TWI337689B - Black photosensitive resin composition - Google Patents

Description

1337689 A composition comprising an adhesive resin (B). It is a diol having more than two epoxy groups, a reaction of a compound with a polycarboxylic acid with an unsaturated unit carboxylic acid, and further reacting with an anhydride of a polycarboxylic acid. The obtained polycarboxylic acid resin (b1), and a polycarboxylic acid resin (b2) obtained by reacting a compound having 2 or more epoxy groups with an unsaturated unit carboxylic acid and then reacting with an acid anhydride of a polycarboxylic acid One of the selected polycarboxylic acid resins, and the photopolymerization initiator (D) is a quinone compound. [2] The black photosensitive resin composition in the item [1], wherein photopolymerization is started

The compound of at least one selected from the group consisting of the formulas (1) to (iv) is contained in the first (D). R3

The R group may be substituted by at least i groups selected from the group consisting of a functional atom, a carbon atom of 16 alkyl groups, a phenyl group, -OR8, -SR9 and -NR»〇Ru. ], methyl, carbon 2 2 〇 alkyl [the alkyl can also be! More than one interruption, and / or more than one hydroxyl substitution. ], a carbon atom number 5-8 cycloalkyl group, a carbon atom number 孓2 decane fluorenyl aglyl group [the alkalyl group can also be derived from a carbon atom alkyl group, a stupid group, -〇R8, _SR? and _ At least one base substitution selected in the group of nr1〇r1i 315724 revision 1337689. i. A number of fluorene atoms 2-12 alkoxyl yl group [The alkoxycarbonyl group may also be substituted by one or more - Ο-t, and/or more than j hydroxy groups. ], an oxycarbonyl group [the phenoxycarbonyl group may also be substituted with at least one group selected from the group consisting of a 1-6 alkyl group, a halogen atom, a phenyl group, a fluorene atom, a ruthenium group, a phenyl group, a fluorene group . ], _c〇NRiQR" base, an aryl group, a nitro group, a halogenated alkyl group having 1 to 4 carbon atoms [the halogen atom is a fluorine atom, a gas atom, a bromine atom or an iodine atom). ], -SO-Z1 [Z1 in the formula is a carbon number of 1-6 fluorenyl group. ;|, β〇2_ζι[where the table is the same as the above. ], -Z2-SO-Z3 [Z2 in the formula, carbon number, 12 alkyl group, 汐 table carbon atom||| number 6-12 aryl. ], _Z4_s〇2_z3 [wherein the z4 carbon atom number i is extended to the base, and the Z3 table is the same as the foregoing. ],·§〇2·〇·ζ5 [The number of carbon atoms in the formula is 6-10 aryl. ], or diphenyl phosphinyl fluorenyl; R 2 represents a carbon number of 2-12 alkyl fluorenyl [the alkyl fluorenyl group can also be! More than one halogen atom or a cyano group is substituted. ], a carbon atom number 4-6 olefin group [but the double bond of the olefin group is not conjugated to a carbonyl group. Benzyl fluorenyl group [The benzoyl group can also be substituted by at least one selected from the group consisting of a 1-6 alkyl group, a self atomic atom, a cyano group, a _〇rS, a _SR9, and a NR1°RU group; The number of the carbonaceous material is 2_6. The oxyalkyl group or the phenoxy group; the phenoxy group may also be substituted by a carbon atom of 1 to 6 or a halogen atom. R3: R7 is independent of each other, and represents a hydrogen atom, a _ atom, a cyclopentyl group, a cyclohexyl group, a phenyl group. The stupid group may also be at least one selected from the group consisting of -8, _Sr9, and NRl 〇Rn. Replace. ], a methyl group, a benzoyl group, a carbon number of 2 to 12 (tetra) groups, a carbon number of 2 to 12 alkoxy groups [the alkyl group of the alkoxy group may be interrupted by more than one] and / or 1 The above basis is taken from the 315724 revision 7 1337689. ], phenoxycarbonyl, -〇R8, _SR9, 乂s〇R9, _s〇2r9 and _NRi°Rii [where _OR8, SR9 and _NR丨0rh may also be substituted by the aforementioned benzene ring in r3_r7 One of the carbon atoms in the base or the stupid ring forms a 5-membered ring or a 6-membered ring via a group in which one hydrogen atom is removed from R8-Rn. However, when a ring is formed, R8-Rn is not a hydrogen atom. ], at least one of R3_R7 is selected from the group consisting of -OR8, -SR9, and -NRiOR1丨; R represents a hydrogen atom, and has a carbon number of 1 to 12 alkyl groups; the alkyl group may also be derived from _〇H, -SH, and cyano group. , carbon atom number ι_4 alkoxy group, carbon number 3_6 alkenyloxy group, -〇CH2CH2CN, 巾ι of the formula is 1-4 alkyl group), -0(C0)-Z6 (wherein Z6 is carbon Atom number 丨4 alkyl), -〇(CO)-Ph (where Ph is phenyl), _(C0)0H or _(〇:〇)〇_丁2 (where T2 is a carbon atom) Substituted by a number of 1 to 4 alkyl groups, the alkyl group may also be interrupted by more than one of -0. ], -(CH2CH2〇)n-H [where n is! To the integer of 2〇. Rabbit atomic number 2-8 calcined base, carbon number 3-1 2 women's base, carbon number 3-6 olefin group, cyclohexyl group, phenyl [this phenyl group may also be derived from dentate atom, carbon number 1 -12 alkyl or a carbon number of N4 alkoxy substituted q'phT3 [wherein Ph is a stupid group. T3 is a carbon atom number ι_3 alkyl group. ],·§ίτ'ρίΐ3 r[T4 is the number of carbon atoms! · 8 alkyl, ph is phenyl, and r is an integer of 丨_3. ] Form (V)

In the formula (V), the R1 and R2 tables have the same meanings as described above, and the Ml form bond, the carbon atom 1 1 -12 -12 -12 -12 -12 Version 8 1337689 - and / or -NRl0 - interrupt. Or a carbon number of 1-12 oxyalkylene group [the oxyalkylene group v may also be interrupted by 1-5 - 〇-, -S- and/or -NR10-. ;| ; R9 represents a hydrogen atom, a methyl group, a carbon number of 2-12 alkyl groups [the alkyl group may also be -〇H, -SH, a fluorenyl group, a carbon atom number 1 _4 alkoxy group, a carbon number of 3-6 Alkenyloxy, -OCH2CH2CN, -OCH2CH2(C0)0-T5 (wherein T5 is 'carbon number 1-4 alkyl.), -〇(CO)-T6 (wherein T6 is a carbon number of 1) -4 alkyl group.), _0(C0)_Ph (wherein ph is phenyl), _(c〇)〇h or •(C0)0-T7 (wherein τ7 is a carbon number of 1-4 alkane Base) replaced. The alkyl group may also be interrupted by one or more of 〇. ], a C 3-12 alkenyl group, a ring % I hexyl group, or a phenyl group [this stupid group may also be substituted by a _ atom, a carbon number of 1 丨 2 alkyl group or a carbon number of 1-4 alkoxy group. ] or formula (VI)

(VI) In the formula (VI) and the rule 2, the same meaning as described above, the M2 form bond or -t14-s-[wherein the carbon atom number ι_12 alkyl group (the alkyl group may also be I-5) _〇-, _S- and/or -NR10-interrupt.). R and R11 are independent of each other's hydrogen atom, carbon atom number 丨12 alkyl group, carbon number 2-4 hydroxyalkyl group, -τΌ-τίο [wherein T9 is a carbon number of 1-6 alkylene a group, Τ10 is a carbon atom number 1-6 alkyl group, a carbon atom number 3_5 alkenyl group, a carbon number of 5-12 cycloalkyl group, a phenyl group [this stupid group may also be a C 1-12 alkyl group or a carbon atom) A number of 丨4 alkoxy groups are substituted. ], the number of carbon atoms is 2-3 alkyl fluorenyl groups, the number of carbon atoms is 2-3 decyl groups or benzamidine groups, and R1 〇 and R ll are bonded to the same nitrogen atom 蛉 ' can also form a carbon number of 2-6 The alkyl group [the alkyl group 9 315724 modified JE version 1337689 - can also be interrupted by 0- or -NR _, and / or by the base, carbon number 4 alkoxy, carbon number 2-4 The oxy or benzyloxy group is substituted. ], when Rl0 - is a hydrogen atom, Rii may also be of the formula (νπ). The formulas of R1 and R2 in the formula (VII) have the same meaning as described above, m3 form bond, shouting group or -T14··[T14 in the formula The number of carbon atoms is 1-12, and the base can also be interrupted by 1-5, 〇·,•, and/or -NRl0_. R is a C 2-12 alkoxycarbonyl group [The alkoxycarbonyl group may also be interrupted by one or more of -0-, and/or may be substituted with one or more hydroxyl groups in some cases. ], an alkoxycarbonyl group [the stupidoxycarbonyl group may also be substituted by one or more: a stone counter atomic number of 1-6 alkyl group, a halogen atom, a phenyl group, a fluorene R8 or an Nr1〇r". ], a carbon number of 5-8 cycloalkyl, _CONRi〇Rn_, cyano, phenyl [this stupid group may also be substituted by SR9, or may form a bond with a carbon atom on a stupid ring containing Rn_Rl5, and remove 1 R9 of a hydrogen atom (but when R9 is not a hydrogen atom or a cyano group at the time of forming a ring structure) forms a 5-membered ring or a 6-membered ring. ], when at least one of R-R is _SR9, Ri2 is a methyl group or a carbon atom number 2-12 alkyl group [the alkyl group may also be a halogen atom, -OH, -OR2, a stupid group, a halogenated stupid group or an SR9) One or more substitutions of the substituted phenyl group may also be interrupted by -〇_ and/or -NH(CO)_. R-R is independent of each other's hydrogen atom, halogen atom, carbon number 1 _ 12 alkyl group, cyclopentyl group, cyclohexyl group, phenyl group [this phenyl group may also be derived from _〇R8, _SR9 ' and -NR10Rn- At least i bases selected in the group are substituted. ], benzyl, 315724 modified version 1337689, benzoyl group, carbon number 2-12 alkyl fluorenyl group, carbon number 2_12 alkoxycarbonyl group [this dazzling ship base can also be interrupted by more than one _ 〇 And/or substituted by one or more hydroxyl groups. ], phenoxycarbonyl, _OR8, _SR9, _S〇r9, _s〇^9 or -NRIOrH [where_0R8, _sr9 and -nr10r丨丨 may also be substituted with the aforementioned substituents of the awkward ring present at ft 3_foot 72 or One of the carbon atoms of the benzene ring forms a 5-membered ring or a 6 M fluorene through a group in which one hydrogen atom is removed, but in the case where 'R8_RU is not a hydrogen atom. ], Rn_Rl5 has at least two or -NR, 丨丨; X represents a carbon number of 1-12 alkyl, cyclohexyl, phenyl, (co)oT-〇 (c〇H below 丨2 is Number of carbon atoms m-alkylene-J ^C〇)〇-(CH2CH2〇)n-(CO)- t ^ η ^ 1-20 < ^ number °b or -(c〇xr丨3_(c〇)• [Formula n-alkyl β]] is a number of gorge atoms 2·12θ. The black photosensitive resin composition in the item [2], which is abbreviated as "the acid group may also be broken by the original; =:=, or Produced to 乂U solid base substitution.]; R3, R6, R7 mutual Aifs stand, surface 虱 atom, halogen shoulder + mutual and tear, the group Yin Shiji [the base can also be detected by 8,

-OR8 〇〇 9 kg of at least 1 base substitution. R5A R, and -NR10Rh [and t is the same as Wt, and the right w-SR and I0Rn may be one, which is a ring of a carbon atom of a substituent or a ring of a benzene ring. However, when forming a ring, the r8^ group forms a 5-member ring or a 6-member [4] as in item [2] or the first is not a scorpion. ]By. , 黑色 black photosensitive resin composition, its 315724 revision 11 1337689. Let 'R3, R6 and R7 are all hydrogen atoms. [A] The black photosensitive resin composition of any one of [2] [4], wherein R1 is a n-hexyl group, R2 is a benzamidine group, and R5 is a stupid thio group. [] The black photosensitive resin composition of any one of the items [1] to [5], which further contains a triterpenoid photopolymerization initiator. The black photosensitive resin composition according to any one of the items [1] to [6], which is selected from the group consisting of a clumsy-type photopolymerization initiator and a clumsy-type photopolymerization initiator. At least one species. The black photosensitive resin composition according to any one of the items [1] to [7] wherein the composition further contains an ethyl phthalocyanine photopolymerization initiator. [9] The black photosensitive resin composition according to any one of [1] to [8], wherein the compound of 32 or more epoxy groups is a compound represented by the formula (νπι) and the formula (ι). At least one compound selected from the group.

