r ′ each independently represents 0 or 1,
An ^q− represents bis (trifluoromethanesulfonyl) imidate ,
X and X ′ each independently represent —CR ⁵¹ R ⁵² — ,
R ⁵¹ and R ⁵² each independently represent a hydrogen atom, a hydroxyl group, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkyl group having 1 to 8 carbon atoms, The aryl group, the arylalkyl group and the alkyl group may be substituted with a hydroxyl group, a halogen atom, a nitro group, a cyano group, —SO ₃ H, a carboxyl group, an amino group, an amide group or a ferrocenyl group,
Z ¹¹ , Z ¹² and Z ¹³ represent a hydrogen atom,
Y and Y ′ each independently represent an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkyl group having 1 to 8 carbon atoms, which may be substituted with a halogen atom. In the above Y and Y ′, the arylalkyl group and the methylene group in the alkyl group are interrupted by —O—, —CO—, —COO—, —OCO—, —CONH—, —NHCO—, or a double bond. It may be. )

(Wherein X ¹¹ represents a hydrogen atom or a methyl group,
Y ¹¹ is a divalent linking group represented by the following general formula (1),
R ¹¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms, and the alkyl group, aryl group, and arylalkyl group in R ¹¹ above. May be substituted with a halogen atom or a hydroxyl group, and the methylene group in the alkyl group and arylalkyl group in R ¹¹ represents —O—, —CO—, —COO—, —OCO— or these groups. May be interrupted by a combination of several,
R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group,
0.1 ≦ t ≦ 0.65, 0.3 ≦ m ≦ 0.8, 0 ≦ n ≦ 0.2, and t + m + n = 1. )

(Wherein, X ¹ represents a divalent chain hydrocarbon group or a divalent group represented by alicyclic hydrocarbon having a carbon number of 3 to 35 carbon atoms 1 to 35,
Z ¹ and Z ² represent a direct bond.
However, the number of carbon atoms of the group represented by the general formula (1) is in the range of 1 to 35. )

  The present invention also provides a cured product of the colored alkali-developable photosensitive composition, a color filter for a display device using the cured product, and a liquid crystal display panel or organic EL display using the color filter for the display device. A panel is provided.

  The colored alkali-developable photosensitive composition of the present invention containing a cyanine compound and a polymerizable compound having a specific structure is excellent in heat resistance. Moreover, the cured product is suitable for a color filter for a display device.

  Hereinafter, the colored alkali-developable photosensitive composition of the present invention (hereinafter also simply referred to as a colored composition) will be described based on preferred embodiments.

  The colored composition of the present invention comprises at least one cyanine compound (A) represented by the above general formula (I) (hereinafter also referred to as cyanine compound (A)), an alkali-developable resin having an ethylenically unsaturated bond ( B) (hereinafter also referred to as alkali-developable resin (B)), a photopolymerization initiator (C), and, if necessary, further contain an inorganic color material and / or an organic color material (D). Hereinafter, each component will be described in order.

<Cyanine compound (A)>
The cyanine compound (A) used in the coloring composition of the present invention is represented by the above general formula (I).

As the halogen atom represented by R ⁵¹ and R ⁵² and Z ¹¹ , Z ¹² and Z ¹³ in R ¹ , R ¹ ′, R ² , R ² ′, X and X ′ in the general formula (I), Fluorine, chlorine, bromine, iodine,
Examples of the metallocenyl group represented by R ¹ , R ¹ ′, R ² and R ² in the general formula (I) include ferrocenyl, nickelocenyl, zirconocenyl, titanocenyl, hafnocenyl,
R ⁵¹ and R ⁵² , Z ¹¹ , Z ¹² and Z ¹³ in R ¹ , R ¹ ′, R ² and R ² ′ X and X ′ in the general formula (I), and R and R ′ in Z ′ Examples of the aryl group having 6 to 30 carbon atoms represented by: phenyl, naphthyl, 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-stearyl Phenyl, 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-butylphenyl, 2,6-di-tert-butylphenyl, 2,4-di-tert-pentyl Phenyl, 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 30 carbon atoms include benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, ferrocenylmethyl, ferrocenylpropyl and the like. ,
Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl, tert-amyl, hexyl, 2- Examples include hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl, tert-octyl and the like.
The aryl group, arylalkyl group and alkyl group in R ¹ , R ¹ ′, R ² , R ² ′, Z ¹¹ , Z ¹² , Z ¹³ , R, R ′, R ⁵¹ and R ⁵² are a hydroxyl group or a halogen atom. , A nitro group, a cyano group, —SO ₃ H, a carboxyl group, an amino group, an amide group or a ferrocenyl group, and the above R ¹ , R ¹ ′, R ² , R ² ′, Z ¹¹ , Z ¹² , Z ¹³ , R, R ′, R ⁵¹ and R ^52, an aryl group, an arylalkyl group and a methylene group in the alkyl group are —O—, —S—, —CO—, —COO—, —OCO—. , —SO ₂ —, —NH—, —CONH—, —NHCO—, —N═CH— or a double bond may be interrupted, and the number and position of these substitutions and interruptions are arbitrary.
For example, examples of the group in which the alkyl group having 1 to 8 carbon atoms is substituted with a halogen atom include chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, and nonafluorobutyl. And
Examples of the group in which the alkyl group having 1 to 8 carbon atoms is interrupted by —O— include methyloxy, ethyloxy, iso-propyloxy, propyloxy, butyloxy, pentyloxy, iso-pentyloxy, hexyloxy, heptyl Alkoxy groups such as oxy, octyloxy, 2-ethylhexyloxy, 2-methoxyethyl, 2- (2-methoxy) ethoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 4-methoxybutyl, 3-methoxybutyl, etc. An alkoxyalkyl group of
Examples of the group in which the alkyl group having 1 to 8 carbon atoms is substituted with a halogen atom and interrupted by -O- include, for example, chloromethyloxy, dichloromethyloxy, trichloromethyloxy, fluoromethyloxy, difluoromethyloxy , Trifluoromethyloxy, nonafluorobutyloxy and the like.

In the general formula (I), R ¹ and R ² or R ¹ ′ and R ² ′, Z ¹¹ and Z ¹² , Z ¹¹ and Z ¹³ , Z ¹² and Z ¹³ can form a ring structure with each other, R ⁵¹ or The ring structure that R ⁵² can be bonded to R ¹ includes benzene ring, naphthalene ring, cyclohexane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, piperidine ring, piperazine ring, pyrrolidine ring. , Morpholine ring, thiomorpholine ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, quinoline ring, isoquinoline ring, imidazole ring, oxazole ring, imidazolidine ring, pyrazolidine ring, isoxazolidine ring, isothiazolidine Rings and the like are mentioned, and these rings may be condensed or substituted with other rings.

  In the above general formula (I), the cycloalkane-1,1-diyl group having 3 to 6 carbon atoms represented by X and X ′ includes cyclopropane-1,1-diyl, cyclobutane-1,1- Examples include diyl, 2,4-dimethylcyclobutane-1,1-diyl, 3,3-dimethylcyclobutane-1,1-diyl, cyclopentane-1,1-diyl, cyclohexane-1,1-diyl and the like.

