TW201142495A - Colored photosensitive resin composition - Google Patents

Abstract

The present invention provides a colored photosensitive resin composition, containing a colored agent, resin, photo-polymerization compounds, photo-polymerization initiator and solvent, wherein the colored agent includes pyridone azo metal malocclusion compound.

Description

201142495 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a colored photosensitive resin composition. [Prior Art] • For the coloring photosensitive resin composition of the red pixel forming the shirt color filter, in order to improve the contrast of the color filter, it is known to use a dye as the coloring in the coloring photosensitive resin composition. Agent. For example, in Patent Document 1, S has carried a colored photosensitive resin composition containing Orasol Red G as a red dye. [Patent Document 1] JP-A-2009-163226 SUMMARY OF THE INVENTION An object of the present invention is to provide a colored cured product (for example, a colored coating film, a colored pattern) having higher solvent resistance and containing the same A colored photosensitive resin composition of a color filter. The present invention provides the following inventions [1] to [9]. Π] a coloring photosensitive resin composition containing a coloring agent, a resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and the coloring agent contains a compound represented by the formula (1),

£153941.doc 201142495 [In the formula (1), R to R18 independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, _s〇2r294_s〇2r32; and R29 represents -OH. Or -NHR30; R30 represents a hydrogen atom, a carbon number aliphatic hydrocarbon group, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, _R3i_〇R32, _r31_c〇〇r32, -R31-0-CO-R32 Or a aryl group having a carbon number of 7 to 10; R31 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms; R32 represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms; and R19 and R20 independently represent a hydrogen atom and a methyl group. And an ethyl group or an amine group; M1 represents Cr or Co; and R21 to R24 independently represent a hydrogen atom, a carbon number aliphatic fluorenyl group or a carbon number 6 to 10 monovalent aromatic hydrocarbon group, the aliphatic hydrocarbon group and the aromatic group The hydrogen atom contained in the radical may be substituted by a hydroxyl group, 〇R32, a repeating group, _s〇3Na, -S03K or a halogen atom; R25 and R26 each independently represent a hydrogen atom or a methyl group; R27 represents an ethyl group and a propane_1. , 3—diyl or propane 4,2•diyl; R28 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; η represents an integer of 1 to 4; when it is an integer of 2 or more, a plurality of feet 27 may be Same or different from each other]. [2] The colored photosensitive composition of [1] wherein the colorant further contains a pigment. [3] The colored photosensitive resin composition according to [2], wherein the pigment is selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, c丄 Pigment Red 177, CI Pigment Red 242, and CI Pigment Red 254. One of the group consisting of 153941.doc 201142495 is one less. [4] The colored photosensitive resin composition according to any one of [1] to [3] wherein the resin is a resin containing a copolymer having a cyclic ether having a carbon number of 2 to 4 and A structural unit of a monomer having an ethylenically unsaturated double bond, and a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. [5] A colored pattern which is formed using the colored photosensitive resin composition of any one of [丨] to [4]. [6] A color light film containing a colored pattern as in [5]. [7] a compound represented by formula (2),

[In the formula (7), 'R1 to Ri*' independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, _s〇2r294_s〇2r32; R 9 represents -OH or -NHR30; a non-hydrogen atom, a monovalent aliphatic hydrocarbon group having an inverse number of 1 to 8, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, -R31-0-R32, -R3丨.dojw-R31-0-C0 -R32 or an aralkyl group having a carbon number of 7 to 10; a divalent aliphatic hydrocarbon group having a carbon number of 1 to 8; 153,941.doc 201142495 R32 represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms; and R19 and R20 are independent of each other a hydrogen atom, a methyl group, an ethyl group or an amine group; M1 represents Cr or Co; and R21 to R24 independently represent a hydrogen atom, a valence aliphatic group having a carbon number of 丨8 or a monovalent aromatic having a carbon number of 6 to 10. The hydrocarbon group, the aliphatic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by a hydroxyl group, 〇R32, a sulfo group, _s〇3Na, -S03K or a halogen atom; and R2 5 and R2 6 each independently represent a hydrogen atom or a ruthenium atom; base]. [8] The compound of [7] wherein Μ! is Cr. At least one of them is a compound of [9] such as [7] or [8], wherein Ri~Rl8 is a base. [Embodiment] A toner (Α), a test solution, a photopolymerization initiator (D), and a solvent (hereinafter referred to as the coloring photosensitive resin composition of the present month may contain a reactive resin (B), The photopolymerizable compound (c) and the photopolymerization (8), and the colorant (4) is a compound (1) represented by the formula (1).

a salt of a cation of a pyran compound.

The wrong anion is derived from dibenzo 153941.doc 201142495 [In the formula (1), a hydrogen atom, a _ element atom, a monovalent aliphatic hydrocarbon group having a carbon number of 1 to 8, a nitro group, _s〇2r29 or _s〇2R32 are independently represented. R29 represents -OH or -NHR30. R3° represents a hydrogen atom, a carbon number, a valent aliphatic hydrocarbon group, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, _r3丨_〇_r32, _r31_chr32, -R31-〇-co-r32 or a carbon number. 7 to 10 aralkyl groups. R represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms. R32 represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms. π and R2. Independent of each other represents a hydrogen atom, a methyl group, an ethyl group or an amine group. M1 represents Cr or Co. R 1 to R 24 independently of each other represent a hydrogen atom, a carbon number aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the aliphatic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may pass through a hydroxyl group, _R32 Substituted with sulfo, _s〇3Na, -S〇3K or a halogen atom. R and R26 each independently represent a hydrogen atom or a methyl group. R27 represents an ethyl group, a propane _i, a diyl group or a propane _i, 2 diyl group. R28 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. η represents an integer from 1 to 4. When it is an integer of 2 or more, a plurality of R27s may be the same or different from each other]. Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include an anthracenyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a second butyl group, a tert-butyl group, a n-pentyl group, and an n-hexyl group. N-heptyl, n-octyl, decylmethylbutyl, M,3,3 tetramethylbutyl, 1,5-dimethylhexyl, anthracene, 6-dimethylheptyl, 2-ethylhexyl And 1,1,5,5-tetraf-hexyl and the like. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an iso- 15394 丨.doc 201142495 propyl group, an n-butyl group, a second butyl group, and a third butyl group. Examples of the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include a methylene group, an exoethyl group, a propane-1,3-diyl group, a propane_ι,2-diyl group, a butane·14-diyl group, and a butyl group. Alkyl-1,3-diyl, pentane-1,5-diyl, hexane-1>6-diyl, heptane-17-diyl, octane-1,8-diyl and the like. Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group, a methyl group, a 'difylphenyl group, a trif-phenyl group, an ethylphenyl group, a propylphenyl group, and a butylphenyl group. An aryl group such as a naphthyl group; an aralkyl group such as a benzyl group, a diphenylmethyl group or a phenylethyl '3-phenylpropyl group. Examples of the cyclohexyl group which may be substituted with an alkyl group having a carbon number of 44 may include a fluorenylcyclohexyl group, a 2-ethylcyclohexyl group, a 2-propylcyclohexyl group, a 2-isopropylcyclohexyl group, and a 2-butyl group. Cyclohexyl, 4-methylcyclohexyl, 4•ethylcyclohexyl, 4-propylcyclohexyl, 4-isopropylcyclohexyl, 4-butylcyclohexyl, and the like. Examples of -R31-〇-R32' include methoxymethyl, ethoxyindolyl-propoxylate methyloxyethyl, ethoxyethyl, propoxyethyl, methoxypropyl. , ethoxypropyl, propoxypropyl, 2-oxo-4-methoxybutyl, octyloxypropyl, 3-ethoxypropyl, 3-(2-ethylhexyloxy)propyl Wait. Examples of the -R31-CO-oxime-R32' include a methoxycarbonylmethyl group, a decyloxycarbonylethyl group, an ethoxycarbonylcarbonyl group, an ethoxycarbonylethyl group, a propoxycarbonyl fluorenyl group, and a propoxy group. Carbonylethyl, butoxycarbonylmethylbutoxycarbonylethyl and the like. Examples of -R31-〇-CO_r32' include an ethoxymethyloxy group, an ethyl ethoxyethyl group, an ethyl carbonyloxy fluorenyl group, an ethyl carbonyloxyethyl group, a propylcarbonyloxymethyl group, and a propyl group. Ethoxyethyl, butyl moxy f, butyl oxyethyl 8 - 153941.doc

201142495 and so on. As -S〇2R29 ' may be exemplified by: sulfo group; amine sulfonyl group; N-methylamine sulfonyl group, ethyl ethyl sulfonyl group, N propyl sulfonyl group, N-isopropyl sulfonate , butylamine sulfonyl, N-isobutylamine sulfonyl, N-butylbutylsulfonyl, hydrazine tert-butylamine sulfonyl, N-pentylamine sulfonyl, N-(l-ethylpropyl)amine sulfonyl, N-(1,b-dimercaptopropyl)amine, Ν·(1,2-dimercaptopropyl)amine sulfonyl, N_ (2,2_Dimethylpropyl)aminesulfonyl, N-(l-decylbutyl)aminesulfonyl, n-(2-methylbutyl)aminesulfonyl, N-(3 -Methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, N-hexylamine sulfonyl, hydrazine (1,3-dimethylbutyl)amine sulfonyl, Ν-( 3,3-Dimethylbutyl)amine sulfonyl, small heptylamine sulfonyl, Yi (1-methylhexyl)amine sulfonyl, N-(l,4-dimethylpentyl)amine Sulfonyl, fluorene-octylamine sulfonyl, fluorenyl-(2-ethylhexyl)amine sulfonyl, N-(i,5-dimethyl)hexylamine sulfonyl, N-(l,l, 2,2-tetramethylbutylamine sulfonyl sulfhydryl, etc., substituted with an aliphatic hydrocarbon group Aminesulfonyl; N-(2-methoxyethyl)amine sulfonyl, Ν·(2-ethoxyethyl)amine sulfonyl, N-(l-methoxypropyl)amine sulfonate Base, ν-(3-methoxypropyl)amine sulfonyl, Ν-(3-ethoxypropyl)amine, Ν-(3-propoxypropyl)amine, ugly, Ν-(3-Isopropoxypropyl)amine hydrazino, Ν-(3·hexyloxypropyl)amine, Ν-(2-ethylhexyloxypropyl)amine , ν-(3-t-butoxypropyl)amine hydrazino, fluorenyl-(4-octyloxybutyl)amine hydrazino, etc. substituted with -R_31-0-R32; -(Methoxycarbonylmethyl)amine sulfonyl, N-(methoxycarbonylethyl)amine, N-(ethoxymethylmethyl)amine acid group, N-(ethoxy Alkylamino)aminesulfonyl, N-(propoxycarbonylmethyl)aminesulfonyl, N-(propoxy 153941.doc 201142495 carbonylethyl)amine sulfonyl, N-(butoxy Aminosulfonyl group substituted with -r31-co-o-r32, such as carbonylsulfonyl, sulfonyl, N-(butoxycarbonylethyl)amine sulfonyl; N-(ethenyloxymethyl) Aminesulfonyl, N-(ethyloxyethyl)amine sulfonyl, N-(ethylcarbonyl Amidoxime, N-(ethylcarbonyloxyethyl)amine sulfonyl, N-(propylcarbonyloxymethyl)amine sulfonyl, N-(propylcarbonyloxy Aminesulfonyl, N-(butylcarbonyloxymethyl)aminesulfonyl, N-(butylcarbonyloxyethyl)aminesulfonyl, etc., substituted by -r31-〇-co-r32 Aminesulfonyl; N-cyclohexylamine sulfonyl, N-(2-decylcyclohexyl)amine sulfonyl, N-(3-decylcyclohexyl)amine sulfonyl, N-(4-曱Aminosulfonyl group substituted with a cyclohexyl group having a substituent such as a cyclohexyl)aminesulfonyl group or an N-(4-butylcyclohexyl)amine sulfonyl group; N-benzylaminesulfonyl group, N-( L-phenylethyl)amine sulfonyl, N-(2-phenylethyl)amine sulfonyl, N-(3-phenylpropyl)amine sulfonyl, N-(4-phenyl butyl Aminesulfonyl, N-[2-(2-naphthyl)ethyl]aminesulfonyl, N-[2-(4-methylphenyl)ethyl]aminesulfonyl, N-( An arylsulfonyl group substituted with an aralkyl group such as a 3-phenyl-1-propyl)aminesulfonyl group or an N-(3-phenyl-1-mercaptopropyl)amine sulfonyl group. Examples of the -S02R32 include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a n-butylsulfonyl group, a second butylsulfonyl group, and a third butyl group. Sulfonyl, pentylsulfonyl, hexylsulfonyl, heptylsulfonyl, octylsulfonyl, 1-mercaptobutylsulfonyl, 1,1,3,3-tetradecylbutyl Sulfonyl, 1,5-didecylhexylsulfonyl, 1,6-didecylheptylsulfonyl, 2-ethylhexylsulfonyl and 1,1,5,5-tetradecylhexyl Sulfonyl and the like. Preferably, the methylsulfonyl group and the ethylsulfonyl group are preferably methylsulfonyl in 153941.doc -10·201142495 because the heat resistance is preferably at least one of R1 to R18 is a nitro group. South tendency. Further, it is preferable that at least one of R1 to R5 and at least one of R6 to R10 are -MR29. When there are multiple -so/, a plurality of " may be the same or different. -S〇2R29 is _s〇2H or ·3〇2ΝΗ]13〇, preferably _S〇2NHR3〇. Among them, a hydrogen atom or an aliphatic hydrocarbon group having a carbon number of 8 is preferable, and a gas atom or a 2-ethylhexyl group is more preferable. When the compound of the present invention has _s〇2R32, it is preferably at least one of r11 to rM and at least one of R15~ is _s〇2r32. When there are a plurality of 1仏1132, the plurality of feet 32 may be the same or different from each other. R to R is preferably a hydrogen atom or a monovalent carbon number of 1 to 8 which may have a substituent, and is preferably a hydrogen atom or an ethyl group because the color density is high. Further, R is preferably an ethyl group and a propane-?, a 2-diyl group, more preferably an ethyl group. R28 is preferably a hydrogen atom. η is an integer of 1 to 4, preferably an integer of 2 to 4, more preferably 3 or 4. As -(R27_〇)n.R28, preferably 2-(2-transethoxyethyl)ethyl and hydroxyethoxy)ethoxy]ethyl, more preferably 2_[2(2-hydroxyl) Ethoxylate) Ethoxy]ethyl is due to the tendency of the solubility of the compound (丨) in an organic solvent to be improved. In the compound (1), preferred examples of the pyrazole azo compound which is a ligand for the wrong anion include a compound represented by the formula (Ι-al) to the formula (l-a64) 153941.doc 201142495 and the like.