[In the formula (VIII), ρ represents an integer of 20 or more; Rl6_Ri9 is independent of each other, and a hydrogen atom, a carbon number of 1-8 alkyl group, a carbon number of 5_丨2 cycloalkyl group, and a carbon number of 6- a 14-aryl group or a 7-20 aralkyl group having a carbon number; Qi_Qu is independently a 'hydrogen atom of a watch, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, and 1 to 8 alkynyl groups; 5-12 ring-burning group, 6-14 aryl group, 7-20 aryl group, carbon number 1, alkoxy group, 1-8 alkenyl group, carbon number 1 alkynyloxy, carbon 12 315724 Xiu Edition (IX) 1337689 Atomic number 6 to M aryloxy, nitro or cyano 'CH2, (〇r2〇^

The sub-number Q i is independent, a hydrogen atom, a 11-atom atom or a carbonogen &base; R20 has a carbon number of 1 to 10; an integer of q 〇 _5; a Y form bond or formula (IX-1) a 2-valent group as shown in any one of formula (IX-8). ]

(K-1) (K-2) (Κ·3)

F3XCF (K-4) H3%i^CH3(K-5), 〇, (财) 八(K~Η»乂%κ.7) [10] as in any of items [1] to [9] Black photosensitive resin composition

The black colorant (Α) contains at least one black colorant selected from the group consisting of carbon black and coated carbon black. [Π] A coloring pattern is formed by using the black photosensitive resin composition according to any one of items [1] to [1]. [12] The color pattern of item [11], which is used in black arrays. [13] A color filter film containing a colored pattern as in item [u] or [12]. [14] A display device comprising the color filter film of the item [13]. [Embodiment] 13 315724 Rev. 1337689 The black photosensitive resin composition of the rabbit is composed of a black coloring agent (A), an adhesive resin (b), a compound containing a vinyl group or a stretching group (^). And a composition of at least one kind of photopolymerization initiator (D), wherein the binder resin (B) is a reactant of a compound containing two or more epoxy groups and a polycarboxylic acid, and an unsaturated unit carboxyl group. a polycarboxylic acid resin (bl) obtained by reacting an acid with a polybasic carboxylic acid anhydride, and a compound having two or more epoxy groups reacted with an unsaturated unit carboxylic acid, and then reacted with an acid anhydride of a polyvalent carboxylic acid. A polycarboxylic acid resin (b2), or a mixture of the foregoing (b1) and (b2), and a photopolymerization initiator (D) thereof is a compound which must contain a quinone compound. The coloring (A) may be one type of pigment or a mixture of two or more kinds of pigments, and the cerium pigment may be an inorganic pigment or an organic pigment or a mixture thereof. The inorganic pigment may be exemplified by a metal oxide. a metal compound such as a composite metal oxide or a metal complex, and specific examples thereof include metal oxides of iron, cobalt, cadmium, lead, copper, titanium, magnesium, chromium, zinc, lanthanum, and the like. Oxide or metal complex, etc. Specific examples of the foregoing organic pigments can be classified as pigments in the classification of dyes (c〇1〇r indeX) (published by The Society of Dyers and C〇l〇rists). The compound or the like. The black colorant (4) may be a kind of a kind or a buckle of two or more kinds of black pigments, or may be a mixture of a red pigment, a green pigment, a blue pigment, a yellow pigment, a cyan pigment, a magenta pigment, or the like. The black coloring agent, which is described in the example of the black pigment, and the black lead, and the special type disclosed in Japanese Unexamined Patent Publication No. Hei No. Hei. Bulletin and special report No. 3_27 side note 315724, Rev. 14 1337689 Inorganic black pigment, organic black pigment such as azo melanin, CI, pigment black No. 1, and CI pigment black No. 7 described in JP-A No. 2-216102, etc. Examples thereof include a yellow pigment, a red pigment, a magenta pigment, a blue pigment, a cyan pigment, a green pigment, etc. Specific examples thereof include CI Pigment Yellow No. 1, CI Pigment Yellow No. 3, CI Pigment Yellow No. 12, and CI. Pigment Yellow No. 13, CI, Pigment Yellow No. 14, CI Pigment Yellow No. 15, CI Pigment Yellow No. 16, CI·Pigment Yellow No. 17, C丄 Pigment Yellow No. 20, CI Pigment Yellow No. 24, C丄 Pigment Yellow No. 31 , C丄 Pigment Yellow No. 55, CI Pigment Yellow No. 60, CI Pigment Yellow No. 61, CI Pigment Yellow No. 65, CI Pigment Yellow No. 71, CI Pigment Yellow No. 73, CI Pigment Yellow No. 74, CI Pigment Yellow No. 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 1 No. 04, CI Pigment Yellow No. 106, CI Pigment Yellow No. 108, CI Pigment Yellow No. 109, CI Pigment Yellow No. 110, C, I. Pigment Yellow No. 113, CI Pigment Yellow No. 114, C, I. Pigment Yellow No. 116 , CI Pigment Yellow No. 117, CI Pigment Yellow No. 119, CI, Pigment Yellow No. 120, CI Pigment Yellow No. 126, CI Pigment Yellow No. 127, CI Pigment Yellow No. 128, CI, Pigment Yellow No. 129, CI Pigment Yellow No. 138 , CI Pigment Yellow No. 139, C丄 Pigment Yellow No. 150, CI Pigment Yellow No. 151, CI Pigment Yellow No. 152, CI Pigment Yellow No. 153 'CI Pigment Yellow No. 154, CI Pigment Yellow No. 155, CI Pigment Yellow 156 15 315724 Xiu version ^37689 Ϋ 唬, CI' pigment yellow M6, c 颜 颜 tree yellow 1G8, c 丨斉 steam 175, CI pigment orange 1, CI • pigment orange 5, >, pigment orange No. 13, CI Pigment Orange No. 14, CL Pigment Orange μ.丄 〒丄 Pigment Orange No. 17, C.I. Pigment Light 24, C I• Pigment. Heart No. CI Pigment Orange No. 36, ς.ι. Pigment Orange No. 38, 匚4 Color No. 4, CI Pigment Orange No. 43, c Γ Pigment Light Color No.; 4: Preparation: No. 49, CI ·Pigment Orange No. 51, c 1 Pigment Orange: C.1' C.1. Pigment lamp color 63 ?Lu, r τ Shangba No. 61, 啼〇C.1. Pigment Orange No. 64, CU. Pigment 扒ώ

唬' CL pigment dial color 73; c. loose color 7! 19, mouth. Pigment purple wide color UC 丄 pigment purple ^ purple 32 $ ^ 唬, CI pigment purple 29, cp color 2 唬, CI pigment purple%丄Pigment pigment C丄Pigment red 1泸, r T s C.1. Pigment i color 38鱿; CJ·Pigment red 4#\C material red 2, C.1. Pigmented color 3rd c.1. Pigment red Heart i' = color 8th, cj. pigment - color f 16th, c 丄 pigment red two pigment red 15th, cl pigment red c cut red pigment red 21th 'heart two? . ' π 巴23号, C Τ twist _LI only oblique red 22, way, CI pigments 丄 丄 paint red 30, Cl _ color 38 color 32, Ch heart 丄 丄 paint red 3! Pigment red 42 ^科红40号*, ci·pigment red number, dV number, C.1. pigment Μ two-color 41, C丄LI pigment 』 color 48:1, Ch red 4Qi '•色48:3, CT * ..Pigment Red 48:2, CI Yan _ 4 β ^ Becco Red 50:1...Pigment Red Heart? ...8:4^^^ 315724 revision 16 "37689

I ... neck material red $ 2. 57 Mirror, C.J. 颜转: Tiger: CJ. Pigment Red, 3; i No. 'Pigment Red Ice 4, c\57: No. 1, C. L Pigment Red 58 2 Pigment Red • No., Pigment Paint Red 6. :] No., No., CJ·/, 'Working Color Number, L.1. Pigment Red β a , 81:1 No., C〇§41 Pigment Red 64.^ r :1 ci 鲔料料料红83号, ch CL pigment called ^ number, pigment red two red 88, pf n I • • pigment red 102, number, CJ • pigment red:,]. Number 5,.丄 Pigment red two, color]. No. 4, ^ " J. Pigment Red 112 Shanghai, e τ #化, CJ. Pigment Red _

Red U4% 丄颜科红多丨ha CJ pigment/1 C 1 pigment red 122, c 颜颜粗1^, CJ. Pigment 149 V V44, C.1. Yankee red 〗 46; color U3 No., 丄Pigment Red 150, e τ ~CI Pigment Red: Red (6), CJ. Pigment: Two, Red (5), CJ. 7U CI Pigment Red 171 仏C·1. Pigment Red 170

, number, cj. Pigment 2, number, marriage = pigment red called.丄Pigment: color = material red" No. 6, amber, CI pigment red 18 、, CI pigment red, color called. Pigment red 87 red 185, C.1. Bu. Pigment red 193, heart::, Pigment Red 19. Color 202, C丄 Pigment Red 2〇6 No. 194旒, CI Pigment j Pigment Red Hi M Pigment Red Color No. 207, 唬, CI Pigment Red 216, k丄 Pigment Red Yanke Red 224轳, Γ T extension 4:1., pigment red 22 、, CI number C.1. Pigment red 226, c τ !. Pigment red 243, CJ. Pigment red; = material, - π, Pakistan 245旎, cI pigment 315724 modified version 17, gonggong 254, CL pigment red (5): c丄 pigment red 2", C 丄 pigment red 265;

Hu material blue 15 'αι• pigment blue 15:3, c i. pigment blue. No. 4 CI pigment color 15 : 6 , c [pigment blue number; c 丄 pigment green 7 , CI · Pigment Green No. 36; CI Pigment Brown No. 23, C丄 Pigment Brown No., etc. The black photosensitive resin composition using a black pigment may further contain a pigment such as a red pigment, a green pigment, an M color pigment, a yellow pigment, a cyan pigment, or a magenta pigment as exemplified above. The black colorant used in the black photosensitive resin composition of the present invention is preferably one containing carbon black, coated carbon black or a mixture of such materials. The particle size of the pigment which can be used in the composition of the black photosensitive resin of the present invention is preferably from 5 cores to G.5//m, and Q to 〇 3

Mm is better. The pigment having an average particle diameter such as the above may be produced by a generally known method such as a kneading method, a sulfuric acid method, a reductive dissolution method, or the like. The surface of the pigment can be further modified by a polymer or the like. The polymer described in Japanese Laid-Open Patent Publication No. 8-259876, or a commercially available polymer for dispersing pigments, and the like, may be, for example, an acrylic resin such as anthraquinone or a vaporized ethylene. Vinyl acetate resin, maleic acid resin, ethyl cellulose resin, cellulose-based resin, and the like. The form of the processed pigment modified by the polymer may be a form in which the resin and the pigment are uniformly dispersed into a powder form, a paste form, or a granular form. The content of the black coloring agent in the black photosensitive resin composition is generally 2% by mass or more and 7% by mass of the solid component after volatilization of the volatile component. 315724 revision 18 1337689, the following is better, 30% or more and 60% More preferably, the adhesive (B) component used in the present invention has a property of dissolving a non-irradiated region of light in a layer formed of a composition for imparting a black photosensitive resin into a developing liquid, and has black photosensitivity. The layer in which the resin composition is formed or the dispersion medium in which the pigment is dispersed in the colored pattern formed. The above-mentioned adhesive resin (B) may be a polycarboxylic acid resin (bl) obtained by reacting a compound containing two or more epoxy groups with a reaction product of a polyhistical acid and an unsaturated unit in a slow acid reaction, and then reacting with a polybasic acid anhydride. And a polycarboxylic acid resin (b2) obtained by reacting a compound having two or more epoxy groups with an unsaturated unit and then reacting with an acid anhydride of a polyvalent carboxylic acid, or a mixture of the above (bl) and (b2). The compound containing two or more epoxy groups is preferably used, and a compound represented by the formula (νπι), a compound represented by the formula (IX), or a mixture of these is preferably used.

The average of the number of repetitive units of the p table in the formula (νπι) is! The above 2 〇 integer. R16-r19 are independent of each other, and represent a hydrogen atom, a carbon number of 1-8 alkyl group, a carbon atom number of 5-12 ring alkyl group, a carbon number of 丨4 aryl group, and a carbon number of aryl group. Q-Q11 is independent of each other, and has a hydrogen atom, a halogen atom, a carbon number of 1-8 alkyl group, a slave atom number of 1-8 alkenyl group, a carbon number of 丨8-8 alkynyl group, and a carbon number of 315724 revision 19 1337689 5 -12 cycloalkyl group, 6-14 aryl group, 7-2() aralkyl group, 1-8 alkoxy group, 丨8 olefin group, carbon number j _8 alkyne An oxy group having 6 to 14 aryloxy groups, a nitro group or a cyano group. The number of carbon atoms of 1-8 alkyl may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, n-pentyl 'neopentyl, n-hexyl Base, n-heptyl, n-octyl, 2-ethylhexyl and the like. The 5-12 cycloalkyl group having a carbon number may, for example, be a cyclopentyl group, a cyclohexyl group or a cyclooctyl group. The number of carbon atoms 6-14 aryl group may be, for example, a phenyl group, (4) a ugly base 'μ甲笨· 醯 group, a p-phenyl ketone group, a 2,4 dimethyl phenyl group, a 4 ethyl group, 2 , 4,6_ trimethylphenyl, pentamethylphenyl, α_caiji, ^Caiji, Lianqiji, and the like. The carbon number of 7-20 aralkyl may be exemplified by phenylmethyl, phenylethyl, cumyl n-propyl, phenyl-n-butyl, phenyl-n-hexyl, phenyl-n-octyl, p-phenyl Methyl, p-phenylene styrene ethyl, p-tolyl decyl n-propyl, p-tolyl-n-butyl, p-phenylene-n-hexyl, p-tolyl-n-octyl, biphenylmethyl Wait.

