TW201237118A - Colored photosensitive resin composition and compound - Google Patents

Abstract

A co1oed photosensithe resin composition comprising a colorant, a resin, a photopoymcrizable compounds a photopolymerization initiator, and a solvent, wherein the colorant comprises a compound represented by formula (i): wherein R1 to R16 independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, R10 and R20 independently represent a hydrogen atom, a methyl group, an ethyl group, or an amino group; M1 represents Cr or Co; R21 to R24 independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms; R26 and R20 independently represent a hydrogen atom or a methyl group; R27 represents an ethylene group, a propane-1, 3-diyl group, or a propanel, 2-diyl group; and n represents an integer of 0 to 3.

Description

201237118 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a colored photosensitive resin composition and a compound. [Prior Art] It is known that a color light-sensitive sheet used in a liquid crystal display element or a solid-state image sensor has a red pixel, and a colored photosensitive resin composition forming the red color pixel uses a dye as a colorant. For example, Patent Document 1 discloses a colored photosensitive resin composition containing Orasol Red G as a red dye. [Prior Art Document] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2009-163226 [Draft of the Invention] [Problems to be Solved by the Invention] The previously known colored photosensitive resin composition is solvent resistant. In terms of aspects, sometimes it may not be fully satisfied. [Technical means for solving the problem] The present invention provides the following [1] to [1]. [1] A colored photosensitive resin composition comprising a colorant, a resin, a photo-synthesizing compound, a photopolymerization initiator, and a solvent, wherein the colorant is a coloring agent containing a compound represented by the formula (1), 161700. Doc 201237118

[In the formula (1), R to R independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having a carbon number of 1 to 8, a nitro group or _s〇2R29, and R29 represents _R32, _〇H or ΝΉΙ130, R30 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, _R31_〇_r32, _r3丨_c〇〇_R32, -R31-〇-CO-R32 or an aralkyl group having 7 to 1 carbon atoms, R31 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R32 represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms. R19 and R20 independently of each other represent 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 monovalent aliphatic hydrocarbon group having a carbon number of 1 to 8 or a carbon number of 6~ The monovalent aromatic hydrocarbon group of 10%, the aliphatic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by a hydroxyl group, _R32, a subgroup, ?S03Na, -S03K or a halogen atom, and R and R26 are each independently Represents a hydrogen atom or a fluorenyl group, R27 represents an ethyl group, a propyl 1,3-diyl group or a propyl group, a 2-diyl group, and π represents an integer of 0 to 3' when n is an integer of 2 or more. Multiple Rs are identical to each other or With]. [2] The colored photosensitive resin composition according to [1], wherein Ri~Ris are each independently a hydrogen atom, a nitro group or -S02R29, R29 is -R32, and R32 is a carbon number of 1 to 8. The monovalent aliphatic hydrocarbon group, R19 and R20 are each independently a fluorenyl group, and R21 to R24 are each independently a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R25 and R26 are each independently a hydrogen atom, and η is hydrazine. [3] The colored photosensitive resin composition according to [2], wherein at least one of ri~ru is a hydrogen atom, at least one of which is a nitro group, and at least one of which is -S02R29. [4] The colored photosensitive resin composition of [3], wherein Ri to R1 are independently a gas atom. [5] The colored photosensitive resin composition according to [4], wherein at least one of Rn to Rl8 is a hydrogen atom, at least one of R11 to R18 is a nitro group, and at least one of R11 to R18 is at least one of _S〇2R29. [6] The color-sensitive photosensitive resin composition of the present invention, wherein the photopolymerization initiator contains a compound selected from the group consisting of an alkylphenone compound, a tri-farming compound, a mercaptophosphine oxide compound, an anthracene compound, and a biimidazole compound. At least one of the group of photopolymerization initiators. [7] The color-sensitive photosensitive resin composition according to [1], wherein W is a color filter of [8], which is a color-sensitive photosensitive resin composition according to any one of π] to [7] And formed. 161700.doc 201237118 m - A display device comprising a color filter as in [8]. [1〇] a compound of the formula (1),

[In the formula (1), R1 to RI8 independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having a carbon number of 1 to 8, a nitro group or a ?s2r29, and R29 represents -R32, -OH or -NHR30. , R30 represents a hydrogen atom, carbon number 1~8! a valence aliphatic hydrocarbon group, a cyclohexyl group which may be substituted with a carbon number of 1 to 4, _r3, _〇_r32, r3i_c〇_〇_R, -R31-〇-CO-R32 or a carbon number of 7 to 10 An aryl group, 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 R 9 and R 2 are independently represented by a hydrogen atom, a mercapto group or an ethyl group. Or an amine group, M1 represents Cr or Co, and R21 to R24 independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms 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 be substituted by a hydroxyl group, 〇R32, an exact group, •S03Na, -S03K or a halogen atom, and R25 and R26 each independently represent a hydrogen atom or a methyl group, 161700.doc 201237118 R27 represents an extension Ethyl, propyl-1,3-diyl or propyl-i,2-diyl, π represents an integer of 〇~3. When η is an integer of 2 or more, a plurality of R27 are the same or different from each other]. [Effect of the Invention] According to the colored photosensitive resin composition of the present invention, a colored cured product (for example, a coating film or a pattern) having high solvent resistance can be formed. [Embodiment] The colored photosensitive resin composition of the present invention contains a colorant, a resin, a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (Ε), and the colorant (VIII) is a content formula. (1) A coloring agent of a compound (hereinafter sometimes referred to as "compound (1)"). The compound (1) is a salt of a chromium cation anion or a cobalt cation anion with a cation derived from a compound of xanthene.

[In the formula (1), R1 to RU are independent of each other.

(1) 1 s eve 1 stretching atomic dentate atom, carbon number η η 之 之 之 aliphatic hydrocarbon group, the exact base or _ called r29, the inverse number R29 represents -R32, -OH or · NHR3. , R represents a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 丨8, a cyclohexyl group which can be substituted with an alkyl group having a carbon number of 161700.doc 201237118, _R31_〇_R32, r31_c〇〇-R32, -R31-〇-CO-R32 or an aralkyl group having a carbon number of 7 to 10, R31 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, R19 And R20 independently of each other represents a hydrogen atom, a mercapto group, an ethyl group or an amine group, M1 represents Cr or Co, and R to R24 independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having a carbon number of i to 8 or a carbon number of 6 to 10. The aromatic hydrocarbon group of the valence, the aliphatic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by a hydroxyl group, 〇R32, a subgroup, -S03Na, _s〇3K or a halogen atom, and R and R26 are each independently Represents a hydrogen atom or a fluorenyl group, R27 represents an extended ethyl group, a propionyl-1,3-diyl group or a C,4,2-diyl group, and η represents an integer of 〇~3. When n is an integer of 2 or more, the plural R27 are the same or different from each other]. Examples of the aliphatic hydrocarbon group having a monovalent number of carbon atoms of 1 to 8 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, a t-butyl group, a n-pentyl group, and a hexyl group. Base, n-heptyl, n-octyl, decyl, methyl butyl, anthracene, 3,3-tetradecylbutyl, didecylhexyl, 16-dimethylheptyl, 2-ethylhexyl and 1, 1,5,5-tetradecylhexyl and the like. Examples of the aliphatic hydrocarbon group having a carbon number of 1 to 4, that is, an alkyl group, may be methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl or t-butyl. . Examples of the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include a methylene group, an exoethyl group, a propionyl-1,3 diyl group, a propionyl group, a diyl group, a butyl group, a diyl group, and a butyl group.丨3-two 161700.doc 201237118 base, penta-1,5-diyl, and so on. A-1,6-diyl group, a heptane-1,7-diyl group, and an octane-1,8-diyl group are exemplified as a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and examples thereof include a phenyl group and a methyl group: a phenyl group. , dimethyl phenyl, trimethyl phenyl, ethyl phenyl, propyl benzene, butyl phenyl, aryl, etc.; aryl, benzyl, phenylethyl, 3- An aralkyl group such as phenylpropyl group. : a cyclohexyl group which may be substituted with a carbon group of a carbon number: 2 - methyl hexyl group, 2-ethylcyclohexyl group, 2 - propyl cyclohexyl group, 2 isopropylcyclohexyl group, butyl ring Hexyl, 4-methylcyclohexyl '4-ethylcyclohexyl, propylcyclohexyl, 4-isopropylcyclohexyl, 4-butylcyclohexyl, and the like. Illustrative examples of -R31-〇-R32 ': methoxydecylethoxymethyl, propoxymethyl, methoxyethyl, ethoxyethyl, propoxy: methoxy propyl Base, ethoxypropyl, propoxypropyl, 2-oxo-4-cyclomethoxybutyl, octyloxypropyl, 3-ethoxypropyl, 3-(2-ethylhexyloxy) Propyl and the like. Examples of the -R31-CO-oxime-R32 include a methoxycarbonylmethyl group, a methoxycarbonylethyl group, an ethoxycarbonylmethyl group, an ethoxycarbonylethyl group, a propoxycarbonylmethyl group, and a propoxy group. Alkylcarbonylethyl, butoxycarbonylindenyl, butoxycarbonylethyl and the like. Examples of -R31-〇-C〇-R32 include etidyloxymethyl, ethoxylated ethyl, ethylcarbonyloxyindenyl, ethylcarbonyloxyethyl, propylcarbonyloxymethyl Base, propyl methoxyethyl, butylcarbonyloxymethyl, butylcarbonyloxyethyl and the like. As -S〇2R29, a sulfo group; an amine sulfonyl group; 161700.doc 201237118 N-mercaptosulfonyl group, N-ethylamine sulfonyl group, N-propylamine sulfonyl group, N- Isopropylamine sulfonyl, N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-butylbutylsulfonyl, N-t-butylamine sulfonyl, N - amylamine sulfonyl, N-(l-ethylpropyl)amine sulfonyl, N-(l,l-dimercaptopropyl)amine sulfonyl, N-(l,2-di Propyl sulfonyl, N-(2,2-dimercaptopropyl)amine sulfonyl, N-(l-decylbutyl)amine sulfonyl, N-(2-methylbutyl Amine sulfonyl, Ν·(3-methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, fluorenyl-hexylamine hydrazino, Ν-(1,3-dimethyl Butyl)amine hydrazino, Ν-(3,3-dimethylbutyl)amine sulfonyl, hydrazine-heptylamine sulfonyl, N-(l-methylhexyl)amine sulfonyl, N -(l,4-didecylpentyl)amine sulfonyl, fluorenyl-octylamine sulfonyl, fluorenyl-(2-ethylhexyl)amine sulfonyl, N-(l,5-dimethyl ) hexylamine sulfonyl, N-(l,l,2,2-tetramethylbutyl)amine sulfonyl, decyl-allylamine sulfonyl, etc. Hydrocarbyl-substituted aminoxime; Ν-(2-methoxyethyl)amine sulfonyl, fluorenyl-(2-ethoxyethyl)amine sulfonyl, N-(l-methoxypropyl) Aminesulfonyl, Ν-(3-methoxypropyl)amine sulfonyl, Ν-(3-ethoxypropyl)amine, Ν-(3-propoxypropyl)amine Sulfonyl, Ν-(3-isopropoxypropyl)amine sulfonyl, Ν-(3-hexyloxypropyl)amine hydrazino, Ν-(2-ethylhexyloxypropyl) Amine sulfhydryl, ν-(3-t-butoxypropyl)amine hydrazino, fluorenyl-(4-octyloxybutyl)amine hydrazino, etc. substituted with -R31-0-R32 Sulfhydryl; N-(decyloxycarbonylmethyl)amine sulfonyl, N-(decyloxycarbonylethyl)amine hydrazino, N-(ethoxylated fluorenyl)amine fluorenyl, N -(ethoxy ethoxyethyl)amine sulfonyl, N.(propoxycarbonylindenyl)amine sulfonyl, N-(propoxymethylethyl)amine hydrazino, N-(butyl Alkyl sulfhydryl group, N-161700.doc 10 201237118 (butoxycarbonylethyl)amine sulfonyl group, substituted with -R31-CO-0-R32; Ethyloxyindenyl)aminesulfonyl, N-(ethyloxyethyl)amine sulfonate , N-(ethylcarbonyloxymethyl)amine sulfonyl, N-(ethylcarbonyloxyethyl)amine sulfonyl, N-(propylcarbonyloxyindenyl)amine sulfonyl, N-(propylcarbonyloxyethyl)aminesulfonyl, N-(butylcarbonyloxyindenyl)aminesulfonyl, N-(butylcarbonyloxyethyl)aminesulfonyl, etc. R3i_〇_C〇_R32 substituted aminoxime; N-cyclohexylamine sulfonyl, N-(2-methylcyclohexyl)amine sulfonyl, N-(3-indolylcyclohexyl)amine a sulfonyl group, an N-(4-fluorenylcyclohexyl)amine sulfonyl group, an N-(4-butylcyclohexyl)amine sulfonyl group, an aminesulfonyl group substituted with a cyclohexyl group having a substituent; -benzylaminesulfonyl, N-(l-phenylethyl)aminesulfonyl, N-(2-phenylethyl)aminesulfonyl, N-(3-phenylpropyl)aminesulfonate Indenyl, N-(4-phenylbutyl)aminesulfonyl, N-[2-(2-naphthyl)ethyl]aminesulfonyl, N-[2-(4-mercaptophenyl) Ethyl]aminosulfonyl, N-(3-phenyl-1-propyl)aminesulfonyl, N-(3-p-styl-1-methylpropyl)aminesulfonyl, etc. Substituted amine sulfonyl and the like. -S02R29 is -S〇2R32, _s〇2H or -so2nhr30. Among them, -S02R32 and -S〇2NHR30 are preferred. R3G as -S〇2NHR3Q, preferably a hydrogen atom or a monovalent aliphatic hydrocarbon group of carbon number 丨8 is more preferably a hydrogen atom or a 2-ethylhexyl group. In the case where the compound of the present invention has _so2r32, it is preferred that at least one of R to R14 and at least one of Rl5 to R18 are _s〇2R32. 161700.doc • 11 · 201237118 In the case of a plurality of -S02R32, a plurality of R32s may be the same or different from each other. R32 of -S〇2R32 is a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, preferably a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms. As the -SOaR32, a mercapto continued base, an ethyl continuation base, a propyl continuation base, an isopropyl continuation base, a n-butyl sulfonyl group, a second butyl sulfonyl group, and a third butyl group are mentioned. Sulfosyl, pentylsulfonyl, hexyl fluorenyl, heptyl aryl, octyl fluorenyl, 1-methylbutylsulfonyl, 1,1,3,3-tetramethyl Base sulfonate, 1,5-didecylhexylsulfonyl, 1,6-methylheptyl aryl, 2-ethylhexyl ruthenium and ι,ι,5,5-tetradecylhexylsulfonate醯基等. Among them, a methylsulfonyl group and an ethyl sulfhydryl group are preferred, and a fluorenylsulfonyl group is more preferred. Preferably, R1 to R18 are each independently a hydrogen atom, a nitro group or _3〇汛29. Preferably, at least one of R1 to R18 is a hydrogen atom. Further, it is more preferable that R1 to R1Q are each independently a hydrogen atom, and at least one of R to g to ru is a hydrogen atom. Further, it is more preferable that at least one of Ri to Ri4 and at least one of Ri5 to Ru are hydrogen atoms. 1 ϋ 1 8 & * ~ R Among them, one to nitro. Since there is a tendency for high heat resistance, it is preferable that one less R is a nitro group, more preferably a Ru~Ru, at least, and more preferably at least one of R"~ and r, 5 to ri8. At least one of them is a nitro group. Further, it is preferable that at least one of R1 to R18 is -S02R29, more preferably A14~, and at least one is -s〇2R29. Further, it is more preferable that at least one of R11 to R and at least one of R15 are ?s2R29. In the case of a plurality of -so2r 9 cases, a plurality of r29 may or may not be the same as 161700.doc -12· 201237118. Further, it is further preferably "丨. Each of them is independently a hydrogen atom, and at least one of Rn~ and one of R15~R丨8 is a hydrogen atom, at least one of R11 to R14 and at least one of R15 to RU. At least one of 丞KR and at least one of R~R is _8〇21129. R19 and R20 are each independently hydrogen "sub-wind mat methyl" ethyl or amine group, preferably independent of each other as f group or B Since m can increase the color density, it is preferably a hydrogen atom or a monovalent aliphatic hydrocarbon group having a carbon number of 1 to 8 which may have a substituent, more preferably a sub- or a carbon number of 1 to r2 to r24. The aliphatic hydrocarbon group having a valence of 8 or more is more preferably an aliphatic hydrocarbon group having a carbon number of 1 to 4 such as an ethyl group. The π and π are each independently a nitrogen atom or a methyl group, and preferably each independently is a wind atom. R27 is preferably an ethylidene group, more preferably an extended group. η is an integer of 0 to 3, preferably 〇铉 && , and a number, more preferably ^ if η is such a value , the raw material of the compound (1) is easily obtained. Further, it is more preferably R丨~R丨0, respectively, molybdenum* * & β is independently a hydrogen atom, and R1丨R14 is a small one and R丨5 R | 'or at least in the - Tin & ^ "RI5 RI8tb to Yi in a wind atoms, W4 of at least one

