CN102636956B

CN102636956B - Photosensitive composition

Info

Publication number: CN102636956B
Application number: CN201210022440.8A
Authority: CN
Inventors: 市冈贤二
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2011-02-09
Filing date: 2012-02-01
Publication date: 2016-04-27
Anticipated expiration: 2032-02-01
Also published as: KR20120092023A; CN102636956A; TW201237109A; JP2012181505A; TWI542644B; KR101910520B1

Abstract

The invention provides a kind of photosensitive composition, can be formed the color filter of high-contrast by this photosensitive composition, described photosensitive composition comprises dyestuff, resin, polymerizable compound, polymerization initiator and ultraviolet light absorber.

Description

Photosensitive composition

Technical field

The present invention relates to a kind of photosensitive composition.

Background technology

Coloring phototonus resin becomes thing to can be used for the manufacture of the color filter used in the display equipments such as display panels, organic electroluminescence panel, plasma display device.

In Japanese Laid-Open Patent Publication 2010-32999 publication, there will be a known a kind of photosensitive composition be made up of xanthene dye, pigment, resin, polymerizable compound, polymerization initiator and solvent.

Summary of the invention

For described photosensitive composition known at present, the contrast of the color filter utilizing this photosensitive composition to obtain may not be fully satisfied.

The invention provides following [1] ~ [9].

[1] photosensitive composition, it comprises dyestuff, resin, polymerizable compound, polymerization initiator and ultraviolet light absorber.

[2] photosensitive composition as described in [1], wherein, ultraviolet light absorber is be selected from least one in the group that is made up of benzophenone series ultraviolet light absorber and benzoic ether system ultraviolet light absorber.

[3] photosensitive composition as described in [1] 1 or [2], wherein, the content of ultraviolet light absorber is below more than 0.1 mass parts 20 mass parts relative to total amount 100 mass parts of resin and polymerizable compound.

[4] photosensitive composition according to any one of [1] ~ [3], wherein, dyestuff is xanthene dye.

[5] photosensitive composition according to any one of [1] ~ [4], wherein, described photosensitive composition also comprises pigment.

[6] photosensitive composition according to any one of [1] ~ [5], wherein, resin is alkali soluble resin.

[7] photosensitive composition according to any one of [1] ~ [6], wherein, polymerizable compound is (methyl) acrylate.

[8] color filter, it utilizes the photosensitive composition according to any one of [1] ~ [7] to be formed.

[9] display device, the color filter that it comprises described in [5].

According to photosensitive composition of the present invention, the color filter of high-contrast can be formed.

Accompanying drawing explanation

Fig. 1 is the skeleton diagram of the manufacture method that color filter of the present invention is described.

Fig. 2 is the skeleton diagram of the manufacture method that color filter of the present invention is described.

Fig. 3 is the skeleton diagram of the manufacture method that color filter of the present invention is described.

Symbol description

21 glass substrates

22TFT (on-off element)

22a gate electrode

22b gate insulating film

22c polysilicon film

22d diaphragm

23 color filter layers

23A photosensitive composition layer (color filter)

23a Red lightscreening plate

23h green color filter

23c blue color filter

24 pixel electrodes

27 signal wires

29 photosensitive resin films (diaphragm)

201,202 connecting holes

Embodiment

Photosensitive composition of the present invention comprises dyestuff (A1), resin (B), polymerizable compound (C), polymerization initiator (D) and ultraviolet light absorber (E).

Photosensitive composition of the present invention preferably also comprises pigment (A2), in this manual, dyestuff (A1) and pigment (A2) is called colorant (A) in the lump.