The number of the f atoms 1-8 alkenyl group may, for example, be a vinyl group or a propylene group. The number of carbon atoms of 1-8 alkynyl may, for example, be ethynyl. The methoxy group may, for example, be an ethyleneoxy group or a propyloxy group. The atomic number of the 1-8 alkynyl group may, for example, be ethynyloxy group or the like. The 6-14 aryloxy group having a carbon number may be, for example, a phenoxytolyloxy group, a palladium oxime, a benzyloxy group, a 2,4 dimethylphenoxy group, and a tetraethyl phenoxy 315724 modified version 20 1337689, 2,4,6-trimethylphenyloxy, pentaphthyl, phenyloxy, etc. 曱 笨 phenyloxy, α _naphthyloxy, 10,000

WziOR'-丨

- (R-CVCH;^ (K) is independent of each other in formula (10), the gas atom of the watch, the atom of (4) or the number of carbon atoms is 1-8 alkyl. The Y form key or the formula is called 8) The 2 price base. R2G table carbon number Μ 〇 extended base. q An integer from Table 0-5. The number of carbon atoms of the 1-6 alkyl group may be 1 to 6 alkyl groups in the above alkyl group. The anti-atomic number of the stone of 1 to 10 may be, for example, an exoskele group, an exoethyl group, a propyl group, an anthracene group, a butyl group, a 2,2-dimethyl propenyl group or the like. (K-1) A (K-2) X (Κ·3) F3^F3(IX^) Η^Η3(Κ-5) Eight (four)~乂〆〇, (财) Others of polyacids can be mentioned Such as cis-butyl diacid, succinic acid, itaconic acid, only τ Kang 3, ^ - formic acid, tetrahydro phthalic acid 'hexahydro phthalic acid, methyl bridge methylene tetrahydro phthalic acid, Hexyl-terenol, tetrahydromethanedicarboxylic acid, trimellitic acid, pyromellitic acid, stearic acid, 4,4'-diphenyldicarboxylic acid, etc. Tetracarboxylic acid, biphenyl ether tetracarboxylic acid, and the like.

21 315724 Rev. 1337689 The polycarboxylic acid described above may also be a relatively spent anhydride such as maleic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride or the like. The above polycarboxylic acid or its acid anhydride may be used singly or in combination of two or more kinds thereof. The above-mentioned unsaturated unit carboxylic acid may, for example, be acrylic acid, mercaptoacrylic acid, crotonic acid, α-gas acrylic acid, cinnamic acid or the like. The above-mentioned unsaturated unit carboxylic acid may be used singly or in combination of two or more kinds thereof. A polybasic acid resin which can be used as a binder resin (Β), and a polycarboxylic acid resin obtained by polycondensation of a compound represented by the formula (X) and a polycarboxylic acid anhydride (refer to Japanese Laid-Open Patent Publication No. 4-355450, No. Japanese Patent Laid-Open No. Hei. No. 09-325494, JP-A-H09-325494, JP-A-H07-325738, etc.), an epoxy compound of a precursor of the formula (χ), a polycarboxylic acid, and/or Or a reaction product obtained by reacting a carboxylic acid reaction product of an unsaturated unit with a polycarboxylic acid resin obtained by polycondensation of a polycarboxylic acid anhydride, an epoxy compound represented by the formula (XI) and a polyvalent carboxylic acid, and an unsaturated unit carboxylic acid. a new reactant obtained by the reaction, a polycarboxylic acid resin obtained by reacting the same with an acid anhydride, a reaction product obtained by reacting an epoxy compound represented by the formula (?π) with a polyvalent carboxylic acid, and then reacted with an unsaturated monoterpenecarboxylic acid, and A polycarboxylic acid resin obtained by reacting a polycarboxylic acid anhydride or the like.

Wherein R21 and R22 are independent of each other, and represent a hydrogen atom, a halogen atom, a 315724 modified version 22 1337689 or a carbon number of 1-6 alkyl group. ·

The Rh table may have a substituent having a carbon number K1 alkyl group. R24 represents a hydrogen atom or a methyl group. The divalent group q1 shown by any one of the formulas (χ-υ to (χ-6)) is an integer of 0 to 5. q2 is an integer of Μ 0.

(Χ-2)

(Χ-3)

(X-6)

FaX(4) H3>〇C (X-7)

Wherein R25 and R26 are each other or the number of carbon atoms is in the form of a sub, a halogen atom, a base Y2 form key or a formula) to a formula (XI Niang Ren--the two-price 315724 revision 23 1337689

FsCV/cf3 (XI-3) /C\ (Xl-l)

(XI-2)

(XI-3)

(XM) pa-5)

HsC\ /ch3 (XI-6) wherein R27 has a carbon number of M and an alkyl group. R is a hydrogen atom, an integer number of 1 to 6 carbon atoms, and a corpse. Silk • oxypropyl. Inverse j, the integer R: but in ^ is 2, the kiss ^ in the early position R4R28 can be the same or different.

Η (ΧΠ) P, the average number of repeating units in the formula, which is an integer of i or more and 20 or less. R'16-r'19 is methyl. P-P and P-P are independent of each other, and represent a hydrogen atom, a carbon atom number J _8 alkyl group, or a carbon atom number of 5-12 ring stimuli. Among them, the number of carbon atoms is 1-6 alkyl groups, the number of carbon atoms is 1-1 alkyl group, and the number of carbon atoms is 5-12 ring groups. In the reaction of an epoxy compound with a few acids, and the reaction of an epoxy compound with an acid, and with a polycarboxylic acid or an anhydride thereof, the reaction can be carried out as in Example 24 315724, revision 1337689, for example, by mixing a compound of the reaction object. The ruthenium temperature is generally 20_250 c. The solvent can also be used in the reaction oxime if necessary. The obtained multi-acid acid resin can be directly used as a reaction mixture, and can also be used after being subjected to a general separation operation such as concentration, steaming, solvent removal, reprecipitation, crystallization, etc. (Current Kaiping No. 9-80220, special Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The amount of the polycarboxylic acid acid needle is generally determined by reacting a reaction with a polycarboxylic acid needle and a polybasic acid (for example, a reaction of a compound having two or more epoxy groups with a polycarboxylic acid and an unsaturated unit carboxylic acid) The total amount of the compound or the like is preferably 5 mol% or more and 95 mol% or less, or more preferably 1 mol% or more and 90 mol% or less. The acid value of the polycarboxylic acid resin obtained in the above reaction is preferably 7 Å to 17 Å, or more preferably 80 to 140. The molecular weight of the Lifan carboxylic acid resin is generally preferably 1,000 or more, 50,000 or less, or more preferably 15 (8) or more and 20,000 or less in terms of the weight average polystyrene. The above-mentioned adhesive resin (Β) generally has a solid content of the black photosensitive resin composition of 5% or more and 90% or less, more preferably 10% or more and 6% or less, and more preferably 20% or more and 45% or less. good. The compound (C) which contains an ethylenically unsaturated bond and can be subjected to addition polymerization in the present invention may be, for example, a compound having a vinyl group or an alkyl group, or the like, having a terminal ethyl group to be unsaturated. a bond, or more preferably two or more aliquots, may be a monomer, or a dimer, a trimer, a polymer, etc. Pre-315724 modified version 25 1337689 Polymer 'may also be a mixture or Its copolymer. Examples of the monomer include an ester of an unsaturated citric acid such as a bupropion acid, a methyl acid, a butyric acid, a methacrylic acid or a maleic acid, and an aliphatic polyol compound, an unsaturated citric acid and an aliphatic plural. Amidamine or the like of an amine compound. The ester of the unsaturated carboxylic acid and the aliphatic polyol compound may, for example, be ethylene di-ol diacrylate, triethylene glycol diacrylate, u-butylene glycol diacrylate, tetramethyl glycol diacrylate, propylene glycol. Diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri(acryloxypropyl)ether, triterpene ethane triacrylate, hexanediol dipropylene__acid Sa, 1,4-cyclohexane diol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, Acrylates such as sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris(propylene methoxyethyl) isocyanate, polyester acrylate polymer; Tetramethylol dimethacrylate, triethylene glycol dimercapto acrylate, neopentyl dimethyl acrylate, triterpene glyceryl trimethacrylate, trimethyl ethane tri methyl Acrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimercapto acrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethyl Alkyl phthalate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, hydrazine [p-_(3_mercapto propylene) Oxy 2 - hydroxypropoxy) phenyl] dimethyl decane, hydrazine [p-(fluorenyl propylene oxyethoxy) phenyl] difluorene 26 315724 modified version 1337689 . Acrylate; ,, ethyl alcohol, itaconic acid, propylene glycol diitaric acid ester, iota, 3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethyl Alcoholic acid, pentaerythritol diitaric acid ester, sorbitol tetrahexanoic acid acetate, etc.; ethylene glycol dimethyl acrylate, tetradecane diol methacrylate, pentaerythritol dibutyl Butenoate such as enoate, sorbitol tetrabutenoate; ethylene glycol dimethacrylate, pentaerythritol diisobutylene a methacrylate such as an acid ester or sorbitol tetramethacrylate; ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol A butyl butyrate such as tetramaleate or the like. Examples of the unsaturated amines of the unsaturated tarenic acid and the polyamine compound can be exemplified by methyl bis-acrylamide, fluorenyl bis-mercapto acrylamide, hydrazine, 6, and hexamethylene bis- Acrylamide, 1,6-hexamethyl-bis-methylpropenylamine, diethylidene allysamine, benzyldimethylacrylamide, benzodimethylene Acrylamide and the like. _ Other examples of the monomer include a vinyl urethane compound obtained by adding an ethylene monomer represented by the formula (XIII)m to a polyisocyanate compound containing two or more isocyanic acid groups in one molecule. R29 R30

CH2=c—C—〇~-CH2-ch~〇H ο (xm) where R and R are independent of each other, and represent a hydrogen atom or a methyl group. The above-mentioned ethylene urethane compound may, for example, be a compound containing two polymerizable vinyl groups of 315724, Rev. 27 1337689 (for example, Japanese Patent Publication No. 48-41708, etc.). Others, for example, the urethane acrylates described in JP-A-53-37193, JP-A-48-64183, JP-A-49-43191, and JP-A-52-3-4(49) A polyfunctional acrylate such as a polyester acrylate or a methacrylate described in each of the publications. The photocurable monomers and polymers described in the Japanese Association of Associations V〇l 20, N〇 7, 3〇〇 _3, 8 pages (] 984) can also be used. The amount of the compound containing an ethylenically unsaturated bond and addition polymerizable, the solid content of the black photosensitive resin composition is preferably 0.5% or more and 50% or less, preferably 1% or more and 4% by weight. The following is better, and 5% or more and 20% or less are even better. The photopolymerization initiator (1) used in the present invention is preferably a compound selected from the group consisting of compounds of the formula (1) to (iv).