(1-37)

(1-a2) (1-a4)

(1-a9)

(1-a6) (1-a8)

(1.alO)

(1-a12)

(1-al4) 0-ai6)

(1-320) 153941.doc -12- 201142495

(1-a2D (1-a23) (1-a25)

(1-a24) (1-a26)

153941.doc 13· 201142495 —V HNO^

(1*a39) (1-840) 〇Ά=ν·^ HNO2SOH HO’ (l-a4i)

(1-a43) (1-a45)

Qr^-μ^

(1*342) (1-a44) (1-a46) gyN^N-.M-Q HNOiS^^ OH0-^N=N-^| (1-a47) (1-a48) (1a-49)

HjMC^S OH HO 〇2n hno2s/ °b"iu=uP N^-N=N-/^ 〇H HO Guang

HNO

CHS (1-a53) HNOjS*

^—H=H 〇H HO

, CI (1-a55)

SOgNH SO^NH SOjNH (1-a50) (Va52) (1-a54) (1-a56)

SO^NI

H3C〇2S J (1-a57)

S02CH3 (1-358)

S02CH3 (1-a59) 〇2 ^VNy^-N=N-&J^ (1-361) ^ OH HO^ -Nv^^-N=N·-S〇2CH3 (1-a63) 〇H HO N〇2

(1-360) (1-362) N02 OH H〇 SO2CH3 (1-a64) 153941.doc -14- 201142495 In the compound (1), the anion shown as the error bl)~ (l-b60)

153941.doc -15- 201142495 ho3s^ 0>-° © HOaS^^ 〇)Cf(〇,ι-υι ” — * 一r Θ (1-b13) _ for production - Θ (1-b15) :"strp I 〇〆\ ^^so2NH2 Ά, - θ (14)17) Η2Ν〇2δγ^Ν^~^Ν_^^ \° ri2 ~ytN [讲夕-· - called A θ (1-b19) [by another 1 [Y _ θ (1-b12) Θ (1-b14) (1-b16) θ (1-b18) θ (1-b20) -16- 153941.doc 201142495

1 θ (1-b21) [body τ _ called only. ' / Θ (1-b23) Γ Ν-( Ν 2 2 -|θ H2N02SvW|!i'f 'N-fj Μ° \ fi zero 2 'ystN - by f Θ - is less... 〇^° N〇2 N〇2 [cans] 1 N-yi!is〇2nh2 y 1 M〇,\〇rf, θ (1-b27) , 妙ΐ 〇·- \ ^γδ02ΝΗ2 J 02N -| 〇Ύ〇θ (1-b29 )-- secret τ J (1-b22) (1-b24) (1-b26) (1 7 28 > (1-b30) I53941.doc -17- s 201142495

θ (1-632) θ (1-b34) (1-b36) Θ (1-b38) e

(1-b40) θ 153941.doc • 18 - 201142495

153941.doc •19- 5 201142495

In the compound (1), it is derived from dibenzo. A preferred example of the cation of the compound is a cation represented by the formula (I-Cl) to the formula (1-C48). 153941.doc -20· 201142495

(1-c1) Φ

(1^2)

®

153941.doc -21 · 201142495

153941.doc -22- 201142495

(1-c25)

(1-c26)

Θ

(1<26)

Θ ^

s 153941.doc -23- 201142495 Φ φ

The compound (1) can be produced by forming a chromium salt with a chromium compound using a compound represented by the formula (Id) (hereinafter sometimes referred to as "compound (Id)"), and then making the chromium salt and dibenzo a pyran compound for salt exchange reaction; or 153941.doc -24 - 201142495 using compound (ld) and cobaltation

At the test, the substance forms a cobalt-staggered salt, and then the cobalt is mis-exchanged with a salt of the compound (b).

(1d) [In the formula (a4), Ri~R5 " A ^ R and R 9 represent the same meaning as in the formula (1)]

[In the formula (b), R21 to r28b. A ^ R and 11 represent the same meanings as those in the formula (1). A- represents a monovalent anion] The valent anion may be exemplified by cr, ΒΓ·, I-, cl〇4-, pf6· or BF4j. The dipyridylpyran compound (b) can be produced by reacting a compound of the formula (b0) with a compound of the formula (bl) in an organic solvent.

(bo)

[In the formula (bo) and the formula (b1), R21 to R28 and η represent the same meanings as those in the formula (1). Α· indicates the same meaning as in the formula (b). In the above reaction, the reaction temperature is preferably 15 〇 c 6 6 〇 t, and the reaction time is preferably 1 hour to 12 hours as compared with 153941.doc • 25· 201142495. Further, in terms of shortening of the reaction time or improvement of the yield, it is preferred to use an acid catalyst and/or a dehydrating agent. Examples of the acid catalyst include sulfuric acid, p-sulfonic acid, and the like. Examples of the dehydrating agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, and 1-ethyl-3-(3-didecylaminopropyl)carbodiimide salt. Carboxylides such as acid salts; alkyl-2_halopyridine rust salts; 1,1,-carbonyldiimidazole; bis(o-oxo-3-oxazolidinyl)phosphinic acid hydride; 2-pyridyl % I acid salt or the like. Among them, as a dehydrating agent, from the viewpoint of ease of post-treatment and purification, "T' is preferably lethyl_3_(3-dimethylaminopropyl)carbodiimide hydrochloride. Examples of the organic solvent used in the above reaction include dichloromethane, imitation, tetrahydrofuran, toluene, acetonitrile and the like. Become a chemical. The compound (10) of the ligand of the wrong anion of the substance (1) is widely known in the field of the art, and can be produced by a method in which a diazo rust salt and a heart compound are coupled to a heavy nitrogen. For example, a compound represented by the formula (1 r^na. π butylamine (diazo component) (hereinafter sometimes referred to as a salt 〇 formula (lb) can be used as a nitrous acid, a cerium nitrate salt or a nitrite ester. Above weight

R

NH2 Rf1 〇H (la)

[In the formula (la) and the formula (lb), R] 丨 ~ 丨 4 indicates that A 丨 indicates an inorganic or organic anion] is not the above-mentioned inorganic cation, and for example, the same as the one in the formula (1) meaning. I5394l.doc, chloride

•26, 201142495 = such as organic ions such as evolutionary ions, mothium ions, perchlorate ions, hypochlorous acid, etc., for example, CH3COO·, PhCOO·f can be cited as subtractive ions, desert ions, and yang coo• Wait. By linearly coupling the compound of the formula (lb) with the compound of the formula (1C) in an aqueous solvent, the compound (9) represented by the formula (1) can be sometimes referred to as a substance (1 d)"). The reaction temperature is preferably -5. (1 to 60 ° C, more preferably 〇 ° C to 3 ° ° C. The reaction time is preferably from 1 hour to 2 hours, more preferably from about 2 hours to 4 hours. As the above aqueous solvent, for example, N- Methyl (4) and so on.

[In the formula (1C), R to R5 & R19 represents the same meaning as in the formula (1)] The compound (Id) has -S02R29, and the ?3〇2 rule 29 is _8〇 to 1〇13. Alternatively, it may be produced by using an amine (la) having -S〇2NHR30, preferably by a coupling reaction using an amine (la) having a sulfo group, followed by sulfonylation with a sulfo group. For example, for the compound (ld), an azo compound having a sulfo group (hereinafter referred to as "compound (ls)") may be synthesized in advance, and the sulfo group (-S〇3H) may be subjected to sulfonium self-crystallization by a sulfinium compound. (_S〇2X, X is a halogen atom), a sulfonium halide compound is obtained, and then a sulfonium halide compound is reacted with an amine (r3〇NH2), whereby a sulfo group is sulfonated to produce a compound (ld). 153941.doc •27· 201142495 Specific examples of the compound (Is) include a compound represented by the formula (1_al), the formula 〇a2), and the formula (1-a5) to (l-a2〇), preferably exemplified. formula. ^), (l-a6), (l-al5) and (1_al6) compounds. Examples of the sulfinium compound include sulfinium fluoride, sulfinium chloride, sulfinium bromide, and sulfinium iodide. Preferred examples thereof include sulfinium gas and sulfinium bromide. Sulfur and sulphur. The sulfene halide is preferably used in an amount of from 1 to 10 moles based on the mole of the compound. Further, in the case where water is mixed in the reaction system, it is preferred to use a sulfoxide halogen compound excessively. The term Sf is preferably carried out in a solvent. Examples of the solvent include ethers such as 1,4-dioxane (particularly cyclic ethers); gas-like, dichlorodecane, carbon tetrachloride, 1,2-diethane, and Halogenated hydrocarbons such as ethylene, trichloroethylene, perchloroethylene, di-propane, gas pentane, i, 2 dibromoethane, and the like. The amount of the solvent to be used is usually 3 parts by mass or more, preferably 5 parts by mass or more, and usually 1 part by mass or less, preferably 8 parts by mass or less, based on 1 part by mass of the compound (ls). Further, when the sulfonium is halogenated, it is preferred to use N,N-dialkylformamide in combination (for example, N,N-dimercaptocarbamide, N,N_:ethylguanamine is equivalent to using N,N_di burned In the case of a mercaptoamine, the amount used is generally 0.05 to 1 mol relative to the sulfinium halide compound 1 mol. If the compound (ls) and the hydrazine dialkylformamide are in a solvent The pre-mixing and addition of the sulfite halogen compound 'suppresses heat generation. The reaction temperature at the time of the granulation is usually 〇 ° C or more, preferably 3 (rc or more ' and 70 ° C or less, preferably 6 〇. The reaction time is, for example, 0.5 hours or more, preferably 3 hours or more, and usually 8 hours or less, and 153941.doc • 28 to 201142495 is preferably 5 hours or less. The compound can be reacted with the amine (h2) directly after the separation from the amine (r3〇nh2) or without isolation, and the reaction mixture is mixed with water in the case of isolation. The precipitated crystals may be used. The reaction of the obtained dentate M mm and peak %H2) is washed and dried as needed. (R30NH2), including n-propylamine, n-butylamine, n-hexylamine, dimethylhexylamine (1,5-dimethylhexylamine, etc.), tetramethylbutylamine (^3-tetramethylbutylamine, etc.) ), ethylhexylamine (2-ethylhexylamine, etc.), aminophenylphenylaminophenyl phenylbutane, etc.), isopropoxypropylamine, and the like. The amount of the amine (R30nh2) to be used is usually in the range of not less than 1 part by mole, more preferably 2 moles or more, and 7 moles or less, relative to the moles of the compound. The order of addition of the sulfonium compound to the amine (R3〇NH2) is not particularly limited, and it is preferred to add (drop) the amine to the sulfonate compound (Han 3 (^^^, saponin compound and WR3〇) The reaction of NH2) is preferably carried out in a solvent. For the solvent, the same solvent as that used in the preparation of the sulfonate compound can be used.