Photosensitive composition of the present invention comprises dyestuff (A1).As dyestuff, can enumerate: the dyestuffs such as the amine salt of oil-soluble dyes, acid dyes, acid dyes or the sulfamide derivative of acid dyes.As dyestuff, the compound with the material of form and aspect or notes of dyeing (dyeing ノ mono-ト that are such as categorized as in Colour Index (TheSocietyofdyersandcolourists publication) beyond dyestuff, i.e. pigment can be enumerated; Se Ran society) in described known dyestuff.In addition, if classified according to chemical constitution, then can enumerate: azo dyes, anthraquinone dye, triphenhlmethane dye, xanthene dye and phthalocyanine dye etc.In these dyestuffs, photosensitive composition of the present invention can preferred with an organic solvent soluble dye.

Specifically, C.I. solvent yellow (solventyellow) 4 can be enumerated (following, omit C.I solvent yellow, only remember numbering), 14,15,23,24,38,62,63,68,82,94,98,99,117,162,163,167,189;

C.I. solvent red (solventred) 45,49,111,125,130,143,145,146,150,151,155,168,169,172,175,181,207,218,222,227,230,245,247;

C.I. solvent orange (solventorange) 2,7,11,15,26,56,77,86;

C.I. solvent violet (solventviolet) 11,13,14,26,31,36,37,38,45,47,48,51,59,60;

C.I. solvent blue (solventblue) 4,5,14,18,35,36,37,45,58,59,59:1,63,67,68,69,70,78,79,83,90,94,97,98,100,101,102,104,105,111,112,122,128,132,136,139;

C.I. the C.L. solvent dye such as solvent green (solventgreen) 1,3,4,5,7,28,29,32,33,34,35,

C.I. Indian yellow (acidyellow) 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251,

C.I. acid red (acidred) 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426,

C.I. acid orange (acidorange) 6,7,8,10,12,26,50,51,52,56,62,63,64,74,75,94,95,107,108,169,173;

C.I. acid violet (acidviolet) 6B, 7,9,17,19,30,34,102;

C.I. acid blue (acidblue) 1, 7, 9, 15, 18, 22, 23, 25, 27, 29, 40, 41, 42, 43, 45, 51, 54, 59, 60, 62, 70, 72, 74, 78, 80, 82, 83, 86, 87, 90, 92, 93, 96, 100, 102, 103, 104, 112, 113, 117, 120, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 229, 234, 236, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324:1, 335, 340,

C.I. the C.I. acid dyes such as acid green (acidgreen) 1,3,5,9,16,25,27,28,41,50,58,63,65,80,104,105,106,109

C.I. direct yellow (directyellow) 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129,136,138,141;

C.I. direct red (directred) 79,82,83,84,91,92,96,97,98,99,105,106,107,172,173,176,177,179,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246,250;

C.I. direct orange (directorange) 34,39,41,46,50,52,56,57,61,64,65,68,70,96,97,106,107;

C.I. direct purple (directviolet) 47,52,54,59,60,65,66,79,80,81,82,84,89,90,93,95,96,103,104;

C.I. direct blue (directblue) 1, 2, 6, 8, 15, 22, 25, 40, 41, 51, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293,

C.I. the C.I. direct dyes such as direct green (directgreen) 25,27,31,32,34,37,63,65,66,67,68,69,72,77,79,82,

C.I. disperse yellow (disperyellow) 51,54,76;

C.I. disperse violet (disperviolet) 26,27;

C.I. disperse blue (disperblue) 1,14,56,60;

C.I. alkaline red (bisicred) 1,10;

C.I. alkali blue (directblue) 1,3,5,7,9,19,21,22,24,25,26,28,29,40,41,45,47,54,58,59,60,64,65,66,67,68;

C.I. basic-dyeable fibre such as C.I. such as Viride Nitens (directgreen) 1 grade,

C.I. reactive yellow (reactiveyellow) 2,76,116;

C.I. reactive orange (reactiveorange) 16;

Reactive dye such as C.I. such as C.I reactive red (reactivered) 36 grade,

C.I. mordant yellow (mordantyellow) 5,8,10,16,20,26,30,31,33,42,43,45,56,61,62,65;