R3 Ο

-X (IV) R is a stupid group. [The base may also be selected from the group consisting of a base group, a phenyl group, a -(10), -SR9, and an atomic number of alkane NR R . 315724 modified version 28 1337689 base substitution. ], a mercapto group, a carbon number of 2 to 20 alkyl groups [the alkyl group may be substituted by one or more of -0-, and/or one or more hydroxyl groups. ], a carbon number of 5-8 cycloalkyl group, a carbon number of 2 2 decane fluorenyl group, a benzoyl fluorenyl group [the benzyl fluorenyl group may also be a 1-6 alkyl group, a phenyl group, a 〇 〇r8, an SR9 And at least one base substitution selected from the group of _NR10Rn. ], the number of carbon atoms 2 to 12 alkoxy groups [the alkoxy group may be interrupted by one or more _ 〇 _, and / or one or more hydroxy groups. a phenoxycarbonyl group [the phenoxycarbonyl group may also be substituted with at least one selected from the group consisting of a 1-6 alkyl group, a halogen atom, a phenyl group, a fluorene R8, a _SR9 & NRR〇Rll group] , -CONRiGRiL, cyano group, nitro group, halogenated alkyl group having 1 to 4 carbon atoms [the spectroscopy atom is a fluorine atom, a gas atom, a bromine atom or an iodine atom. ], 4〇·Ζι[where zl is a carbon atom number 1-6 alkane 2 group. ], -S〇2_Z丨[The Z1 table of the formula is the same as the foregoing. ], -z2-so-z3 [wherein z2 represents a carbon atom number M2 alkyl group, and an aged carbon number of 6-12 square groups. ], -Z4_s〇2_Z3 [wherein the z4 carbon atom number ι·ΐ2 alkylene group, ζ3 table has the same meaning as described above. ], _s〇2_z5 [Formula 5 of the formula, carbon number 6-10 aryl. ], or diphenyl-phosphonium. The R2 represents a carbon number of 2-12 alkyl fluorenyl groups. [The alkyl fluorenyl group may also be substituted by more than one dentate atom or a cyano group. ], the carbon number is 4_6 dilute sulfhydryl [but the double bond subunit of the dilute fluorenyl group is not shared with the carbon group. ], stupid Awakening base [The benzamidine group can also be derived from carbon atoms! At least one substitution selected from the group consisting of a sulfhydryl group, a dentate atom, a cyano group, _〇r8, _sr9, and _NWRh. ], the number of carbon atoms ^ an alkoxy ketone group or a phenoxy group; the phenoxy group may also be substituted by a 1-6 alkyl group or a halogen atom. ]. R and R7 are independent of each other, hydrogen atom, cyclopentyl group of the atom of the atom, ring 315724 modified version 29 1337689 hexyl group, stupid base [The phenyl group may also be substituted by at least one group selected from sir, sr9 and _nr10ru:·. ], 笈鲜中所> J 曱 曱 base, awkward base, carbon mat early private 2-12 alkyl fluorenyl., carbon number 2_12 anti-atomic number 虱 叉 base [the alkoxycarbonyl tiger chain Can be interrupted by more than one _〇_, . and / or more than one hydroxyl

generation. ], methoxy group, -(10), SR9, _SOR9, _so2R • NR1°Rn [wherein (10)8, -SR9 and m, oxime, or the above substituents in the benzene ring may be present in 8 (4) or stupid One of the carbon atoms in the ring is separated by a R-R towel to form a 5-membered ring or a 6-membered ring. However, in the case of forming a ring, R«-Rn is not a hydrogen atom. ], at least g of R3_R7 is selected from the group consisting of -OR8, -SR9, and -NR1GR". The hydrogen atom of the table, the number of carbon atoms M2 alkyl [the alkyl group may also be 〇η, SH, cyano, the number of carbon atoms ι_4 alkoxy, the number of carbon atoms 3-6 alkenyl '-0CH2CH2CN, _0CH2CH2 (C0) 0_t1 ( Wherein τ1 is a carbon atom of 14 alkyl group, -0(C〇)-Z6 (wherein y is a carbon atom and a tetraalkyl group), and -0(C0)-Ph (wherein Ph is a stupid group) , _(c〇)〇h or _(c〇)〇-T2 (the formula τ is a carbon number of 1-4 alkyl) is substituted, and the alkyl group can also be derived from! More than one 〇 _ interrupt. ], -(CH2CH2〇)n-H [wherein n is an integer of Table 1-20. ], a carbon number of 2-8 calcined base, a carbon number of 3 to 12, a carbon number of 3-6, a cyclyl group, a cyclohexyl group, a phenyl group [the phenyl group may also be a halogen atom, a carbon number of 1-12 alkane The group or the number of carbon atoms is substituted with 丨4 alkoxy groups. ], _ph_T3 [wherein Ph is a phenyl group. T3 is a C 1-3 alkyl group. ], -SiT4rPh3-r [wherein T is a carbon number of 1-8 alkyl group, and ph is a phenyl group] r is an integer of 1-3. ] or (V) 30 315724 Rev. 1337689 Ο

The formulas of R1 and R2 in the formula (ν) have the same meanings as described above, and the 表单1 form bond, the primary number 1-12 alkoxy group can also be obtained by ι_5__, _s• and/or NR1G-interrupted. Or a carbon number of 12 oxyalkylene groups [the oxyalkylene group may also be interrupted by 1-5 of _〇_, -S_ and/or _NRi〇_. . R9 represents a hydrogen atom, a methyl group, and a carbon number of 2 to 12 alkyl groups [the alkyl group may also be -OH, -SH, a cyano group, a carbon number of 1-4 alkoxy group, a carbon number of 3-6 alkenyloxy group, -OCH2CH2CN, -OCH2CH2 (C0)0-T5 (wherein T5 is a carbon number of 1-4 alkyl group), _〇(CO)_T6 (wherein τ6 is a carbon atom number 14 alkyl group), -0 (C0) -Ph (wherein Ph is a phenyl group), _(CO)〇h or _(CO)0-T7 (wherein T7 is a carbon number alkyl group) is substituted. The alkyl group may also be interrupted by more than one or _s_. The number of carbon atoms is 3 - 12 alkenyl, cyclohexyl or phenyl [the stylyl group may be substituted by a halogen atom, a 碳12 alkyl group or a 1-4 alkoxy group. Or the formula (VI) ιΡΥ^ΥΒ, in the formula 71), R and R2 have the same meanings as described above, Μ2 form bond or -τ-s-[wherein t14 is a carbon atom Μ2 alkyl group (the alkylene group) The base can also be interrupted by 1-5 -〇-, -S- and / or -NR10-.). ]. R and R are independent of each other, and the hydrogen atom, the number of carbon atoms, 12 alkyl groups, and the number of carbon atoms are 2-4, and the _T9 is used. Work only 1 lane 1 ϋ·Τ [T9 in the formula is carbon number 1-6 315724 revision 31 1337689, extension base 'T1Q is carbon number 1-6 alkyl group>, carbon atom number base, rabbit atom The number 5 -12 ring cyclyl, stupid base [the stupid group may also be substituted by a carbon atom number 1 _ 12 alkyl group or a carbon number of 1-4 alkyl group. ], the number of carbon atoms is 2-3, and the number of carbon atoms is 3-6 olefin or alum. And R10 and R11 are bonded to the same nitrogen atom, and may also form an alkylene group having 2 to 6 carbon atoms. The alkyl group may also be interrupted by _〇_4_NR8_, and/or by a hydroxyl group or a carbon atom. The number is 1-4 alkoxy, the number of carbon atoms is 2-4, or the benzyl methoxy group is substituted. Where R1Q is a hydrogen atom, it may also be a formula (VII)

R2 (VD) wherein R1 and R2 in the formula (VII) have the same meaning as defined above, Μ3 form bond piperidinyl or -τ14-ΝΗ-[wherein Τ14 is a carbon atom Μ2 alkyl group (the alkyl group is also It can be interrupted by 1·5·〇·, -8_ and/or -NR10·. ].

Rl2 is a C 2-12 alkoxycarbonyl group [the alkoxycarbonyl group may preferably be interrupted by one or more] and/or may be substituted by one or more potential groups in some cases. ], phenoxycarbonyl [The phenoxycarbonyl group may also be substituted by a number of carbon atoms, an alkyl group, a dentate atom, a phenyl group, a fluorene R8 or an NR10Riii. ] carbon atom number 5-8 cycloalkyl, _c〇NRiQRn_, cyano group, stupid base [The phenyl group may also be substituted by SM, or may form a carbon bond with the carbon atomic ring on the stupid ring containing Rl3_Rl5 to remove 1 In the case where the hydrogen atom has a ring structure of r9 (but in 幵), R9 is not a hydrogen atom or a cyano group, and forms a 5-membered ring or a 6-membered ring. ]. . When at least i of R13# is _sr9, r12 is a methyl group or a carbon atom 315724. It is a 32-337689 sub-, -OH, -OR2, phenyl, or more, or may be substituted by _〇·2-12 The base [far-base group may also be interrupted by a halogen-substituted phenyl group or a phenyl group 1 and/or -NH(CO)- substituted by SR9. 】.

RR is independent of each other, and is represented by a hydrogen atom, a halogen atom, a carbon atom, a cyclopentyl group, a cyclohexyl group, and a stupid group. [The stupid group may also be at least one of a group of 8, 8, and -NR丨V丨- ! Substituted. ], benzyl, benzhydryl, the number of slave atoms 2-12 alkyl fluorenyl, the number of carbon atoms 2 to 12 alkoxycarbonyl [the alkoxy group may also be interrupted by -0 - and / or by More than one is replaced by more than one. ], stupid carbonyl, _0R8, _SR9, _s〇r9, _ShR9 其中 [where - (10), -SR9 and visual, or one of the aforementioned substituents of a stupid ring or a stupid ring of carbon atoms present in r3 r7, The group in which one hydrogen atom is removed in the r8_r11 forms a 5-membered ring or a 6-membered fluorene, but in the formation of a ring, R8-R11 is not a hydrogen atom. ]] Ru_Rl5 has at least one of _〇r8, -SR9 or -NR10Rn 〇

X table carbon number 1 -12 stretching base, ring extension hexyl group, stretching base, -(α)) 〇-τ12-〇π〇)-[wherein τι2 is carbon number 2·12 extension ^ burning base .卜(C〇)(MCH2CH2〇)n_(CO)·[where η is an integer of 1-2〇. ], or -(co)-t13-(Tu in the formula c is a carbon number of 2 to 12 alkyl groups.) Among the compounds represented by the formulae (I) and (III), Ri, R2, r3, R5, r6, and Han are preferably the following groups. R1 is a phenyl group [The phenyl group may also be selected from the group consisting of a halogen atom, an alkyl group having a carbon number, a phenyl group, a group of -OR8, -SR9, and -NRWRii\ Substituent substitution.], mercapto group, carbon number 2-20 alkyl group [The alkyl group may also be interrupted by i 315724 revision 33 1337689 or more, and/or one or more hydroxyl groups.], The number of carbon atoms is 5-8 ring-based. R is the number of atoms 2-12 and the ruthenium group. [The ruthenium group may be substituted by one or more halogen atoms or cyano groups.], the number of carbon atoms is 4-6 olefin groups [but The double bond of the olefin group is not conjugated to a carbonyl group.], a fluorenyl group [the benzoinyl group may also be a carbon atom having 1 to 6 alkyl groups, a halogen atom, a cyano group, a 〇R8, a _SR9, and a NR1GR" At least one substitution selected in the group.] RR, r, r7 are mutually independent, hydrogen atom, halogen atom, % pentyl group, cyclohexyl group, phenyl group [this stupid group may also be -OR8, -SR9 And at least i group substitutions selected in the group of -NR10Rn.] Awkward base, s and collar, [in which, ice and .NR, „R, or 8 of them, the presence of one of the aforementioned substituents in the benzene ring or one of the benzene rings, removed from the R8-Rn The base of one hydrogen atom forms a 5-membered ring or a 6-membered ring. However, in the case of forming a ring, R8_Rh is not a hydrogen atom. In the formulae (I) and (III), R1, R2, R3, r5, r6, and r7 are each The following are preferred. R1 is a phenyl group and a carbon number of 2-8 alkyl groups. Examples of the carbon number of 2-8 alkyl groups include ethyl, n-propyl, isopropyl and n-butyl 'second butyl groups. , a second butyl group, a n-pentyl group, a neopentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a decyl ethyl hexyl group, etc. R 2 is a C 2-6 alkyl fluorenyl group, a benzoyl group [the benzene The formazan group may be substituted by at least one selected from the group consisting of a 1-6 alkyl group and a group of dentate atoms.] Examples of the carbon number of 2-6 alkyl fluorenyl group include a vinyl group and an ethyl carbonyl group. , n-propylcarbyl, isopropylcarbonyl, n-butylcarbonyl, second butyl carbonyl 315724 modified version 34 1337689

Base, second butylcarbonyl, and the like. Examples of the above-mentioned arachidyl group include a benzylidene group, an athranyl carbonyl group, an m-tolylcarbonyl group, a fluorenylcarbonyl group, a dimethylphenylcarbonyl group, a 4-phenylphenylcarbonyl group and the like. R, R, and R are each independently a hydrogen atom, a halogen atom, or a phenyl group. [The stupid group may be substituted with at least one selected from the group consisting of -OR8, -SR9, and -NR1〇rH. ]. Examples of the above-mentioned stupid base include a silly group, a 2-methoxyl group, a 3-methyl group, a 4-methoxyphenyl group, a 2 ethoxy group, and a ethoxylate. Stupid, 4-ethoxyphenyl, 2·n-propoxyphenyl, 3-n-propoxyphenyl, 4-n-propoxyphenyl, 2-isopropoxyphenyl, 3-isopropyl Oxyphenyl, 4__p|isopropoxyphenyl, 2-n-butoxyphenyl, 3-n-butoxyphenyl, card n-butoxyphenyl, 2-n-octyloxy, 3 _n-octyloxyphenyl, 4-n-octyloxyphenyl, 4-phenyloxyphenyl, 4-methoxymethoxyphenyl, 4-ethoxyethoxyphenyl, 2-methyl Stupid thiol, 3_mercaptophenylthio, 4·fluorenyl, 4-ethyl thiol, 4-thio, 2-ethyl thiol, 3-ethyl thiosulfanyl 4-phenyl Stupid thiol, 4-dimethylaminophenyl, 4-diethylamino, bis(2-ethylethyl)aminophenyl, 4-phenylaminoethylbutylamino, etc. . 4-cyclohexylamino group, 4-