At least one of them is Nitrate &Rr> 15 n IQ L 八<芏> At least one of - and ~ is -SOj29, A, p2, D24, 'R and R20 are mutually independent methyl R ~R is independent of each other as a carbon number A, A, an aliphatic hydrocarbon group having a valence of 1 4, and r25 Han κ is independently 1; Qiaofeng mat, η is 0, R2, _r32, r32 1~4 A fatty hydrocarbon group of a valence. I61700.doc -13·201237118 A preferred example of the pyrazole azo compound which is a ligand of a wrong anion among the compounds (1) is exemplified by the formula (1-al) to the formula (l-a64). Compounds, etc.:

(1-a1) (1-a3) ho3s ho3s H03S

(1-a4) (1-a8) HO

(1-a9) H03S ^ OH H〇y

〇H HO too N〇2

H03S ^ OH HO N02

SO3H SO3H •so3h 〇H HO

HO HO3S ^ OH

N〇2 N=N. 1 d-a16)

OH HO

SO3H 14- 161700.doc 201237Π8 . N〇2V J 〇H H〇 .CH3

Άη=η- /_

H〇# 〇2N'i H〇3S

〇H H〇

〇H

C\ ,C\ n j4> o-a19)

(A-a2〇) N, fp, s〇3H 6h (8) H2H〇2?

Qr or

==νΛ ^s〇2hh2° OH H〇 〇H H〇 N=^

H^°2S

CrN

N

N two N-\ recognize (1-a23)

H〇2 〇2N

OH h^n=n_\>s〇2nh2 ^-a24) 〇H H〇

Qr ch3 (1-a25) HOa OH H〇H〇. ch3 nH H〇S〇2^^ (1-a26) σ (Va27) 0Γ N〇2 n^n=n^^s〇2nh2 〇HH〇( 1-a28) ^1-a3〇)

N=H- -s〇^H2

H3^ W=H- (Va29) H#〇多

H〇2

〇2N

OH H〇 H〇

Cl Pcr

N=N

H〇

n=n-A ^

N 丄, (1-a33) 〇H H〇 H2N°^ 〇钌 [ Η2Ν〇2^

仂V?〇〇.d〇c

(1 a-32) £r SJ OH HO H〇2 ^m=h^Xs H〇N〇2 S02HH2 U〇2 , N〇2 nU) — S〇2^H2 H〇H〇2 (A-a36 ) SO^iHz OH H〇

〇H HO hV>w=n^ OH HO

,c\

(Va3*H

H〇

(1-a38) • \5- 201237118

HN〇as

Qr (1-a3S) c

HO

HN〇2s cr", OH H〇 (1-a4D N〇2

1J

N〇2 U=\ factory "\ (1-a*»3) , N > -N=N-

HN〇2S

OH HO

HN〇2s,

Cr

OH HO (1-a45) H〇2 Oj

HN〇2s

Η3αΆν=ν~^ OH HO (1-a47) H〇2 0a-49) N〇2

HN〇2s

HO

M〇/^ 0H H〇 , OH H〇

(1-a5D (Va5^)

HNO2S ί HN〇2S

N= OH H〇 (1-a55)

Orcrr

N — I N H3C02S, 〇H H〇

(1-a57)

Wide N OH HO S〇2CH3 (1-359) (6)700.doc 201237118

Preferred examples of the wrong anion in the compound (1) include an anion represented by the formula (1-b1) to the formula (1-b60):

161700.doc -17-

S 2〇1237ll8

161700.doc •18 2〇1237ll8

s 201237118

s

,6,7〇〇.d〇c 22. 201237118

Among the compounds (1), preferred examples of the cation derived from the dibenzopyran compound include a cation represented by the formula (1-cl) to the formula (1-C36):

161700.doc -23- 201237118

161700.doc ·24· 201237118

201237118

The compound (1) can be formed by using a compound represented by the formula (ld) (hereinafter sometimes referred to as a compound (ld)") and a chromium compound to form a chromium salt, and then the chromium is I and a benzo The piper compound is subjected to a salt exchange reaction, or a compound (Id) and a cobalt compound are used to form a cobalt salt, and then the cobalt salt is subjected to a salt exchange reaction with the dibenzopyran compound (b).

[In the formula (4), 'R丨~R, Rl丨~Rl4* r19 means the same as above]

Anion of the price]. Examples of the monovalent anion include cl-, Br·, r, Cl〇4.

BF4- and so on. The 6 S monobenzopyran compound (b) can be produced by reacting a compound represented by the formula (bo) with a compound represented by the formula 161700.doc •26·201237118 (bl) in an organic solvent.

[In the formula (b0) and the formula (bl), 〜r", η and A- represent the same meanings as described above]. 0 In the above reaction, the reaction temperature is preferably i 5 <»c to 60 ° C, reaction time It is preferably from 1 hour to 2 hours. Further, in order to shorten the reaction time or increase the yield, β is preferably an acid catalyst and/or a dehydrating agent. As the acid catalyst, sulfuric acid or p-benzenesulfonate may be mentioned. Acid, etc. As a dehydrating agent, there may be mentioned dicyclohexylcarbodiimide, diisopropyl rock anti-imine, and hydrazine-ethyl-3-(3-dimethylaminopropyl)carbon dioxime. Isoimine hydrochloride, such as imine hydrochloride; 丨-alkyl-2_halogenated pyridine rust; 丨, 丨, -carbonyl, ° 嗤; bis(2-oxo-3-oxazolidine)次phosphine gas; carbonic acid (2-pyrobitate) sleeping complex # Ay ^ with 'in the dehydrating agent, because of post-treatment and purification is easy, so the car 乂 is 1 · ethyl _3_ (3 dimethyl The organic solvent for the aminopropyl)carbodiimide hydrochloride L may, for example, be dimethylbenzene, acetonitrile or the like. The alkane, chloroform, tetrahydrofuran, toluene used in the above reaction may be the compound (1). Wrong anion Materials is well known in the field.

The compound (1 d) of the ligand of the ion can be produced by a method of making a ratio of diazonium salt to η. For example, an amine represented by the formula 161700.doc -27- 201237118 (la) (hereinafter sometimes referred to as "amine (la)") can be used to carry out money by succinic acid, nitrite or nitrous acid (four). The compound represented by the formula (10) obtained as hydrazine is used as the above diazonium salt.

[In the formula (U) and formula (in UO, R"~Rh represents the same meaning as above; ν. represents an inorganic or organic anion; I» as the above inorganic anion, for example, a vaporized ion, a vaporized ion, and a desert Examples of the organic anion include CH3C〇〇·, QHsCOO·, etc. Preferred examples thereof include a vaporized ion, a bromide ion, and a CH3CO. 〇-, etc. By diazo coupling of a compound represented by the formula (lb) and a compound of the formula (le) in an aqueous solvent, a compound represented by the formula (ld) can be produced (hereinafter sometimes referred to as " The compound (Id)"). The reaction temperature is preferably rd, more preferably 0 ° c to 3 (TC » reaction time is preferably from 丨 to 12 hours, more preferably from 1 hour to 4 hours. For example, N-methylpyrrolidone or the like can be mentioned.