In the general formula (I), substituted with a hydroxyl group, a halogen atom, a nitro group, a cyano group, a —SO ₃ H group, a carboxyl group, an amino group, an amide group or a metallocenyl group represented by Y, Y ′ and Y ¹² Examples of the aryl group having 6 to 30 carbon atoms, the arylalkyl group having 7 to 30 carbon atoms, and the alkyl group having 1 to 20 carbon atoms include aryl groups and arylalkyls exemplified in the description of R ^{1 and the} like. Groups, alkyl groups, and hydrogen atoms in these groups are substituted with a hydroxyl group, a halogen atom, a nitro group, a cyano group, a —SO ₃ H group, a carboxyl group, an amino group, an amide group or a metallocenyl group. The position and number of these substituents are not limited.
In addition, the aryl group, arylalkyl group and methylene group in the alkyl group in Y, Y ′ and Y ¹² are —O—, —S—, —CO—, —COO—, —OCO—, —SO _2. It may be interrupted by-, -NH-, -CONH-, -NHCO-, -N = CH- or a double bond. Examples of such substituents include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl, tert-amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl, tert-octyl, 2-ethylhexyl, nonyl, iso-nonyl Alkyl groups such as decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl; phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-iso-propyl Nyl, 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, cyclohexylphenyl and other aryl groups; benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, etc. , Interrupted by thioether bonds, etc. For example, 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-butoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-phenoxyethyl, 3-phenoxypropyl, 2-methylthio Examples thereof include ethyl and 2-phenylthioethyl.

The q-valent anion represented by pAn ^q- in the general formula (I) (excluding perchlorate anion) includes methanesulfonate anion, dodecylsulfonate anion, benzenesulfonate anion, toluenesulfonic acid Anion, trifluoromethanesulfonate anion, naphthalenesulfonate anion, diphenylamine-4-sulfonate anion, 2-amino-4-methyl-5-chlorobenzenesulfonate anion, 2-amino-5-nitrobenzenesulfonate anion, 235999, JP 10-337959, JP 11-102088, JP 2000-108510, JP 2000-168223, JP 2001-209969, JP 2001-322354, JP 2006-248180, JP 2006-2979. 7, in addition to organic sulfonate anions such as sulfonate anions described in JP-A-8-253705, JP-T-2004-503379, JP-A-2005-336150, International Publication 2006/28006, etc. Chloride ion, bromide ion, iodide ion, fluoride ion, chlorate ion, thiocyanate ion, hexafluorophosphate ion, hexafluoroantimonate ion, tetrafluoroborate ion, octyl phosphate ion, dodecyl phosphate ion, Octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, 2,2'-methylenebis (4,6-di-t-butylphenyl) phosphonate ion, tetrakis (pentafluorophenyl) borate ion, excited state De-excited active molecules in Nchingu is allowed) carboxyl group or a phosphonic acid group to the quencher anion or a cyclopentadienyl ring having the function, ferrocene having anionic groups such as sulfonic acid group, a metallocene compound anion such as Ruteosen like.

  Specific examples of the cyanine compound (A) used in the present invention include the following compound No. 1-1 to 1-66. In the following examples, cyanine cations without anions are shown.

  Among the cyanine compounds (A) represented by the general formula (I), the compounds represented by the following general formula (IA) are preferable because the raw materials can be easily obtained and produced.

（式中、環Ａ及び環Ａ’は、それぞれ独立に、ベンゼン環、ナフタレン環、フェナントレン環又はピリジン環を表し、
Ｒ³及びＲ³’は、それぞれ独立に、水酸基、ハロゲン原子、ニトロ基、シアノ基、−ＳＯ₃Ｈ、カルボキシル基、アミノ基、アミド基、フェロセニル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数１〜８のアルキル基を表し、
上記Ｒ³及びＲ³’におけるアリール基、アリールアルキル基及びアルキル基は、水酸基、ハロゲン原子、ニトロ基、シアノ基、−ＳＯ₃Ｈ、カルボキシル基、アミノ基、アミド基又はフェロセニル基で置換されていてもよく、上記Ｒ³及びＲ³’におけるアリール基、アリールアルキル基及びアルキル基中のメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＳＯ₂−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｎ＝ＣＨ−又は二重結合で中断されていてもよく、
ｒ及びｒ’は、それぞれ独立に、０又は環Ａ及び環Ａ’において置換可能なＲ³又はＲ³’の数を表し、
Ａｎ^q-はｑ価の有機スルホン酸アニオンを表し、ｑは１又は２を表し、ｐは電荷を中性に保つ係数を表し、
Ｘ、Ｘ’、Ｚ¹¹、Ｚ¹²、Ｚ¹³、Ｙ及びＹ’は、上記一般式（Ｉ）と同じである。）

(Wherein, ring A and ring A ′ each independently represent a benzene ring, a naphthalene ring, a phenanthrene ring or a pyridine ring,
R ³ and R ³ ′ are each independently a hydroxyl group, a halogen atom, a nitro group, a cyano group, —SO ₃ H, a carboxyl group, an amino group, an amide group, a ferrocenyl group, an aryl group having 6 to 30 carbon atoms, Represents an arylalkyl group having 7 to 30 carbon atoms or an alkyl group having 1 to 8 carbon atoms;
The aryl group, arylalkyl group and alkyl group in R ³ and R ³ ′ are substituted with a hydroxyl group, a halogen atom, a nitro group, a cyano group, —SO ₃ H, a carboxyl group, an amino group, an amide group or a ferrocenyl group. The aryl group, arylalkyl group and methylene group in the alkyl group in R ³ and R ³ ′ are —O—, —S—, —CO—, —COO—, —OCO—, —SO _2. -, -NH-, -CONH-, -NHCO-, -N = CH- or may be interrupted by a double bond,
r and r ′ each independently represents 0 or the number of R ³ or R ³ ′ that can be substituted in ring A and ring A ′;
An ^q− represents a q-valent organic sulfonate anion, q represents 1 or 2, p represents a coefficient for maintaining a neutral charge,
X, X ′, Z ¹¹ , Z ¹² , Z ¹³ , Y and Y ′ are the same as those in the general formula (I). )

The halogen atom represented by R ³ and R ³ ′ in the general formula (IA), an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkyl group having 1 to 8 carbon atoms As the aryl group, arylalkyl group and alkyl group exemplified in the description of R ¹ etc. in the general formula (I),
The aryl group, arylalkyl group and alkyl group in R ³ and R ³ ′ are substituted with a hydroxyl group, a halogen atom, a nitro group, a cyano group, —SO ₃ H, a carboxyl group, an amino group, an amide group or a ferrocenyl group. The aryl group, arylalkyl group and methylene group in the alkyl group in R ³ and R ³ ′ are —O—, —S—, —CO—, —COO—, —OCO—, —SO _2. It may be interrupted by-, -NH-, -CONH-, -NHCO-, -N = CH- or a double bond, and the number and position of these substitutions and interruptions are arbitrary.

Examples of the organic sulfonate ion represented by pAn ^q− in the general formula (I) include the organic sulfonate ions exemplified as the anion represented by pAn ^q− in the general formula (I).
Among these organic sulfonate ions, since acquisition and production of raw materials are easy, methanesulfonate anion, 1-butanesulfonate anion, 1-hexanesulfonate anion, 1-heptanesulfonate anion, hydroxypropanesulfonic acid Anion, 2-aminoethanesulfonic acid anion, p-toluenesulfonic acid anion, 1,3-benzenedisulfonic acid, 3-aminobenzenesulfonic acid, 1-naphthol-8-sulfonic acid anion, p-styrenesulfonic acid anion, allyl Sulfonate anion, methacryloxyisethionate anion, methacryloxypropane sulfonate anion, 2-acrylamido-2-methylpropane sulfonate anion, trifluoromethanesulfonate anion, bis (trifluoromethanesulfonyl Imido acid anion is preferable, p-toluenesulfonic acid anion, 1,3-benzenedisulfonic acid anion, 1-naphthol-8-sulfonic acid anion, methacryloxypropanesulfonic acid anion, bis (trifluoromethanesulfonyl) imidic acid anion are more. preferable.