The reaction of S and the two dentate compounds with an amine (R3?NH2) is preferably carried out in the presence of an inert catalyst. Examples of the basic catalyst include aromatics such as aliphatic tertiary amines such as triethylamine and triethanolamine; tertiary amines 1 and secondary amines (aliphatic secondary amines such as diethylamine; Or a cyclic aliphatic secondary amine), etc. Among them, a tertiary amine is preferred, and an aliphatic tertiary amine such as triethylamine is particularly preferred. The amount of the basic catalyst used is relative to the amine (RUN%). Usually 1.1 moles or more, 6 moles or less, preferably u moles above 2, 5 moles = 153941.doc •29·201142495. Adding amines (R3〇NH2) and alkaline touches to the sulfonate compounds In the case of the medium, the addition timing of the alkaline catalyst is not particularly limited, and the amine (R^NH2) may be added before or after the addition, and may be added at the same timing as the amine (R3〇NH2). The amine may be added after premixing, and may be separately added separately from the amine (R3〇NH2). The reaction temperature of the sulfonium compound and the amine (R30NH2) is usually from 01 to 50 C or less, preferably from 0 °c to 30 °. The reaction time is usually 1 to 5 hours. The compound which is the target compound is obtained from the reaction mixture (the method of the magic is not particularly limited) Various known methods can be employed. For example, it is preferred to mix the reaction mixture with an acid (e.g., acetic acid, etc.) and water to extract the precipitated precipitate. With respect to the above acid, it is preferred to prepare an aqueous acid solution in advance. The reaction mixture is added to the above aqueous solution, and the temperature at which the reaction mixture is added is usually 10 C or more and 5 〇t or less, preferably 20 〇 c or more and 5 Å or less, more preferably more than three or less. After the reaction mixture is added to the water bath of the crucible, it is preferably stirred at the same temperature for about 0.5 to 2 hours. The crystals to be filtered and washed are preferably washed with water or the like, followed by drying. Further, it can be further purified by a known method such as recrystallization. In the case where the anion portion of the compound (1) is a chromium cation anion (W in the formula (1) is (7), the compound (10) and the chromium compound can be used in an aqueous solution. It is usually produced by a reaction at 70 to HHTC. It is preferred to react the compound (10) with a chromium compound at a molar ratio of 2:1 to 4:1. Examples of the chromium compound include chromium formate, chromium acetate, and chromium chloride.153941.doc • 3〇· 201142495 Chromium fluoride, etc., preferably include chromium formate, chromium acetate, etc. The sigma (1) can be dissolved by dissolving the chromium salt with the dibenzopyran compound (b). It is produced by performing a salt exchange reaction. Preferably, the chromium salt is reacted with the dibenzopyran compound (b) at a molar ratio of 1:1 to 1:4. The anion portion of the compound (1) is cobalt. In the case of a wrong anion (Ml*Co in the formula (1)), it can be produced by reacting the compound (ld) with a cobalt compound in an aqueous solvent at 70 to 100 C. Preferably, the compound ( Ld) reacts with the cobalt compound at a molar ratio of 2:1 to 4:1. Examples of the cobalt compound include cobalt chloride, cobalt acetate, cobalt sulfate '(2'4-pentanedionate) cobalt (m), and the like, and preferably tris(24-pentanedionate) cobalt ( 111) and so on. The compound (1) can be produced by subjecting a cobalt stearate to a dibenzopyran compound (b) in a dissolution reaction in a salt J. It is preferred to make the salt and dibenzo. The specific compound (b) is reacted at a molar ratio of 1:1 to 1:4. Specific examples of the compound (1) include a compound represented by the formula (1_υ~formula (126), etc. 15394I.doc -31- 201142495

ι^^ΟΗ 153941.doc -32- 201142495 Θ 'Ν

Ο〆. ,

S〇2NH2

SC^NH, so2nh2 Θ Θ

©

Θ

'0, (1-6) (1-7) (1*8)

-ο Η, ρ,'

© S〇2NH2

(1-10) 153941.doc -33- 201142495

153941.doc -34- 201142495

153941.doc -35- 201142495

153941.doc -36- 201142495

In the case where the solubility is high, it is sometimes referred to as "the compound (1) in the organic solvent" is preferably a compound of the formula (2) ((7)").

[In the formula (2), R to R18 are independent of each other. The monovalent aliphatic hydrocarbon group of 1 to 8 and the exact group, and R29 represents -OH or -NHR30. No hydrogen atom, halogen atom, carbon number -S〇2R29 or -s〇2r32. R3 represents a hydrogen atom, a carbon number of 1 to ..., a hydrocarbon group, a carbon number

S 153941.doc •37· 201142495 1~4 alkylate substituted hexanyl group, _r31_〇_r32, r31_c〇_〇_r32, -R31-0-C0-R32 or aryl group with carbon number 7~10 . R31 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms. R32 represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms. R and R independently of each other represent a hydrogen atom, a thiol group, an ethyl group or an amine group. M1 represents Cr or Co. R to R each independently represent a hydrogen atom, an i-valent aliphatic hydrocarbon group having a carbon number of 丨8 or a monovalent aromatic hydrocarbon group having a carbon number of 6 to 10, and the aliphatic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may pass through a hydroxyl group. , _〇R32, sulfo, _s〇3Na, -SO3K or a halogen atom. R and R26 each independently represent a hydrogen atom or a methyl group. M1 is preferably Cr. Further, it is preferred that at least one of R to R丨8 is a peach «·········· By having a nitro group, there is a tendency for the heat to become higher. Preferably, at least one of R1 to R5 and at least R6 to Ri

The one is -S02R, which is: at least one selected from the group consisting of W2H (i.e., R29 is the collar) and Yang3 (i.e., R is -NHR). When the compound (7) has _S〇2R32, it is preferred that at least one of r15 to Rl8 is -so2r32. The solid 1 to 8 monovalent aliphatic hydrocarbon group. Examples of the U-bean aliphatic group having a carbon number of 1 to 8 include the compounds of the above-mentioned Na R29 and m·Bao 33 which can be used as 2/, (fNH(10)-amine (R33NH2), and the above-mentioned amine.靱(1) Method of making a method i5394J.doc 38- 201142495 Specific examples of the compound (2) include the formula (1-1), the formula (13) to the formula (1_21), and the formula (1-23). a compound represented by the formula (1-26), wherein a compound of the formula (1-3), the formula (1-21) and the formula (1-23) to the formula (1-26) is preferred. The content of the colorant (Α) is preferably i% by mass or more and 99% by mass or less, more preferably 1% by mass or more and 8% by mass or less, and further preferably 3% by mass or more and 70% by mass. The coloring agent (A) may further contain a dye different from the compound (丨). Examples of the dye include dyes such as oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes, for example. It can be listed as a compound in the dye index (published by The Society of Dyers and Colourists), or as a dyeing note (dyeing company) The known dyes are specifically described as CI solvent yellow 4 (hereinafter, the description of the CI solvent yellow is omitted, and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98. '99, 162; CI Solvent Red 45, 49, 125, 130; CI Solvent Orange 2, 7, 11, 15, 26, 56, etc. CI·solvent dye; CI Acid Yellow 1, 3 '7, 9, 11 > 17, 23 > 25 '29 , 34 , 36 , 38 ' 40 ' 42 , 54 , 65 , .72 ' 73, 76 ' 79 '98 , 99 ' 111 , 112 , 113 , 114 , 116 , 119 , 123 , 128, 134 ' 135 ' 138 , 139 , 140 , 144 , 150 , 155 , 157 , 160 , 161 , 163 , 168 ' 169 , 172 , 177 , 178 , '179 , 184 , 190 , 193 , 196 , 197 , 199 , 202 , 203 , 204 , 205 , 207 ' 212 , 214 , 220 ' 221 , 228 , 230 , 232 , 235 ' 238 , 240 , 242 , 243 , 251 ;

S 153941.doc -39- 201142495 CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42 '44, 50, 51, 52 ' 57, 66 , 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206 , 211 , 215 , 216 ' 217 , 227 , 228 , 249 , 252 , 257 , 258 , 260 , 261 , 266 , 268 , 270 , 274 , 277 , 280 , 281 , 195 , 308 , 312 , 315 , 316 , 339 , 341 , 345 , 346 , 349 , 382 , 383 , 394 , 401 , 412 , 417 ' 418 , 422 , 426 ; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169 ' 173 ; CI acid violet 6B, 7, 9, 17, 19 and other CI acid dyes; CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182 '184 '204, 207 '211, 213 , 218 , 220 , 221 , 222 , 232 , 233 , 234 , 241 , 243 , 246 , 250 ; CI direct orange 34 , 39 , 41 , 46 , 50 , 52 , 56 , 57 , 61 , 64 ' 65 , 68 , 70 ' 96 ' 97 ' 106 , 107 ; CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104 Such as CI direct dye; as CI mordant dye, can be cited: CI mordant yellow 5, 8, 10, 16, 40. I53941.doc 201142495 20, 26, 30, 31, 33, 42, 43, 45, 56, 61 , 62 ' 65 ; CI mordant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; C·1. mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CJ. mordant purple 1, 2, 4, 5'7, 14 , 22, 24, 30, 31, 32, 37, 40, 41, 44 '45, 47, 48, 53, 58 etc. C.I. mordant dyes, and the like. The colorant (A) may further contain a pigment. Examples of the pigment include organic pigments such as violet pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38; ci·pigment xanthine, 3, 12, 13, 14, 15, 16, 17, 20 , 24, 31, 53, 83, 86, 93, 94, 109, 11〇, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, etc. Yellow pigment; CI pigment lamp 13, 31, 36 '38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigment; CI pigment red 9, 97, 105, 122, Red pigments such as 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, and the like. Among them, it is preferred to contain at least one selected from the group consisting of C.I. Pigment Yellow 138, 139, 150, C.I. Pigment Red 177, 242, and 254. By containing the above pigment, the transmission spectrum of the red photosensitive resin composition is optimized, and the chemical property is improved. • 41 · 153941.doc 201142495 These pigments may be used alone or in combination of two or more. The organic pigment may be subjected to a rosin treatment, a surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, a graft treatment on the surface of the pigment by a polymer compound, or the like, or a particle using a sulfuric acid micronization method. The treatment or the removal treatment using an organic solvent or water for removing impurities, the removal treatment by an ion exchange method using ionic impurities, or the like. The organic pigment preferably has a uniform particle size. The pigment dispersion liquid in a state in which the pigment is dispersed in the solution by the dispersion treatment of the pigment dispersant is used. Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, and polyester. A surfactant such as a polyamine system or a bupropion acid system. These pigment dispersants may be used singly or in combination of two or more. Examples of the pigment dispersant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), s'(10) (manufactured by Zeneca), and efka (Ciba) _ (AJin_. Fine_Techn. Manufactured by 公司___), etc. When using a pigment dispersant, it is better to use _ _ _ _ _ _ _ _ _ _ _ _ _ It is 5% by mass or more and 50% by mass or less. If the amount of the pigment dispersing agent is used in the above-mentioned 笳囹", it is possible to obtain a tendency to disperse the pigment dispersion of the sorrowful color. In the coloring agent (A) The content of the pigment is preferably from 1 to 97% by mass. The material is preferably (four) mass%, more preferably the ratio of the compound (1) to the pigment (mass ratio) is preferably MW: 153941.doc 201142495 1 more preferably 3 97 to 90: 1〇. By setting such a ratio, the optimum of the transmitted light 4 is easy to change, and high contrast and high brightness are favorably obtained. Further, heat resistance and chemical resistance are improved. 1) and selected from CI Pigment Yellow 138, CI Pigment Yellow U9, CI Pigment Yellow 15〇, c] the ratio of at least one of the group consisting of pigment red 177, c" pigment red 242 and CM_pigment red 254, preferably 3 · 97 to 90 · 10, more preferably 3 : 97 to 70 : 30. The solid content of the coloring sensation (A) 3 i is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, even more preferably from 10 to 50% by mass, based on the solid content of the colored photosensitive resin composition. Here, the solid content refers to the total of the components excluding the solvent in the colored photosensitive resin composition. If the coloring agent (A) contains a ® in the above range, the color concentration of the coloring sheet is sufficient, and the necessary amount of the binder polymer can be contained in the combination 4, so that the mechanical strength can be sufficiently formed. pattern. The colored photosensitive resin composition of the present invention contains a resin (B). The tree 曰 (B) ‘ is not particularly limited, and is preferably an alkali-soluble resin. Examples of the resin (1))' include, for example, the following resins [K1] [reverse 4]. [K1] a monomer having a cyclic ether having 2 to 4 carbon atoms is hereinafter sometimes referred to as (a)"), and at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (b) (hereinafter sometimes referred to as "(b)")). [K2] (a), (b), and a copolymer which can be copolymerized with (a) is different from (&) and (匕) (hereinafter sometimes referred to as "(4)") copolymer [K3] (b) Copolymer with (c) Copolymer [K4] A resin obtained by reacting (a) with a copolymer of (b) and (c). s 153941.doc -43- 201142495 By the resin (B) containing the structural unit derived from (4), the reliability of heat resistance and chemical resistance of the obtained colored pattern can be further improved. (a) is, for example, a cyclic ether having a carbon number of 2 to y · μ ", _ inverse 4 (for example, selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydroanthone ring (oxygen) The polymerizable compound (4) of at least one of the groups consisting of the heterocyclic pentane ring) and the polymerizable group other than the cyclic surface (4) is preferably a ring having a carbon number of 2 to 4 and an ethylenic carbon-carbon double bond. The early body is more preferably a monomer having a ring-shaped scale of 2 to 4 carbon atoms and a (meth)acrylic acid. In the present specification, "(meth)acrylic acid"" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expression "(Yin Yin Acrylic)" "(Meth) Acrylic Brewing" has the same meaning. For example, ^(4)' can be exemplified by a monomer having an epoxy group (8) (hereinafter sometimes referred to as "( "Al)"), a monomer having an oxetan group (4) may be referred to as "(10)" or a monomer (6) having a tetrahydroanthracene group (hereinafter sometimes referred to as (a3)"). Among them, the monomer (8) having an oxiranyl group is preferably a body (al-2) having a structure in which a cyclic olefin is epoxidized* (hereinafter sometimes referred to as "(ai 2)" ). 7 is a monomer (al) having an epoxy group, and means a polymerizable compound having a polymerizable group other than an epoxy group and an ethene group. (4)) A monomer having a structure in which a chain type smog is epoxidized (hereinafter, the stalk is "(4)..."), and a monomer having a structure in which a cyclic olefin is epoxidized is exemplified. (al_2). As (al), it is preferred to have an oxirane group and an ethylenic carbon-carbon double bond. 153941.doe 201142495 early body 'better for right-handed, ethene-based and (meth) propylene-oxygen Base monomer. Examples of (a 1 1) include (meth)acrylic acid glycidol, (meth) propylene & -β-methyl glycidol s, (meth)acrylic acid, ethyl fluoroacetic acid, and glycidol. Ethyl ether bond, _ vinyl group glycidyl (10), m-vinyl f-glycidyl hydrazine, p-glycidyl hydrazine, alpha-methyl-o-vinyl-glycidyl glycidyl, a_f-based Ethyl benzyl glycidyl ether, a-fluorenyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-bis(glycidyloxymethyl) Styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris (glycidoxymethyl) Styrene, 2.3.5-bis(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidyloxy) Styrene), 2.4.6-tris(glycidoxymethyl)styrene, and the like. As (al-2) ' may be exemplified by vinyl oxyethylene cyclohexene, i, 2 epoxide _4_ vinyl ring hexhouse (for example, Celloxide 2000, manufactured by Dasailu Chemical Industry Co., Ltd.), (mercapto) acrylic acid -3,4-epoxycyclohexyl decyl ester (for example, 0丫(:1〇1^1·A400 'made by Daicel Chemical Industry Co., Ltd.), (meth)acrylic acid-3,4·epoxycyclohexyl fluorene An ester (for example, Cyclomer® 100' manufactured by Daicel Chemical Industries Co., Ltd.), a compound represented by the formula (I), a compound represented by the formula (Π), and the like.