R is -OR8, -SR9 and -NR10rH [wherein _〇r8, n _NRl0 R ' may also be derived from one of the aforementioned substituents or a stupid ring in the stupid ring present in R3-R7, in R8-Rl1 The base of one hydrogen atom is removed to form a 5-membered ring or a 6-membered ring. However, in the case of forming a ring, 纟r8_r11 is not a hydrogen atom. Specific examples thereof include a thiol group, a methoxy group, an ethoxy group, a phenoxy group, a decyloxy group, a thio group, a methylthio group, an ethylthio group, a thiol group, and a methylamine. Base, dimethylamino, ethylamino, dimethylamino, stupid 315724 modified version 35 1337689 amino group and the like. Among the above compounds, among the compounds represented by the formulae (1) and (III), wherein R3, r6 and R7 are a hydrogen atom, it is preferred that R1 is a n-hexyl group, R2 is a clumpy group, and R is a thiol group. A compound wherein R3, R6 and R7 are a hydrogen atom, and a compound wherein R1 is a n-hexyl group, R2 is a clumpy group, and R5 is a strepylthio group is more preferable. In the photopolymerization initiator (D) used in the present invention, in addition to the compounds of the above formulas (I) to (IV), other photopolymerization initiators may be used at the same time. The other photopolymerization initiator is not particularly limited as long as it is a compound capable of starting polymerization of a compound capable of undergoing addition polymerization of an ethylenically unsaturated bond, and may be exemplified by photopolymerization of acetamidine. Agent, benzoin photopolymerization initiator, benzoquinone photopolymerization initiator, thioxanthone photopolymerization initiator, bismuth photopolymerization initiator, oxadiazole photopolymerization initiation Agents, etc. The photopolymerization initiator of the present invention is exemplified by diethoxyethyl benzene, 2-hydroxy-2-methyl-1-phenylpropane oxime ketone, alum fluorenyl ketal, hydrazine. Hydroxy-2-methyl-l-[4-(2-hydroxyethoxy)phenyl]propane oxime-ketone, hydrazine-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholinylmethyl Thiophenyl)propane 丨 ketone, 2- benzyl-2 dimethylamino-1-(4-morpholinylphenyl)butane 丨 ketone, oxime hydroxy 2 methyl-l - [4-(l-methylethionyl) stupid] anthracene and ketone oligomers. The benzoin-based photopolymerization initiator may, for example, be benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether or styrene isobutyl ether. The photopolymerization initiator of the benzoquinone benzene may be, for example, benzoquinone benzene, decylmercaptobenzoic acid oxime ester, 4-phenylbenzoquinone benzene, 4 phenanthrenyl _4,-methyldiphenyl Base 315724 Rev. 36 IJJ7689 • Sulfide, 3,3,, 4,4,-tetra (t-butylperoxy) benzene, 2,4,6-trimethylbenzoquinone, etc. The thioxanthone photopolymerization initiators may be exemplified by 2-isopropyl thioxanthone, .4: isopropyl thioxanthone, 2, diethyl thioxanthene, and 2,4-dithioxanthene. Ketone, chloro-4-propoxythioxanthone and the like. The above-mentioned triterpenoid photopolymerization initiator may be, for example, 2,4-bis(trichloromethyl-p-methoxystyrene), and 2,4•bis (trismethyl)·6_(ι_ p-Dimethylaminophenyl.un), 2•tris-methylmethyl·4•amine _6•p-methoxyphenylidene-tri-morphine, 2—(naphtho-yl)·4, 6-bis-tris-methylmethyl are triterpenoid, 2; (4. methoxy-naphtho-1-ylindole 6-bis-tris-decyl), tris(2-(4-ethoxy-naphthyl) -丨-yl)·4,6_bis-trismethyl methyl all three tillage, 2_(cardobutoxy-naphtho-1-yl)-4,6-bis-trismethylmethyl allopurin, 2 ·[4·(2-decyloxyethyl)-naphtho-1-yl b, 4,6·bis-trismethylmethyl, three-till, 2_[4_(2-ethoxyethyl)-naphtho -1-yl]-4,6-bis-tris-carbyl-tris-yl- 2_[4_(2-butoxyethyl)-nino-1-yl]-4,6-bis-trisole基均三明:, 2_(2_methoxy-naphtho-1-yl)-4,6-bis-trismethylmethyl are triterpene, 2_(6_曱oxy_5•methyl·naphtho -2-yl)-4,6-bis-trimethylmethyl, three-till, 2_(6-methoxy-naphtho-2-yl)-4,6-bis-trimethylmethyl, three tillage, 2_ (5_methoxy-naphtho-indole_yl)·4,6_ bis-dione fluorenyl is triterpene, 2-(4,7-di Oxy-naphthyl-1 -yl)_4,6_bis-dioxanyldi-diindole, 2-(6-ethoxy-naphthyl-2-yl)-4,6-bis-tris Methyl three-till, 2-(4,5-dimethoxy-naphthyl-1-yl)_4,6_bis-tris-methylmethyl allotriazole, 4-[p-N,N-di ( Ethoxycarbonylmercapto)aminophenyl-2,6-bis(tris,methyl)-trientrine, 4-[o-indolyl-_N,N-di(ethoxycarbonylmethyl)amine Phenyl phenyl]-2,6-di(trismethyl) all three ploughed, 4_[p-_n, n_bis (gas ethyl) amine group 37 315724 revision 1337689 stupid base-2,6-two ( Three gas ) base):;: [1 servant J spoon of dimorphine, 4-[o-indolyl Ν Ν, Ν _: (gas ethyl) amine stupid base]-2,6-two (three teachings its , a milk methyl) is a triterpene, 4, (p-·······························曱-ylamino-phenyl)-2,6-di(tris-methyl) are triterpene, 4·[p.·ν,ν·bis(phenyl)'aminoethyl]-2'6_one ( Dimethyl group) is a three-D well, 4-(p-Ν-gas-ethyl-ethylphenylaminophenyl)_2,6_two (tri-methyl) all three wells, heart [to _Ν·( Oxyloxyalkylamine Stupid base]-2,6-di (tri-gas methyl) are all three-plowed, 4·[m.·Ν,Ν_二(ethoxyl fluorenyl)amine stupyl]_2,6·two (three Gas enthalpy) three tillage, 4-[m-bromo-p-anthracene, fluorenyl-bis(ethoxycarbonylmercapto)amino stupyl]_26 two (three ip gas oxime), two tillage, 4-[ Inter-gas-p-_N,N_:(ethoxycarbonylcarbenyl)amino styryl]-2,6-di(di-halofluorenyl)-tri-morphine, 4·[inter-fluorine·p-Ν,Ν· Di(ethoxycarbonylguanidino)aminophenyl]-2,6-di(trimethyl fluorenyl)-all triterpene, 4-[o-bromo-p-v, ν-bis(ethoxycarbonylfluorenyl) Amino-based strepyl]_2,6-di (trioxan) is triturated, 4-[o-chloro-p-indole, indole-bis(ethoxycarbonylmethyl)aminophenyl b 2,6_ (dimethylmethyl) are all triterpenoid, 4_[o-fluoro-p-anthracene, fluorenyl-(ethoxymethyl)aminophenyl]-2,6-di(tris) Tillage, 4_[o-bromo-p-Ν, Ν_:(qi_ethyl)aminophenyl]-2,6-di(trismethyl)-tri-morphine, 4-[o-gas·p-v, Ν_((ethylethyl)aminophenyl]-2,6-di(tris) group, three π wells, 4-[o-fluoro-p-anthracene, fluorene-one (gasified ethyl)amine Base-based]-2,6-di(tris-methyl) are triterpenoid, 4-[m-di-p-indole, indole-di(chloroethyl)aminophenyl]_2,6_di(three Gas methyl), three-till, 4-[m-chloro-p-anthracene, fluorenyl-di(a)ethylaminophenyl]_2,6·di(tris), bismuth, 4-[ Fluorine-p-indole, fluorene-bis(vaporated ethyl)aminophenyl]_2,6-bis(trismethyl) all three-pile, 4-(m-bromo-p-fluorenyl-ethoxycarbonyl fluorenyl) Aminophenyl)-2,6-bis(trismethylmethyl)-all triterpene, 4-(m-gas-p-indole-ethoxycarbonyl 38 315724 modified version 1337689 decylaminophenyl)-2, 6-di (three gas sulfhydryl) are all three-till, 4-(m-fluoro-p-ethoxymethylaminophenyl)-2,6-di(trimethylmethyl)-tri-morphine, 4- (Non-p-N-ethoxyl-decylaminophenyl)-2,6-di(trimethylsulfonyl)-tetrazine, 4-(o-gas-p-N-ethoxycarbonyl) Methylaminophenyl)-2,6-bis(tris-methyl)-triazine, 4-(o-fluoro-p-N-ethoxycarbonylmethylamino)phenyl, -2,6- One (di-methyl) mesitylene, 4-(m-di-p-N-gas ethylamino stupyl)-2,6-one (dione fluorenyl) are all triterpene, 4 (intermediate gas) -to-N - gas ethylamino stupyl)-2,6-di (trioxanyl) all three tillage, 4_(m-fluoro-p-?; ^_-gas ethylaminophenyl)-2,6-di ( Tri-gas methyl) is three-ploughed, 4_(o-bromo-p-pair; ^_-gas ethylamine stupid g-)-2,6-di (di- gas sulfhydryl) all three tillage, 4-(o-gas- _N_gasethylamino stupyl)-2'6-di(dimethylmethyl;) are all triterpenoid, 4_(o-fluoran-p-_N_aeroethylamino stupyl)-2,6 - Two (three gas methyl groups) are all three. The smectic photopolymerization initiator can be exemplified by tris-methylphenylvinyl-1,3,4-.恶二零坐 2-三气methyl_5_(p-cyanostyrene

-5-(p-butoxy group)_m. base)-1,3,4-oxadiazole, 2-triyl)-1,3,4-oxadiazole, 2_dij->豸Base) Ethyl)_1,3,4-. Ester _ base)_1,3,4_oxadiazole and the like. Base)-1,3,4- 11 dioxins, 2. base)-1,3,4-oxadiazole, 2. base)-1,3,4-oxadiazole, 2_trioxan Azole, 2-trisole, 1,3,4-oxadiazole, 2-trichloromethyl_5-(2-naphthalene-tris-methyl_5-(cold_(2_benzofuranyl) Ethylene dimethylmethyl-5-( /3 -(6-decyloxy-2- benzopyrene $2 sitting, 2_trimethylsulfonyl-5-(2-stuppyfuran 315724 revision) 39 1337689 Other examples of the photopolymerization initiator which can be used are, for example, 2,4,6-trimethylbenzamide-diphenylphosphine oxide, 2,2,_bis (o-phenyl), 4,5,5'-tetra-stupyl-1,2'-diimidazole, 1 〇butyl-2-acridone, 2-ethyl onion, stupid base, 9,1 〇 - non-i-kun, camphor, phenylacetic acid, acid vinegar, titanocene compound, etc. Among the other photopolymerization initiators mentioned above, photopolymerization using acetophenone photopolymerization initiator and acetophenone benzene The initiator, the trioxane-based photopolymerization initiator which introduces a trimethyl group, the oxadiazole-based photopolymerization initiator which introduces a trimethyl sulfhydryl group, etc. are preferable. Examples of the polymerization initiator may be, for example, 2,4_bis(dihalofluorenyl)- 6-(4-methoxyphenyl)_ι,3,5-trimorphine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5- Three tillage, 2,4-bis(trimethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trimethyl)methyl-6_(4_decyloxy stupid vinyl )-1,3,5-three tillage, 2,4-bis(trimethylmethyl)_6_[2_(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2, 4-double (three gas fluorenyl) _6_[2_(furan_2_yl) vinyl]-1,3,5-three tillage, 2,4-bis (triantryl)·6·[2·( Furan·2_yl)vinyl]-1,3,5-three tillage, 2,4-bis(trimethylmethyl)-6_[2-(4-diethylaminomethylphenyl)ethene Base]-1,3,5·tris, 2,4-bis(trimethyl)-6_[2_(3,4-dimethoxyphenyl)vinyl]-1,3,5-trimorphine Etc. 'Examples of the above-mentioned trimethyl group-based photopolymerization initiators can be exemplified by 2-trimethylmethyl-5-phenethyl-1,3,4-. ·Two gas A-5-(p-cyano stupid vinyl 2, 2_trimethylmethyl methoxy, stupid vinyl) _1,3,4 oxadiazole, 2-trimethyl sulfhydryl 5_(p-butoxystyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(cold-( 2-benzofuranyl)ethyl 315724 modified JL version 40 1337689 gynecological)-1,3,4-. dioxin or sitting. It can also be further photopolymerized to form the black photosensitive resin composition starting agent of the present invention. Examples of light: = adjuvants include triethanolamine, methylamine diisopropanolamine, 4-didecylaminobenzoic acid f vinegar, benzoic acid ethyl acetonate, 4-di? Amino acid "isoamyl vinegar, 4 dimethyl: benzoic acid - 2 - ethyl hexanoic acid, benzoic acid - 2 - dimethylamino acetonitrile - T base aniline, 4, 4, _ double ( Dif-amino-phenyl) benzene is stupid (commonly known as rice bran: keyi et al., 9,10. diethoxy money '2. ethyl-9,10-diethyl which uses 4,4,- A photopolymerization starting adjuvant such as bis(dimethylamino)phenyl benzene or 4,4,-bis(diethylamino) alum benzene or the like is preferred. They may be used singly or in combination of two or more kinds thereof. '''