Among the compounds represented by the general formula (IA), the following are preferable.
Ring A or ring A ′ is preferably a benzene ring or a naphthalene ring.
r or r ′ is preferably 0 to 2.
When r or r ′ is 1 or more, R ³ and R ³ ′ are a halogen atom, a nitro group, a carboxyl group, a ferrocenyl group, an unsubstituted alkyl group having 1 to 8 (particularly 1 to 4) carbon atoms, or carbon A halogen-substituted alkyl group having 1 to 8 atoms (particularly 1 to 4 atoms) is preferred.
Z ¹¹ , Z ¹² and Z ¹³ may be substituted with a hydrogen atom, a halogen atom, and a halogen atom or a nitro group, and may have 6 to 30 carbon atoms which may be interrupted with an oxygen atom or a sulfur atom. Particularly, an aryl group having 6 to 12), an arylalkyl group having 7 to 30 carbon atoms (particularly 7 to 15), and an alkyl group having 1 to 8 carbon atoms (particularly 1 to 4) are preferable, and a hydrogen atom or a halogen atom. An alkyl group having 1 to 4 carbon atoms is more preferable.
X and X ′ are an oxygen atom, a sulfur atom, —CR ⁵¹ R ⁵² — [particularly, R ⁵¹ and R ⁵² may be unsubstituted or substituted by a halogen atom, or may be interrupted by a double bond. C1-C8 (especially 1-4) alkyl groups, unsubstituted or substituted with halogen atoms and optionally interrupted with double bonds 7-20 (especially 7- 15) arylalkyl group] or a cycloalkane-1,1-diyl group having 3 to 6 carbon atoms, preferably an oxygen atom, a sulfur atom, —CR ⁵¹ R ⁵² — [particularly, R ⁵¹ and R ⁵² are unsubstituted. More preferably an alkyl group having 1 to 4 carbon atoms].
Y and Y ′ may be substituted with a halogen atom, a nitro group, a carboxyl group or a ferrocenyl group, and may have 6 to 30 carbon atoms (particularly 6 to 12) optionally interrupted by an oxygen atom or —CO—. An aryl group having 7 to 30 carbon atoms (especially 7 to 15 carbon atoms) or an alkyl group having 1 to 8 carbon atoms, which may be substituted with a halogen atom and interrupted with an oxygen atom. An arylalkyl group having 7 to 30 carbon atoms (especially 7 to 15 carbon atoms) or an alkyl group having 1 to 8 carbon atoms is more preferable.

  The production method of the cyanine compound (A) used in the present invention is not particularly limited, and can be obtained by a method using a well-known general reaction. For example, the route described in JP2010-209191A is used. And a method of synthesizing by reacting a compound having a corresponding structure with an imine derivative.

  The cyanine compound (A) preferably has a maximum absorption wavelength (λmax) of the coating film of 430 to 610 nm, and more preferably 480 to 600 nm. When the maximum absorption wavelength (λmax) of the coating film is less than 430 nm, the effect of the present invention is not exhibited because it does not absorb light of the target wavelength, and when it is larger than 610 nm, the heat resistance is lowered, which is not preferable.

  In the colored composition of the present invention, the content of the cyanine compound (A) is a single or a total of a plurality of types, and is preferably 0.01 to 50% by mass, more preferably 0.00% in the colored composition of the present invention. 1 to 30% by mass. When the content of the cyanine compound (A) is less than 0.01% by mass, a color having a desired concentration may not be obtained in the cured product of the present invention. When the content is more than 50% by mass, the cyanine is contained in the coloring composition. Precipitation of the compound (A) may occur.

<Alkali developable resin (B)>
The alkali-developable resin (B) is not particularly limited as long as it has an ethylenically unsaturated bond, and those conventionally used in photosensitive compositions can be used, but the following general formula (II) Is preferable because it has high developability and heat resistance.

（式中、Ｘ¹¹は水素原子又はメチル基を表し、Ｙ¹¹は、二価の結合基であり、Ｒ¹¹は、炭素原子数１〜２０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、
上記Ｒ¹¹におけるアルキル基、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、上記Ｒ¹¹におけ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、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨ−、又はこれらの基を複数組み合わせた基で中断されていてもよく、Ｒ¹²、Ｒ¹³及びＲ¹⁴は、それぞれ独立に、水素原子又はメチル基であり、０．１≦ｔ≦０．６５、０．３≦ｍ≦０．８、０≦ｎ≦０．２であり、ｔ＋ｍ＋ｎ＝１である。）

(In the formula, X ¹¹ represents a hydrogen atom or a methyl group, Y ¹¹ is a divalent linking group, R ¹¹ is an alkyl group having 1 to 20 carbon atoms, or 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 in R ¹¹ may be substituted with a halogen atom, a hydroxyl group, or a nitro group, and the methylene group in the alkyl group and arylalkyl group in R ¹¹ is —O—, -S-, -CO-, -COO-, -OCO-, -NH-, or a group formed by combining a plurality of these groups may be interrupted, and R ¹² , R ¹³ and R ¹⁴ are each independently , A hydrogen atom or a methyl group, 0.1 ≦ t ≦ 0.65, 0.3 ≦ m ≦ 0.8, 0 ≦ n ≦ 0.2, and t + m + n = 1. )

Examples of the divalent linking group represented by Y ¹¹ in the general formula (II) include a structure represented by the following general formula (1).

（式中、Ｘ¹は、−ＣＲ²⁰Ｒ²¹−、−ＮＲ²⁰−、二価の炭素原子数１〜３５の鎖状炭化水素基、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の芳香族炭化水素基、二価の炭素原子数２〜３５の複素環基、これらの基を複数組み合わせた基又は下記〔化１３〕〜〔化１５〕で表される基を表し、Ｒ²⁰及びＲ²¹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、Ｚ¹及びＺ²は、それぞれ独立に、直接結合、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＳＯ−、−ＮＲ¹⁰−又は−ＰＲ¹⁰−を表し、Ｒ¹⁰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、
上記Ｒ²⁰、Ｒ²¹及びＲ¹⁰におけるアルキル基、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、上記Ｒ²⁰、Ｒ²¹及びＲ¹⁰におけ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、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨ−、又はこれらの基を複数組み合わせた基で中断されていてもよい。但し、上記一般式（１）で表される基の炭素原子数は１〜３５の範囲内である。）

(In the formula, X ¹ is —CR ²⁰ R ²¹ —, —NR ²⁰ —, a divalent chain hydrocarbon group having 1 to 35 carbon atoms, and an alicyclic carbon atom having 3 to 35 carbon atoms. A hydrogen group, a divalent aromatic hydrocarbon group having 6 to 35 carbon atoms, a divalent heterocyclic group having 2 to 35 carbon atoms, a group obtained by combining a plurality of these groups, or the following [Chemical Formula 13] to [Chemical Formula] 15], wherein R ²⁰ and R ²¹ are 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. Z ¹ and Z ² each independently represents a direct bond, —O—, —S—, —SO ₂ —, —SO—, —NR ¹⁰ — or —PR ¹⁰ —, wherein R ¹⁰ is 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 alkyl group, aryl group and arylalkyl group in R ²⁰ , R ²¹ and R ¹⁰ may be substituted with a halogen atom, hydroxyl group or nitro group, and the alkyl group and aryl in R ²⁰ , R ²¹ and R ¹⁰ above. The methylene group in the alkyl group may be interrupted by —O—, —S—, —CO—, —COO—, —OCO—, —NH—, or a group obtained by combining a plurality of these groups. However, the number of carbon atoms of the group represented by the general formula (1) is in the range of 1 to 35. )