153941.doc • 45· 201142495 [In the formulae (1) and (II), Ra & Rb independently of each other represents a hydrogen atom or a condensed group having a carbon number of 1 to 4, and a hydrogen atom contained in the alkyl group may be substituted with a radical. X1 and X2 are independent of each other and represent a single bond, -R,, *, "_〇_, * _RC_S_, and -R ·ΝΗ- 〇R, which represents a carbon number of 1 to 6; Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, and a third butyl group. Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxyl group include a hydroxymethyl group, a hydroxyethyl 2 I ylethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a benzyl-1-yl group. Ethyl ethyl, 2-cysyl small methyl ethyl, hydrazine, butyl butyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like. The preferred examples thereof include a hydrogen atom, a methyl group, a hydroxyindenyl group, and a benzylidene group, and a hydrogen atom or a methyl group. Examples of the alkanediyl group include a methylene group, an ethylidene group, a propanediyl group, a propyl group-1,3.diyl group, and a butyl group. - 丨, 4--based, pentylene, 10-5-diyl, hexene + 6-, as X1 and X2, preferably preferred are early bond, methylene, ethyl, 2-〇_ (* 〇 〇 社 社 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 The compound is a compound represented by the formula (1-1) to the formula (1-15), etc. Preferably, the formula (M) (1-9), the formula d-11) to the formula (115, , ) are exemplified. () Equation (4), Equation (1_15) Cut 5). More preferably, it can be enumerated (4), (4), 153941.doc -46· i? 201142495 Ο II H2C=CH-C-0 ch3 ou ^ I II H2c =c—C—0—ch2 ch3o u . I II li2c =c —c—o—c2h4 ο II H2C=CH-C—Ο—CH ο II h2c=ch-co-c2h4 Η2〇=ΟΗ—C —Ο—Ο ch3o 1 "

Inyn {J (1-11) H2C=i-S oII h2c=ch-c-o-c2h4-n ch3o I 11 Η2〇=0—C—0—C2H4—s 2Hsi? h2c=c-c—o CH2OH ο

HjCsCH-C -O -C2H4-S CH3o I II H2C=C-C-O-C2H4-N

(i-io)

Ch30 H2C=sc—c (1-13) "0~C2H4—〇

H2c=c C2H4OH o —c- (1-15)

Examples of the compound of the formula (n) include a compound represented by the formula (nD to formula (5), and the like. The formula of the car can be exemplified (π-D, formula („.3), cut 15), and formula (π). 7), Formula (11-9), Formula (nn) to Formula (ΙΜ5) β are more preferably a formula (111), a formula (11_7), a formula (ΙΙ-9), and a formula (11-15). .doc S. •47· 201142495 Η2〇:ΟΗ**〇**·〇Η2〇:〇Η一C—〇—CH2 H2C:CH—C—〇—C2H44 H2C:CH—C—〇—C2H4 — 〇 CH30 h2c=c—c—〇—

CH30 I II H2〇=C—C—0—C2H4—N 9η3〇...” II »2〇^〇—〇·~0' ch3o u π I 11 H2C=5C—C—0—CH2 fH3〇Η20=〇 —〇一q一〇2h4—O o H2C:CH—c—〇—C2H4—s (Π·2) o « , H2C:CH—C—〇-C2H4—丨ch30 I II H2C=c一c—ο ^ο2η4—s

Wn one. Ch2oh o I II H2C—C c—o

(Π·15) C2H4OH o Η2〇=〇 c-o

The compound of the formula (I) and the compound of the formula (II) can be used alone. Further, these may be mixed at any ratio. When mixing, the mixing ratio is preferably Formula (I) in terms of molar ratio: Formula (II) is 5: 95 to 95: 5, more preferably 10: 90 to 90: 10 'Specially 20: 8〇~ 8〇: 2〇. The monomer (a2) having an oxetanyl group means a polymerizable compound having a polymerizable group other than an oxetane group and an oxetanyl group. Preferably, the second () is preferably an oxetan group and a B field; the 6 carbon-carbon double bond monomer is more preferably an oxetane group and a (meth) propylene oxide group. Single t as (a2) ' can be exemplified by 3 · methyl _ 3 • methyl propylene oxy methoxy oxa oxa ternary 3 fluorenyl-3- propylene fluorenyl oxetane oxetane, 3_B Alkyl acryloxymethyl methyl benzoate, 3-ethyl-3- propylene oxime 153941.doc -48· 201142495 _oxazepine, 3-methyl-3-f Propylene oxyethyl oxetane, 3-f-methyl-3-propenyloxyethyl oxetane, % ethyl _3_f propylene ethoxyethyl oxetane垸, 3 · ethyl _ 3 · propylene oxyethyl oxetane and the like. The so-called tetrahydrogen. The monomer (6) of the fluoromethyl group means a polymerizable compound having a polymerizable group other than tetrahydro sulfhydryl group and tetrahydrofuranyl group. The (4))' is preferably a monomer having a tetrahydroindenyl group and an ethylene carbon-carbon double bond, more preferably a monomer having a tetrahydrofuranyl group and a (sub)acryloyloxy group. Specific examples of the oxime 3) ′ are tetrahydrofurfuryl acrylate (for example, v# 150' manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetramethyl methacrylate, and the like. (4)) is preferable as (a)' in terms of further improving the reliability of heat resistance and chemical resistance of the obtained colored pattern. Further, from the viewpoint of excellent storage stability of the colored photosensitive resin composition, it is more preferably (al-2). Specific examples of (b) include unsaturated monocarboxylic acids such as acrylic acid, mercaptoacrylic acid, crotonic acid, o-/m-/p-vinylbenzoic acid, and maleic acid and antibutene. Acid, methyl maleic acid, decyl fumaric acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrogen Unsaturated dicarboxylic acids such as phthalic acid, i, 2,3,6 tetrahydrophthalic acid, dimercaptotetrahydrophthalic acid, anthracene, 4_cyclohexene dicarboxylic acid; methyl-5 _northene-2,3.dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene,5·carboxyl 5-methylbicyclo[2 2"] 153941.doc •49· 201142495 Hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxyl-6_曱a bicyclic unsaturated compound containing a carboxyl group such as a bis-cyclo[2.2.1]hept-2-ene, a 5-carboxy-6-ethylbicyclo[2.2.^heptene-ene; maleic anhydride, decyl cis-butane Adipic anhydride, itaconic anhydride, % vinyl phthalic acid gf, 4_ethylene phthalic acid needle, 3,4,5,6•tetraqi phthalic anhydride, 1,2,3 ,6-tetrahydroortene Non-saturated acid anhydride such as phthalic anhydride, dimercaptotetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2丄^heptane, phthalic anhydride (bicycloheptene dicarboxylic anhydride); Unsaturation of dibasic or higher polycarboxylic acids such as acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid mono [2-(methyl) propylene methoxyethyl] ester Mono[(meth)acryloxyalkylene]ester; α-(hydroxyindenyl)acrylic acid or the like which contains a trans-group and a slow-group unsaturated acrylic acid in the same molecule. Among these, from the viewpoint of the copolymerization reactivity or the solubility in an aqueous alkali solution, s ' is preferably a propene acid, a mercapto acrylic acid, a butyl succinic acid anhydride or the like. Examples of (c) include (meth)acrylic acid methyl ester, (mercapto)ethyl acrylate, (meth)acrylic acid n-butyl ester, and (mercapto)acrylic acid second butyl ester (mercapto)acrylic acid. Tributyl ester, (mercapto)acrylic acid _2·ethylhexyl ester, (decyl)decyl acrylate, lauryl (mercapto) acrylate, stearyl phthalate, (fluorenyl) acrylate Cyclopentyl ester, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0''6] fluoren-8-yl (meth) acrylate (this In the technical field, it is commonly used as (diylpentyl acrylate), dicyclopentyloxyethyl (decyl) acrylate, (fluorenyl) propyl 153941.doc • 50· 201142495 isodecyl enoate, Adamantyl (meth) acrylate, propyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (methyl) propyl methacrylate, (meth) propylene (Methyl) acrylates such as benzyl acetate; hydroxyl groups such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate (meth) acrylates; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate; bicyclo [2.2.1] hept-2-ene 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5- Hydroxymethyl dinucleus [2.2.1] hept-2-ene, 5-(2|-hydroxyethyl)bicyclo[221]hept-2-ene, 5-methoxybicyclo[2.2.1]hept_2_ Alkene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5'6-dihydroxydicycloalken, 5,6•di(hydroxyindenyl)bicyclo[2.2.1]heptan-2-diene, 5,6_bis(2,-transethylidene)bicyclo[2.21]hept-2-ene, 5,6-dimethoxybicyclo[221]hept-2-ene, 5,6-diethoxybicyclo [2.2.1] Hept-2-ene, 5-hydroxy-5-methylbicyclo[221]hept-2-ene, 5-hydroxyl 5 ethyl double 3 coat [2.2.1] hept_2_lean, 5-ylaminomethyl-5-fluorenylbicyclo[2.2.1]hept-2-ene, 5-t-butoxycarbonylbicyclo[221]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[ 2 2.im _2• ene, hong oxycarbonylbicyclo[2.2.1] heptane-2-, 5,6-bis(t-butoxy)bicyclo[2.2.1]heptane-2-thracene , 5'6-bis(cyclohexyloxycarbonyl)bicyclo[2 2 Dilute bicyclic unsaturated compounds; —N-phenyl cis-butane di-imine, N-cyclohexyl cis-butane-imide, N. benzyl, butene-imide, N-amber Amine _3 · maleimide benzoic acid S, N-bominoimine _4 cis-butan: brewing imine butyric acid s 153941.doc • 51- 201142495 ester, N-succinimide _6_ maleimide hexanoate, N_amber succinimide-3-synylene diimide propionate, N_(9-acridinyl) maleicene Dicarbonyl ruthenium derivatives such as amines; styrene, α-methylstyrene, m-based styrene, p-nonyl styrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacryl Nitrile, vinyl chloride, vinylidene chloride, acrylamide, acrylamide, vinyl acetate, 1,3-butadiene, isoprene '2,3-dimethyl", butadiene Wait. In the above, in terms of copolymerization reactivity and heat resistance, styrene, N-phenyl maleimide, N-cyclohexyl maleimide, N- are preferred. The group is a cis-butenylene imine, a bicyclo[2 21]hept-2-ene, and the like. In the resin [K1], the ratio of the structural unit derived from each monomer is preferably within the following range among all the structural units constituting the resin [K1]. The structural unit derived from (4): 60 to 98 mol% (more preferably 65 to 95 mol%), the structural unit derived from (b); 2 to 4 mol% (more preferably benevol%) When the ratio of the structural unit of the resin [K1] is within the above range, storage stability, developability, and solvent resistance of the cured pattern tend to be improved. The resin [K1] can be referred to, for example, the method described in the "Experimental Method for Polymer Synthesis" (Dazu Takashi, Chemical Tongren (Stock) Publishing House, the first edition of the i-print, the second edition of the second year of March 2). It is produced by reference to the documents described in the literature. Specifically, the following method can be exemplified: a predetermined amount of (4) and (b), a polymerization initiator, a solvent, and the like are added to a reaction vessel, and oxygen is replaced with nitrogen, whereby 153941.doc -52· 201142495 is used for mixing in a deoxidizing environment. 'heating, heat preservation. Further, the polymerization initiator, the solvent and the like used herein are not particularly limited, and any of the users in the field can be used arbitrarily. For example, examples of the polymerization initiator include an azo compound, -azobisisobutyronitrile, 2,2.-azobis(2,4-dimethyloxime), or an organic peroxide ( As a solvent, as long as it dissolves each monomer, the solvent described above can be used as a solvent for the photosensitive resin composition, and the obtained copolymer can be directly used for the reaction. The solution after the use may also use a solution which is diluted or diluted. It may also be used in the form of a solid (powder) by a method such as re-deeping, etc. 1 by using the solvent (D) described later in the polymerization. The solvent can be used directly after the reaction, so that the manufacturing steps can be simplified. The resin [K2]t, preferably, the ratio of the structural units derived from the respective monomers is within the following range among all the structural units constituting the resin [K2]. The structural unit derived from (4): 2 to 95% by mole (more preferably 5 to 8 inches), the structural unit derived from (8): 2 to (four) ear% (more preferably 5 to 35 mole%) from (4) The structural unit: 丨~65 mol% (better ^~ear %) If the structural unit of the resin (10)] is in the range of ±, there is storage stability, developability, solvent resistance of the hardened pattern, The heat resistance and the mechanical strength tend to be good. The square resin [K2] can be produced, for example, in the same manner as the method described in the production method of the resin [K1]. Specific examples thereof include the following methods: (4), (8), and (4) The initiator and the solvent are added to the reaction vessel, and the oxygen is replaced by nitrogen. 153941.doc -53· 201142495 This is mixed, heated and kept in a deoxidizing environment. The obtained copolymer can be directly used as the solution after the reaction. A concentrated or diluted solution may also be used, and a solid (powder) form may be used by reprecipitation or the like. In the resin [K3], the ratio of the structural unit derived from each monomer is preferably constituted. All structural units of the resin [K3] are in the following ranges. (b) 2 to 40 Ear %, more preferably 5 to 35 moles 0 / 〇 (c) 60 to 98 moles / 〇, more preferably 65 to 95 moles. / 〇 resin [K3] can be used, for example, as a resin [K1]t The method described in the production method is similarly produced. The resin [K4] can be obtained by adding (b) to ((a copolymer of hydrazine, and adding a cyclic ether having a carbon number of 2 to 4 (a)) The carboxyl group has a carboxyl group. First, the copolymer of (b) and (c) is produced in the same manner as the method described in the production method of [K1]. In this case, a structural unit derived from each monomer is preferred. The ratio of all the structural units constituting the copolymer of (b) and (c) is in the following range: (b) 5 to 50 mol%, more preferably ~μ mol% (c) 50 to 95 mol More preferably, it is 55 to 9 mole %, and then the cyclic ether having 2 to 4 carbon atoms of (a) and the slow base and/or carboxyl group contained in the structure derived from (4) in the above copolymer. After the manufacture of the copolymer of (b) and (4), the flask is replaced with air. (4), relative to (4) to (c), the environment inside the flask is set by nitrogen.