(1C) [In the formula (1C), the compound (Id) of R1 to R5 and R19 has -S02R29 which has the same meaning as described above]. When _S02R29 is -s〇2NHR30, 161700.doc -28- 201237118 can also be produced using amine (la) having ·s〇2NHR3Q, but it is preferred to use a 4-group amine (u) for coupling reaction. The money and the base are manufactured by continuous amination. For example, an 'azo compound having a recurring group (hereinafter referred to as "compound (ls)") can be synthesized in the compound 〇d, and the thiol compound can be used as a base (by ss2X). The sulfonium halide compound is obtained, and then the sulfonium halide compound is reacted with the amine (r3〇nh2), whereby the sulfo group is subjected to sulfoximation to produce the compound (Id). Specific examples of the compound include a formula (1 ai), a formula Ο-β), and a compound represented by the formula (1_a5) to (1_a2〇), and preferably a formula (b (9), (1-a6), ( a compound represented by 1_al5) and (1_al6). Examples of the sulphur-based carcass compound include sulfinium a, sulfinium, sulfoxide, sulfoxide, and the like. And sulfinium bromide, etc., particularly preferably sulphur ruthenium chloride. The amount of sulfinium halide used is relative to the compound (mole, preferably 1 to 10 moles. Further in the reaction system) In the case of water, it is preferred to use a sulfite compound in excess. The sulfonate is carried out in a solvent. As a solvent, for example, it can be used. Ethers such as M-dioxane (especially cyclic ethers); chloroform, dioxo, carbon tetrachloride, 1,2-dichloroethane, dichloroethylene, triethylene glycol, and perchloroethylene , aeronautical hydrocarbons such as di-propane, chloropentane, 1,2-dibromoethane, etc. The amount of dissolved solute used is relative to the compound (1 _ parts by weight: for example: above (preferably 5 mass) More than or equal to), 10 parts by mass or less (preferably 8 parts by mass or less) ” Further, in the sulfonate cleavage, it is preferred to use N,N-dialkylformamide in combination (Example 161700.doc •29- 201237118 Such as 'N,N-dimercaptoamine, N,N_: ethylformamide, etc.). When using Ν'Ν-二院基甲胺胺, its use is relative to sulfoxide The halogen compound 1 mol is, for example, 0.054 mol. If the compound (ls) and the N,N-dialkylformamide are mixed in a solvent in advance, the addition of the sulfinium halide compound can suppress heat generation. The reaction temperature of the halogenation is, for example, 〇 or more, preferably 3 Å or more, 70 ° C or less, preferably 6 Torr or less. The reaction time is, for example, 5 hours or more, preferably 3 hours or more, 8 The following is preferably 5 hours or less. The sulfonate compound prepared by the above method may be reacted with an amine (R3GNH2) after isolation, or may be directly reacted with an amine (R3GNH2) in a state of a reaction mixture without isolation. Further, in the case of separation, for example, mixing the reaction mixture with water, and filtering to obtain precipitated crystals. The obtained crystals of the sulfonate compound can be washed as needed before reacting with the amine (R^NH2). And drying. As an amine (r30nH2), it contains n-propylamine, n-butylamine, n-hexylamine dimethylhexylamine (I,5·dimethylhexylamine, etc.), tetradecylbutylamine methylbutylamine, A hexylamine (2-ethylhexylamine or the like), an aminophenyl butyl compound (3-amino group, 1-phenylbutyring or the like), isopropoxypropylamine or the like. Amination 3. The amount used is 2 mol or more, 10 mol or less, preferably 7 mol or less, relative to the sulfonium compound. The order of addition of the phase-tooth compound and the amine (R3〇NH2) is not particularly limited, and it is preferred to add (drop) the amine ^3%4) to the sulfonate compound. Further, the reaction of the sulfonate compound with the amine (R3?NH2) is preferably carried out in a solvent. I61700.doc -30-201237118 is a solvent, and the same solvent as that used in the preparation of the sulfonium compound can be used. Further, the reaction of the sulfonium compound with the amine (R^NH2) is preferably carried out in the presence of a basic catalyst. As an organic catalyst, for example, a grade amine (diethylamine, a di-ethylamine, an aliphatic tertiary amine; an aromatic first-degree female such as a bite), and a primary amine (monoethylamine) can be cited. Secondary amine; η bottom bite and other cyclic guanidine aliphatic secondary amines). Among these, a tertiary amine is preferred, and an aliphatic tertiary amine such as triethylamine is preferred. The amount of the basic catalyst used is 1.1 mol or more and 6 mol or less with respect to the amine (R ΝΗ 2) ', preferably 5 Å or more, and 5 mol or less. When the amine (r3〇NH2) and the basic catalyst are added to the saponin compound, the addition timing of the alkaline catalyst is not particularly limited, and may be before or after the addition of the amine (r3QnH2). It can also be added at the same timing as the amine (r3〇NH2). Further, it may be added after mixing with a reactive amine in advance, or may be added separately from the amine (R3GNH2). The reaction temperature of the sulfonium halide compound and the amine (r3〇NH2) is, for example, 〇β (: above, 50 ° C or less, preferably 〇 ° c or more, 30 ° C or less. Further, the reaction time is 1 to 5 hours. The method of obtaining the compound (ld) as the target compound from the reaction mixture is not particularly limited, and various known methods can be employed. For example, it is preferred to mix the reaction mixture with an acid (for example, acetic acid or the like) and water, and to obtain a precipitate by filtration. The above-mentioned acid is preferably prepared by adding an aqueous solution of an acid to the aqueous solution in advance, and the temperature at which the reaction mixture is added is preferably 10 ° C or more and 50 ° C or less, more preferably 2 〇r or more. 5 〇 t or less, and more preferably 20 ° C or more 30. (: The following. Further, it is preferred to add the reaction mixture to 161700.doc • 31 · 201237118 to an aqueous acid solution, and then mix at the above temperature. 5~2 hours or so. The crystal obtained is preferably washed with water or the like, and then (4). Further, if necessary, it can be further purified by a known method such as recrystallization. The anion portion of the compound (1) is chromium. Anion In the case of (1) in the case of Cr), it can be produced by reacting the compound 〇d) with a complex compound in an aqueous solvent at 70 to 1 〇〇e C. Preferably, the compound and the complex compound are The molar ratio of 2:1 to 4:1 is exemplified. Examples of the chromium compound include chromium formate, chromium carbonate vapor, chromium fluoride, and the like. Preferred examples thereof include chromium formate, chromium acetate, and chromium sulfate. III) sulphate or the like. The compound (1) can be produced by subjecting a chromium salt to a salt exchange reaction with a dibenzopyran compound (b) in a solvent. Preferably, the chromium salt is mixed with diphenyl. And the piper compound (b) is reacted at a molar ratio of 1:1 to 1:4. When the anion portion of the compound (1) is a cobalt-substituted anion (the river enthalpy in the formula (丨) is C〇) It can be produced by reacting the compound (ld) with a cobalt compound in an aqueous solvent at 70 to 1 ° C. Preferably, the compound and the starting compound are in a molar ratio of 2:1 to 4:1. The reaction is carried out. As the above-mentioned indicating compound, cobalt chloride, cobalt acetate, sulfuric acid, and cobalt(III) acetate (III) (tris(2,4-pentanedionat) can be cited. o) cobalt (III)), etc., preferably acetonitrile, cobalt (in), etc. The compound (1) can be subjected to a salt exchange reaction with a dibenzopyran compound (b) in a solvent by a cobalt salt. Preferably, the cobalt salt is reacted with the dibenzophenan compound (b) at a molar ratio of 1:1 to L4. Specific examples of the compound (1) ' can be exemplified by the formula (1-1) to (1·26) shown in the 161700.doc •32- 201237118 compound.

(1-1) (1-2)

161700.doc •33- ,6l?00.d〇c

(1-6) •34· 201237118

161700.doc -35- l6l7〇〇.d〇c 2〇l237ll8

-36. 201237118 h3co2s

(1-21) (1-22) so2ch3 Θ σ /bu N=N— 〇〆 o2n

-Ν=Ν—ι sN

@, 〇 〜 (1-23)

匕 H3C〇2S σ

SOoCHs

O2n H3C02S

N=N—f ι N \ J〇 Θ

0'^'o^<S (1-24)

161700.doc •37· 201237118

Once ^. °The content of (1)! It is preferably 1 mass in the colorant (4). The above 99 / 〇 or less is more preferably 1% by mass or more and 8 % by mass or less, more preferably 3% by mass or more and 7 % by mass or less. The coloring agent (A) may contain a dye different from the compound (1) together with the compound (1). Examples of the dye include dyes such as an oil-soluble dye, an acid dye, an amine salt of an acid dye, or a sulfonamide derivative of an acid dye, and examples thereof include a dye index (published as a dye in The Society of Dyers and Colourists). A well-known dye disclosed in the Dyeing note. Specific examples include CI Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted, 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; CI solvent dye, CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 161700.doc • 38· 201237118 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; 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 · Acidic Oranges 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; etc. CI acid dye, 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; 161700.d Oc •39- 201237118 CI Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 1〇6, 1〇7; CI·Direct Purple 47, 52, 54, 59, 60, 65, 66, 79, 8〇, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CU direct dye, as CI mordant dye CJ mediated yellow 5 10, 16, 20, 26, 3 〇, 31, 33, 42, 43, 45, 56, 61, 62, 65 19, 39, 86' 23, <^.1. mordant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85 88, 90, 94, 95; CI mordant lamps 3, 4, 5, 8, 12, U, 14, 20, 21 24 28, 29, 32, 34, 35, 36, 37, 42 , 43 , 47 , 48 ; CI · mordant purple 1, 2, 4, 5, 7, 14, 22, 24, 3〇, 3ι, &, 37, 40, 41, 44, 45, 47' 48, 53 58; etc. The mordant dye (0) may further contain a pigment together with the compound (丨). Examples of the pigment include organic pigments such as violet pigments such as CI Pigment Violet 1, 19, 23 '29, 32, 36, and 38; and 丄 pigment jaundice, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93 '94, 109, 11 〇, ι 17, 125, 128, 137, 138, 139, 147, 148 ' 150 ' 153 ' 154 ' 166, 173, 194, 214 Etc. yellow pigment; 〇.1. Pigment lamps 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; 161700.doc • 40· 201237118 Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 16 ό, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. . Among them, it is preferred to contain one selected from the group consisting of C.I. Pigment Yellow 138, 139, 15 〇, and 〇 颜料 Pigment Red 177, 242, 254; By containing the above pigment, it is possible to optimize the transmission spectrum. The chemical resistance is improved. 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 a pigment surface by a polymer compound or the like, a sulfuric acid micronization method, or the like, as needed. The micronization treatment or the removal treatment of the ionic impurities by washing with an organic solvent or water to remove impurities, etc., by an ion exchange method or the like. The organic pigment preferably has a uniform particle size. The dispersion treatment is carried out by containing a pigment dispersant, and a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained. Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used alone or in combination of two or more. Examples of the pigment dispersant include κρ (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoei Chemical Co., Ltd.), (made by Zeneca), EFKA (manufactured by CIBA), and Ajispe. "Ajinomoto Fine-Techn〇c〇 Inc.") manufactured by Disperbyk (manufactured by BYK-Chemie Co., Ltd.). In the case of using a pigment dispersant, it is used in a weight ratio of 161700.doc • 41 · 201237118 (A2), preferably 1% by mass, more preferably 5% by mass or more, and 5% by mass. the following. When the amount of the pigment dispersant used is in the above range, there is a tendency that a pigment dispersion liquid in a uniformly dispersed state can be obtained. In the case where the colorant (A) contains a pigment, the content of the pigment is preferably from 1 to 99% by mass, more preferably from 10 to 97% by mass. The content ratio (mass ratio) of the compound (1) to the pigment is preferably from 1:99 to 99:m, more preferably from 3:97 to 90:10. By setting such a ratio, it is preferable to optimize the transmission spectrum and obtain high contrast and high luminance. Further, heat resistance and chemical resistance become good. More preferably, the compound (1) and at least one selected from the group consisting of ruthenium pigment yellow 138, c 丨 pigment yellow 139, CI·pigment yellow 150, CI pigment red 177, ci pigment red 242, and CI pigment red 254. The mass ratio is 3.97~90:10', preferably 3:97~7〇: 3〇. The content of the coloring agent (A) is preferably 5 to 6 % by mass, more preferably 8 to 55% by mass, still more preferably 10 to 50% by mass, based on the solid content of the colored photosensitive resin composition. β Here, the solid content component refers to the total of the components of the coloring photosensitive resin composition excluding the solvent. When the content of the coloring agent (ytterbium) is in the above range, the color density when the color filter is used is sufficient, and a necessary amount of the binder polymer can be contained in the composition, so that a pattern having sufficient mechanical strength can be formed. The color-sensitive t-resin composition of the present invention contains a resin (8). The tree 曰 (8)' is not particularly limited, and is preferably a soluble resin. Examples of the contact Ha(B)' include the following resins [κι] to [κ4]. [Κ1] A cyclic ether structure having a carbon number of 2 to 4 and an ethylenically unsaturated bond. 161700.doc -42 - 201237118 The body (a) (hereinafter sometimes referred to as "(4)")) is selected from the group consisting of unsaturated acid And a copolymer of at least one of (8) (hereinafter sometimes referred to as "(9)")). [K2] (4) and (8) and copolymers [K3] (b) and (c) which are copolymerizable with (4) monomer (4) (which is different from (4) and (b)) (hereinafter sometimes referred to as "(4)"). The copolymer [K4] is a resin obtained by reacting the copolymer of (b) and (e) with (4). By including the structural unit derived from (a) in the resin (B), the reliability of heat resistance and chemical resistance of the obtained colored pattern can be further improved. (a) is, for example, a cyclic ether structure having a carbon number of 2 to 4 (for example, selected from the group consisting of an ethylene epoxide ring, an oxetan ring, and a tetrahydro fluorene ring (oxocyclohexyl ring)). At least one of the group) is a polymerizable compound having an ethylenically unsaturated bond. (a) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group. In the present specification, the term "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth) acrylonitrile" and "(mercapto) acrylate vinegar have the same meaning. Examples of (4)' include a monomer (4) having an epoxy group and an ethylene bond and a bond (hereinafter sometimes referred to as "(al)"), and having an oxetane group and an ethylenic unsaturated group. The monomer (a2) of the bond (hereinafter sometimes referred to as "(&2)"), the monomer (a3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(4))")). (al), for example, 161700.doc -43 - 201237118 °° body (al 1) (hereinafter sometimes referred to as "(al l)") having a structure in which a chain olefin is epoxidized, and has a ring type A monomer (al_2) having a structure in which epoxidized epoxidation is carried out (hereinafter sometimes referred to as "(Μ)") (4)·1) ', exemplified by: (meth)acrylic acid glycerin vinegar, (meth) = acidated β - mercapto-glycidyl vinegar, (meth)acrylic acid ρ·ethyl glycidyl ester, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, vinyl Benzyl glycidyl ether, & methyl-based vinyl? Dimethyl sulphate (iv) U-based. Inter-ethylene di-f-hydrating glycerol ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3 bis (glycidoxymethyl) styrene, 2, 4 _bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxycarbonyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4 - tris(glycidoxymethyl)styrene, 2.3.5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4 , 5-tris(glycidyloxyindenyl)styrene, 2.4.6-tris(glycidoxyfluorenyl)styrene, and the like. Examples of (al-2) include vinylcyclohexene oxide, 12 epoxy-4-vinylcyclohexane (for example, Ceii〇xide 2000; manufactured by Daicel Chemical Industry Co., Ltd.), and 3,4- Epoxycyclohexylfluorenyl (fluorenyl) acrylate g (for example, Cyclomer A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexyldecyl (fluorenyl) acrylate (for example, Cyclomer M100; A compound represented by the formula (I), a compound represented by the formula (I), and the like are produced by Daicel Chemical Industry Co., Ltd.