（式中、Ｚ¹¹は、炭素原子数１〜１０のアルキル基若しくは炭素原子数１〜１０のアルコキシ基により置換されてもよいフェニル基、炭素原子数１〜１０のアルキル基若しくは炭素原子数１〜１０のアルコキシ基により置換されてもよい炭素原子数３〜１０のシクロアルキル基、又は、水素原子を表し、Ｙ¹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、上記Ｙ¹におけるアルキル基、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てもよく、ｄは０〜５の整数である。）

(In the formula, Z ¹¹ is a phenyl group which may be substituted with an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or 1 carbon atom. Represents a cycloalkyl group having 3 to 10 carbon atoms which may be substituted by an alkoxy group having 10 to 10 carbon atoms, or a hydrogen atom, and Y ¹ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. Represents an alkenyl group having 2 to 10 carbon atoms or a halogen atom, the alkyl group, alkoxy group and alkenyl group in Y ¹ may be substituted with a halogen atom, and d is an integer of 0 to 5. )

（式中、Ｙ²及びＺ¹²は、それぞれ独立して、ハロゲン原子で置換されてもよい炭素原子数１〜１０のアルキル基、ハロゲン原子で置換されてもよい炭素原子数６〜２０のアリール基、ハロゲン原子で置換されてもよい炭素原子数６〜２０のアリールオキシ基、ハロゲン原子で置換されてもよい炭素原子数６〜２０のアリールチオ基、ハロゲン原子で置換されてもよい炭素原子数８〜２０のアリールアルケニル基、ハロゲン原子で置換されてもよい炭素原子数７〜２０のアリールアルキル基、ハロゲン原子で置換されてもよい炭素原子数２〜２０の複素環基、これらの基を複数組み合わせた基、又はハロゲン原子を表し、上記Ｙ²及びＺ¹²におけ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−で中断されていてもよく、Ｚ¹²は、隣接するＺ¹²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。）

Wherein Y ² and Z ¹² are each independently an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or an aryl having 6 to 20 carbon atoms which may be substituted with a halogen atom. Group, an aryloxy group having 6 to 20 carbon atoms that may be substituted with a halogen atom, an arylthio group having 6 to 20 carbon atoms that may be substituted with a halogen atom, and the number of carbon atoms that may be substituted with a halogen atom An arylalkenyl group having 8 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom, a heterocyclic group having 2 to 20 carbon atoms which may be substituted with a halogen atom, and these groups; A plurality of groups or halogen atoms are represented, and the methylene group in the alkyl group and arylalkyl group in Y ² and Z ¹² is interrupted by an unsaturated bond, —O— or —S—. Z ¹² may form a ring with adjacent Z ¹² , e represents a number of 0 to 4, f represents a number of 0 to 8, and g represents 0 to 4 And h represents a number from 0 to 4, and the total number of g and h is 2 to 4.)

Examples of the aryl group having 6 to 20 carbon atoms or the arylalkyl group having 7 to 20 carbon atoms represented by R ¹¹ in the general formula (II) are exemplified in the description of the cyanine compound as the component (A). An aryl group or an arylalkyl group is mentioned.
Examples of the alkyl group having 1 to 20 carbon atoms include nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, heptadecyl, octadecyl and the like in addition to the alkyl group exemplified in the description of the cyanine compound (A). It is done.

In the general formula (1), the divalent chain hydrocarbon group having 1 to 35 carbon atoms represented by X ¹ includes methane, 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-methyloctane, iso-octane, tert-octane And the like include groups substituted with Z ¹ and Z ² ,
The divalent alicyclic hydrocarbon carbon atoms from 3 to 35, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2,4-dimethyl-cyclobutane, 4-methylcyclohexane etc., Z ¹ and Z ² A group substituted with
Examples of the divalent aromatic hydrocarbon having 6 to 35 carbon atoms include groups in which groups such as phenylene, naphthylene, and biphenyl are substituted with Z ¹ and Z ² .
The divalent heterocyclic carbon atoms from 3 to 35, pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexahydrotriazine, furan, tetrahydrofuran, chroman, xanthene, thiophene, thiolane etc., Z ¹ and Examples include a group substituted with Z ² , and a plurality of these groups may be combined.

As 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 represented by R ²⁰ , R ²¹ and R ¹⁰ in the general formula (1). Includes the alkyl group, aryl group and arylalkyl group exemplified in the description of the cyanine compound (A).
The alkyl group, aryl group and arylalkyl group in R ²⁰ , R ²¹ and R ¹⁰ may be substituted with a halogen atom, hydroxyl group or nitro group, and the alkyl group and aryl in R ²⁰ , R ²¹ and R ¹⁰ above. The methylene group in the alkyl group may be interrupted by —O—, —S—, —CO—, —COO—, —OCO—, —NH—, or a group obtained by combining a plurality of these groups. The replacement position and the interruption position are not particularly limited.

In the group represented by the above [Chemical Formula 13], an alkyl group having 1 to 10 carbon atoms represented by Z ¹¹ or an alkoxy group having 3 to 10 carbon atoms which may be substituted with an alkoxy group having 1 to 10 carbon atoms. Examples of the alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctyl and the like, and groups in which these groups are substituted with an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. Named,
Examples of the alkyl group having 1 to 10 carbon atoms and the halogen atom represented by Y ¹ include the alkyl group and the halogen atom exemplified in the description of the cyanine compound (A),
Examples of the alkoxy group having 1 to 10 carbon atoms include methyloxy, ethyloxy, propoxy, iso-propoxy, butyloxy, sec-butyloxy, tert-butyloxy, iso-butyloxy, amyloxy, iso-amyloxy, tert-amyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 1-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, iso-heptyloxy, tert-heptyloxy, 1-octyloxy, iso-octyl Oxy, tert-octyloxy 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 Y ¹ may be substituted with a halogen atom, and the substitution position is not limited.

In the group represented by the above [Chemical Formula 15], an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, or a halogen atom Examples of the arylalkyl group having 7 to 20 carbon atoms which may be substituted include the alkyl group, aryl group and arylalkyl group exemplified in the description of the cyanine compound (A), and a group in which these groups are substituted with a halogen atom. Are mentioned,
Examples of the aryloxy group having 6 to 20 carbon atoms which may be substituted with a halogen atom include phenyloxy, naphthyloxy, 2-methylphenyloxy, 3-methylphenyloxy, 4-methylphenyloxy and 4-vinylphenyloxy. 3-iso-propylphenyloxy, 4-iso-propylphenyloxy, 4-butylphenyloxy, 4-iso-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-dimethylphenyloxy, 3 , 4-Dimethylphenylo 3,5-dimethylphenyloxy, 2,4-di-tert-butylphenyloxy, 2,5-di-tert-butylphenyloxy, 2,6-di-tert-butylphenyloxy, 2,4- Groups such as di-tert-pentylphenyloxy, 2,5-di-tert-amylphenyloxy, 4-cyclohexylphenyloxy, 2,4,5-trimethylphenyloxy, ferrocenyloxy, etc., and these groups are halogen atoms A group substituted with
The arylthio group having 6 to 20 carbon atoms which may be substituted with a halogen atom is a group in which the oxygen atom of the aryloxy group having 6 to 20 carbon atoms which may be substituted with a halogen atom is substituted with a sulfur atom Etc.
As the aryl alkenyl group having 8 to 20 carbon atoms which may be substituted with a halogen atom, the oxygen atom of the aryloxy group having 6 to 20 carbon atoms which may be substituted with the halogen atom may be vinyl, allyl, 1 A group substituted with an alkenyl group such as -propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl, and the like;
Examples of the heterocyclic group having 2 to 20 carbon atoms which may be substituted with a halogen atom include pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexahydrotriazine, furan, tetrahydrofuran, chroman, xanthene, thiophene and thiolane. And groups in which these groups are substituted with a halogen atom.