C.I. mordant rouge (mordantred) 1,2,3,4,9,11,12,14,17,18,19,22,23,24,25,26,27,30,32,33,36,37,38,39,41,43,45,46,48,53,56,63,71,74,85,86,88,90,94,95;

C.I. mordant dyeing orange (mordantorange) 3,4,5,8,12,13,14,20,21,23,24,28,29,32,34,35,36,37,42,43,47,48;

C.I. mordant dyeing purple (mordantviolet) 1,2,4,5,7,14,22,24,30,31,32,37,40,41,44,45,47,48,53,58;

C.L mordant dyeing indigo plant (mordantblue) 1,2,3,7,8,9,12,13,15,16,17,19,20,21,22,23,24,26,30,31,32,39,40,41,43,44,48,49,53,61,74,77,83,84;

C.I. the C.I. mordant dye such as viridon (mordantgreen) 1,3,4,5,10,15,19,26,29,33,34,35,41,43,53,

C.I. the C.I. reducing dye etc. such as vat green (vatgreen).

As dyestuff (A1), preferred xanthene dye (Aa).

Xanthene dye (Aa) is for comprising the dyestuff of the compound with xanthene skeleton, such as can enumerate: C.I. CI 45430, 52, 87, 92, 94, 289, 388, C.I. acid violet 9, 30, 102, C.I. alkali red 1:1 (rhodamine 6G), 2, 3, 4, 8, C.I. alkali red 1:1 0 (rhodamine B), 11, C.I. alkaline purple 10, 11, 25, C.I. solvent red 218, C.I. mordant rouge 27, C.I. reactive red 36 (rose red b), Sulforhodamine G, the xanthene dye that Japanese Unexamined Patent Publication 2010-32999 publication is recorded and the xanthene dye etc. that No. 4492760th, patent is recorded.

As xanthene dye (Aa), the dyestuff of the compound (following, to be sometimes referred to as " compound (1) ") preferably shown in contained (1), compound (1) also can be its dynamic isomer.When using compound (1), the content of the compound (1) in preferred xanthene dye (Aa) is more than 50 quality %, more preferably more than 70 quality %, further preferred more than 90 quality %.As xanthene dye (Aa), in fact particularly preferably only use compound (1).

[in formula (1), R ¹~ R ⁴separately represent hydrogen atom, carbon number to be the saturated hydrocarbyl of 1 valency of 1 ~ 20 or carbon number be the aromatic hydrocarbyl of 1 valency of 6 ~ 10, hydrogen atom contained in this aromatic hydrocarbyl also can by halogen atom ,-R ⁸-,-OH ,-OR ⁸,-SO ₃ ^-,-SO ₃h ,-SO ₃ ^-m ⁺,-CO ₂h ,-CO ₂ ^-m ⁺,-CO ₂r ⁸,-SR ⁸,-SO ₂r ⁸,-SO ₃r ⁸or-SO ₂nR ⁹r ¹⁰replace.Hydrogen atom contained in above-mentioned saturated hydrocarbyl can be replaced by the aromatic hydrocarbyl of carbon number 6 ~ 10 or halogen atom, and hydrogen atom contained in this aromatic hydrocarbyl can be replaced by the alkoxy of carbon number 1 ~ 3 ,-CH contained in above-mentioned saturated hydrocarbyl ₂-can by-O-,-CO-or-NR ¹¹replace.R ¹and R ²the ring comprising nitrogen-atoms can be formed together, R ³and R ⁴the ring comprising nitrogen-atoms can be formed together.

R ⁵represent-OH ,-SO ₃ ^-,-SO ₃h ,-SO ₃ ^-m ⁺,-CO ₂h ,-CO ₂ ^-m ⁺,-CO ₂r ⁸,-SO ₃r ⁸or-SO ₂nR ⁹r ¹⁰.

M represents the integer of 0 ~ 5.When m is 2, multiple R ⁵can be identical or different.