161700.doc 201237118 [In the formulae (1) and (II), Ra and Rb independently of each other represent a hydrogen atom or a carbon group having 1 to 4 carbon atoms. The hydrogen atom contained in the alkyl group may be substituted with a base; X1 and X2 Independent of each other means a single bond, _RC *-Rc-NH-; *-Rc-0- *-Rc-S_, 1^ represents an alkyldiyl group having a carbon number of 1 to 6; * represents a bond with hydrazine] as carbon The alkyl group of 1 to 4 may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group or a t-butyl group. Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl '1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a 1-hydroxy-1 group. -methylethyl, 2, hydroxy-hydrazine-hydrazinoethyl, hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like. The Ra & Rb is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a fluorenyl group. Examples of the alkanediyl group include an anthracene group, an exoethyl group, a propionium U2 diyl group, a propane 1,3-methyl group, a 1,4-14-diyl group, a pentyl-15-diyl group, and a hexa-diyl group. X1 and X2 are preferably a single bond, a methylene group, an ethylidene group, a bond group with a fluorene bond, a *-CH2CH2-fluorenyl group, and more preferably a single bond or a *-CH2CH2_0. group. . 2 is a compound represented by the formula (I), and examples thereof include a compound represented by the formula (1_1} to the formula (115), and preferably a formula (4), a formula (1_3), a formula (15), and a formula (1)) 1-9), Formula (1-11)~Formula (1-15) »More preferably can be enumerated...丨), Formula + 7 (1-9), Formula (1_15). " 161700.doc -45- i?201237118 Η2〇=ΟΗ—c~o

H2c=ch-c—o—ch2

H2C=CH ~C —O CjH,

CH30 u 0 I 11 H2C=C—C-〇-C2h4 ) Ο (1-1) C—0—C2H4· -0 〇(1-3) HjCsCH—C—Ο*C2H4 CH30 Hi C2H5O H2C=C—c —o

-C—〇—C2 H4 —s CH30 H2C=C—C-0-C2H4-N

As shown in the formula (II), D, ～, 〜 叭, 1 卜 i 5) household / no compound, etc. ° can be exemplified by the formula (Π-3) 'form („_5), 弋 (7 Formula (11_9), formula (Π-11)~Formula (11-丨5). More preferably, the compound of the formula (11) 1(11-7)4(19)1(11-15)0 can be used. List: Formula (IM) ~ (II15)

HjCjCH—C——Ο一C2H4—S 0 || μ H2C:CH—C—0—C2H4—N ch3〇 / II HjC=0 —-0 一 〇_C2H4—S

161700.doc 201237118

H2c:ch - L 0~C2H4-0

H2c=c 11

Ul H2C=i '' 〇 h2c=c-M ^

Ch3〇 I II H H2C=C—C_O—C2H4—N η2ο=Π-ο ch2oh o I II h2c=c-c—o

CH3 o H2C=d〇—C2H4.