In the case where the above photopolymerization starting adjuvant is used, it is preferably used in an amount of 1 Torr or less per mole of the photopolymerization initiator of 丨 Mo, and more preferably 莫 莫 1 mol or more and 5 mA or less. The total amount of the photopolymerization initiator and the photopolymerization initiator in the black light-breaking resin composition of the present invention is generally 1% or more by mass fraction of the black photosensitive resin composition. The following is appropriate, and 3% or more and 30% or less are more preferable, and 3%/❶ or more and 15% or less are more preferable. The black photosensitive resin composition of the present invention may further contain a thermal polymerization inhibitor, a filler, and a polymer compound other than the above-mentioned adhesive resin (Β). 41 315724 Rev. 1337689 Ultraviolet absorber, surfactant, promotion Additives such as a sealant and an antioxidant anti-coagulant. The thermal polymerization inhibitor may also contain a compound (C) which contains an ethylenically unsaturated oxime-preserving # a ΛΑ ^ . Μ"^ bond and may be added to the polymerization in the black photosensitive resin, in order to prevent Start the thermal polymerization. The aforementioned thermal polymerization inhibitors may be exemplified by a pair of dioxin, p-methoxy oxy, a second butyl p-cresol, pyrogallol, t-butyl catechol, awkward, ", thiobis ( 3_methyl·6_third butyl age), 2,2, _methyl bis (4 methyl hexabutyl butyl phenol), fluorenyl-nitrosophenyl hydroxy hydroxy guanidinium salt, etc. In the case of the above-mentioned content, the mass fraction of the total amount of the black-sensitive resin composition is preferably 0.01% or more and 5% or less. For example, glass, alumina, etc. The polymer compound other than the above-mentioned adhesive resin (Β) may, for example, be a poly-vinyl alcohol, a poly-propanol, a polyethylene glycol, or a polyfluorene (IV).

The above surfactant may, for example, be a nonionic surfactant, a cationic surfactant, an anionic surfactant or the like. The aforementioned adhesion promoting agent may, for example, be ethylene trioxoxane, ethylene triethoxyoxane, ethylene ginate (2-methoxyethoxy) decane, Ν_(2·aminoethyl)_3_aminopropyl fluorenyl Dimethoxy decane, Ν-(2-aminoethyl)-3-aminopropyltrimethoxy oxime, 3-aminopropyldiethoxylate, 3-glycidoxypropyltrimethyl Oxygen sulphur, 3-glycidoxypropyl fluorenyl dimethoxide, 2_(3,4-epoxycyclohexyl)ethyltrioxazole, 3-apropylmethyl Dioxonium oxyhydrazine, 3_gas propyltrimethoxane, 3-methylpropoxypropyltrimethoxy decane, 3_ thiol 42 315724 modified propyltrimethoxy decane, and the like. The base is oxygen, and the tributyl ortho-alkylene is awkward and so on. The aforementioned anti-condensation agent may, for example, be sodium polyacrylate. The black photosensitive resin composition of the present invention may further contain an organic carboxylic acid, an organic amine compound or the like. & (1) The organic slow-relevant can be mentioned as m, acetic acid, propionic acid, butyric acid, pentane: monomethyl hydrazine, hexanoic acid, diethyl acetic acid, heptanoic acid, octanoic acid and other aliphatic early carboxylic acids ¥acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, sebacic acid, methylmalonic acid, ethylmalonic acid, Dimethylmalonic acid, succinic acid, tetradysyl succinic acid, succinic acid, sulphuric acid, glycerol, aconitic acid, camphoric acid, etc. An aromatic monocarboxylic acid such as phenylacetic acid, cumene acid, dimercaptoic acid, dimethyl benzoic acid, phthalic acid, isoparadicarboxylic acid, p-dicarboxylic acid, trimellitic acid, trimesic acid An aromatic polycarboxylic acid such as pyromellitic acid or pyromellitic acid, phenylacetic acid, hydrogenated atropic acid, hydrogenated cinnamic acid, mandelic acid, stupid acid, atopic acid, cinnamic acid, cinnamic acid An organic carboxylic acid having a molecular weight of 丨〇〇〇 or less, such as methyl vinegar, benzoyl cinnamate, cinnamyl acetate, coumarinic acid or umbrella acid. As the above organic amine compound, an organic amine compound having a molecular weight of 1,000 or less can be generally used. Specific examples thereof include n-propylamine, isopropylamine, n-butylamine, iso-43 315724 modified version 1337689 butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptyl Amine, n-octylamine, n-decylamine, n-decylamine, n-decylcarboamine, n-decyldiamine, cyclohexylamine, o-methylcyclohexylamine, m-methyl ring Mono(cyclo)alkylamines such as hexylamine, p-methyl-dehexylamine, o-ethylcyclohexylamine, m-ethylcyclohexylamine, p-ethylcyclohexylamine; methyl ethylamine, diethyl Base amine, subunit, n-propylamine, ethyl. n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, a second butylamine, Di(cyclo)alkylamines such as di-n-pentylamine, di-n-hexylamine, methyl.cyclohexylethylhexylamine, dicyclohexylamine; dimethyl.ethylamine, methyl.diethyl Amine, triethylamine, dimeryl. ^propylamine, diethyl-n-propylamine, methyl.di-n-propylamine, ethyl.-n-propylamine, di-n-propylamine, three Isopropylamine, three positive: base? , tri-tert-butylamine, tri-n-decylamine, tri-n-hexylamine,:. = hexyl hexylamine, diethyl.cyclohexylamine, methyl dicyclohexylamine, benzyl hexylamine Tricyclohexylamine or the like tri(cyclo)in:amine=,3-amino+propanol...amine-...heterool=pentyl hexanol, 4·aminosuccinyl alcohol, monodiethanolamine, etc. N-propanolamine, dibutanolamine, di-n-pentanolamine, di-n-di-n-butanolamine, di-alkanolamine; ",-(4'-hexanol)amine, etc. di(cyclo)diethanolamine, three This is a glycerol, butanol, di-n-propanolamine, tri-n-butanolamine, triiso-alcoholamine amine, tri-n-hexanolamine, tris(4-cyclohexanol)amine, etc., three (ring) 315724 Revised; 44 1337689-3-Amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3- Butanediol, 4-amino-1,2-cyclohexanediol, 4-amino-1,3-^-hexanol, 3-didecylamino-1,2-propanediol, 3- Amino (cyclo)alkanediols such as diethylamino-1,2.propanediol, 2-dimethylamino-indene, 3-propanediol, 2-diethylamino-1,3-propanediol; 1-aminocyclopentane methanol, 4- Cyclopentane decyl alcohol, 1-aminocyclohexane methanol, 4-aminocyclohexane decyl alcohol, 4-didecylaminocyclopentane methanol, 4-diethylaminocyclopentanol , an amino group-containing cycloalkanol such as 4-didecylaminocyclohexane decyl alcohol or 4-diethylaminocyclohexane decyl alcohol; no-alanine, 2-aminobutyric acid, 3 - aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminopentanoic acid, 5-aminopentanoic acid, 6-aminocaproic acid, An amino group-containing carboxylic acid such as 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid or 4-aminocyclohexanecarboxylic acid. Other compounds which are directly bonded to a base group by an amine group, a compound which bonds an amino group to a carbon chain, and the like can also be used. The amine-based direct bonding compound may be exemplified by aniline, o-nonylaniline, m-decylaniline, p-nonylamine, p-ethylaniline, p-propylaniline, p-isopropylaniline, n-butylene. Base amide, p-tert-butylaniline, i-naphthylamine, 2-naphthylamine, N,N-dimercaptoamine, N,N-diethylmethane, p-mercapto-purine, Ν_二f An aromatic amine such as a strepamine; an amine group such as 'ortho-aminobenzyl alcohol, m-amino benzyl alcohol, p-amino benzyl alcohol, p-dimethylamino phenyl sterol, p-diethylamino benzyl alcohol Phenyl sterols; o-aminophenols, m-aminophenols, p-aminophenols, p-dimethylaminophenols, p-bis; i-ethyl-ethyl thiophene-amines; 315724 revision 45 !337689 .. m-aminobenzoic acid, p-amino berylic acid, p-dimercapto phenyl phthalic acid, p-ethyl amide hydroxy carboxylic acid (derivatives) and the like. - The above-mentioned organic carboxylic acid or organic amine compound may be used singly or in combination of two or more kinds thereof. The content of the organic photosensitive carboxylic acid or organic amine compound % S in the black photosensitive resin composition is generally preferably 0 to 001% or more and 15% by mass or less. More than 10% of the above is better. The black photosensitive resin composition of the present invention can be generally applied to the substrate (2) in a solvent-exhausted state (as shown in Fig. 2(a)). The solvent to be used therein may, for example, be an ester, an ether, a ketone or an aromatic hydrocarbon. Examples of the S are exemplified by ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyrate B. Ester, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, decyl acetate, ethyl hydroxyacetate, butyl glycolate, methyl methoxyacetate, ethyl methoxyacetate, Butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, decyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, 3-A Ethyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, decyl 2-hydroxypropionate, ethyl 2-propionate, ethyl 2-hydroxypropionate Ester, decyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionic acid Ester, 2-oxo-2-propenyl propionate decyl ester, 2-oxy-2-mercaptopropionic acid ethyl acetonate, 2-decyloxy-2-methylpropionate decyl ester, 2-ethoxyl -2-methyl acetoacetate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, acetamidine 46 315724 Xiu version 1337689 - B Methyl ester, ethyl acetate, methyl 2-oxobutyrate, 2-oxobutyric acid, ethyl ester, etc. - Examples of scales include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene Alcohol • Monomethyl acetonide, Ethyl alcohol monoethyl sulphate, Methyl lysine acetate vinegar, Ethyl cellulose acetate vinegar, Diethylene glycol monoterpene ether, Diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, Propylene glycol Methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate, etc. Examples of the _ class include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc. Aromatic hydrocarbons Examples of the class include benzene, xylene, etc. In the solvent, methyl ethoxy propionate, ethyl ethoxyacetate, ethyl cellulose acetate, ethyl lactate, Diethylene glycol dioxime ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol The above-mentioned solvent may be used singly or in combination of two or more kinds thereof. The amount of the solvent used may generally be 2% or more and 50% by mass of the solid matter of the black photosensitive resin composition. The solid content of the black photosensitive resin composition referred to therein is the total of the remaining components of the composition excluding the solvent (E). The black photosensitive resin composition of the present invention may be, for example, a spin coating method v ( A general coating method such as a sPin coat method, a slit coating method, a spin coating method, a pore coating method, a washing method, or a roll coating method is applied to the substrate (2). The substrate (2) can be exemplified. Such as glass plate, silicone plate, etc., as well as polycarbonate I substrate, polyester substrate, aromatic polyamide substrate, poly uramide substrate, poly 315724 modified version 47 1337689 imine substrate and other resins. The treatment may be carried out by a drug such as a stone stagnation coupling agent, a power treatment, an ion ore treatment, a de-coating treatment, a gas reaction, a treatment, and a vacuum evaporation treatment. After the black photosensitive resin composition is applied onto the substrate (2) and then dried to volatilize the bulking agent, a black photosensitive resin composition layer (1) can be formed on the substrate (Fig. 2(a)). The layer is a layer formed of a solid of a black photosensitive resin composition, and has a thickness of generally 〇1/1/〇1 to 1〇//m, preferably 〇2"m to 5.0//m, 〇.2 /zm to 3.0ym is better. Next, the black photosensitive resin composition layer (1) is further irradiated with _j| rays (4) through the mask (3) (Fig. 2(b)). The photomask (3) is, for example, a light shielding layer (32) provided on the surface of a glass plate (31) or the like. The light shielding layer shields the light (4). The portion of the glass plate (31) where the light shielding layer (32) is not provided is the light transmitting portion (33), that is, the light is transmitted through the light transmitting portion (33) to the black photosensitive resin composition layer (丨). The pattern of the light transmissive portion is exposed on the layer (1).

The light (4) generally uses ultraviolet light such as g light (wavelength 436 nm) or i light (wavelength 365 nm). It is preferable that the light is irradiated on the black photosensitive resin composition layer (1) in parallel light. A general mask locator (not shown) is irradiated. According to the formation method of the present invention, a color pattern having a high resolution can be formed, and a stable color pattern of, for example, a width of 20 // m or less, or a degree of 10 y in or less, particularly 5/zm or less can be easily formed. The amount of light to be irradiated may be appropriately determined according to the content of the black colorant | (A) used in the use thereof, the kind and content of the adhesive resin (1), and the compound having an ethyl group-unsaturated bond and addition polymerization ( C) Type and content, photopolymerization 48 315724 Rev. 1337689 - Selection of the type and content of the starting agent (D). It can be imaged after exposure (Fig. 2(c)). The image is formed even if the photosensitive resin composition layer (1) is in contact with the developing solution. After contact with the developing solution, the developing solution dissolves the unirradiated light region (11) of the unexposed light on the black photosensitive resin composition layer (1). As the developing liquid, for example, an alkaline aqueous solution can be used.

Alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sulfonium (tetra), ammonia, ethylamine, diethyl H-ethanol L-based hydroxytetraethylammonium, urethane An aqueous solution of a water-soluble test compound such as a base, a pyrrole, a pulse bite, or an H-hetero-cyclo[5,4,0]-7-eicone. The concentration of the aqueous solution is generally -0.01% by weight or more. The amount of f is less than or equal to 100%. The aqueous solution of the face may also contain a water-soluble organic solvent such as methanol or ethanol, or an interfacial surfactant. As the developing liquid, an organic solvent such as the solvent used in the case of diluting the black photosensitive resin composition, or the like can be used. There are no special limits on the method of imaging, such as dip-coating (ie, impregnation imaging), mouth-leaf imaging, spray imaging, and search imaging (additional liquid imaging). ) and other methods can be used for visualization. The imaging temperature is generally in the range of 1 〇 nc, and the imaging time is generally 10 seconds to 300 seconds. (4) Development The developing material dissolves and removes the unirradiated light region (1) which is not irradiated with light in the black photosensitive resin composition layer. On the other hand, the light-irradiated area (12) of the irradiated light remains as a colored pattern (7). ; "Page image later, dry" can get the coloring pattern (5) (Fig. 2 (c)), 315724 modified version 49 13376 «^ The use of liquid water 'f raw water bath' is generally in the image After that, it is washed with water and dried. After drying, it can be heated again. ^ I. The black photosensitive resin composition of the invention has high sensitivity and can reduce the light, the amount of radiation, and the wide range of development, which can improve the yield. Therefore, the color pattern of the black photosensitive resin composition of the present invention is excellent in resolution, so that a fine coloring pattern can be easily formed. The colored pattern formed is suitable as a black array. The yield of a display device such as a color filter film including the black array and a liquid crystal display device including the color light-emitting film. [Examples] Hereinafter, the present invention will be described in more detail with reference to examples but the present invention is of course not limited to EXAMPLES Example 1 [Preparation of black light-breaking resin composition 1] (A) Black colorant [for black pigment. Pigment black No. 7) 198 mass damage and dispersant 45.5 parts by mass] 184 Parts by mass, (B) adhesive resin [ The compound represented by the formula (XIV) is in an amount of 3 parts by mass and 50 parts by mass of the phenylidene tetracarboxylic dianhydride, and 5 parts by mass of tetrahydro succinic anhydride, as described in JP-A-H08-278630. Method: 100 parts by mass of a polycarboxylic acid resin obtained by the same reaction,

315724 Rev. 50 1337689 23 c The image can be displayed in 90 seconds. After the development, it was washed with water and heated at 23 Torr to form a black color (four) (black array) on the plate (7). The black; the column can be observed to have a good reproducibility to form a line width and a Coba pattern. [Formation of Black Pattern (Evaluation of Development Limit)] - A black photosensitive resin composition layer is formed on the substrate by exposure to form a black photosensitive resin composition layer, and is similarly immersed in the developing liquid as described above. In the middle image, the result of the development time range of 1 〇 #m reproduction is observed, and the pattern of ym is formed between 40 seconds and 120 seconds, that is, the development limit of 8 sec., so that the reproducibility is good. [Evaluation of Sensitivity] The mask pattern is used to expose the mask pattern in which the light transmittance of the light-shielding layer changes in stages, and the other operations are the same as described above to determine the minimum amount of light (sensitivity) required to form the pattern. . The sensitivity obtained is 80 mJ/cm2, which is a very high sensitivity. Example 2 [Preparation of Black Photosensitive Resin Composition 1 and Formation of Black Photosensitive Resin Composition Layer] The adhesive resin used in Example 1 was used as an adhesive resin [Compound 461 of the formula (XVI)] And after reacting with 87 parts by mass of itaconic acid, and then reacting with 48 parts by mass of acrylic acid, and then reacting with 102 parts by mass of tetrahydro phthalic anhydride to obtain 33 parts by mass of the polycarboxylic acid resin], and other examples and examples The same operation of 1 means that the black photosensitive resin composition 52 315724 modified version 1337689 2 $ is a black light-breaking resin composition layer (thickness 1 _ 〇 # m).

[Evaluation] The substrate (2) formed of the black photosensitive resin composition layer (1) obtained in Example 1 was replaced with the substrate obtained by forming the black photosensitive resin composition layer described above, and was the same as in Example Operation, evaluate its resolution, development limits, and sensitivity. The results are shown in Table 1. Example 3 [Preparation of Black Photosensitive Resin Composition 3 and Formation of Black Photosensitive Resin Composition Layer] The photopolymerization initiator used in Example 1 was 7.4 parts by mass of the compound represented by the above formula (χν) A mixture of the compound of the formula (χνιι) and 7 parts by mass of the compound was replaced by the same operation as in the example i, that is, a black photosensitive resin composition was obtained to form a black photosensitive resin composition layer (thickness 1.0).

[Evaluation] The black photosensitive resin composition layer obtained in Example 2 was replaced by a 315724 modified plate 53 1337689. The substrate (7) was replaced by the substrate obtained by forming the black photosensitive resin composition layer described above, and the other was carried out. The same operation of Example 2 're-evaluates its resolution, development limit, and sensitivity. The results are shown in Table 1. Example 4 [Preparation of Black Photosensitive Resin Composition 4 and Formation of Black Photosensitive Resin Composition Layer] The adhesive resin used in Example 1 was an adhesive resin (a compound represented by the formula (XV III)) The softening point, the epoxy equivalent, and the hydrolyzable gas content of each of 74 C, 336 g/eq, and 230 ppm) are reacted with 21 parts by mass of acrylic acid, and then reacted with 7 parts by mass of tetrahydro succinic anhydride. The carboxylic acid resin was replaced by 33 parts by mass, and the black photosensitive resin composition 4 was formed in the same manner as in Example , to form a black photosensitive resin composition layer (1.0/5 m thick).

[Evaluation] The substrate (2) formed of the black photosensitive resin composition layer (1) obtained in Example 1 was replaced with the substrate obtained by forming the black photosensitive resin composition layer described above. For the same operation, evaluate the resolution, development limit, and sensitivity. The results are shown in Table 1. 54 315724 Rev. 1337689 - Example 5 [Preparation of black photosensitive resin composition 3 and formation of black photosensitive resin layer] The photopolymerization initiator used in Example i is represented by the above formula (χν) A mixture of a compound u" by mass and a compound of the formula (?): 7 parts by mass is substituted for 'others. The same procedure as in the example i is carried out to obtain a black photosensitive resin composition to form a black photosensitive resin composition layer (thick ... 1.0 # m).

(XK) N (C2Hs) 2 [Evaluation] The substrate (2) formed of the black photosensitive resin composition layer obtained in Example 2 was replaced with the substrate obtained by forming the black photosensitive resin composition layer described above, and the others were In the same manner as in Example 2, the resolution, development limit, and sensitivity were evaluated. The results are shown in Table 1. Example 6 [Preparation of Black Photosensitive Resin Composition 3 and Formation of Black Photosensitive Resin Composition Layer] The photopolymerization initiator used in Example 1 was 7.4 parts by mass of the compound represented by the above formula (XV). A mixture of 7 parts by mass of the compound represented by the formula (XIX) and 3.7 parts by mass of the compound represented by the formula (XX) was replaced, and the same operation as in Example 1 was carried out to obtain a black photosensitive resin composition in the form of 55 315724. .Revision 1337689 Black photosensitive resin composition layer (thickness 1 ·〇M m)〇

[Evaluation] The substrate (2) formed of the black photosensitive resin composition layer (1) obtained in Example 2 was replaced with the substrate obtained by forming the black photosensitive resin composition layer described above. For the same operation, evaluate the resolution, development limit, and sensitivity. The results are as shown in Table 1. Comparative Example 1 [Formation of Black Photosensitive Resin Composition 5 and Formation of Black Photosensitive Resin Composition Layer] The photopolymerization initiator used in Example 1 was subjected to the above formula (XV). 14.8 parts by mass of the compound shown in Η) was substituted, and the same procedure as in the Example was carried out to obtain a black photosensitive resin composition 4 to form a black photosensitive resin composition layer (thickness: 〇m). [Evaluation] The substrate (2) formed of the black photosensitive resin composition layer (1) obtained in Example 1 was replaced with the substrate obtained by forming the black photosensitive resin composition layer described above, and the other examples were For the same operation, evaluate the resolution, development limit, and sensitivity. The results are shown in Table 。. Comparative Example 2 [Modulation of Black Photosensitive Resin Composition 6 and Black Photosensitive Resin Composition 315724 Revision 56 1337689 Formation of Particle Layer] The adhesive resin used in Example 1 was methyl methacrylate and methyl methacrylate The copolymer of acrylic acid [the molar content of the methyl methacrylate monomer content is 65%, the molar content of the methacrylic acid unit content is 35/〇', and the weight average molecular weight of the polystyrene is 丨3. 〇 (9)] parts by mass, used in an amount of 53 parts by mass of dipentaerythritol hexaacrylate, and the same operation as in Example 1 to obtain a black photosensitive resin composition 5' to form a black photosensitive resin composition layer (thick 1 〇# m).

[Evaluation] The substrate (2) formed of the black photosensitive resin composition layer (1) obtained in Example 1 was replaced with the substrate on which the black photosensitive resin composition layer was obtained as described above, and the same operation as in Example 1 was carried out. , then evaluate its resolution, imaging limits, and sensitivity. The results are shown in Table 1. Table 1 Resolution (β m) Development limit (seconds) Sensitivity (mJ/cm2) _Example 1 4 80 ---- ---/ 80 _Example 2 4 80 80 _ Example 3 4 80 88 __Example 4 4 80 80 __Example 5 4 80 88 _____ Example 6 4 80 88 ___tb Comparative Example 1 6 40 160 ^ Comparative Example 2 30 5 140 Sound [Simple Description] 1 (a) And (b) a schematic diagram of a portion of a color filter film. Figure 315724 Revision 57 1337689 The second (a) to (c) drawings are formed on a substrate by a colored photosensitive resin composition: a colored pattern A schematic diagram of the steps. The third (a) to (c) are schematic views showing the steps of forming a colored pattern on the substrate by coloring the photosensitive resin composition. Figs. 4(a) to 4(c) are schematic views showing the steps of forming a colored pattern on the substrate by coloring the photosensitive resin composition. [Main component symbol description]

1 Colored photosensitive resin composition layer 2 Substrate 3 Photomask 4 Light 5 Coloring pattern 5R Red pixel 5G Green pixel 5B Blue pixel 5BM Black array 6 Color filter film 11 Light-irradiated area 12 Light-irradiated area 31 Glass Board 32 shading layer 33 light transmission 315724 correction version sound 58

Claims (1)