Among the resins represented by the general formula (II), the following are preferable.
R ¹¹ is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
Y ¹¹ is a structure in which the divalent linking group is represented by the following general formula (1), X ¹ is preferably an alkylene group having 1 to 10 carbon atoms, and has 7 carbon atoms having a cycloalkylene group. 10 to 10 alkylene groups are more preferred.
Z ¹ and Z ² are preferably direct bonds.

  The alkali-developing resin (B) preferably has an acid value of 10 to 200 mg / KOH, more preferably 30 to 150 mg / KOH. If the acid value is less than 10 mg / KOH, sufficient alkali developability may not be obtained, and if it is greater than 200 mg / KOH, it may be difficult to produce the resin.

  In the colored composition of the present invention, the content of the alkali-developable resin (B) is preferably 30 to 99% by mass, particularly 60 to 95% by mass in the colored composition of the present invention. If the content of the alkali-developable resin (B) is less than 30% by mass, the cured product may have insufficient mechanical strength and may crack or develop poorly. If it is greater than 99% by mass, There are cases where the curing due to exposure becomes insufficient and tackiness occurs, or the development time becomes long and the cured portion is also damaged by an alkali.

<Photopolymerization initiator (C)>
As the photopolymerization initiator (C), conventionally known compounds can be used. For example, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzoin, benzyldimethyl ketal, 1-benzyl- 1-dimethylamino-1- (4′-morpholinobenzoyl) propane, 2-morpholyl-2- (4′-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl Anthraquinone, 4-benzoyl-4′-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4′-isopropyl) benzoylpropane, 4-butyl Benzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9′-acridinyl) heptane, 9-n-butyl-3,6-bis (2′-morpholinoisobutyroyl) carbazole, 2 -Methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s -Triazine, 2,2-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1-2'-biimidazole, 4,4-azobisisobutyronitrile, triphenylphosphine, Examples include camphorquinone and benzoyl peroxide, and commercially available products include N-1414, N-1717, N-1919, PZ-4. 8, (manufactured by (Corporation) ADEKA Corporation) NCI-831, NCI-930, IRGACURE369, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02 (BASF (Co.) Co., Ltd.).

Among the photopolymerization initiators (C), from the viewpoint of sensitivity, 2-morpholy-2- (4′-methylmercapto) benzoylpropane and 9-n-butyl-3,6-bis (2′-morpholinoiso) are used. Butyroyl) carbazole is preferred, and 2-morpholyl-2- (4′-methylmercapto) benzoylpropane is more preferred.

  In the colored composition of the present invention, the content of the photopolymerization initiator (C) is preferably 0.1 to 30% by mass, particularly preferably 0.5 to 10% by mass in the colored composition of the present invention. When the content of the photopolymerization initiator (C) is less than 0.1% by mass, curing by exposure may be insufficient. When the content is more than 30% by mass, the photopolymerization initiator ( C) may precipitate.

<Inorganic color material and / or organic color material (D)>
The coloring composition of the present invention may further contain an inorganic color material and / or an organic color material (D). These color materials can be used alone or in admixture of two or more.

Examples of the inorganic color material and / or organic color material (D) include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, Isoindoline compounds, quinacridone compounds, anthanthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalene tetracarboxylic acids; azo dyes, metal complex compounds of cyanine dyes Rake pigments; carbon black obtained by furnace method, channel method, thermal method, or carbon black such as acetylene black, ketjen black or lamp black The carbon black prepared and coated with an epoxy resin, the carbon black previously dispersed with a resin in a solvent and adsorbed 20 to 200 mg / g of the resin, the carbon black is acidic or alkaline Surface treatment, average particle size of 8 nm or more, DBP oil absorption of 90 ml / 100 g or less, CO in volatile matter at 950 ° C., total oxygen calculated from CO ₂ is 9 mg per 100 m ^{2 of} carbon black surface area Above, graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; hydrophobic resin, chromium oxide green, Milori blue, cobalt green, koval Blue, manganese, ferrocyanide, phosphate ultramarine, bitumen, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red rose (red iron (III) oxide), cadmium red, synthetic Inorganic pigments or organic pigments such as iron black and amber can be used.

  As said inorganic color material and / or organic color material (D), a commercially available pigment can also be used, for example, pigment red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38. 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202 , 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 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, 3, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 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.

  As the inorganic color material and / or organic color material (D), known dyes can be used. Known dyes include, for example, 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, Examples thereof include phthalocyanine dyes and cyanine dyes.

  In the colored composition of the present invention, the content of the inorganic color material and / or the organic color material (D) is preferably 0 to 350 parts by mass with respect to 100 parts by mass of the alkali developable resin (B). Preferably it is 0-250 mass parts. When it exceeds 350 parts by mass, the light transmittance of the cured product using the colored composition of the present invention, in particular, the color filter for display device using the same may decrease, and the luminance of the display device may decrease. .

<Solvent (E)>
A solvent (E) can be further added to the colored composition of the present invention. The solvent is usually a solvent capable of dissolving or dispersing each of the above components (cyanine compound (A), etc.) as necessary, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl. Ketones such as ketone, cyclohexanone, 2-heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, Ester solvents such as acetic acid-n-propyl, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol; and the like such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether Solve solvents; alcohol solvents such as methanol, 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 -Ether ester solvents such as acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate; BTX solvents such as benzene, toluene, xylene; hexane, heptane, octane, cyclohexane, etc. Aliphatic hydrocarbon solvents; terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; mineral spirits, swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Paraffin solvents such as Besso # 100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, and 1,2-dichloroethane; Halogenated aromatics such as chlorobenzene Hydrocarbon solvents; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water, etc. These solvents can be used as one or a mixture of two or more. Among these, ketones, ether ester solvents and the like, particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, and the like are preferable because the compatibility between the resist and the photopolymerization initiator is good in the colored composition.

  In the colored composition of the present invention, the amount of the solvent (E) used is preferably such that the concentration of the composition other than the solvent (E) is 5 to 30% by mass. If the concentration of the composition other than the solvent (E) is less than 5% by mass, it may be difficult to increase the film thickness or may not be able to absorb the desired wavelength light sufficiently, and if it exceeds 30% by mass, The storage stability of the composition due to precipitation of the composition may decrease, or the viscosity may improve and handling may decrease.

  The coloring composition of the present invention can 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; lamellar clay mineral, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper Among these, titanium oxide, silica, layered clay mineral, silver and the like are preferable. In the colored composition of the present invention, the content of the inorganic compound is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the alkali-developable resin (B). These inorganic compounds can be used alone or in combination of two or more.

  These inorganic compounds are used, for example, as fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellents, and the like.

  In the coloring composition of the present invention, when a pigment and / or an inorganic compound is used, a dispersant can be added. The dispersant is not particularly limited as long as it can disperse or stabilize a pigment and / or an inorganic compound, and a commercially available dispersant, for example, BYK series, BYK series, etc. can be used. Among these, Polymer dispersing agent composed of polyester, polyether, polyurethane having basic functional group, nitrogen atom as basic functional group, functional group having nitrogen atom is amine and / or quaternary salt thereof, amine Those having a value of 1 to 100 mgKOH / g are preferably used.