Amino fluorenyl) benzoate, etc., and relative to 0) Catalyst (for example, a total amount of tris(dimethyl)(C) is usually 153941.doc •54. 201142495 0.001~5 mass% of polymerization inhibitor (for example, p-benzoquinone, etc.), etc., can be added to the p-bottle, and the reaction can be carried out at 60 to 13 C for 1 to 10 hours, whereby the resin [K4] can be obtained. The reaction conditions such as the addition method, the reaction temperature and the time can be obtained. The amount of heat generated by the production equipment or the polymerization is appropriately adjusted. The polymerization method is the same as the polymerization condition. The addition method or the reaction temperature can be appropriately adjusted in consideration of the production equipment or the calorific value of the polymerization, etc. At this time, the amount of use (a) is relatively Preferably, it is 5 to 80 mol%, more preferably 10 to 75 mol%, and still more preferably 15 to 70 mol%. By setting it as the range, it has storage stability and developability. The balance between solvent resistance, heat resistance, mechanical strength and sensitivity tends to be good. Specific examples of the resin (B) ': (meth)acrylic acid_3,4_epoxycyclohexylmethyl ester/(meth)acrylic acid Copolymer, acrylic acid_3,4_epoxytricyclo[5.2.1.02·6]decyl ester/(meth)acrylic acid copolymer Resin [K1]; glycidyl (meth)acrylate / benzyl (meth) acrylate / (mercapto) acrylic copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer ,Acetyl-3,4-epoxytricyclo[5.2.1.02·6]decyl ester/(meth)acrylic acid/fluorene-cyclohexylmethyleneimine copolymer, 3-mercapto-3- (Mercapto) propylene fluorenyl fluorenyl oxetane / (mercapto) acrylic acid / styrene copolymer resin [K2]; benzyl (meth) acrylate / (mercapto) acrylic copolymer, styrene Resin such as /(mercapto)acrylic copolymer [K3]; resin obtained by adding benzyl (meth) acrylate / (mercapto) acrylate copolymer to glycidyl acrylate, p-(meth)acrylic acid Resin obtained by adding tricyclodecyl ester/styrene/(indenyl)acrylic acid copolymer to glycidyl (meth)acrylate, tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(A) (Acrylic acid) copolymer addition 153941.doc -55- 201142495 (mercapto) styrene glycidyl acrylate obtained by resin such as resin [K4], etc. Among them, preferably resin [ 1] and resin [Κ2], more preferably resin [Κ1], and thus preferably 3,4-epoxytricyclopropane [5.2.1.〇2.6]decyl ester / (mercapto) propionic acid The weight average molecular weight of the polyphenylene oxide of the resin (Β) is preferably 3,000 〜1 〇〇, 〇〇〇, more preferably 5, 〇〇〇 5 〇〇〇〇, and further preferably 5,000 〜 35,000, and more preferably 6, 〇〇〇~3〇〇〇〇, especially good 7, 〇〇〇~28,000. If the molecular weight is within the above-mentioned specifications, the hardness of the coating film is increased and the residual film rate is also The southerly and unexposed portions have a good solubility in the developer and a tendency to increase the resolution. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (?η)] of the resin (Β) is preferably from 1.1 to 6, more preferably from 2 to 4. The acid value of the resin (Β) is preferably from 50 to 15 Å, more preferably from 6 Torr to 135, and still more preferably from 70 to 135. Here, the acid value is a value obtained by subtracting the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be obtained, for example, by titration using a water-splitting aqueous solution. The content of the resin (B) is preferably 7 to 65 mass%, more preferably 13 to 6 mass%, still more preferably 17 to 55 mass%, based on the solid content of the colored photosensitive resin composition. When the content of the resin (8) is within the above range, the pattern ' can be formed and the resolution and the residual film ratio tend to be improved. The colored photosensitive resin composition of the present invention contains a photopolymerizable compound (to a photopolymerizable compound (as long as it is an active radical, an acid, or the like which is produced by the photopolymerization initiator (D) by irradiation of light). The polymerized compound 'is not particularly limited. The column can be exemplified by having a polymerizable carbon_carbon not 153941.doc

•56· 201142495 Compounds such as saturated bonds. The photopolymerizable compound (c) is preferably a trifunctional or higher functional photopolymerizable compound. Examples of the trifunctional or higher polyfunctional photopolymerizable compound' include, for example, pentaerythritol tetraacrylate vinegar, pentaerythritol tetramethacrylate 6, dipentaerythritol penta acrylate, propylidene, dipentaerythritol, and quinone酝8 acrylate, dipentaerythritol hexamethacrylate vinegar and the like. The photopolymerizable compound (c) may be used singly or in combination of two or more. The content of the photopolymerizable compound (C) is preferably from 7 to 65 % by mass, more preferably from 13 to 6 Gf %, based on the solid content of the colored photosensitive resin composition, and is preferably 17 55 % by mass. When the content of the photopolymerizable compound (c) is within the range described above, the curing is sufficiently performed, and the film thickness ratio before and after development is increased, and the undercut is less likely to occur in the pattern, and the adhesion tends to be good. The colored photosensitive resin composition of the fluorescing color contains a photopolymerization initiator (D). As the photopolymerization initiator (9), a polymerization initiator which is known to be a reactive active radical or an acid by the action of light is not particularly limited. The photopolymerization initiator (D) can also be used to produce a compound of an active radical, an acid or the like by the action of light, and a photopolymerization 5 starting assistant (9)). The photopolymerization initiation aid (9)) is a compound or a sensitizer for promoting polymerization of a photopolymerizable compound which initiates polymerization by a photopolymerization initiator. As the photopolymerization initiator (D), it is preferred to produce a living compound 15394I.doc • 57· 201142495 by the action of light. More preferably, it is an acetophenone compound, a tri-p compound, and a oxidative oxidation. A phosphine compound, a hydrazine compound, and a biimidazole compound. As the acetophenone compound, 'diethoxyphenyl benzene can be exemplified|, 2 - methyl 2 - phenanthyl-1-(4-methylthiophenyl) propyl- ketone, 2 dioxin Amino-1-(4-indolylphenyl)_2-benzylbutyring-1_鲷,2-didecylamino-1_(4-tylinylphenyl)-2-(4-indole Phenyl phenyl) butane-1-one, 2-hydroxy-2-methylphenylpropan-1-one, benzoic dimethyl ketal, 2_trans-base 2 fluorenyl-l -[4-(2-P-ethoxyethoxy)phenyl]propanone_ι·ketone, 丨_ylcyclohexyl phenyl ketone, 2-hydroxy-2-indolyl-1·[4-(1- The oligomer of a methyl vinyl) phenyl] propane ketone or the like is preferably 2-methyl-2-micolinyl-1 -(4-mercaptothiophenyl)propan-1-one, 2-Dimercaptoamino-1-(4-morpholinylphenyl)_2-benzylbutane-1-one and the like. Commercial products such as 1rgacure 369 '907 (the above is manufactured by Ciba Japan Co., Ltd.) can also be used. Examples of the three-tillage compound include 2,4-bis(trimethylsulfonyl)-6-(4-methoxyphenyl)-1,3,5-tri-n, 2,4-bis (trimethyl) _6·(4-decyloxynaphthyl)-1,3,5-three tillage, 2,4-bis(trichloromethyl)-6-to holly-base, ι, 3,5-three tillage, Bis(trichloroindenyl)_6_(4_nonyloxystyryl)_153,5_three tillage, 2,4_bis(dichloroindenyl)-6-[2-(5-methyl0fu°nan -2-yl)ethenyl]-indole, 3,5-triphthene, 2,4-bis(trimethylmethylfuran-2-yl)vinyl]_U3,5 three tillage, bis(dichloropurine -6-[2-(4-diethylamino-2-mercaptophenyl)ethenyl]-1,3,5-three-spray, 2,4-bis(tris-methyl)_6_ [2_(3,4-dioxalyl)vinyl]-1,3,5-three tillage, and the like. Examples of the fluorenylphosphine oxide-based initiator include 2,4,6-trimethylphenylnonyldiphenylphosphine oxide. Commercial products such as Irgacure 819 (manufactured by Ciba Japan 153941.doc • 58 - 201142495) can also be used. As the hydrazine compound, N-benzylideneoxy-i-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzoquinone-oxime-(4-benzene) can be cited. Alkylthiophenyl)octane-1-one-2-imine, N-ethyloxyl_ι_[9-ethyl-6-(2-methylphenylhydrazone)·9Η-carbazolyl -3-yl]ethane·ι_imine, N_acetoxy-purine, ethyl-6-{2·methyl-4-(3,3-dimethyl-2,4-di Oxecyclopentyloxy)phenylphenyl}}-9-oxazolyl-3-yl]ethane-indole-imine. Commercial products such as Irgacure OXE-01, 〇χΕ-02 (above, Ciba Japan) and N-1919 (made by ADEKA) can also be used. As the biimidazole compound, 2,2'-bis(2-phenylphenyl)-4,4,5,5'tetraphenylbiimidazole, 2,2·-bis(2,3·dichlorophenyl) can be mentioned. )_4,4,,5,5,_tetraphenylimidazole (for example, refer to Japanese Patent Laid-Open No. Hei 6-75372, Sakamoto Special Spike No. 6-75373, etc.), 2, 2, _ double (2) _Chlorophenyl)_4,4,,5,5,_e phenylbiimidazole, 2,2,·bis(2-indolyl)_4,4,,5,51_tetra(alkoxyphenyl Saliva, 2,2,-bis(2- chlorophenyl)_4,41,5,5,_tetra(di-oxyalkyl)m-imidazole, 2,2'-bis(2-chlorophenyl) · 4,4,,5,5ι·tetrakis(trialkoxyphenyl)-linked oxazole (for example, refer to Japanese Patent Publication No. Sho 48-38403, 曰本专利专开昭62·1742〇罐公(4)) The phenyl group in which the phenyl group at the 4, 4|, 5, 5, and _ positions is substituted with an alkoxy group is exemplified (for example, refer to Japanese Patent Laid-Open Publication No. Hei 7 No. 913, etc.), etc. Preferably, 2, 2, _ double is used. (2_Chlorophenyl^yi^-tetraphenyl such as rice, 2,2-bis(2,3-dichlorophenyl)_4,4,,5,51_tetraphenyl-linked miso, 2' 2-bis(2,4-dichlorophenyl)_4,41,5,5,_tetraphenylbiimidazole. Further, 'as a photopolymerization initiator (9)' can be exemplified by benzoin, benzoin, scent (4), benzoin, benzoin, isobenzoquinone, etc. I53941.doc • 59· 201142495 Aroma compounds; benzophenone, ortho-benzene Ethyl mercaptobenzoate, 4-phenylidene benzophenone, 4-benzylidene-4,-methyldiphenyl sulfide, 3,3,,4,4,_four (second a benzophenone compound such as oxycarbonyl)benzophenone or 2,4,6•trimethylbenzophenone; an antimony compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine or camphor roller '· 10-butyl-2-gas acridine, benzophenone, methyl phenylglyoxylate, titanocene compound, etc. These are preferably the photopolymerization start aids (D1) described later ( In particular, amines are used in combination. Examples of the acid generator which generates an acid by light include, for example, 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate and 4-hydroxyphenyldimethylsulfonium hexafluorophosphate. Citrate, 4-acetoxyphenyl bisheptyl hydrazide p-benzoate, 4-ethyloxy-p-styl-fluorenyl-benzyl hexafluoroantimonate, triphenyl hydrazine Benzate, diphenyl sulphate, diphenyl hydrazine a sulfonium salt such as a dibasic acid salt or a diphenylphosphonium hexafluoroantimonate or a nitrobenzyl phthalic acid ester, a benzoin benzenesulfonate or the like. The photopolymerization initiator (D) may also be used, for example. The compound of the photoactive starter (D) is preferably 〇. The total amount of the photopolymerization initiator (D) relative to the resin (B) and the photopolymerizable compound (C) is preferably 〇. 1 to 3 〇 mass%, more preferably i 〜 2 〇 mass 〇 / 〇. When the content of the photopolymerization initiator is within the above range, the sensitivity is increased, the exposure time is shortened, and the productivity is improved. The colored photosensitive resin composition of the present invention may further contain a photopolymerization initiation aid (D1). The photopolymerization initiation aid (D1) is usually a compound or a sensitizer for use in combination with a photopolymerization initiator (D) for promoting polymerization of a photopolymerizable compound which initiates polymerization by a photopolymerization initiator. 153941.doc 201142495 The photopolymerization initiation aid (D1) may, for example, be an amine compound, a methoxy oxime compound, a 9-oxothiop-xanthene compound or a carboxylic acid compound. Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid ethyl acetate, and 4-dimethylamine. Isoamyl benzoate, _2-didecylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4, 4, · bis (dimethylamino) dibenzophenone (commonly known as miconesone), 4,4 · bis (diethylamino) benzophenone, 4, 4, bis (ethyl A mercaptoamino)diphenyl fluorenone or the like, of which 4,4,-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used. Examples of the alkoxy hydrazine compound include 9,1 fluorene-dioxaoxy onion, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9. , 10-diethoxy hydrazine, 9,1 fluorene dibutoxy fluorene, 2-hexyl -9, 1 fluorene dibutoxy ketone, and the like. As the 9-oxygen sulphate, the sulphate compound can be exemplified by 2_isopropyl-9-oxathione, 4-isopropyl-9-oxythione, 2,4-diethyl-9-oxythione 2,4-Dichloro_9_oxysulfur "Shanxixing, 1-chloro-4-propoxy-9-oxopurine p-star, etc. Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethyl stearylacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, and methoxyphenylthioacetic acid. , bis-oxyphenylthioacetic acid, gas phenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxy Acetic acid and the like. The photopolymerization initiation aid (D1) may be used singly or in combination of two or more. When the photopolymerization start-up aid (D1) is used, the amount thereof is preferably 0.015 to 5.00 - 201142495, preferably 0.01 to 5 moles of the polymerization initiator (D), and 1 mole is preferably 〇〇. 1~1 〇 Mo ear. The colored photosensitive resin composition of the present invention contains a solvent (8). The solvent (8) is not particularly limited, and a solvent which is usually used in the field can be used. For example, it can be used from vinegar solvent (solvent containing _c〇〇_), oxime solvent other than ester solvent (solvent containing -0-), ether ester solvent (solvent containing _c〇〇·and _〇_), ester A ketone solvent other than a solvent (a solvent containing _co·), an alcohol solvent, an aromatic hydrocarbon solvent, a guanamine solvent 'dimercapto sulfoxide, etc. are selected and used. Examples of the ester solvent include decyl lactate, ethyl lactate, butyl lactate, methyl 2-mercaptoisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetonate, amyl formate, and isoamyl acetate. , butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, decyl pyruvate, ethyl pyruvate, propyl pyruvate, decyl acetate, ethyl acetate, ring Hexanol acetate, γ-butyrolactone, and the like. Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoterpene ether, diethylene glycol monoethyl ether, and diethyl ether. Glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl hydrazine, propylene glycol monopropyl acrylate, propylene glycol monobutyl bond, > methoxybutanol, decyloxy-3-methylbutanol, tetrahydrofuran, tetra Hydropyran, 1,4-bis", adiethylene glycol dioxime ether, diethylene glycol diethyl ether, diethylene glycol oxime ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl Ether, anisole, phenethyl ether, methyl anisole, and the like. Examples of the ether ester solvent include methyl methoxyacetate, ethyl decyloxyacetate, butyl oxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate 153941.doc 201142495, 3-methoxy Ethyl propyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, decyl 2-methoxypropionate, 2 methoxy Ethyl propyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, decyl 2-methoxy-2-methylpropionate, 2. Ethoxy 2 - ethyl methacrylate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Monoacetic acid vinegar, propanol monopropion acetate, ethylene glycol monoacetate, ethylene glycol monoacetate, diethylene glycol monoethyl ether acetate, diethylene glycol Monobutyl ether acetate and the like. Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butylene, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2-pentyl Ketone, cyclopentanone, cyclohexanone, isophorone and the like. Examples of the alcohol solvent include decyl alcohol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin. Examples of the aromatic hydrocarbon solvent include benzene, methyl bromide, diterpene benzene, and trichome. Examples of the guanamine solvent include N,N-dimethylamine, N[,N-dimethylacetamide, fluorenyl-pyridylpyrrolidone, and the like. These solvents may be used alone or in combination of two or more. Among the above solvents, in terms of coatability and drying property, an organic solvent having a boiling point of i atm of from i20 ° C to 180 ° C is preferred. Wherein 'preferably propylene glycol monomethyl acetic acid g, lactic acid ethyl, propylene glycol monomethyl mystery, ethyl 3-ethoxypropionate, ethylene glycol monoterpene ether, diethylene glycol monomethyl ether, two Glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone 'N, N-dimethyl