C2h4oh o h2c=c-c-o

The compound of the formula (I) and the compound of the formula (II) may be separately and in combination, and these may be mixed in any ratio. In the case of mixing, the ratio of α is expressed in molar ratio, preferably Formula (I): Formula (II) is 5:95 to 95:5, more preferably 1:9 () to 90:10 ' Yu Jia is 20:80~80:20. The monomer (a2) having an oxetane group and an ethylenically unsaturated bond is more preferably a monomer having an oxetan group and a (meth) acryloxy group. Examples of (a2)' include: 3-methyl·3·mercaptopropene oxymethyloxetane, 3-mercapto-3-propenyloxymethyloxetane, and fluorenyl group. Oxetane...-oxyl I: ''m-m-methylpropenyl-ethyloxy=^=_ylethyloxetane, 3.ethyl-propylpropanyl-ethylate_3 _ propylene oxiranyloxy oxirane is preferred, the monomer of the south and the ethylenically unsaturated bond (a3), more preferably has a 虱 虱 ° ° South base and (meth) propylene brewing A monomer of an oxy group. I6I700.doc •47·201237118 Specific examples of (a3) include tetrahydrofurfuryl acrylate (for example, visc〇at V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and f-based tetrahydrofurfuryl acrylate. (a) is preferably (4)) in terms of further improving the reliability of heat resistance and chemical resistance of the obtained colored pattern. Further, it is more preferably (al-2) from the viewpoint of excellent storage stability of the colored photosensitive resin composition. Specific examples of (b) include unsaturated monobasic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; Acid, fumaric acid, methyl maleic acid, methyl fumaric acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3, 4 , 5,6-tetrahydrophthalic acid, tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1&gt;4•cyclohexene dicarboxylic acid, unsaturated dicarboxylic acids; methyl -5-norkenylene-2'3-dicarboxylic acid, 5-carboxybicyclo[221]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5 -Methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]g a bicyclic unsaturated compound containing a carboxyl group such as -2-thin, 5-enyl- 6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, methyl maleic anhydride, clothing Tonic anhydride, 3 • vinyl phthalate, 4-vinyl phthalic anhydride ' 3,4,5,6-tetra-argon phthalic anhydride, 1,2,3,6-four O-diacetic acid anhydride, dimercapto tetra-tetra- ortho-phthalic anhydride, 5,6-di-resylbicyclo[2.2.1]hept-2-ene anhydride (bicycloheptene II 161700.doc •48· 201237118 And other unsaturated dicarboxylic acid anhydride; benzo [2-(methyl) propylene oxyethyl] vinegar, phthalic acid mono [2-(indenyl) propylene oxyethyl] ester, etc. Unsaturated mono[(meth)acryloxyalkyl]esters of polyvalent carboxylic acids of 2 or more; such as α-(p-fluorenyl)acrylic acid, the same molecule contains osmotic and thiol-saturated Acrylates, etc. Among these, acrylic acid, methacrylic acid, anhydrous cis-butenedioic acid, and the like are preferable in terms of the aspect of the copolymerization reactivity or the solubility to the alkaline aqueous solution. Examples of (c) include (mercapto) decyl acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, and (meth) acrylate. Tributyl ester, (2-mercapto)acrylic acid 2-ethylhexyl ester, (decyl) decyl acrylate, lauryl (meth) acrylate, stearyl methacrylate, (fluorenyl) Cyclopentyl acrylate, cyclohexanic acid (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.〇2'6]癸-8-yl ester (In the technical field, as a conventional name, it is called (meth)acrylic acid dicyclopentanyl ester), (meth)acrylic acid dicyclopentyloxyethyl ester, (decyl)isodecyl acrylate, ( Adamantyl adamantyl acrylate, (mercapto) allyl acrylate, propargyl (meth) acrylate, phenyl methacrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate Ethyl (meth) acrylates; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. (Meth) acrylates; diethyl maleate, diethyl fumarate, diethyl itaconate 161700.doc -49- 201237118 and other dicarboxylic acid diester; double ring [2.2. 1]hept-2-ene, 5-mercaptobicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]g 2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2.hydroxyethyl)bicyclo[2.2.1]hept-2-ene, % methoxybicyclo[ 2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di (hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2.-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxy Bicyclo[2.2_1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene , 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-fluorenylbicyclo[2.2.1]hept-2-ene, 5-t-butoxy Carbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5, a bicyclic unsaturated compound such as 6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenyl succinimide, N-cyclohexyl succinimide Amine, N-benzyl maleimide, N-butylenedimino-3-methyleneimine benzoate, N-butylenediamine-4-pentene Diterpenoid butyl sulphate, N-butyl succinimide -6-m-butylene imidate hexanoate, N-butyl quinone imino-3-butyl succinimide propionic acid Dicarbonyl quinone imine derivatives such as ester, ν·(9-acridinyl)-cis-diimide, styrene, α-methylstyrene, m-methylstyrene, p-methylethene , vinyl toluene, p-methoxystyrene, acrylonitrile, mercaptopropyl nitrile, ethylene, ethylene, propylene, methacrylic acid, ethylene 161700.doc -50- 201237118 , 1,3-butadiene, isoprene, 2,3-dimethyl-anthracene, etc. Among these, 'styrene, N-phenyl maleimide, N•cyclohexyl maleimide, N_ are preferable in terms of copolymerization reactivity and heat resistance. Benzylmethyleneimine, bicyclo[2 2丨]hept-2-ene, and the like. In the resin [K1], the ratio of the structural units derived from (a) and (b), respectively, is preferably in the following range from the total structural unit constituting the resin [K1]. The structural unit from (a): 6〇~98mol% (more preferably 65~95mol%) The structural unit from (b): 2~4〇% by mole (more preferably 5~35 moles) 0/〇) When the ratio of the structural unit of the right resin [K1] is in the above range, the storage stability, the developability, and the solvent resistance of the cured pattern tend to be good. The resin [K1] can be disclosed, for example, in the literature "Experimental method for polymer synthesis" (published by Otsuka Ryokan, Ltd., i.S., ed., ith, MU, March 1). The citations are made by reference. Specifically, it can be exemplified that a specific amount of (a) and (b), a polymerization initiator, a solvent, and the like are injected into a reaction vessel to be scrambled, heated, and kept warmed by deoxidizing oxygen by replacing nitrogen with nitrogen. Methods. Furthermore, the initiators and solutions used herein are not specifically defined and can be used in any of the ten users in the field. For example, examples of the polymerization initiator include an azo compound (2,2,-azobisisobutyronitrile, 2,2,-azobis(2,4-dimethylcarbonitrile), etc.) or organic A peroxide (such as a ruthenium benzoate) may be used as a solvent, and a solvent which is a solvent of the photosensitive resin group 161700.doc 201237118 and a solvent to be described later may be used. Further, the obtained copolymer may be directly used as a solution after the reaction, or a solution obtained by concentration or dilution, or a solid (powder) by a method such as reprecipitation. In particular, in the polymerization, by using the solvent (D) described later as a solvent, the solution after the reaction can be used as it is, and the production steps can be simplified. In the resin [K2], the ratio of the structural units derived from (a), (b) and (4), respectively, is preferably in the range of the total structural unit constituting the resin [K2]. The structural unit from (a): 2 to 95 mol% (more preferably 5 to 8 m Mo from the structural unit of (b): 2 to 4 〇 mol% (more preferably 5 to 35 mol%) The structural unit derived from (c): 丨~65 mol% (more preferably, the ratio of the structural unit of the 〇6〇莫耳右树脂 [K2] is the above range, and there are impurities for storage stability, developability, hardening pattern The resin, the heat, and the mechanical strength tend to be good. The resin [K2] can be produced, for example, in the same manner as the method disclosed as a method for producing a resin [κι]. (4), (b) and (4), a polymerization initiator and a solvent are introduced into a reaction vessel, and the mixture is stirred, heated, and kept warm by replacing oxygen (10) with nitrogen. The obtained copolymer can be directly used after the reaction. The solution may also be a concentrated or diluted solution, or may be used as a solid (powder) extractor by reprecipitation or the like. The ratio of structural units derived from (8) and (4) in the resin [K3], respectively. It is in the total structural unit constituting the resin [K3] which is in the following 161700.doc -5 2- 201237118 0 (b) 2 to 40 mol%, more preferably 5 to 35 mol% (060 to 98 mol%, more preferably "~^ mol % resin [K3] can be manufactured, for example. The tree MK4J can be obtained by obtaining the reductive group of the copolymer of (8) and (4) in the cyclic (4) addition (4) having a carbon number of 4 (4). First, by the method of producing the resin [K1] The copolymers of (8) and (4) are produced in the same manner as disclosed. In this case, the ratio of the structural units derived from (b) and (c), respectively, is preferably the total structural unit of the copolymer constituting (8) and (4). Medium, in the following range: (b) 5 to 50 mol ° / °, more preferably 10 to 45 mol % (c) 50 to 95 mol %, more preferably 55 to 9 m Mo % % The ester group and/or the taurine-if portion contained in the structural unit derived from (4) in the copolymer is reacted with the ring-shaped ring having the carbon number of 2 to 4 in (4). (8) and (c) After the copolymer, the environment in the flask is replaced by air from air, and the reaction catalyst of (a), a carboxyl group and a cyclic ether (for example, tris(dimethylaminomethyl)phenol, etc.) is relative to (a) The total amount of (c)i is 〇〇〇丨5 to 5% by mass, and the polymerization inhibitor (for example, hydroquinone or the like) is 0.001 to 5% by mass based on the total amount of h (c). The amount of the raw material is calcined, for example, under H耽, and the reaction is carried out for 1 to 10 hours, whereby the resin [K4] can be obtained. The input method is based on reaction conditions such as temperature and time, and the heat generation amount of the manufacturing equipment or the polymerization can be considered. Appropriate adjustment is carried out. In addition, the polymerization conditions are the same as α, considering the heat generated by the manufacturing equipment or polymerization, etc., and it is appropriate to adjust the input method or the reaction temperature. In this case, the usage amount of (4) is Preferably, it is 5 to 8 mol%, more preferably 10 to 75 mol%, more preferably 15 to 7 mol%, and is set to be in this range, and has storage stability and developability. The balance between solvent resistance, thermomechanical strength, and sensitivity tends to be good. Specific examples of the resin (B) include (meth)acrylic acid 3, a core epoxycyclohexyl decyl ester/(meth)acrylic acid copolymer, and an acrylic 3,4_epoxy triple <ring [5.2.1.02,6). ] resin such as vinegar/(meth)acrylic copolymer [κι]; (fluorenyl) glycidyl acrylate / benzyl (meth) acrylate / (meth) acrylate copolymer, glycidyl (meth) acrylate /styrene/(indenyl)acrylic acid copolymer, 3,4-epoxytricyclo[5.2丄〇2,6]anthracene vinegar/(mercapto)acrylic acid/Ν_cyclohexylmethyleneimine Copolymer, 3·mercapto-3((fluorenyl) propylene methoxymethyl oxetane / (mercapto) acrylic acid / styrene copolymer resin [Κ 2]; (mercapto) benzyl acrylate / (Mercapto) acrylic copolymer, styrene/(meth)acrylic copolymer, etc. [Κ3]; (meth)acrylic acid benzyl ester / (meth)acrylic acid copolymer addition (fluorenyl) a resin of glycidyl acrylate, a tricyclodecyl (meth) acrylate/styrene/(meth)acrylic acid copolymer, a resin obtained by adding glycidyl (meth)acrylate, and (meth)acrylic acidDecyl acrylate / (Yue-yl) benzyl acrylate / (meth) acrylic acid adduct has a (meth) acrylate resin resin [Κ4] and the like. Among them, preferred are resin [Κ1] and resin [Κ2], more preferably resin [Κ1], and more preferably 3,4-epoxytricyclo[5.2.1.〇2,6]decyl acrylate/( The polystyrene-equivalent weight average molecular weight of the fluorenyl acrylate copolymer 0 resin (Β) is preferably 161700.doc -54 - 201237118 3,000~100, _ 't preferably 5 〇〇〇~5〇〇〇〇 , and more preferably 5, _~ 3 5,000, especially good for 6 〇〇〇~3〇, _, especially good? , 〇〇〇 ~ (10) 〇. When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is also high, and the solubility of the unexposed portion to the developer is good, and the resolution tends to be improved. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably from 1.1 to 6, more preferably from 1.2 to 4. The acid value of the tree 曰 (曰) is preferably from 5 〇 to 15 〇, more preferably from 6 〇 to 135, and still more preferably from 70 to 135. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing the resin (β) of i g , and can be obtained, for example, by titration with an aqueous solution of potassium hydroxide. A1 of the sapphire (B) is preferably 7 to 65 mass%, more preferably 13 to 6 mass%, and still more preferably 17 to 55 mass, based on the solid content of the colored photosensitive resin composition. %. When the content of the resin (7)) is in the above range, a 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 (C), and the photopolymerizable compound (C) is an active radical and an acid which can be produced from a photopolymerization initiator (D) by light irradiation. The compound to be polymerized is, for example, a compound having a polymerizable ethylenically unsaturated bond, and the like, and a (meth) acrylate compound is preferred. In particular, the photopolymerizable compound (c) is preferably a photopolymerizable compound having three or more ethylene-unsaturated bonds. Examples of such a photopolymerizable compound include, for example, pentaerythritol tetraacrylate vinegar, pentaerythritol tetraammine acrylate, g-pentaerythritol penta-propionic acid, dipentaerythritol pentamethyl acrylate S, and pentaerythritol hexaacrylate. Ester dipentaerythritol hexamethyl propyl 161700.doc • 55· 201237118 enoate. Used above. The photopolymerizable compound (c) may be used alone or in combination of the two photopolymerizable compounds (C), and the solid content of the colored photosensitive resin composition is preferably from 7 to 65 % by volume, more preferably 13~60 quality. /. More preferably, it is (10)% by mass. When the content of the photopolymerizable compound (6) is in the above range, the curing is sufficiently performed, and the film thickness ratio before and after the development is increased. The undercut (under (10)) is less likely to occur, and the adhesion tends to be good, which is preferable. The colored photosensitive resin composition of the present invention contains a photopolymerization initiator (D). The photopolymerization initiator (D) is not particularly limited as long as it is a compound which generates an active radical, an acid or the like by the action of light to initiate polymerization, and a known polymerization initiator can be used. The photopolymerization initiator (D) may contain a photopolymerization initiation aid (D1) together with a compound which generates an active radical, an acid or the like by the action of light. The photopolymerization initiation aid (D1) is a sensitizer or a sensitizer for promoting polymerization of a photopolymerizable compound which starts polymerization by a photopolymerization initiator. The photopolymerization initiator (D) is preferably a compound which generates an active radical by the action of light. More preferably, it contains a compound selected from the group consisting of an alkylphenone compound, a di-compound, a mercaptophosphine oxide compound, and an anthracene. The photopolymerization initiator of at least one of the compound and the biimidazole compound is more preferably a photopolymerization initiator containing a fat compound. Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-tomolinyl 4-(4-methylsulfanylphenyl)propanone, and 2-dimethyl Alkylamine 161700.doc -56· 201237118 -1-(4-imidylphenyl)_2-benzylbutanyl- ketone, 2-dimethylamino _ι_(4_ 琳 phenyl) 2-(4-methylphenylmethyl)butan-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzilidine ketal (benzildimethy)[keta丨), 2-hydroxy-2-indolyl-l-[4-(2-hydroxyethoxy)phenyl]propanone-one, hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 a [00-(4- mercaptovinyl)phenyl]propan-1-one valence polymer or the like, preferably 2-methyl-2-phenylolino-i-(4-methylthioalkyl) Phenyl)propan-1-one, 2-dimethylaminoporphyrinylphenyl)_2-benzylbutan-1-one, and the like. Commercial products such as lrgacure 369 and 9〇7 (above, manufactured by Ciba Japan Co., Ltd.) can be used. As three. Well compounds, may be exemplified by 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-trimorphine, 2,4-bis(tris). · (4-methoxynaphthyl)-1,3,5-two tillage, 2,4-bis(trimethylmethyl)-6-sunflower base_1,3,5-three tillage, 2.4-double ( Trichloromethyl methoxy styrene) 丨, 3, 5 _ three tillage, 2, 4 · bis (trimethyl fluorenyl) · 6-[2-(5-methylfuran-2-yl) ethylene Base] three tillage, 2.4-bis (di-mercapto)_6-[2-(pyrano-2-yl)vinyl]_1,3,5-three'? well, 2.4-bis (three gas sulfhydryl) _6·[2_(4_Diethylamino-2-mercaptophenyl)vinyl]-1,3,5-three tillage, 2,4-bis(trismethyl)-6_[2-(3 , 4-dimethoxyphenyl)vinyl]-1,3,5-three tillage, and the like. Examples of the mercaptophosphine oxide-based initiator include 2,4,6-trimercaptobenzoyldiphenylphosphine oxide. Commercial products such as Irgacure 819 (manufactured by Ciba) can be used. The hydrazine compound 'is exemplified by N-indoleoxy_丨_(4·phenylsulfanylphenyl)butan-1-one-2-imine, N-benzylformyloxy-oxime ( 4-phenylsulfanylphenyl)oct-1-one-2-imine, Ν_乙醯oxy_ι_[9_ethyl_6_(2_methylbenzene 161700.doc -57- 201237118 曱Mercapto)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-i-[9-ethyl-6-{2-mercapto-4-(3,3 -Dimethyl-2,4-diindenylpentylmethyloxy)phenylhydrazinyl}-9H-indazol-3-yl]ethane-1-imine and the like. Commercial products such as Irgacure OXE-01, 〇XE-02 (manufactured by the above-mentioned 'Ciba Japan Co., Ltd.), and N-1919 (manufactured by ADEKA Co., Ltd.) can be used. As the biimidazole compound, 2,2'-bis(2.4,4',5,5'-tetraphenylbiimidazole, 2,2,-bis(2,3-diphenyl)- 4,4·,5,5'-tetraphenyl pyridine (for example, refer to Japanese Patent Laid-Open No. Hei 6-75372, Japanese Patent Laid-Open No. Hei 6-75373, etc.), 2, 2, -double ( 2-chlorophenyl) 4,4',5,5'-tetraphenylbiimidazole, 2,2,bis(2-hydrophenyl)_4,4,5,5,_tetra(p-oxyl Phenyl)biimidazole, 2,2,-bis(2-phenylphenyl)-4,4,5,5·-tetrakis(dialkylnonylphenyl)biimidazole, 2,2,·bis (2) _ gas phenyl)·4,4,,5,5·-tetrakis(lutaneoxyphenyl)biimidazole (for example, refer to Japanese Patent Special Publication No. 48_384〇3, Japanese Patent Laid-Open No. 62_1742〇4 The imidazole compound which is substituted with an alkoxycarbonyl group in the 4th, 4th, 5th, 5th, and 5th positions (for example, refer to Japanese Patent Laid-Open No. Hei 7-10913, etc.), etc. Preferably, 2, 2, _ double (2· gasping base KW tetraphenyl linkage. rice saliva, 2, 2, · bis (2,3 · dichlorophenyl) 4,4,,5,5.·tetraphenyl linkage (four) , 2,2,_bis(2,4•dichlorophenyl)_4,4,,5,5,_ four The basal flavor β is sitting. Further, as the photopolymerization initiator (9), exemplified by benzoin, amphibious methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.: : compound; benzophenone _, o-benzonitrile醯 笨 笨 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲2,4,6-trimethylbenzophenone and other two 161700.doc • 58 - 201237118 ketone compound; 9,1 〇-phenanthrenequinone, 2-ethyl hydrazine, camphorquinone and other hydrazine compounds; 10-butyl a chloro-2-hydrazinone, a diphenylethylene di-, a phenylglyoxylate methyl ester, a 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-phenylphenyldimethylphosphonium p-toluenesulfonate and 4-hydroxyphenyldimethylene. Nickel hexamidine, 4-ethyl methoxy phenyl dimethyl ruthenium p-toluene sulfonate, 4 ethoxylated phenyl • methyl • benzyl rust hexafluoroantimonate, triphenyl Base rusting bismuth sulfonate, diphenyl Cadmium hexahydrate acid salt, diphenyl sulfonium terephthalate, diphenyl sulfonium hexafluoroantimonate and other rust salts, or basal toluene sulfonate, benzoin toluene The photopolymerization initiator (D) may be, for example, a compound such as a tri-p well compound which simultaneously generates an active radical and an acid by light. As a photopolymerization initiation aid (D1)' An amine compound, an alkoxy quinone compound, a thioxanthone compound, a slow acid compound, or the like. Examples of the amine compound include triethanolamine, methyldiethanolamine, diisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-didecylaminobenzoate, and 4-diindole. Isoamyl phenyl benzoate, 2-didecylaminoethyl benzoate, 2-ethylhexyl 4-didecylaminobenzoate, hydrazine, hydrazine-dimethyl-p-anilide , 4,4'-bis(dimethylamino)dibenzophenone (commonly known as mickleone), 4,4'-bis(diethylamino)benzophenone, 4,4, _ double (Ethylmethylamino)diphenyl fluorenone or the like ' Among them, 4,4,-bis(diethylamino)dibenzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used. 161700.doc • 59- 201237118 The content of the photopolymerization initiator (D) is preferably 0.1 part by mass based on the total amount of the resin (B) and the photopolymerizable compound (C). More preferably, it is 1 to 20 parts by mass. When the content of the photopolymerization initiator is in the above range, high sensitivity is obtained, and the exposure time is shortened to improve productivity. Further, the coloring photosensitive resin composition of the present invention may further contain a photopolymerization initiation aid (D1). The photopolymerization initiation aid (D1) is usually used in combination with a photopolymerization initiator (D) to promote the polymerization of a photopolymerizable compound which starts polymerization by a photopolymerization initiator, or sensitization. Agent. The photopolymerization initiation aid (D1) may, for example, be an amine compound, an alkoxy fluorene compound, a thioxanthone compound or a carboxylic acid compound. Examples of the amine compound include triethanolamine, decyldiethanolamine, triisopropanolamine, decyl 4-dimethylaminobenzoate, ethyl 4-didecylaminobenzoate, and 4-dimethyl Isoamyl phenyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, n,N-dimethyl-p-anilide, 4 , 4'·bis(dimethylamino)dibenzophenone (commonly known as mickleone), 4,4·-bis(diethylamino)benzophenone, 4,4,_double (B The methylamino) benzophenone or the like is preferably 4,4'-bis(diethylamino)benzophenone. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used. Examples of the alkoxy hydrazine compound include 9,1 fluorene dimethoxy hydrazine, 2-ethyl-9, 1 fluorene dimethoxy fluorene, 91 〇 diethoxy fluorene, and 2-ethyl group. _91〇_Diethoxy hydrazine, 9,10-dibutoxy fluorene, 2_ethyl·9,10-dibutoxy fluorene, etc. β As the thioxanthone compound, 2-isopropyl Isothioxanthone, 4-isopropylthioxanthone, 2,4-diethylthiaxanone, 2,4-dioxathioxanthone, 1-gas-4-propoxythiazepine Anthrone and the like. 161700.doc •60· 201237118 As the carboxylic acid compound, phenylthioalkylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid Di-nonylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylthioalkylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N -phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like. The photopolymerization initiation aid (D1) may be used alone or in combination of two or more. When the photopolymerization initiation aid (D1) is used, it is used in an amount relative to the resin (B) and the polymerizable compound. The total amount is 1 part by mass, preferably 0.01 50 mass A, more preferably the mass part by weight. Further, with respect to the photopolymerization initiator (D), it is preferably 〇〇1 to 1 Torr, more preferably 〇〇ι 5 摩尔. When the amount of the polymerization starting aid (D1) is in this range, there is a tendency that the sensitivity can be further formed into a pattern to improve the productivity of the pattern. The colored photosensitive resin composition of the present invention contains a solvent (E). / Gu Qi 1 (E) is not particularly limited, and a solvent generally used in the field can be used. For example, it may be an ester solvent (a solvent containing _c〇〇·), an ether bath other than an ester solvent (a solvent containing _〇_), an ether ester solvent (a solvent containing _c〇〇_ and 〇〇-), A ketone solvent (solvent containing ·c〇_) other than the ester solvent, an alcohol solvent, an aromatic hydrocarbon solvent, a guanamine solvent, dimethyl sulfoxide, or the like is optionally used. Examples of the ester solvent include decyl lactate, decyl ethyl acrylate, butyl lactate, decyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, and amyl acetate. Amyl pentoxide, butyl propionate isopropyl butyrate, butyl sulfonium Sa, butyl butyrate, decyl pyruvate, ethyl pyruvate, pyruvic acid 161700.doc • 61- 201237118 B, acetic acid, glycerin, butyrolactone and the like. Cyclohexanol acetate, γ- as a butterfly, a mixture, may be exemplified by r-homomethyl ether, ethylene glycol monoethyl ether, ethyl alcohol monopropyl ether, ethylene _ mu early 』-ethyl alcohol monoterpene ether, two Ethylene glycol monoethyl _1, - 7 - L _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ^ μλ3 Λ , 3mn : oxy-3 · Methyl butanol, tetrahydro (tetra), tetra-argon n an- ethoxylated dioxime ether, di- _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Pro_Taji; ^ monoterpene alcohol - butyl ether, benzoin ether, stupid ether, mercapto anisole and the like. Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl oxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid. Methyl ester, ethyl 3-methoxypropionate, decyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl ethoxyacetate, 2-methoxy-2-methylpropionic acid, 2-B Ethyl oxymethylpropionate, butyl 3-methoxyoxyacetate, butyl 3-methyl-3-methoxyacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like. The ketone solvent may, for example, be 4-transyl-4-mercapto-2-pentanone, propyl-, butanone, 2-heptanone, 3-gly-, 4-heptanone or 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone, isophorone, and the like. 161700.doc -62- 201237118 The alcohol solvent may, for example, be methanol, ethanol, propanol, butanol, hexane, cyclohexanol, ethyl bromide, propylene glycol or glycerin. Examples of the aromatic solvent include benzene, toluene, toluene, and the like. T J — 乍 is a brewing agent. Examples thereof include hydrazine, hydrazine dimethyl carbamide, and N,N dimethyl acetamide. , N-methylpyrrolidone and the like. These solvents may be used singly or in combination of two or more. In the above-mentioned solvent, in terms of coatability and drying property, an organic solvent having a height of 12 〇t or more and 18 or less generations is preferable. Wherein 'preferably propylene glycol monoterpene acetate vinegar, lactic acid ethyl vinegar, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, 4-hydroxyl_4-methyl-2-indene, N,N-dimethylamine, N-methylhydrazine, etc., more preferably propylene glycol monoterpene _, propanol Early test of acetic acid vinegar, lactic acid ethyl acetate, 3 ethoxy propionate ethyl vinegar and so on. When these solvents are contained, the flatness at the time of coating is excellent. The content of the solvent (E) in the colored photosensitive resin composition is preferably from 7 to 95% by mass, more preferably from 7 to 95% by mass based on the photosensitive photosensitive resin composition. The solid content of the colored photosensitive resin composition is preferably % by mass, more preferably 8 to 25 % by volume. When the content of the solvent (8) is in the above range, the flatness at the time of coating becomes good, and when the light-sensitive sheet is formed, the color density is not A', and the display property tends to be good. The colored photosensitive resin composition of the present invention may further contain an interface lingual agent (7). The surfactant (F) may, for example, be an oxygenated surfactant, a surfactant of 161700.doc-63 to 201237118, a fluorine-based surfactant, and a fluorene-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain. Examples of the rhodium-based surfactant include an interface active agent having a decane bond. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Polyether Modified Shishing Oil SH8400 (trade name, Toray Dow Corning) (manufacturing), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 Illustrated by Momentive Performance Materials Japan, etc. The fluorine-based surfactant may, for example, be an interface active agent having a fluorocarbon chain. Specific examples include Fluorad (trade name) FC430, Fluorad FC431 (manufactured by Sumitomo 3M), Megafac (trade name) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac R30, Megafac RS- 718-K (manufactured by DIC), Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (trade name) S381 , Surflon S382, Surflon SC101, 81^1〇1130:105 (made by Asahi Glass Co., Ltd.), £5844 (made by Daikin Institute of Precision Chemistry). 161700.doc -64-201237118 The above-mentioned azeoxy-based surfactant having an IL atom may, for example, be a surfactant having a siloxane chain or a fluorocarbon chain. Specific examples are:

Megafac (registered trademark) R〇8, Megafac BL2〇, Megafac F475, Megafac F477, Megafac F443 (manufactured by DIC), and the like. These surfactants may be used singly or in combination of two or more. The content of the surfactant (F) is preferably 0.001% by mass or more, 〇2% by mass or less, preferably 0.002% by mass or more, and 〇% by mass or less, more preferably less than the coloring photosensitive resin composition. The mass% or more and the 〇·〇5 mass% or less. When the content of the surfactant (F) is in the above range, the flatness of the coating medium can be improved. The colored photosensitive resin composition of the present invention contains a coloring agent (A), a soluble resin (B), a photopolymerizable compound (6), photopolymerization (4) (D) 'mixture (E), and a surfactant (F). In the composition, the coating property is excellent, and a coloring pattern excellent in solvent resistance and spectral separation can be obtained. In the colored photosensitive resin composition of the present invention, the colorant (A) is preferably contained in an amount of 5 to 10% by mass, and the content of the resin (B) is 0% by mass, and the photopolymerizable compound ( The content of bismuth is 1 to 15 mass%, the photopolymerization initiator 〇(D) is set to 〇, 5 to 1% by mass, and the solvent (the content of phantom is Μ-&quot; The content of the coloring agent (4) is Η% by mass, and the resin (8) is 3 to 1% by mass. The content of the photopolymerizable compound (C) is 3 to 12% by mass, and the content of the photopolymerization initiator (9) is 5 mass%, the content of the solvent (8): 92 texture / 〇. Further, the content of the coloring agent (Α) is 2 to 5 mass: the content of the tree 曰 (8) is set to 4 to 8 mass%, 丨 polymerizability The content of the compound (.) is 5 to 1%. The content of the photopolymerization initiator (D) is 2 to 4 mass. /, I61700.doc • 65- 201237118 The content of the solvent (E) is 73. In the case of using the photopolymerization initiation aid (D1), the coloring photosensitive resin composition towel of the present invention is formed in a weight ratio of 1 part by weight relative to the solid content in the colored photosensitive resin composition. The content of the photopolymerization initiation aid is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, still more preferably 3 parts by mass. Interfacial activity is used in the colored photosensitive resin composition of the present month. In the case of the If of the agent (F), the content of the surfactant (F) is preferably 〇.〇〇!~〗 by mass of the content of the solid content of the coloring photosensitive resin composition in 100 parts by weight. G1 to G.5f parts, and more preferably Q core parts by mass. The colored photosensitive resin composition of the present month may contain a filler, other polymer compound, adhesion promoter, antioxidant, ultraviolet rays, if necessary. Various additives such as an absorbent, a light stabilizer, and a chain transfer agent. The method of forming a colored pattern by using the colored photosensitive resin composition of the present invention, for example, is to apply the colored photosensitive resin composition of the present invention to a substrate or The other resin layer (for example, another colored photosensitive tree residue layer formed on the substrate, etc.) is removed, and the volatile component such as a solvent is removed/dried to form a colored layer. The colored layer is exposed through a photomask, and the developed layer is formed. And a method of using an inkjet apparatus that does not require a photolithography method, etc. The film thickness of the coating film in this case is not particularly limited, and it is suitable for adjustment of materials and uses, for example, 〇. 1~3 〇μηι 'better It is 1 to 6 μηι. The coating method of the coloring photosensitive resin composition of U0 can be used according to the material used, for example, extrusion coating method, direct gravure coating method, reverse gravure Printing coating method, CAP coating method, die coating method, etc. Dip coating 161700.doc • 66 - 201237118 machine, bar coater 'rotary coater, slit &amp; rotation A coater or a slit coater (also sometimes referred to as a die coater, a curtain flow coater, or a spinless coater) The coating machine is applied. The solvent removal/drying&apos;s may, for example, be naturally dried, ventilated, dried under reduced pressure, dried by heating, or the like. The specific drying temperature is preferably from 10 to 120 ° C, more preferably from 25 to 100 ° C. The drying time is preferably from 10 seconds to 6 minutes, more preferably from 30 seconds to 30 minutes. The drying under reduced pressure is preferably at a pressure of 5 Torr to 15 Torr Pa at 2 Torr to 25 °. The coating film after drying is exposed through a mask for forming a target pattern. The pattern shape on the mask is not particularly limited, and a pattern shape corresponding to the intended use can be used. The light source used is preferably a light source that generates light having a wavelength of 25 〇 to 45 〇 nm. Specifically, a mercury lamp, a light emitting diode, a metal toothed lamp, a light element lamp, etc. can be used to cut off a specific band of light. The device is cut off or exposed by selective extraction using a band pass filter for extracting a specific band. Since the entire exposed surface can be illuminated with parallel I lines, or the correct alignment of the mask substrate can be performed, Preferably, it is a device such as a calender (four) machine, a stepper, etc. After exposure, a specific portion such as an unexposed portion is dissolved and developed by contact with a developing solution, whereby a pattern can be obtained. An aqueous solution of ^ Hydroxide _, carbon _, hydrogen oxy fine methyl material). The developer may contain a surfactant. 161700.doc -67· 201237118 The development method may be any one of a puddle method, a dipping method, and a spray method. Further, the substrate can be tilted at any angle during development. It is preferred to carry out water washing after development. Further, post-baking can be performed as needed. The post-baking is, for example, preferably in the range of 150 to 23 〇C '10 to 240 minutes. In the colored photosensitive resin composition of the present invention, a coating film or pattern which is excellent in color density, brightness, contrast, sensitivity, resolution, heat resistance, etc. can be used as the color filter. Further, it is known that all of the display devices having such color filters as their constituent parts, such as known liquid crystal display devices, organic EL devices, solid-state imaging devices, and the like, are associated with colored images. In the machine. [Examples] Hereinafter, the colored photosensitive resin composition of the present invention will be described in further detail by way of examples. In the examples, "%" and "parts", unless otherwise stated, mean % by mass and parts by mass. Synthesis Example 1 3 parts of Rose Bengal B (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in chloroform 288 wound, and 2.3 parts of N,N-dimethyl-4-aminopyridine and 1〇_camphorsulfonic acid 1.75 were added. A portion of dehydroglycerin (16.24 parts) was stirred at 20 ° C for 1 hour. While stirring, 17.41 parts of 1-ethyl_3_(3·dimethylaminopropyl)carbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 72 parts of the sample was added dropwise. After the completion of the reaction, the organic layer was obtained by adding a 1 N aqueous hydrochloric acid solution to the reaction mixture to carry out liquid separation. This operation was repeated twice more on the organic layer. Next, 10% saline solution was added to the organic layer to carry out liquid separation to obtain an organic 16I700.doc • 68 · 201237118 layer. This operation was repeated twice more on the organic layer. After adding magnesium sulfate to the obtained organic layer for dehydration, the mixture was filtered to obtain a filtrate. The solvent was removed from the filtrate by means of an evaporator, and the obtained red solid was evaporated under reduced pressure. The mixture was dried under a crucible to obtain 30 parts of the compound of the formula (d-?) (yield: 89.5%). Identification of the compound represented by formula (d-Ι) (mass analysis) ionization mode = ESI+: m/z = 499.3 [M-Cl_] +