  In addition, the coloring composition of the present invention includes, if necessary, thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; plasticizer; adhesion promoter; filler; Conventional additives such as an agent, a leveling agent, a surface conditioner, an antioxidant, an ultraviolet absorber, a dispersion aid, a coagulation inhibitor, a catalyst, an effect accelerator, a cross-linking agent, and a thickener can be added.

  In the colored composition of the present invention, optional components other than the above-mentioned cyanine compound (A), alkali-developable resin (B) and photopolymerization initiator (C) (however, inorganic color material and / or organic color material (D)) And the content of the solvent (E) is appropriately selected depending on the purpose of use and is not particularly limited, but is preferably 50 parts by mass or less in total with respect to 100 parts by mass of the alkali-developable resin (B). And

In the coloring composition of this invention, the characteristic of the hardened | cured material which consists of a coloring composition of this invention can also be improved by using another organic polymer with the said alkali developable resin (B). 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, polyamideimide resin, polyamic acid resin, epoxy resin, etc. are mentioned. Among these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, epoxy resin are used. Masui.
When using another organic polymer, the usage-amount is preferably 10-500 mass parts with respect to 100 mass parts of the said alkali developable resin (B).

  The colored composition of the present invention can further contain a monomer having an unsaturated bond, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine compound, and the like.

  Examples of the monomer having an unsaturated bond include: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, acrylic acid Methoxyethyl, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate, methacrylic acid Tertiary butyl, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentae Thritol tetraacrylate, pentaerythritol triacrylate, bisphenol A diglycidyl ether (meth) acrylate, bisphenol F diglycidyl ether (meth) acrylate, bisphenol Z diglycidyl ether (meth) acrylate, tripropylene glycol di (meth) acrylate, etc. Can be mentioned.

  As the chain transfer agent or sensitizer, a sulfur atom-containing compound is generally used. 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- Mercapto compounds such as mercaptopropionate), disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Alkyl compound, 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, trishydroxyethyl tristhiopropionate, the following compound no. 125, aliphatic polyfunctional thiol compounds such as trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, Karenz MT BD1, PE1, NR1 manufactured by Showa Denko KK and the like.

  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 halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

  As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used, and among these, an isocyanate group such as KBE-9007, KBM-502, KBE-403, etc., a methacryloyl group, and an epoxy group are included. A silane coupling agent is preferably used.

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

  The coloring composition of the present invention is a known means such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, soda glass, quartz glass, semiconductor substrate, metal, paper, plastic, etc. It can be applied on the supporting substrate. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

  Moreover, as the light source of the active light used when curing the colored composition of the present invention, one that emits light having a wavelength of 300 to 450 nm can be used, for example, ultrahigh pressure mercury, mercury vapor arc, carbon arc. Xenon arc or the like can be used.

  Furthermore, by using laser light as the exposure light source, the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy. As the laser light, light having a wavelength of 340 to 430 nm is preferably used, but an argon ion laser, a helium neon laser, a YAG laser, a semiconductor laser, etc. are visible to infrared region. Those that emit light are also used. When these lasers are used, a sensitizing dye that absorbs the region from visible to infrared is added.

  The colored composition of the present invention (or its cured product) is a photocurable paint or varnish, a photocurable adhesive, a printed circuit board, or a color display liquid crystal display such as a color TV, PC monitor, portable information terminal, digital camera, etc. Color filters in panels, color filters for CCD image sensors, electrode materials for plasma display panels, powder coatings, printing inks, printing plates, adhesives, dental compositions, resin for stereolithography, gel coats, photoresists for electronics , Electroplating resist, etching resist, both liquid and dry film, solder resist, structure for manufacturing color filters for various display applications or in the manufacturing process of plasma display panel, electroluminescent display device and LCD A composition for encapsulating resist, electrical and electronic components -Resist, magnetic recording materials, micromechanical parts, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, stencils for screen printing, materials for producing 3D objects by stereolithography Holographic recording material, image recording material, fine electronic circuit, decoloring material, decoloring material for image recording material, decoloring material for image recording material using microcapsules, photoresist material for printed wiring board, UV and visible It can be used for various applications such as a photoresist material for a laser direct image system, a photoresist material used for forming a dielectric layer in the sequential lamination of printed circuit boards, or a protective film, and the application is not particularly limited.

The colored alkali-developable photosensitive composition of the present invention is used for the purpose of forming a pixel of a color filter, and in particular, a photosensitizer for forming a color filter for a display device for an image display device such as a liquid crystal display panel or an organic EL. It is useful as a sex composition.
Moreover, the color filter for display devices of the present invention may have red, green, blue, orange, purple and black optical elements in addition to the cured product of the present invention.

The color filter for a display device includes (1) a step of forming a coating film of the colored composition of the present invention 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 a step, (3) a step of developing the film after exposure with a developer (particularly an alkali developer), and (4) a step of heating the film after development. The colored composition of the present invention is also useful as a colored composition for an ink jet system or a transfer system without a development step.
The production of a color filter for use in a liquid crystal display panel or the like is produced by repeating the above steps (1) to (4) using a coloring composition of the present invention or other combination, and combining patterns of two or more colors. Can do.

Hereinafter, although an example etc. are given and the present invention is explained still in detail, the present invention is not limited to these examples. In addition, Production Examples 3 to 5, Examples 1 to 5 and 7 to 17, and Evaluation Examples 1 to 5 and 7 to 17 are reference examples.

  Production Examples 1 to 5 show production examples of the alkali-developable resin (B), Examples 1 to 17 show preparation examples of the colored alkali-developable photosensitive composition of the present invention, and Comparative Examples 1 to 6 are Examples of preparation of comparative colored alkali-developable photosensitive compositions are shown. In Evaluation Examples 1 to 17, the colored alkali-developable photosensitive compositions of the present invention prepared in Examples 1 to 17 are evaluated, and comparative evaluation examples are shown. In 1-6, the comparative colored alkali-developable photosensitive composition prepared in Comparative Examples 1-6 was evaluated.

[Production Example 1] Alkali developable resin No. 1 having an ethylenically unsaturated bond Preparation of 1 40 parts by mass of acrylic acid and 50 parts by mass of butyl methacrylate are dissolved in 200 parts by mass of propylene glycol-1-monomethyl ether-2-acetate (PGMEA), and azobisisobutyrate is used as a radical polymerization initiator in this solution. 4 parts by mass of nitrile was added and stirred at 80 ° C. for 3 hours. Subsequently, 10 parts by mass of Celoxide 2021P (Daicel Chemical Co., Ltd. alicyclic epoxy resin) modified with acrylic acid was added, stirred at 120 ° C. for 3 hours, and an alkali-developable resin No. 1 having an ethylenically unsaturated bond. 1 was obtained.
Alkali developable resin No. 1 having this ethylenically unsaturated bond. 1, the general formula (II), X ¹¹ is a hydrogen atom or a methyl group, Y ¹¹ is a divalent linking group represented by the general formula (1) (X ¹ is 1-methyl - 2-hydroxycyclohexane diyl group, Z ¹ and Z ² are direct bonds), R ¹¹ is an alkyl group having 1 to 8 carbon atoms, and R ^{12 to} R ¹⁴ are methyl groups. It is resin which is.

[Production Example 2] Alkali developable resin No. 1 having an ethylenically unsaturated bond Preparation of 2 20 parts by mass of methacrylic acid, 20 parts by mass of glycidyl methacrylate and 50 parts by mass of benzyl methacrylate were dissolved in 500 parts by mass of cyclohexanone, and 4 parts by mass of azobisisobutyronitrile was added as a radical polymerization initiator at 80 ° C. Stir for 3 hours. Subsequently, 20 parts by mass of acrylic acid was added, and the mixture was stirred at 120 ° C. for 3 hours. 2 was obtained.