S 153941.doc • 63· 201142495 carbamide, N-methylpyrrolidone, etc., more preferably propylene glycol monomethyl ether acetate, ethyl lactate, ethyl 3-ethoxypropionate or the like. The content of the solvent (E) in the coloring photosensitive resin composition is preferably 70 to 95% by mass, more preferably 75 to 92% by mass based on the coloring photosensitive resin composition. In other words, the solid content of the colored photosensitive resin composition is preferably from 5 to 30% by mass, more preferably from 8 to 25 parts by mass. /〇. When the content of the solvent (E) is within the above range, the flatness at the time of coating is improved, and the color density is not insufficient when the color filter is formed, so that the display characteristics tend to be good. The colored photosensitive resin composition of the present invention may further contain an interface active agent (F). Examples of the surfactant (F) include a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant containing a fluorine atom. These may also have a polymerizable group on the side chain. The polyoxo-based surfactant may, for example, be an interfacial surfactant having a decane bond. Specific examples include: Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Polyether Modified Polyoxyl SH8400 (trade name, Toray Dow Corning) ))), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Mitto Hi-Tech) Material Japan Co., Ltd. (manufactured by Momentive Performance Materials Japan LLC) and the like. Examples of the fluorine-based surfactant include an interface activity of a fluorocarbon chain, 153941.doc-64·201142495, and the like. Specific examples include: Fluorad (trade name) FC430, Fluorad FC43 1 (manufactured by Sumitomo 3M), Megaface (trade name) F142D, Megaface F171, Megaface F172, Megaface F173, Megaface F177, Megaface F183, Megaface R30, Megaface RS -718-K (manufactured by DIC), Eftop (trade name) EF301, Eftop EF303, Eftop EF35 1, Eftop EF352 (Mitsubishi Materials Electronics Co., Ltd.), Surflon (trade name) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.), and the like. The polyfluorene-based surfactant containing a fluorine atom may, for example, be a surfactant having an anthracycline bond or a fluorocarbon chain. Specific examples

Megaface (registered trademark) R〇8, Megaface BL20, Megaface F475, Megaface F477, Megaface F443 (manufactured by DIC), and the like. These surfactants may be used singly or in combination of two or more kinds of the β-surfactant (F). The content of the coloring photosensitive resin composition is preferably 0.001% by mass or more and 〇2% by mass or less, more preferably 〇. 〇〇 2% by mass or more and 0.1% by mass or less, and further preferably 〇. 〇 1% by mass or more, 〇·〇 5% by mass or less. When the content of the surfactant (F) is within the above range, the flatness of the coating film can be improved. The coloring photosensitive resin composition of the present invention contains a coloring agent (A), a solvent-soluble resin (B), a photopolymerizable compound (c), a photopolymerization initiator (D), a solvent (E), and a surfactant. (F) is excellent in coatability, and a coloring pattern excellent in solvent resistance and spectroscopicity can be obtained. Forming a colored pattern as the colored photosensitive resin composition of the present invention

The method of S 153941. doc-65-201142495, for example, applies the colored photosensitive resin composition of the present invention to a substrate or another resin layer (for example, another colored photosensitive resin composition layer formed on the substrate) In the above, a volatile layer such as a solvent is removed/dried to form a colored layer, and the colored layer is exposed through a photomask to develop a method; and a method using an inkjet apparatus that does not require a photolithography method is used. The film thickness of the coating film at this time is not particularly limited, and may be appropriately adjusted depending on the material to be used, the use, and the like, and is usually O.iyO μηη, preferably Buj μ m ' is more preferably 1 to 6 μ claw. Examples of the coating method of the colored photosensitive resin composition include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAp (capillary) coating method, and a die coating method. Alternatively, a dip coater, a bar coater, a spin coater, a slit spin coater, or a slit coater (sometimes referred to as a die coater or a curtain coater) may be used. Coating by a coater such as a non-rotating coater. Examples of the solvent removal/drying include natural drying, air drying, pressure reduction drying, heat drying, and the like. The specific drying temperature is preferably from 1 〇 to 12 〇, more preferably from 25 to 100 ° C. The drying time is preferably from 1 second to 6 minutes, more preferably from 30 seconds to 30 minutes. The drying under reduced pressure is preferably carried out at a pressure of from 5 Torr to 15 Torr at a temperature of from 20 to 25 °C. The dried coating film is exposed through a reticle for forming a target pattern. The pattern shape on the photomask at this time is not particularly limited, and a pattern shape corresponding to the target use can be used. As the light source used in the exposure, it is preferable to generate a wave of 25 〇 to 45 〇 nm 153941.doc -66- 201142495. Specifically, a mercury lamp, a light-emitting diode, a metal toothed lamp, a funnel lamp, etc. may be mentioned, or a chopper that cuts off a specific wavelength range may be used for cutting off, or a band pass chopper that sweeps a specific wavelength domain may be selectively used for plucking. And exposure. It is preferable to use a mask to align the exposure machine, the stepper, etc., because the entire exposure surface can be illuminated with parallel rays or the alignment of the mask and the substrate can be accurately performed. The pattern can be obtained by performing development by dissolving a predetermined portion, for example, an unexposed portion, which is in contact with the developing solution after the exposure. The developer may, for example, be an aqueous solution containing a basic compound (potassium hydroxide, sodium carbonate, tetramethylammonium or the like) which may contain a surfactant. The developing method may be any one of a scouring method, a dipping method, a spraying method, and the like. Further, the substrate may be inclined at an arbitrary angle during development, and preferably washed after development. Further, post-baking can be performed as needed. The post-baking is preferably in the range of 150 to 230 ° C for 1 to 240 minutes. According to the present invention, it is possible to form a colored cured product (e.g., a colored coating film or a colored pattern) having high solvent resistance, and a high-quality color filter containing the same can be obtained. The colored photosensitive resin composition of the present invention can obtain a colored pattern and a color filter which are excellent in color density, brightness, contrast, sensitivity, resolution, heat resistance and the like. Further, a known display device can be used for a display device having such a color filter or a colored pattern as a part of a constituent member thereof, for example, a known liquid crystal display device, an organic EL (Electr 〇 luminescence, 153941.doc - 67- 201142495 Light) All kinds of machines related to color images, such as devices and solid-state imaging devices. EXAMPLES Hereinafter, the colored photosensitive resin composition of the present invention will be described in more detail by way of examples. In the examples, "%" and "parts" are % by mass and parts by mass unless otherwise stated. (Synthesis Example 1) <Synthesis of Compound (1-1)> After adding 75 parts of water to 7 parts of 2-amino-4-nitrophenol (manufactured by Wako Pure Chemical Industries, Ltd.), 'Addition of hydrogen 2_0 parts of sodium hydride was dissolved. Add 35% sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) to an aqueous solution under ice cooling, 9.5 wounds, and then add 3 5 % hydrochloric acid 3 0.0 parts and dissolve it, and collect for 2 hours to obtain a heavy weight. A suspension of a nitrogen salt. Then, 8.9 parts of a solution of hydrazine sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 36 parts of water was slowly added to consume excess sodium nitrite. Then, 13 parts of 3-mercapto-1(3,-aminosulfonyl)- 5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in 1 part of water, using hydrogen. Sodium oxide adjusts the pH to 8 〇. To the above, the suspension containing the heavy nitrogen rust salt was added dropwise thereto for 15 minutes, and a 10% sodium hydroxide solution was appropriately added so that the pH was controlled within the range of 7 to 7.5. After the completion of the dropwise addition, the mixture was further stirred for 30 minutes to obtain a yellow suspension. Stir for 1 hour. The resulting yellow solid was subjected to a reduced pressure of 60. (: Drying was carried out to obtain 17.9 parts of the compound represented by the formula (p_1) (yield 85°/.). 153941.doc .68- 201142495

H2N02S

(P,1) N〇2 10 parts of the compound of the formula (p-1) was added to 1 part of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolved 'addition of ammonium sulphate (III) After 3.1 parts of sodium pentoxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), it was heated under reflux for 4.5 hours. After cooling to room temperature, the reaction solution was poured into 15 parts of 20% saline solution, and the orange-red solid obtained after filtration was dried at 60° (:, to obtain 12.8 parts of the compound represented by the formula (2-1) ( 60%) 〇

θ ten

Na (2-1) In the 18 parts of Ruo Danming B (manufactured by Tokyo Chemical Industry Co., Ltd.), 170 parts of anhydrous chloroform (manufactured by Kanto Chemical Co., Ltd.) and camphor sulfonic acid (made by Aldrich) were added. 4-(N,N-dimethylamino)pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.), 18 parts of triethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) and searched for (10) minutes. 'Slowly added to i-ethyl·3_(3_dimethylaminopropyl)carbodiimide salt ❹ (and money pharmacy f (share) made of pottery added with water to mess with 47 parts pre-dissolved After the solution is formed, it is taken at room temperature for abundance. The liquid separation operation is carried out twice with 1 Ν hydrochloric acid solution _, then 10 〇 /