Exact Mass: 534.2

Example 1 After adding 65 parts of water to 7 parts of 2-amino-4-indolyl fluorenyl-6-succinyl benzene (CAS No. 101861-04-5), 1.3 parts of sodium hydroxide was added. Dissolve it. After cooling in an ice bath, 6.1 parts of an aqueous solution of 35% sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and then 19.4 parts of 35% hydrochloric acid was added little by little to dissolve and mix for 2 hours to obtain a heavy weight. A suspension of nitrogen salts. Then, an aqueous solution in which 5.6 parts of an aminosulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 26 parts of water was slowly added, and excess sodium nitrite was quenched. Then, 5.6 parts of '33-yl-1-phenyl-5-η than 唾 顚 顚) (made by Wako Pure Chemical Industries Co., Ltd.) was suspended in 70 parts of water, and the pH was adjusted to 8.0 using sodium hydroxide. . One of the above suspensions containing the heavy sulfonium salt was added dropwise thereto over 15 minutes, and a 1% by weight sodium hydroxide solution was added thereto to have a pH of 7 to 7.5. After the completion of the dropwise addition, the mixture was further disturbed for 30 minutes to obtain a yellow suspension of 161700.doc -69 - 201237118. Stir for 1 hour. The yellow solid obtained by filtration was dried at a reduced pressure of 60 ° C to obtain 11.7 parts of a compound of the formula (p_2) (yield: 87%).

Add 1 part of the compound of the formula (p-2) to 100 parts of dimercaptocarboxamide (manufactured by Tokyo Chemical Industry Co., Ltd.) to dissolve it, and add chromium (III) ammonium sulfate decahydrate (and pure light) Manufactured by the pharmaceutical industry (stock), 3.1 parts, sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), 1 part, and heated under reflux for 4 hours and a half. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% saline solution, and the orange-red solid obtained after filtration was dried at 60 ° C to obtain 13.6 parts of the compound of the formula (z-2). 63%).

© Na (z-2) Identification of the compound of formula (z-2) (mass analysis) Ionization mode = ESI-: m/z = 882.1 [M-Na+]·

Exact Mass : 905.1 Dissolve 5 parts of the compound of the formula (z-2) in 75 parts of the meaning of methyl 2-pyrrolidinone. Adding 63 parts of the compound represented by the formula (d-Ι) to the solution is dissolved. 161700.doc ·70· 201237118 A solution of 35 parts of N-mercapto-2-pyrrolidone was stirred for 2 hours. After completion of the reaction, it was added dropwise to 300 parts of water, and the precipitated red solid was collected by filtration to dryness under reduced pressure 6 (TC), whereby 6.4 parts of the compound of formula (b) was obtained (yield 86.8%). Identification of the compound represented by formula (1_2 7) (mass analysis) ionization mode = ESI+: m/z = 1382.4 [M-Cn +

Exact Mass : 138 1.3

Synthesis Example 2 &lt;Synthesis of Resin B 1 Solution> In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen was introduced at 0.02 L/min to form a nitrogen atmosphere, and 5 parts by mass of ethyl lactate was charged. Heat to 70 ° C while stirring. Then, 6 parts by mass of methacrylic acid, 3,4-epoxytricyclo[sj.i.o2,6] vinegar of acrylic acid (the compound represented by the following formula (1) and the formula (ΙΜ)) The compound shown is dissolved in a molar ratio of 5 〇:5 )) in an amount of 240 parts by mass to a solution prepared from the 14Qf portion of the lactic acid, and is used in a dropping funnel for 4 hours; the solution is added to the heat retention at 7 〇e&gt;c in the flask. On the other hand, using a different dropping funnel, a solution of the starting agent 2,2,· azobis(2,4-dimethylvaleronitrile (tetra) in 225 parts by mass of lactic acid was added dropwise over 4 hours. In the flask, the solution of the polymerization initiator was added dropwise to I61700.doc 71 201237118, and kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 1.3·1χ4, solid content. It is a mass of 33% by weight of a resin Β1 solution having a solution acid value of 34 mg-KOH/g. The acid value of the solid content of the resin B1 is calculated from the above solid content and the acid value of the solution to be 1 〇〇 mg-KOH/g. .

Synthesis Example 3 &lt;Synthesis of Resin B2 Solution&gt; 333 g of propylene glycol monoterpene ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a gas introduction tube. Thereafter, nitrogen gas was introduced into the flask through a gas introduction tube, and the atmosphere inside the flask was replaced with an air gas. Thereafter, the solution in the flask was heated to 1 Torr. (: After that, using a dropping funnel to contain N-benzyl maleimide imine 18.7 g, benzyl methacrylate 70.5 g, methacrylic acid 5 17 g, methyl methacrylate 9 以. A mixture of 〇g, 5.2 g of azobisisobutyronitrile and 182 g of propylene glycol monoterpene ether acetate was added dropwise to the flask, and after the completion of the dropwise addition, stirring was continued for 5 hours at 10 ° C. The air was introduced into the flask through a gas introduction tube, and the environment inside the flask was replaced with air, and then 28.5 g of glycidyl methacrylate, 13 g of bis(dimethylaminomercapto)phenol, and 0.165 g of hydroquinone were put. The reaction in the flask was carried out at 11 (TC for 6 hours to obtain a weight average molecular weight of 161700.doc • 72· 201237118

The resin B2 solution having a Mw of 16×10 3 and a solid content of 31% and an acid value of 80 mg-KOH/g (solid content conversion). The measurement of the polystyrene-equivalent weight average molecular weight of the above resin was carried out under the following conditions using a GPC method. Device String Column Temperature Solvent Flow Rate Concentration of Solid Content of Inspected Liquid Injection Injector Detector Standard Material for Calibration : HLC-8120GPC (Manufactured by Tosoh)

:TSK-GELG2000HXL :40°C :THF

:1.0 mL/min :0.001 ~0·01〇/〇 :50 μί :RI

:TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh) Example 2 [Preparation of colored photosensitive resin composition] Mixed (A) compound (1) ): 30 parts of the compound represented by the formula (1-27) (B) Resin: Resin B1 (in terms of solid content) 40 parts (C) Photopolymerizable compound: dipentaerythritol pentaacrylate and dipenta tetra 161700 .doc -73-

S 201237118 Mixture of alcohol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 60 parts (D) Photopolymerization initiator: N-benzoquinone-1-(4-phenylsulfanylbenzene) Base) oct-1-one-2-imine (Irgacure OXE 01; manufactured by BASF Japan) 12 parts (D) Photopolymerization initiator: 2-benzyl-2-dimethylamino-1-(4) -Phenolinylphenyl)butan-1-one (Irgacure 369; manufactured by BASF Japan) 6 parts (D1) photopolymerization starter: 4,4·-bis(diethylamino)benzophenone (EAB-F; manufactured by Baotu Valley Chemical Co., Ltd.) 2 parts (E) Solvent: propylene glycol monomethyl ether 597 parts (E) Solvent: ethyl lactate 43 parts (F) Surfactant: polyether modified eucalyptus oil (Toray Silicone SH8400;