[Production Example 3] Alkali developable resin No. 1 having an ethylenically unsaturated bond 3 Preparation 50 parts by weight of glycidyl methacrylate, 5 parts by weight of benzyl methacrylate and 40 parts by weight of styrene were mixed with propylene glycol-1-monomethyl ether-2-acetate (PGMEA).
It melt | dissolved in 500 mass parts, 1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane 1 mass part was added as a radical polymerization initiator, and it stirred at 140 degreeC for 2 hours. Next, 20 parts by mass of acrylic acid was added, and the mixture was stirred at 120 ° C. for 3 hours. 3 was obtained.

[Production Example 4] Alkali-developable resin No. 1 having an ethylenically unsaturated bond Preparation of 4 Glycidyl methacrylate 40 parts by mass, benzyl methacrylate 5 parts, styrene 40 parts by mass propylene glycol-1-monomethyl ether-2-acetate (PGMEA)
It melt | dissolved in 500 mass parts, and stirred at 80 degreeC for 3 hours using 10 mass parts of azobisisobutyronitrile as a radical polymerization initiator. Next, 20 parts by mass of acrylic acid was added, and the mixture was stirred at 120 ° C. for 3 hours. 4 was obtained.

[Production Example 5] Alkali developable resin No. 1 having an ethylenically unsaturated bond Preparation of 5 Propylene glycol-1-monomethyl ether-2-acetate (PGMEA) containing 40 parts by mass of glycidyl methacrylate, 5 parts of benzyl methacrylate, and 40 parts by mass of styrene
It melt | dissolved in 500 mass parts, 5 mass parts of azobisisobutyronitrile was added as a radical polymerization initiator, and it stirred at 80 degreeC for 3 hours. Subsequently, 20 mass parts of acrylic acid was added and it stirred at 120 degreeC for 3 hours. Next, 5 parts by mass of tetrahydrophthalic anhydride was added and stirred at 120 ° C. for 3 hours, and then an alkali developing resin No. 1 having an ethylenically unsaturated bond was used. 5 was obtained.

[Example 1] Colored alkali-developable photosensitive composition No. 1 Preparation of Step 1 <Step 1> Alkali-developable photosensitive composition No. 1 Preparation of Alkali Developable Resin No. 1 having an ethylenically unsaturated bond obtained in Production Example 1 as component (B). 30.13 g of 1 and Irgacure 907 (2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one; photopolymerization initiator; manufactured by BASF) as 1 as component (C) .93 g, 55.90 g of PGMEA as component (E), 0.01 g of FZ2122 (polydimethylsiloxane; manufactured by Toray Dow Corning) as the other component, and Aronix M-405 (polyfunctional acrylate; manufactured by Toa Gosei) Was mixed until the insoluble matter disappeared, and the alkali-developable photosensitive composition No. 1 was mixed. 1 was obtained.

<Step 2> Dye solution No. Preparation of Cyanine Compound No. 1 as component (A) 1.90 g of dimethylacetamide was added to 0.10 g of para-toluenesulfonic acid salt of 1-44, and the mixture was stirred and dissolved. 1 was obtained.

<Step 3> Colored alkali-developable photosensitive composition No. Preparation of alkali-developable photosensitive composition No. 1 obtained in Step 1 1 of 5.0 g and the dye solution No. obtained in Step 2. 1 was mixed and stirred until uniform, and the colored alkali-developable photosensitive composition No. 1 was mixed. 1 was obtained.

[Example 2] Colored alkali-developable photosensitive composition No. Preparation of the colored alkali-developable photosensitive composition No. 2 in the same manner as in Example 1 except that the component (B) was changed to ACA Z251 (acrylated acrylate; manufactured by Daicel Cytec). 2 was obtained.
The ACA Z251 used as the component (B) is a divalent linking group represented by the above general formula (II), wherein X ¹¹ is a hydrogen atom or a methyl group, and Y ¹¹ is represented by the above general formula (1) ( X ¹ is a diyl group of 1-methyl-2-hydroxycyclohexane, Z ¹ and Z ² are direct bonds), R ¹¹ is an alkyl group having 1 to 8 carbon atoms, R ^{12 to} R ¹⁴ are resins that are methyl groups.

[Example 3] Colored alkali-developable photosensitive composition No. Preparation of 3 The component (C) in Step 1 of Example 1 was converted to NCI-930 (1,2-propanedione, 1- [4-[[4- (2-hydroxyethoxy) phenyl] thio] phenyl] -2- (O-acetyl oxime); photopolymerization initiator; manufactured by ADEKA), a colored alkali-developable photosensitive composition No. 3 was obtained.

[Example 4] Colored alkali-developable photosensitive composition No. Preparation of 4 The same procedure as in Example 1 except that the component (B) in Step 1 of Example 1 was changed to SPC-1000 (acrylate; manufactured by Showa Denko KK), and the component (C) was changed to NCI-930. Colored alkali-developable photosensitive composition No. 4 was obtained.

[Example 5] Colored alkali-developable photosensitive composition No. Preparation of No. 5 Alkali developable resin No. 5 having an ethylenically unsaturated bond obtained in Production Example 2 was used as the component (B) in Step 1 of Example 1. In the same manner as in Example 1, except that the component (C) was changed to NCI-930, the colored alkali-developable photosensitive composition No. 5 was obtained.

[Example 6] Colored alkali-developable photosensitive composition No. Preparation of No. 6 Component (A) in Step 2 of Example 1 was changed to Compound No. The colored alkali-developable photosensitive composition No. 1 was prepared in the same manner as in Example 1 except that it was changed to bis (trifluoromethanesulfonyl) imidate of 1-44. 6 was obtained.

[Example 7] Colored alkali-developable photosensitive composition No. Preparation of No. 7 The component (A) in Step 2 of Example 1 was changed to Compound No. The colored alkali-developable photosensitive composition No. 1 was prepared in the same manner as in Example 1 except that it was changed to 1-44 methacryloxypropane sulfonate. 7 was obtained.

[Example 8] Colored alkali-developable photosensitive composition No. Preparation of No. 8 Component (A) in Step 2 of Example 1 was changed to Compound No. The colored alkali-developable photosensitive composition No. 1 was prepared in the same manner as in Example 1 except that the hexafluorophosphate was 1-44. 8 was obtained.

[Example 9] Colored alkali-developable photosensitive composition No. Preparation of No. 9 Component (A) in Step 2 of Example 1 was changed to Compound No. The colored alkali-developable photosensitive composition No. 1 was prepared in the same manner as in Example 1 except that the bis (trifluoromethanesulfonyl) imido salt of 1-4 was used. 9 was obtained.

[Example 10] Colored alkali-developable photosensitive composition No. Preparation of No. 10 Component (A) in Step 2 of Example 1 was changed to Compound No. A colored alkali-developable photosensitive composition No. 1 was prepared in the same manner as in Example 1 except that the compound was changed to 1-4, 1,3-benzenedisulfonate. 10 was obtained.

[Example 11] Colored alkali-developable photosensitive composition No. Preparation of component No. 11 (A) in step 2 of Example 1 was changed to compound no. The colored alkali-developable photosensitive composition No. 1 was prepared in the same manner as in Example 1 except that the bis (trifluoromethanesulfonyl) imidoate of 1-1 was used. 11 was obtained.

[Example 12] Colored alkali-developable photosensitive composition No. Preparation of No. 12 The component (A) in Step 2 of Example 1 was changed to Compound No. A colored alkali-developable photosensitive composition No. 1 was prepared in the same manner as in Example 1 except that the salt was changed to 1-1, 1,8 naphthol sulfonate. 12 was obtained.