S 153941.doc -69· 201142495 β 孤尺15 0 Injury The organic layer was washed twice. Then, anhydrous magnesium sulfate was added and stirred for about 30 minutes, and the solvent was removed by evaporation of the drying agent, whereby 2 parts of the compound of the formula (g-indole) (yield: 9 %) was obtained. Determination of the compound of formula (g-1) (Beta analysis) Ionization mode = ESI+ : m/z = 575 +

Preparing a solution (si) by adding 4 〇 3 parts of methanol to 253 parts of the compound represented by the formula (ζ-1), and adding a methanol logo portion to 153 parts of the compound represented by the formula (g-1) to prepare a solution (tl ). Thereafter, the solution (si) was mixed with the solution (u) at room temperature, and stirred for about 1 hour. The resulting red solid was dried under reduced pressure at 60 ° C, washed with water (3500 parts), filtered, and dried under reduced pressure (10) to give 263 parts of the compound (dye Al) of formula (1). The yield was 65%). The structure of the compound of the formula (?-1) is determined by elemental analysis. The analysis machine thief system uses an ICP (Inductively Coupled Plasma) luminescence analyzer (ICPS-8100, manufactured by Shimadzu Corporation). C 55,6 Η 4.7 Ν 12.0 Cr 3.57

153941.doc 201142495 (Synthesis Example 2) <Synthesis of Compound (1-2)> Anhydrous chloroform (manufactured by Kanto Chemical Co., Ltd.) was added to 5 parts of Rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.). 4 parts, camphorsulfonic acid (manufactured by Aldrich Co., Ltd.), 3 parts of 4-(N,N-dimethylamino)pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.3 parts, diethylene glycol ( 39 parts manufactured by Wako Pure Chemical Industries Co., Ltd. and stirred for about 30 minutes. Then, it is added to the ethyl _3 (3-dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) in 2 parts of 9 parts, and 10 parts of anhydrous chloroform is added in advance. After dissolving the resulting solution, it was stirred at room temperature for about 2 hours. After two times of liquid separation operation with 1 Ν hydrochloric acid aqueous solution, 1 〇〇 /. The organic layer was washed twice with 100 parts of saline. Then, 12 parts of anhydrous magnesium sulfate was added and stirred for about 30 minutes, and then the desiccant was filtered and the solvent was distilled off, whereby a compound (yield: 85%) of the compound of the formula (g-2) was obtained. Identification of the compound of formula (g-2) (mass analysis) ionization mode = ESI+ :

Exact Mass : 566.3

A solution (S2) was prepared by adding a hydrazinopyrrolidinone oxime to 10 parts of the compound of the formula (ζ-1). Further, a solution (t2) was prepared by adding N-mercaptopyrrolidine to 5 parts of the compound of the formula (IV). Thereafter the solution is allowed at room temperature

S 153941.doc 201142495 (s2) was mixed with the solution (t2), and after stirring for about 1 hour, it was poured into 500 parts of water. The resulting red solid was filtered and dried under reduced pressure at 60 ° C, whereby 15 parts of the compound (yield A2) of the formula (1-2) (yield 95%) was obtained. The structure of the compound represented by the formula (1-1) is determined by elemental analysis. The analysis system was manufactured using an ICP luminescence analyzer (ICPS-8100, manufactured by Shimadzu Corporation). C 56.0 Η 4.9 Ν 12.2 Cr 3.47

θ

(1-2) (Synthesis Example 3) <Synthesis of Compound (1-3)> Formula (g-3) was obtained from the compound represented by the formula (rh-Ι) by the same method as in Synthesis Example 1. Compound. Further, a compound of the formula (1-3) (dye A3) was obtained by the same method as in Synthesis Example 1.

(rti-1) (g-3) 153941.doc -72- 201142495

(Synthesis Example 4) <Synthesis of Resin Solution B1> In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen gas was introduced at 0.02 L/min to adjust to a nitrogen atmosphere, and 305 parts by mass of ethyl lactate was added thereto. Heat to 70 ° C while stirring. Then, it is dissolved in 60 parts by mass of mercaptoacrylic acid, 3,4-epoxytricyclo[5.2.1.〇2.6]decylpropionate (the compound represented by the following formula (1-1) and the formula (II) -1) The compound was prepared by mixing 240 parts by mass of a molar ratio of 50:50 with 140 parts by mass of ethyl lactate, and the solution was added to the solution at a temperature of 7 for 4 hours using a dropping funnel. In a 0 °C flask. On the other hand, 30 parts by mass of the polymerization initiator 2,2 azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts by mass of ethyl lactate using another dropping funnel over 4 hours. The solution was added dropwise to the flask. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 1.3 χΙΟ 4, a solid content of 33% by mass, and an acid value of 34 mg-KOH/g. (solution) resin solution B

153941.doc •73· 201142495 (Synthesis Example 5) &lt;Synthesis of Resin Solution B2&gt; Introduction of Propylene Glycol Monomethyl Acetate in a Flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a gas introduction tube 〇〇 mass parts. Thereafter, nitrogen gas was introduced into the flask using a gas introduction tube, and the atmosphere inside the flask was replaced with nitrogen. Thereafter, the solution in the flask was heated to 1 Torr (r2, and then 2 parts by mass of benzyl methacrylate ι76, 30.2 parts by mass of methacrylic acid, and 36 parts by mass of azobisisobutyronitrile were contained in a dropping funnel over 2 hours. And a mixture of propylene glycol monomethyl acetate and 197 parts by mass was added dropwise to the flask, and further stirring was continued at 100 ° C for 2.5 hours after the completion of the dropwise addition to obtain a weight average molecular weight Mw of 9.8×103, a solid content of 34% by mass, and an acid. A resin solution B2 having a value of 1 〇 2 mg_KOH/g (in terms of solid content) (Synthesis Example 6) &lt;Synthesis of Resin Solution B3&gt; With a mixer, a thermometer, a reflux cooling tube, a dropping funnel, and a gas 333 g of propylene glycol monomethyl ether acetate was introduced into the flask of the introduction tube. Thereafter, the gas was introduced into the flask through a gas introduction tube, and the atmosphere inside the flask was replaced with nitrogen. Thereafter, the solution in the flask was heated to 1 After 〇〇 ° C, using a dropping funnel for 2 hours will contain N-benzyl maleimide Η.? g, benzyl methacrylate 70.5 g, mercapto acrylic acid 51.7 g, A Acrylic vinegar 90.0 g, azobisisobutyronitrile 5.2 g and propylene glycol A mixture of 185 g of vinegar acetate was added dropwise to the flask. After the dropwise addition, stirring was further continued for 5 hours at 1 ° C. After the stirring was completed, air was introduced into the flask through a gas introduction tube, which was 153941.doc - 74· 201142495 After replacing the atmosphere in the flask with air, 28.5 g of glycidyl methacrylate, 1.3 g of tris(dimethylamino)methylphenol and 0.165 g of hydroquinone were placed in a flask at 110 ° C. The reaction was continued for 6 hours, and a resin solution B3 having a weight average molecular weight Mw of 16×103, a solid content of 31%, and an acid value of 80 mg-KOH/g (in terms of solid content) was obtained. » Polystyrene-equivalent weight average molecular weight of the above resin The measurement was carried out by GPC (Gel Permeation Chromatography) under the following conditions: Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG2000HXL Column temperature: 40 °C Solvent: THF (Tetrahydrofuran, tetrahydro 0 013 012) Flow rate: 1.0 mL / min Solid concentration of the test solution: 0.001~0.01% Injection volume: 50 μΐ^ Detector : RI (Refractive Index, refractive index) Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, Fl, A-2500, A-500 (manufactured by Tosoh Corporation) (Example l) [Coloring sensitivity Preparation of Resin Composition 1] (A) Pigment: CI Pigment Red 242 22 parts Acrylic Pigment Dispersant 6.7 parts (B) Resin: Resin Solution B2 27 parts of propylene glycol monomethyl ether acetate 131 parts

S 153941.doc -75· 201142495 Mixing, using a bead mill to fully disperse the pigment, then mixing 7.1 parts 37 parts 32 parts 9.5 parts 1.6 parts 172 parts 33 parts 22 parts 0.1 parts (A) Compound (1): Dyes A1 ° (B) Resin: Resin solution B1 (C) Photopolymerizable compound: Dipentaerythritol pentanoic acid and a mixture of dipentaerythritol and hexaacrylic acid (KAYARADDPHA, manufactured by Nippon Pharmaceutical Co., Ltd.) (D) Light Polymerization initiator: JIANGg-specific compound (Ν-1919, manufactured by ADEKA Co., Ltd.) (D1) Photopolymerization initiation aid: 4,4'-bis(diethylamino)benzophenone (EAB- F, manufactured by Baotu Valley Chemical Co., Ltd.) (E) Solvent: propylene glycol monoterpene ether (E) Solvent: propylene glycol monoterpene ether acetate (E) Solvent: 3-ethoxypropionate ethyl ester (F) Interfacial activity Agent: Megaface F554 (manufactured by DIC) was used to obtain a colored photosensitive resin composition 1. [Formation of Pattern] The colored photosensitive resin composition 1 was applied onto a glass substrate (manufactured by Eagle 2000' Corning Co., Ltd.) by a spin coating method, and then prebaked at 100 c for 3 minutes. After cooling, the distance between the substrate coated with the colored photosensitive resin 'composition 1 and the mask made of quartz glass was set to 1 〇〇' using an exposure machine (TME-150RSK, manufactured by Topcon) under atmospheric conditions. Light irradiation was performed at an exposure amount of 8 〇mJ/cm 2 (365 nm reference). Further, as the reticle, a line and a gap pattern formed with 100 μm are used. After light irradiation, &lt; 吏 The substrate was at 23 in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of cesium hydroxide. (: under the dipping for 80 seconds for development, after washing, 'in the # box at 230. (: After 30 minutes, bake. After cooling, use the film 153941.doc -76- 201142495 thick measuring device (DEKTAK3, The film thickness of the obtained coloring pattern was measured and found to be 2.0 μm. [Evaluation of Solvent Resistance] In the above pattern formation, the same operation was carried out except that exposure was not performed using a photomask, and a coloring coating was produced. The obtained coating film was immersed in Ν-mercapto-2-pyrrolidone at 23 ° C for 30 minutes, and the spectrophotometer (OSP-SP-200, manufactured by Olympus Co., Ltd.) was used to measure the light, and the C light source was used. The isochromatic function determines the xy chromaticity coordinates (Rx, Ry) (ie, chromaticity) and brightness RY before and after the immersion in the XYZ color system of the CIE (Commission internationale de l'0clairage, International Commission on Illumination), and calculates the immersion When the Δ Eab wood was 2 or less, it was judged that the solvent resistance was good. The results are shown in Table 1 (Example 2) The same as Example 1 except that the dye A1 was replaced with the dye A2. The colored photosensitive resin composition 2 was obtained. In the same manner as in Example 1, except that the dye A1 was changed to the dye A3, the coloring photosensitive resin composition was obtained in the same manner as in Example 1. (Example 3) 3. The colored photosensitive resin composition 3 was evaluated in the same manner as in Example 1. As a result, good solvent resistance was obtained. (Example 4) (A) Pigment: CI Pigment Red 242 23 parts of acrylic pigment dispersant 6.8 parts (B) Resin: Resin solution B2 27 parts of propylene glycol monomethyl ether acetate 132 parts 153941.doc -77- 201142495 Mixing, using a bead mill to sufficiently disperse the pigment to obtain a dispersion a. : CI Pigment Red 177 5.1 parts of acrylic acid pigment dispersant 2.0 parts (B) Resin: Resin solution B2 5.3 parts of propylene glycol monoterpene ether acetate 24 parts were mixed, and the pigment was sufficiently dispersed and dispersed using a bead mill Compound a is mixed and further mixed with (A) compound (1): dye A3 6.4 parts (B) Resin: resin solution B1 25 parts (C) Photopolymerizable compound: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARADDPHA, Japan Manufactured by drug (stock) 29 parts (D) Photopolymerization initiator: oxime ester compound (N-1919, manufactured by ADEKA) 8.6 parts (D1) photopolymerization starter: 4,4'-double ( Diethylamino)benzophenone (EAB-F, manufactured by Hodogaya Chemical Co., Ltd.) 1.0 part (E) Solvent: propylene glycol monoterpene ether 180 parts (E) Solvent: propylene glycol monoterpene ether acetate 20 parts (E) Solvent: ethyl 3-ethoxypropionate 6 parts (F) Surfactant: 0.1 part of Megaface F554 (manufactured by DIC) to obtain a colored photosensitive resin composition 4. The colored photosensitive resin composition 4 was evaluated in the same manner as in Example 1. The results are shown in Table 1. (Example 5) 153941.doc -78 · 201142495 (A) Pigment: CI Pigment Red 242 22 parts Acrylic Pigment Dispersant 6.7 parts (B) Resin: Resin Solution B2 27 parts of propylene glycol monomethyl ether acetate 131 parts Mixing 'Use a bead mill to fully disperse the pigment, and then mix (A) Compound (1): Dye A1 7.1 parts (B) Resin: Resin solution B1 3 7 parts (C) Photopolymerizable compound: Dipentaerythritol pentaacrylate Mixture with 32 parts of pentaerythritol hexaacrylate in two seasons (KAYARAD DPHA, manufactured by Sakamoto Chemical Co., Ltd.) (D) Photopolymerization initiator: oxime ester compound (N-1919, manufactured by ADEKA Co., Ltd.) (D) Photopolymerization initiator: 2,4-bis(trichloromethyl)-6-sunflower base - 3.2 parts 1,3,5-three tillage (the compound represented by the following formula (Dt) XTAZ-PP, Nihon