Toray Dow Corning (manufactured by Toray Dow Corning Co., Ltd.) was 0.09 parts to obtain a colored photosensitive resin composition. [Formation of Pattern] The colored photosensitive resin composition was applied by a spin coating method on a glass substrate (Eagle 2000; manufactured by Corning Incorporated) of 2 inches square, and then prebaked for 3 minutes in 1 time. After cooling, the distance between the substrate coated with the colored photosensitive resin composition and the mask made of quartz glass was set to 1 μm, and the exposure machine (TME-150RSK; TOPCON) was used in an atmosphere. Light irradiation was performed at an exposure amount of 100 mJ/cm 2 (365 nm reference). Further, as the photomask, a line which can form a line of 100 μm and a gap pattern can be used. After the light irradiation, the substrate was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide for 8 seconds to develop, and the water was 161700.doc • 74-201237118 after washing In the flood box, at 230. (: After baking for 30 minutes, the film thickness of the obtained pattern was measured by using a medium thickness measuring device (DEKTAK3; manufactured by Sakamoto Vacuum Technology Co., Ltd.)), and the result was 2.0 μm 〇 [color performance evaluation] The obtained pattern was measured for spectroscopicity using a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinates (X, y) before and after immersion in the XYZ color system of CIE were measured using the color matching function of the C light source. (ie chromaticity) and brightness Y. The results are shown in Table 1. [Evaluation of Solvent Resistance] In the above pattern formation, a coating film was produced by performing the same operation except that the mask was not exposed. The obtained coating film was immersed in 23 〇c of N•曱基_2·° piroxone for 30 minutes, and a color measuring machine (〇sp_sp_2〇〇; 〇lyjnpus (manufactured by 〇)) was used to measure the spectroscopic use of the C light source. The color matching function determines the xy chromaticity coordinates (Rx, Ry) (ie, chromaticity) and the brightness RY ' before and after the immersion in the XYZ color system of CIE to calculate the color difference Δ Eab* before and after the immersion. The smaller the color difference Δ Eab*, the better the solvent resistance. The results of the color difference Δ Eab* are shown in Table 1. Further, on the coating film after the immersion, a slit and a supei· cutter guide (manufactured by Taiyukizai Co., Ltd.) were used to cut the slits at intervals of 1 mm to make 100 grids of 1 mm x 1 mm. Paste on the grid

Sellotape (registered trademark) 24 mm wide (manufactured by Nichiban Co., Ltd.), from

On the Sellotape (the main book mark), rubber friction is used to attach the §eii〇tape (registered trademark) to the hardened enamel. After 2 minutes, hold the side of the Sellotape (registered trademark) and keep it at right angles to the coated surface. 'One side stripped. Thereafter, the number of the grids remaining on the substrate without peeling off the coating film was visually counted. The grid number 161700.doc .75 - 201237118 is shown as the adhesion, as shown in Table 1. Comparative Example 1 Mixing (A) Colorant: Orasol Red G (manufactured by Ciba Japan Co., Ltd.) 47.5# (B) Resin: Resin B2 solution 16 parts (C) Photopolymerizable compound: dipentaerythritol pentaacrylate and dipentaerythritol Acrylate mixture (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 23.9 parts (D) Photopolymerization initiator: 2-methyl-2-indolyl-1-(4-methylsulfanylphenyl) Propan-1-one (Irgacure 907; manufactured by BASF Co., Ltd.) 3.6 parts (D) Photopolymerization initiator: 2,4-bis(trichloromethyl)-6-to geranyl-1, 3,5-three tillage (TAZ-PP; manufactured by Nihon Siber Hegner) 2.8 parts (D1) photopolymerization starter: 4,4·-bis(diethylamino)benzophenone (EAB- F; manufactured by Baotu Valley Chemical Co., Ltd.) 1.2 parts (E) Solvent: 267 parts of propylene glycol monomethyl ether (E) Solvent: 138 parts of propylene glycol monomethyl ether acetate (F) Surfactant: Megafac F475 (DIC) )) 0.1 part of the obtained photosensitive resin composition was obtained. The colored photosensitive resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1. 161700.doc -76- 201237118 [Table 1]

Solvent resistance _^AEab* o.i

-—---_Ijoo ^~~ ' ” In the N-A, 0~~ί... sulphide immersion, the colored coating film is peeled off from the peeling substrate, and the color difference Δ Eab* and the adhesion are measured. The coating film formed by the coloring photosensitive resin composition of the invention has a good solvent resistance. Therefore, according to the colored photosensitive resin composition of the present invention, it is possible to obtain a coating film, a pattern, and a high quality which are excellent in lightness. [Colorful filter] [Industrial Applicability] According to the colored photosensitive resin composition of the present invention, a coating film, a pattern, and a high-quality color filter excellent in solvent resistance can be obtained. 161700.doc 77·

Claims (1)

201237118 VII. Patent application scope: 1 - a coloring 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 formula (1) Coloring agent, [In the formula (1), R1 to R18 each independently represent an argon atom, a monovalent aliphatic hydrocarbon group having a carbon number of 1 to 8 in a halogen atom, a nitro group or _s〇2R29, and R29 represents -R32, -OH or -NHR30, R3() 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, _R31_〇_R32, r31_c〇_〇_R32, -r31 -〇-c〇-r32 or an aralkyl group having a carbon number of 7 to 10, R31 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R32 represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, R19 and R2G independently represents 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 monovalent aliphatic hydrocarbon group having a carbon number of 1 to 8 or a carbon number of 6 to 1 0. The monovalent aromatic 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 base group, -S〇3Na, -S03K or a halogen atom, 161700.doc 201237118 R25 and R26 each independently represent a hydrogen atom or a methyl group, R represents an ethyl group, a propionyl-1,3-diyl group or a propyl-i,2_diyl group, and η represents an integer of 0 to 3, and η is 2 or more. In the case of an integer Two R27 the same or different]. 2. The colored photosensitive resin composition of claim 1, wherein r1~, 〜K are each independently a hydrogen atom, a nitro group or -S02R29, R29 is -R32, and R32 is a monovalent aliphatic group having a carbon number of 1 to 8. The hydrocarbon group, R19 and R20 are each independently a methyl group, and R to R24 are each independently a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R25 and R26 are each independently a hydrogen atom, and η is 0. 3. The colored photosensitive resin composition of claim 2, wherein at least one of r1 to rU is a hydrogen atom, at least one is a nitro group, and at least one is -so2r29 〇4. A resin composition in which R1 to rW are each independently a hydrogen atom. Photopolymerization initiator of at least one of 201237118. 7. The colored photosensitive resin composition of the present invention, wherein the color filter is formed by the photosensitive resin composition of any one of claims (1). 9. A display device 'which contains a color light film as claimed in claim 8. a compound represented by the formula (1), In the formula (1), R to R each independently represent a hydrogen atom, a crypto-atom atom, a monovalent aliphatic hydrocarbon group having a carbon number of 1 to 8, a fluorenyl group or _s〇2R29, and R29 represents -R32, -OH or - NHR30, R30 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, _R3丨_〇R32, r3i_c〇〇_R32, -R31- 0-C0-R32 or an aralkyl group having 7 to 1 carbon atoms, R31 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R32 represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, R19 and R20. Independent of each other, represents a hydrogen atom, a sulfhydryl group, an ethyl group or an amine group, M1 represents Cr or Co, and R21 to R24 independently represent a hydrogen atom and a monovalent aliphatic group having a carbon number of 1 to 8 161700.doc 201237118 Hydrocarbyl group or carbon number 6 ～1 0 of 1 price &quot; 番心... Hydrocarbyl group, the aliphatic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may be via a hydroxyl group 32, a sulfo group, -SC^Na, _S〇3K or Substituted by a halogen atom, R25 and R26 each independently represent a hydrogen atom or a methyl group, and represent an ethyl group, a propyl group, a dimethyl group, a dimethyl group, a propylene group, a bisylene group, and a fluorene group, and η represents an integer of 0 to 3, which is η. Integer of 2 or more In the shape, a plurality of R27s are the same or different from each other]. 161700.doc 201237118 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: 161700.doc 201237118 Inventor patent description t 1 year adjustment (this manual format, order and bold type, please do not change anymore, ※ ※ application number: ... 丨 ※ application date: m ※ (four) classification contains Yiqiyi, invention Name··(Chinese/English) 二&gt;r^ Coloring photosensitive resin composition and compound COLORED PHOTOSENSITIVE RESIN COMPOSITION AND COMPOUND II. Abstract of the invention · The present invention provides a coloring photosensitive resin composition, the coloring sensitivity The resin composition contains a colorant, a resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The colorant is a coloring agent containing a compound represented by the formula (1), wherein 'R1 to R18 represent a hydrogen atom and a carbon number of 1. An aliphatic hydrocarbon group or a nitro group having a value of 8% or less. R19 and R2G each represent a hydrogen atom, a fluorenyl group, an ethyl group or an amine group. M1 represents Cr or Co. R24 represents a hydrogen atom and a carbon number of 1 to 8 An aliphatic hydrocarbon group or an aromatic hydrocarbon group having a carbon number of 6 to 10, and r25 and r26 represent a hydrogen atom or a fluorenyl group. R27 represents an ethyl group, a propyl-1,3-diyl group or a propyl-l,2-di group. Base η represents an integer from 0 to 3. III. English Abstracts: 161700-1010605.doc 201237118 Description of invention patents t 1 year adjustment (this manual format, order and bold type, please do not change anymore, ※ ※Application number: ...丨※ application date: m ※ (4) Classification, including Yiyiyi, invention name··(Chinese/English) II&gt;r^ Coloring photosensitive resin composition and compound COLORED PHOTOSENSITIVE RESIN COMPOSITION AND COMPOUND II. Abstract of the invention ·· The present invention provides a coloring sensitivity In the resin composition, the colored photosensitive resin composition contains a colorant, a resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The colorant is a coloring agent containing a compound represented by the formula (1), wherein 'R1~ R18 represents a hydrogen atom, an aliphatic hydrocarbon group having a monovalent number of carbon atoms of 1 to 8, or a nitro group, etc. R19 and R2G each represent a hydrogen atom, a fluorenyl group, an ethyl group or an amine group. M1 represents Cr or Co. An aliphatic hydrocarbon group having a carbon number of 1 to 8 or a monovalent aromatic hydrocarbon group having a carbon number of 6 to 10. R25 and r26 represent a hydrogen atom or a mercapto group. R27 represents an ethyl group and a propane-1,3-diyl group. Or C-l,2-two .η of integer of 0 to 3. III. English Abstracts: 161700-1010605.doc 201237118 Patent Application No. 101104094 Replacement Page (June 101) A colored photosensitive resin composition comprising a colorant, a resin, a photopoJymorizable compound, a photopolymerization ioitiator, and a Solvent, the colorant comprises ή compound represented by formula (l)* R10〇E38autorepresent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, R30 and R20 independently represent a hydrogen atom, a methyl group, an ethyl group, or an amino Ml represents Cr or Co»* R2i to B»4 independently repreaent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atom$, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms;; Ra6 and KBe Exceptional a hydrogca atom or a methyl group; represents an ethylene group, a propane-1,3-diyl group, 〇ra pxopano*l,2-diyl group; and η represents an integer of 0 to 3, Figure: (1) The representative representative of the case is: (none) (2) A brief description of the symbol of the representative figure: 5. If the case is clarified, the formula can best show the characteristics of the invention. 16170CM010605.doc 201237118 Patent No. 101104094 Patent Application Replacement Page (June 101) A colored photosensitive resin composition includes a colorant, a resin, a photopoJymorizable compound, a photopolymerization ioitiator, and a solvent, the colorant comprising ή compound represented by formula (l)* R10〇E38autorepresent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, R30 and R20 independently represent a hydrogen atom, a methyl group, an ethyl group, or an amino Ml represents Cr or Co»* R2i to B»4 independently repreaent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atom$, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms;; Ra6 and KBe Exceptional a hydrogca atom or a methyl group; represents an ethylene group, a propane-1,3-diyl group, 〇ra pxopano*l,2-diyl group; and η represents an integer of 0 to 3, Figure: (1) The representative representative of the case is: (none) (2) A brief description of the symbol of the representative figure: 5. If the case is solvable, please describe the chemistry that best shows the characteristics of the invention. 16170CM010605.doc