[Example 13] Colored alkali-developable photosensitive composition No. Preparation of No. 13 The component (A) in Step 2 of Example 1 was changed to Compound No. The colored alkali-developable photosensitive composition No. 1 was prepared in the same manner as in Example 1 except that it was changed to 1-35 bis (trifluoromethanesulfonyl) imidate. 13 was obtained.

[Example 14] Colored alkali-developable photosensitive composition No. Preparation of the alkali-developable resin No. 14 having the ethylenically unsaturated bond obtained in Production Example 3 as the component (B) in Step 1 of Example 1 In the same manner as in Example 1, except that the component (C) was changed to NCI-930, the colored alkali-developable photosensitive composition No. 14 was obtained.

[Example 15] Colored alkali-developable photosensitive composition No. Preparation of 15 The same procedure as in Example 1 except that the component (B) in Step 1 of Example 1 was changed to SPC-3000 (acrylate; manufactured by Showa Denko KK), and the component (C) was changed to NCI-930. Colored alkali-developable photosensitive composition No. 15 was obtained.

[Example 16] Colored alkali-developable photosensitive composition No. Preparation of No. 16 The alkali-developable resin No. 16 having an ethylenically unsaturated bond obtained in Production Example 4 was used as the component (B) in Step 1 of Example 1. In the same manner as in Example 1, except that the component (C) was changed to NCI-930, the colored alkali-developable photosensitive composition No. 16 was obtained.

[Example 17] Colored alkali-developable photosensitive composition No. Preparation of No. 17 The alkali-developable resin No. 1 having the ethylenically unsaturated bond obtained in Production Example 5 was used as the component (B) in Step 1 of Example 1. In the same manner as in Example 1 except that the component (C) was changed to NCI-930, the colored alkali-developable photosensitive composition No. 17 was obtained.

[Comparative Example 1] Comparative colored alkali-developable photosensitive composition No. Preparation of Comparative Colorable Photosensitive Photosensitive Composition No. 1 in the same manner as in Example 1 except that the component (A) in Step 2 of Example 1 was changed to rhodamine B base. 1 was obtained.

[Comparative Example 2] Comparative colored alkali-developable photosensitive composition No. Preparation of No. 2 Comparative colored alkali-developable photosensitive composition No. 2 was prepared in the same manner as in Example 1 except that the component (A) in Step 2 of Example 1 was changed to rhodamine 6GCP. 2 was obtained.

[Comparative Example 3] Comparative colored alkali-developable photosensitive composition No. Preparation of comparative colored alkali-developable photosensitive composition No. 3 in the same manner as in Example 1 except that component (A) in Step 2 of Example 1 was changed to rhodamine 6GCP-N. 3 was obtained.

[Comparative Example 4] Comparative colored alkali-developable photosensitive composition No. 4. Preparation of component (A) in Step 2 of Example 1 The comparatively colored alkali-developable photosensitive composition no. 4 was obtained.

[Comparative Example 5] Comparative colored alkali-developable photosensitive composition No. Preparation of Component (A) in Step 2 of Example 1 was changed to the following Comparative Compound No. A comparative colored alkali-developable photosensitive composition No. 1 was prepared in the same manner as in Example 1 except that the composition was changed to 2. 5 was obtained.

[Comparative Example 6] Comparative colored alkali-developable photosensitive composition No. Preparation of No. 6 Component (A) in Step 2 of Example 1 was changed to Compound No. The comparative colored alkali-developable photosensitive composition No. 1 was prepared in the same manner as in Example 1 except that it was changed to the perchlorate of 1-35. 6 was obtained.

[Evaluation Examples 1 to 17 and Comparative Evaluation Examples 1 to 6]
The colored alkali-developable photosensitive composition No. obtained in Examples 1-17. Comparative colored alkali-developable photosensitive composition Nos. 1 to 17 and Comparative Examples 1 to 6 Each of 1 to 6 was applied to a glass substrate under conditions of 410 rpm × 7 seconds, and dried on a hot plate (90 ° C., 90 seconds). The obtained coating film was exposed (150 mJ / cm ² ) with an ultrahigh pressure mercury lamp. The coated film after exposure was heated at 230 ° C. for 30 minutes to evaluate heat resistance. Evaluation was performed by measuring the color difference before and after heating. These results are shown in [Table 1].

  From the results of [Table 1], it is clear that the colored alkali-developable photosensitive composition of the present invention has little change in color difference and high heat resistance.

  From the above results, the colored alkali-developable photosensitive composition of the present invention using the cyanine compound (A) and the alkali-developable resin (B) has excellent heat resistance. Therefore, the colored alkali-developable photosensitive composition of the present invention is useful for a color filter for display devices.

Claims (4)

At least one cyanine compound (A) represented by the following general formula (IA), an alkali-developable resin (B) having an ethylenically unsaturated bond represented by the following general formula (II), and 2-methyl-1 [ 4- (Methylthio) phenyl] -2-morpholinopropan-1-one or 1,2-propanedione, 1- [4-[[4- (2-hydroxyethoxy) phenyl] thio] phenyl] -2- A colored alkali-developable photosensitive composition containing a photopolymerization initiator (C) which is any one of (O-acetyloxime) .

(Wherein, ring A and ring A ′ each independently represent a benzene ring or an unsubstituted naphthalene ring which may be substituted with R ³ or R ^{3 ′} ;
R ³ and R ^{3 ′} each independently represent a halogen atom or a cyano group ,
r and r ′ each independently represents 0 or 1,
An ^q− represents bis (trifluoromethanesulfonyl) imidate ,
X and X ′ each independently represent —CR ⁵¹ R ⁵² — ,
R ⁵¹ and R ⁵² each independently represent a hydrogen atom, a hydroxyl group, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkyl group having 1 to 8 carbon atoms, The aryl group, the arylalkyl group and the alkyl group may be substituted with a hydroxyl group, a halogen atom, a nitro group, a cyano group, —SO ₃ H, a carboxyl group, an amino group, an amide group or a ferrocenyl group,
Z ¹¹ , Z ¹² and Z ¹³ represent a hydrogen atom,
Y and Y ′ each independently represent an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkyl group having 1 to 8 carbon atoms, which may be substituted with a halogen atom. In the above Y and Y ′, the arylalkyl group and the methylene group in the alkyl group are interrupted by —O—, —CO—, —COO—, —OCO—, —CONH—, —NHCO—, or a double bond. It may be. )

(Wherein X ¹¹ represents a hydrogen atom or a methyl group,
Y ¹¹ is a divalent linking group represented by the following general formula (1),
R ¹¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms, and the alkyl group, aryl group, and arylalkyl group in R ¹¹ above. May be substituted with a halogen atom or a hydroxyl group, and the methylene group in the alkyl group and arylalkyl group in R ¹¹ represents —O—, —CO—, —COO—, —OCO— or these groups. May be interrupted by a combination of several,
R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group,
0.1 ≦ t ≦ 0.65, 0.3 ≦ m ≦ 0.8, 0 ≦ n ≦ 0.2, and t + m + n = 1. )

(Wherein, X ¹ represents a divalent chain hydrocarbon group or a divalent group represented by alicyclic hydrocarbon having a carbon number of 3 to 35 carbon atoms 1 to 35,
Z ¹ and Z ² represent a direct bond.
However, the number of carbon atoms of the group represented by the general formula (1) is in the range of 1 to 35. )   The colored alkali-developable photosensitive composition according to claim 1, further comprising an inorganic color material and / or an organic color material (D).   A cured product of the colored alkali-developable photosensitive composition according to claim 1.   A color filter for a display device comprising at least a part of the cured product according to claim 3.