(Manufactured by Siber Hegner Co., Ltd.) (D1) Photopolymerization start-up aid: 1.6 parts of 4,4'-bis(diethylamino) dioxinone (EAB-F, manufactured by Hodogaya Chemical Co., Ltd.) E) Solvent: propylene glycol monomethyl ether 172 parts (E) Solvent: propylene glycol monoterpene ether acetate 33 parts (E) Solvent: 3_ethoxy propionate ethyl ester 22 parts (F) Surfactant: Megaface F554 ( DIC (manufactured by DIC)) The coloring photosensitive resin composition 5 was obtained in 1 part. The colored photosensitive resin composition 5 was evaluated in the same manner as in Example 1. The results are shown in Table 1. 153941.doc -79- 201142495

CI3C

CI3C

(Dt) (Example 6) 12 parts 6.9 parts 8.1 parts 81 parts 11 parts 3·3 parts 13 parts (A) Pigment: CI Pigment Red 254 Acrylic Pigment Dispersant (A) Compound (1): Dye A2 Propylene Glycol Monomethyl Ether acetate mixing 'Use a bead mill to fully disperse the pigment to obtain a dispersion b. (A) Pigment: CI Pigment Red 242 Acrylic Pigment Dispersant (B) Resin: Resin Solution B2 Propylene Glycol Monomethyl Ether Acetate Mixing 65 parts, body b, mixing 7.0 parts, 30 parts, 39 parts, 8.9 parts, 1.0 part, 160 parts, 48 parts, 6 parts, 0.1 parts, 'after the pigment is sufficiently dispersed using a bead mill, after dispersing, and then mixing (Α) the compound (1) : Dye A3 (C) Photopolymerizable compound: a mixture of dipentaerythritol penta acrylate and dipentaerythritol (KAYARADDPHA, manufactured by Nippon Chemical Co., Ltd.) (B) Resin: Resin solution B1 (D) Light Polymerization initiator: bismuth vinegar compound (Nl%9, manufactured by ADEKA) (D1) Photopolymerization starter: 4,4,-bis(diethylamino) bismuth F, Baotu Valley Chemistry (manufactured by) () solvent: propylene glycol monoterpene ether (Ε) solvent: propylene glycol monoterpene ether acetate (Ε) solvent: 3-ethoxypropionate ethyl ester (F) interface Agent: Megaface F554 (DIC (shares) manufactured) 153941.doc -80 - 201142495 obtain colored photosensitive resin composition 6. The colored photosensitive resin composition 6 was evaluated in the same manner as in Example 1. The results are shown in Table 1. (Comparative Example 1) (A) Colorant: 〇rasolRedG (manufactured by Ciba Japan Co., Ltd.) 47.5 parts (B) Resin: Resin solution B3 16 parts (C) Photopolymerizable compound: dipentaerythritol pentaacrylate and dipentaerythritol 23 9 parts of hexaacrylate mixture (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 3.6 parts 2.8 parts 1.2 parts 267 parts 138 parts 〇.1 part (D) photopolymerization initiator. 2-methyl-2- T-linyl-1-(4-methylthiophenyl)propan-1-one (Irgacure 907, manufactured by Ciba Japan) (D) Photopolymerization initiator: 2,4-bis(trichloromethyl) )-6-Sunflower-based 1,3,5-tri-p well (TAZ-PP, manufactured by Nihon Siber Hegner) (〇1) Photopolymerization start-up aid: 4,4'-bis(diethylamino) ) benzophenone out of 8^F, manufactured by Baotu Valley Chemical Co., Ltd.) (E) Solvent: propylene glycol monoterpene ether (E) Solvent: propylene glycol monoterpene ether acetate (F) Surfactant: MegafaceF475 (DIC( (Production)) The colored photosensitive resin composition 7 was obtained by mixing, and the photosensitive resin composition 7 was colored and evaluated similarly to Example 丨. The results are shown in the table. (Comparative Example 2) 47.5 parts 13 parts 19 parts 2_9 parts 2.2 parts (A) Colorant: Orasol Red G (manufactured by Ciba Japan Co., Ltd.) (B) Resin: Resin solution B3 (C) Photopolymerizable compound: two Mixture of pentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD DPHA 'Daily Chemicals Co., Ltd. (D) Photopolymerization initiator: 2-mercapto-2- morpholinyl-1-(4-A Base thiophenyl)propane-1-one (Irgacure 907, manufactured by Ciba Japan Co., Ltd.) Soil (D) photopolymerization initiator: 2,4-bis(trichloromethyl)-6-sunflower base_13 5_三17井(TAZ-PP, manufactured by NihonSiberHegner Co., Ltd.) s 153941.doc -81 - 201142495 1.0 part 203 parts 203 parts 0.1 parts 9.6 parts (1) 1) Photopolymerization start-up aid: 4,4' - bis(diethylamino)benzophenone (five into 3-F 'Budonggu Chemical Co., Ltd.) (E) Solvent: propylene glycol monomethyl ether (E) Solvent: propylene glycol monomethyl ether acetate ( F) Surfactant: Megaface F475 (manufactured by DIC) Epoxy compound: Sumiepoxy ESCN-195XL-80 (manufactured by Sumitomo Chemical Co., Ltd.) The colored photosensitive resin composition 8 was obtained by mixing. The colored photosensitive resin composition 8 was evaluated in the same manner as in Example 1. The results are shown in Table 1. [Table 1] EXAMPLES EXAMPLES EXAMPLES EXAMPLES Comparative Example Comparative Example 1 2 4 5 6 1 2 Rx 0.641 0.641 0.650 0.642 0.642 0.645 0.645 Color Ry 0.325 0.326 0.327 0.327 0.325 0.295 0.296 RY 20.0 20.2 19.2 20.3 21.5 11.8 11.9 Solvent AEab1 0.9 0.9 0.8 1.1 1.2 *) 65 153941.doc • 82-1 The colored coating film was peeled off from the glass substrate during the N-methyl-2-pyrrolidone impregnation process, so the color difference AEab氺 could not be measured. (Synthesis Example 7) &lt;Synthesis of Compound (1-23)&gt; Addition to 7.5 parts of 2-amino-4-mercaptosulfonamide-6-nitrophenol (CAS No. 101861-04-5) After 65 parts of water, 1·3 parts of sodium hydroxide was added and dissolved. 6 parts of an aqueous solution of 35% sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto under ice cooling, and then 19.4 parts of 35% hydrochloric acid was added little by little and dissolved, and stirred for 2 hours to obtain a diazo content. A suspension of strontium salt. Then, an aqueous solution obtained by dissolving 5.6 parts of decylamine sulfuric acid (manufactured by Wako Pure Chemical Industries Co., Ltd.) in 26 parts of 201142495 water was gradually added to consume excess sub-sodium; 6 sodium sulphate β'-pyrrolidone (and The Wako Pure Chemical Industries Co., Ltd., in turn, made 5.6 parts of 3-methyl-1-phenyl-5-) suspended in 7 parts of water, and adjusted the value of ρ 为 to 8.0 using sodium hydroxide. The above-mentioned diazonium salt-containing suspension liquid was added dropwise thereto for 15 minutes, and a 10% sodium hydroxide solution was appropriately added so as to control the pH to a range of 7 to 7.5. After the addition, the mixture was further mixed for 30 minutes. • Litian This was obtained as a yellow suspension. Stir for 1 hour. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 11.7 parts of the compound of formula (p-2) (yield: 87%).

Add 1 part of the compound of the formula (p-2) to 100 parts of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolve it, and add ammonium sulfate (III) dodecahydrate (Wako Pure Chemical Co., Ltd.) Industrial (manufactured by the company) 3.1 parts, sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 1.1 parts, and then heated under reflux for 4.5 hours. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% saline solution, and the red solid obtained after filtration was dried at 60 ° C to obtain a compound of the formula (z-2), 13 parts (63 parts). %) 〇

(2-2) 153941.doc •83- 201142495 Identification of the compound of formula (z-2) (mass analysis) Ionization mode=ESI- : m/z=882.1(;M-Na+;r

Exact Mass: 905.1 A solution (S3) was prepared by adding 4030 parts of methanol to 253 parts of the compound of the formula (z-2). Further, a solution (t3) was prepared by adding 1 〇 8 parts of methanol to 153 parts of the compound represented by the formula (g-i). Thereafter, the solution (s3) was mixed with the solution (t3) at room temperature for about 1 hour. The resulting red solid was dried under reduced pressure at 6 (rc, washed with water, 3500 parts, and then dried under reduced pressure to give a compound of formula (1-23). A4) 263 parts (yield is 65%) The structure of the compound represented by the formula (1-23) is determined by elemental analysis. The analytical apparatus is an ICP luminescence analyzer (ICpS_810〇, manufactured by Shimadzu Corporation) C 55.6 Η 5.1 Ν 11.9 Cr 3.71

(Example 7) The colored photosensitive resin composition 7 was obtained in the same manner as in Example 1 except that the dye A1 was changed to the dye A3. In the same manner as in Example 1, the chromaticity coordinates of the colored coating film obtained by performing the coloring of the colored photosensitive cerium composition 7 were 153941.doc • 84· 201142495 (Rx ' Ry) (chromaticity) was (0.641 ' 0.326), the brightness RY is 20.3. Further, in the solvent resistance test, the color difference AEab* before and after the impregnation was 〇·7 and was good. The colored photosensitive resin compositions of Examples 1, 2 and 4 to 7 were used to form a colored coating film, which was able to withstand good solvent resistance. From this, it is understood that a color pattern and a high-quality color filter having good solvent resistance can be obtained [Industrial Applicability] The L color photosensitive resin composition of T:: can be well-formed. Patterns and high quality color filters.

S 153941.doc •85-

Claims (1)

201142495 VII. Patent Application Range: 1. A colored photosensitive resin composition containing a coloring agent, a resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and the coloring agent is a compound containing the compound represented by the formula (1). , [In the formula (1), R1 to R18 each independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, _s〇2R294_s〇2R32, and R29 represents -OH or -NHR30; R30; A hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, · R3L〇_r32, _r3丨_c〇_〇_ R32, -R31- 〇-CO-R32, or an aralkyl group having a carbon number of 7 to 1 ;; R represents a divalent aliphatic hydrocarbon group having a carbon number of 1 to 8, and R32 represents a monovalent aliphatic hydrocarbon group having a carbon number of 1 to 8; R19 and R2Q Independent of each other, represents a hydrogen atom, a methyl group, an ethyl group or an amine group; M1 represents Cr or Co; and R21 to R24 independently of each other represent a hydrogen atom, a carbon number aliphatic hydrocarbon group or a carbon number 6 to 10 monovalent aromatic hydrocarbon group. The aliphatic hydrocarbon group and the hydrogen atom contained in the aromatic smoky group may be substituted by a hydroxyl group, _ 〇R 3 2, a cis group, -S03Na, -S03K or a halogen atom; S 153941.doc 201142495 R25 and R26 each independently represent a hydrogen atom. Or a fluorenyl group; R27 represents an ethyl group, a propane-1,3-diyl group or a propane-1,2-diyl group; r28 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; η represents an integer of 1 to 4; At n When an integer of 2 or more is used, a plurality of R27s may be the same or different from each other]. 2. The colored photosensitive composition of claim 1, wherein the coloring agent further comprises a pigment. 3. The colored photosensitive resin composition of claim 2, wherein the pigment is selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Red 177, CI Pigment Red 242, and CI Pigment Red 254. At least one of the group consisting of. 4. The colored photosensitive resin composition according to claim 1 or 2, wherein the resin is a resin containing a copolymer having a cyclic ether having a carbon number of 2 to 4 and an ethylenically unsaturated double bond. A structural unit of a monomer and a structural unit derived from at least one selected from the group consisting of unsaturated tickic acid and unsaturated acid anhydride. A coloring pattern formed by using the colored photosensitive resin composition of claim 1 or 2. 6. A color filter 'which contains a colored pattern as claimed in claim 5. 7. a compound of the formula (2), 153941.doc 201142495 [In the formula (2) 'R~R丨8 are independent of each other, the dry gas shield point is not the atom, the halogen atom, the monovalent aliphatic hydrocarbon group of the carbon number 1~8, the nitro group s〇2R294_s〇2R32; R29 represents -OH or -NHR30; R represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, _r3I-〇- R32, HC0_0_ or a carbon number of 7 to 10; R31 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms; R32 represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms; methyl group, ethyl group or amine group R and R independently of each other indicate that the hydrogen atom Μ1 represents Cr or Co; R: R24 independently of each other represents a hydrogen atom, a carbon number (1) valent aliphatic nicotine group or a carbon number 6 to a valent aromatic hydrocarbon group, and the month is an aliphatic nicotine group. And the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a hydroxyl group, -OR32, sulfo 'S〇3Na, -s〇3k: or a dentate atom; and R and R6 each independently represent an argon atom or a methyl group]. 8. The compound of claim 7, wherein ^ is 〜 9. The compound of claim 7 or 8. At least one of R1~R18 is 153941.doc 201142495 IV. Designated representative figure: (1) The representative figure of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case , please reveal the chemical formula that best shows the characteristics of the invention: 153941.doc