1337689 Patent Application No. 93110072 (November 2, 1999) I. A black photosensitive resin composition comprising a black colorant (A), a binder resin (B), and an ethylenically unsaturated bond. a polymerized compound (C) and at least one photopolymerization initiator (D), wherein the binder resin (B) is a compound obtained by reacting a compound having two or more epoxy groups with a polycarboxylic acid Further reacting with an unsaturated unit carboxylic acid, further reacting with a polybasic carboxylic acid anhydride to obtain a polycarboxylic acid resin (bl), and reacting a compound containing two or more decyloxy groups with an unsaturated unit carboxylic acid, and then reacting with a polybasic carboxylic acid a polycarboxylic acid resin selected from the group consisting of polycarboxylic acid resins (b2) obtained by reacting a carboxylic acid anhydride, wherein a compound having two or more epoxy groups is a formula (vm) and a formula a compound selected from at least one of the group of compounds, (vm) 16 〇1 9 long T, J bis 8 alkyl group, carbon atom number 5.12 ring alkyl group, carbon number 6_14 aryl group, or carbon number 7_2 () aryl courtyard based QQ mutually independent 'table Hydrogen atom, self-prime atom, number of carbon atoms ^ burnt group, number of carbon atoms 1 - 8 homing, broken labor slave ts Qiu 丞妷 atomic number 1-8 alkynyl, carbon original bow = (1) smoldering base, carbon number 6_14 aryl group, number of carbon atoms = number of carbon atoms W alkoxy group, number of carbon atoms W diloxy group 1 atom number W alkynyl group, carbon number 6_14 aryloxy group, schlossyl group or aryl group 315724 amendment 59 59110072 Patent application (November 2, 1999 ^ Λ (IX) [mountain (ίχ), q12-q15 are independent of each other, hydrogen progeny?, halogen atom or stone anti-atomic number 1-8 炫 base; R2Q table Carbon shoulder number 1-10 extension base; ^ 0-5 integer; Y form key or formula (IX-υ-式 (IX-8) - the two-valent base of the dry] (Κ-1) X (K-3) F^CF3(IX^) Η3%Λ(κ.5) S>V* %, (called), and its photopolymerization initiator (D) contains anthracene a compound and at least one selected from the group consisting of a triterpene photopolymerization initiator, a benzoquinone photopolymerization initiator, a benzoquinone photopolymerization initiation adjuvant, and an acetophenone photopolymerization initiator _ compound. The black photosensitive resin composition of the ninth aspect of the invention, wherein the photopolymerization initiator (D) comprises at least one selected from the group consisting of compounds of the formulae (1) to (IV) Compound, 315724 repair JL this 60 UJ/689 Patent Application No. 93110072 (November 2, 1999) [In the formulae (I) to (IV), the following are the RLR15 tables, and the R1 represents a phenyl group [the phenyl group may also be a sulfonyl group, a carbon atom number -6 alkyl group, a stupid group, -OR8, -SR9 and -NR1 至少Rl丨 group selected at least one base substitution] thiol group, carbon number 2_2 〇 基 group [This alkyl group may also be interrupted by "solid, _〇', and/or more than one The hydroxy group is substituted with a carbon atom number of 5 8 ring, the carbon number is 2 2 〇, and the benzoyl group is [the benzoyl group can also be composed of a carbon number of 1-6 alkyl group, a stupid group, a _0R8, a _SR9 and a At least one group of substituents selected in the group of NR R], a number of carbon atoms, a 2 - 12 alkoxycarbonyl group [the alkoxycarbonyl group may be one or more _ 〇 _ =, and / or one or more hydroxyl groups Substituted], phenoxycarbonyl [the phenoxycarbonyl group may also be selected from at least one selected from the group consisting of a 1-6 alkyl group, a halogen atom, a phenyl group, a _〇rS group, an -SR9 group, and a fluorene group 〇Rn. Substituent], CONR R group, cyano group, nitro group, carbon atom number 丨4 halogenated alkyl group [the halogen atom is a fluorine atom, a gas atom, a bromine atom or an iodine atom], -S〇-Zl [in the formula Z1 is a carbon number of 1-6 alkyl], -S〇2-Zi [formula The z-form is the same as the above-mentioned], -Z2-SO-Z3 [wherein the z2 carbon atom number M2 alkyl group, the z3 table carbon number 6_12 aryl group], 61 315724, the patent application No. 1337689, No. 93110072 Case (November 2, 1999 B) -Z4-SCVZ3 [Z4 in the formula, carbon number: 1-12 alkyl, Z3 is the same as previously described], _S〇2_〇_Z5 [Z5 in the formula The number of carbon atoms is 6 to 10 aryl groups, or diphenyl-phosphonium fluorenyl; R is a carbon number of 2 to 12 calcined bases. [The ruthenium group may be substituted by more than one atom or cyano group] a carbon atom having a 4-6 olefin group [but the double bond of the olefin group is not conjugated to a carbonyl group], a clumpy group [the phenyl fluorenyl group may also have a carbon atom number of from 1 to 6, a halogen atom , cyano group, _〇r8, _SR9 and - at least one substitution selected in the group of -NRlGRl1, a carbon number of 2-6 alkoxycarbonyl or a phenoxycarbonyl group [the phenoxycarbonyl group may also be substituted by a 1-6 alkyl group or a dentate atom) R _R7 are independent of each other, and represent a hydrogen atom, a halogen atom, a cyclopentyl group, a cyclohexyl group, and a benzyl group. [The phenyl group may also be substituted with at least one group selected from the group consisting of _〇R8, SR9 and _nr10r1 1 ], benzoinyl, benzhydryl, 2-12 alkylcarbonyl, carbon 2 to 12 alkoxycarbonyl [the alkoxy group) A few base chains can be! More than _〇_interrupt, and/or more than one hydroxy substitution], phenoxycarbonyl, _〇r8, _sr9, _s〇2R9 and -NRWri 1 [where -〇R8, _SR9 and _nr10r1 1, It may also be a 5-membered ring or a 6-membered ring formed by R3_R7 2#, a carbon atom in a substituent or a stupid ring in R8-Ru, but a 5-membered ring or a 6-membered ring in the R8-Ru. When the ring is formed, its R8_RU is not a hydrogen atom, and r3_r7 is selected from a group selected from -OR8, -SR9, and -NR10RU; R represents a hydrogen atom, and the number of carbon atoms is (4) silk [the base may also be paved, SH, cyano group, carbon atom number i cardio, carbon number 3_6 dilute oxygen 〇 CH2CH2CN, -〇ch2ch2(c〇)0_ti (where τ! is carbon source 315724 revision 62 1337689 Patent No. 93110072 Case (November 1999, 2曰5 subnumber 1-4 炫), -0 (C0> Z6 (where 6 is carbon number alkyl), -0(CO)-Ph (Ph in the formula) Substituting phenyl), _(c〇)〇H or -(CO)OT (wherein τ2 is a carbon atom number 1-4), the alkyl group may be interrupted by more than one], -(CH2CH2〇) nH [wherein η is an integer of 1 to 20], a carbon number of 2 to 8 alkyl fluorenyl groups, and a carbon number of 3 12 alkenyl group, 3-6 carbon atom, cyclohexyl group, phenyl group [the phenyl group may also be substituted by a dentate atom, a carbon number alkyl group or a carbon number alkoxy group], -Ph-T3 [formula Wherein Ph is a phenyl group; τ3 is a carbon number of 1-3 alkyl group; -SiT4rPh; 3_r [wherein butyl 4 is a carbon number of 1-8 alkyl group, Ph is a phenyl group, and r is 1-3 Integer] or formula (V) The formulas of R1 and R2 in the formula (V) have the same meanings as described above, and the oxime form bond has a carbon number of 1 to 12 alkoxy groups. [The alkoxy group may also be composed of ι_5... and/or ΝΚΐ()- Interrupted] or a C 1-12 oxyalkylene group [the oxyalkylene group may also be interrupted by 1-5 - 〇-, -S- and/or -NR10-); R9 represents a hydrogen atom, a thiol group, The number of carbon atoms is 2 to 12 alkyl groups [the alkyl group may also be -OH, -SH, cyano group, alkoxy group having 1 to 4 carbon atoms, 3 to 6 alkenyloxy group, -OCH2CH2CN, -OCH2CH2 (CO)O-T5 (wherein butyl 5 is a carbon number of 1-4 alkyl), _0(C0)_T6 (wherein τ6 is a carbon number of 1-4 alkyl), _〇(c〇)_ph (in the formula ph Substituting phenyl), _(c〇)〇H or -(CO)〇-T7 (wherein T7 is a C 1-4 alkyl group), the alkyl group may also be composed of one or more _〇_ or _s _Interruption], carbon number 3_12 63 315724 Amendment 1337689, Patent No. 93110072 Patent Application (November 2, 1999) Alkenyl, cyclohexyl, phenyl [The phenyl group may also be derived from a halogen atom or a carbon atom 1-12 alkyl or carbon atom 1-4 alkoxy substituted] or formula (VI) 0 M2 (VI) The meanings of R1 and R2 in the formula (VI) are the same as those described above, and the M2 form bond or -T-S-[wherein T14 is a carbon number of 1 to 12 extended alkyl group (the extended alkyl group may also be 1-5) -0-, and / or -NR10-interrupt)]; ® R1G and R11 are independent of each other, the hydrogen atom, the number of carbon atoms 丨 丨 2 烧 2, 2-4 hydroxyalkyl groups, _ Τ 9_ 〇_Τι〇[wherein T9 is a carbon number of 1 to 6 alkyl, T1G is a carbon number _6 alkyl], a carbon number alkenyl group, a carbon number 5-12 cycloalkyl group, a phenyl group [ The stupid group may also be substituted by a C 1-12 alkyl group or a C 1-4 alkoxy group], a C 2 - 3 alkyl fluorenyl group, a 2-3 olefin group or a phenyl fluorenyl group. And when Rio and R11 are bonded to the same nitrogen atom, they may also form an alkylene group having 2 to 6 carbon atoms. The alkyl group may also be interrupted by -〇- or -NR8-, and/or by hydroxyl group or carbon. The atomic number is 1-4 alkoxy, the number of carbon atoms is 2 to 4 alkyloxy or the benzhydryloxy group is substituted]' Ri. When it is a hydrogen atom, Rll can also be a formula (10)) The formulas of R1 and R2 in the formula (VII) have the same meanings as described above, 乂3 form bond, 卩 well group or -Τ14·ΝΗ_ [wherein Tu is a carbon atom M 2 stretching group (the alkyl group may also be I-5-0-, and/or -NR10-interruption)]; 315724 Amendment 1337689 Patent No. 93110072 (November 2, 1999) R12 is a carbon number 2-12 alkoxycarbonyl group [ The alkoxycarbonyl group may be substituted by more than one -0-interruption and/or optionally by one or more hydroxyl groups], and the phenoxy group may also be composed of one or more: carbon Atomic number 1-6 alkyl, halogen atom, phenyl, fluorene R8 or N riorii substituted], carbon number 5-8 cycloalkyl, -C〇NR1GRn-, cyano, phenyl [this phenyl can also be by SR9 Alternatively, a carbon atom bond to a stupid ring containing Ri3_Ri5 may be formed, and R9 may be formed by removing one hydrogen atom (but when R% is not a hydrogen atom or a cyano group in forming a % structure), a 5-membered ring or 6 member ring], when at least one of R13-R15 is _SR9, Rlz is a fluorenyl group or a carbon number of 2-12 alkyl groups [the alkyl group may also be a halogen atom, _〇H, -OR2, a stupid group, Halogenated phenyl or substituted phenyl by SR9 The upper substitution may also be interrupted by _〇- and/or _NH(CO)-; r13-r15^ is independent, hydrogen atom, halogen atom, carbon atom number η alkyl group, % pentyl group, cyclohexyl group, benzene a base [the phenyl group may also be substituted by at least one selected from the group consisting of _〇r8, _sr9 = NR R], a benzyl group, a benzoyl group, a stone counter atomic number 2-12, an acid group, a carbon atom Number 2-12 oxycarbonyl [The alkoxycarbonyl group may also be interrupted by more than one -0-, and/or substituted by more than one hydroxyl group], phenoxycarbonyl, seven R8, -SR9, -S〇R9 -S〇2R9 or collar 1〇Ru[wherein _〇r8, ice and -nr1〇rU may also be discarded with the aforementioned substituent of the abrupt ring or the carbon atom of the benzene ring] 15 members: 2) t The base of one hydrogen atom is removed to form a 5-membered ring or 6-shell: 2, when forming a ring, R8_R11 is not a nitrogen atom], and r1 and / are 1 -OR8, -SR9 or -NR1()R";乂 乂 厌 厌 厌 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 65 65 65 65 65 65 第 第 931 931 931 931 931 931 931 931 931 931 931 931 931 931 931 931 931 931 931 931 931 931 931 931 )-[wherein T12 is a carbon atom number 212 alkyl group], (C〇)C)-(CH2CH2〇)n_(c〇) ·[where η is an integer of 12〇], or -(co)-T13-(co)·"In the formula, Xi Ding 13 goes, mountain π 7 AL flies T, T is the number of slave atoms 2-12 *Base J]. 3. The black photosensitive resin composition of claim 2, wherein R1 is a phenyl group or a carbon number of 2-8 (tetra); r2 is a carbon atom number of 6 fluorene groups, or a phenyl fluorenyl group. The fluorenyl group may also be substituted by at least a working group selected from the group consisting of a carbon atom and a group of (4) atoms. · RR and R are independent of each other, and represent a hydrogen atom, a pixel atom or a phenyl group. -OR8, SR9 and _NRl〇Rll selected at least one base substitution LR5 is _OR8, -SR9 and _nr丨〇RU [and _〇r8, ♦ and 〒 〒 can also be present in ❿7 The carbon atom of the aforementioned substituent or the benzene ring on the stupid ring forms a 5-membered ring or a 6-membered ring via a group in which r gas atoms are removed from r8_r11, but in the formation of a ring, R8_Rl! is not a germanium atom] By. The black photosensitive resin composition of claim 2, wherein R3, R6 and R7 are each a hydrogen atom. The black photosensitive resin composition of claim 2, wherein R1 is a n-hexyl group, R2 is a benzamidine group, and R5 is a phenylthio group. The black photosensitive resin according to any one of the items 1-5 to 5, wherein the 'black colorant (4) contains at least one black selected from the group consisting of carbon black and coated carbon black. Coloring agent. A colored pattern' is formed by using a enamel or a color photosensitive resin composition as s. 315724 Amendment 66 8. 9. 10 Patent Application No. 93110072 (November 2, 1999) :: Please apply the color scheme of item 7 of the patent scope, which is used in the black array, which is included in the patent application system. Amended by the 7th or 8th 315724 of the color range as in the scope of the patent application - 67