R ⁶and R ⁷separately represent the alkyl of hydrogen atom or carbon number 1 ~ 6.

M ⁺represent ⁺n (R ¹¹) ₄, Na ⁺or K ⁺.

X represents halogen atom.

A represents the integer of 0 or 1.

R ⁸represent that the hydrogen atom comprised in the saturated hydrocarbyl of 1 valency of carbon number 1 ~ 20, this saturated hydrocarbyl can be replaced by halogen atom.

R ¹¹separately represent the saturated hydrocarbyl of 1 valency of hydrogen atom, carbon number 1 ~ 20 or the aralkyl of carbon number 7 ~ 10.

R ⁹and R ¹⁰separately represent the saturated hydrocarbyl of 1 valency of hydrogen atom or carbon number 1 ~ 20, hydrogen atom contained in this saturated hydrocarbyl can be replaced by hydroxyl or halogen atom ,-CH contained in this representative examples of saturated aliphatic alkyl ₂-can by-O-,-CO-,-NH-or-NR ⁸-replace, R ⁹and R ¹⁰the heterocycle comprising 3 ~ 10 rings of nitrogen-atoms can be formed by bonding mutually.]

As R ¹~ R ⁴in the aromatic hydrocarbyl of 1 valency of carbon number 6 ~ 10, such as can enumerate: phenyl, tolyl, xylyl, sym-trimethyl benzene base, propyl group phenyl and butyl phenyl etc.

To R ¹~ R ⁴in the aromatic hydrocarbyl of 1 valency of carbon number 6 ~ 10, alternatively base, preferably has and is selected from by-SO ₃ ^-,-SO ₃h ,-SO ₃ ^-m ⁺and-SO ₂nR ⁹r ¹⁰at least one in the group formed, more preferably has and is selected from-SO ₃ ^-m ⁺and-SO ₂nR ⁹r ¹⁰at least one in the group formed.As-SO now ₃ ^-m ⁺, preferably-SO ₃ ^-+n (R ¹¹) ₄.R ¹~ R ⁴during for these groups, can form by the photosensitive composition of the present invention of inclusion compound (1) few foreign and the color filter of excellent heat resistance that produce.

As R ¹and R ²the ring formed together and R ³and R ⁴the ring formed together, such as, can enumerate following material.

As R ⁸~ R ¹¹in the saturated hydrocarbyl of 1 valency of carbon number 1 ~ 20, can enumerate: the alkyl of the carbon numbers 1 ~ 20 such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, amyl group, isopentyl, neopentyl, hexyl, heptyl, octyl group, 2-ethylhexyl, nonyl, decyl, dodecyl, cetyl, eicosyl; The naphthenic base etc. of the carbon numbers 3 ~ 20 such as cyclopropyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, three ring decyls.

As-OR ⁸, such as can enumerate: methoxyl, ethoxy, propoxyl group, butoxy, amoxy, own oxygen base, heptan oxygen base, octyloxy, 2-ethyl hexyl oxy and eicosane oxygen base.

As-CO ₂r ⁸, such as, can enumerate: methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxy carbonyl and eicosane oxygen base carbonyl etc.

As-SR ³, such as, can enumerate: methylsulfanyl, Ethylsulfanyl, butyl sulfanyl, hexyl sulfanyl, decyl sulfanyl and eicosyl sulfanyl etc.

As SO ₂r ⁸, such as, can enumerate: methyl sulphonyl, ethylsulfonyl, butyl sulfonyl, hexyl sulfonyl, decyl sulfonyl, eicosyl sulfonyl etc.

As-SO ₃r ⁸, such as, can enumerate: methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxy sulfonyl, own oxygen base sulfonyl and eicosane oxygen base sulfonyl etc.

As-SO ₂nR ⁹r ¹⁰, such as, can enumerate: sulfamoyl;

N-Methylsulfamoyl, N-ethylsulfamovl, N-propylsulfamov, N-isopropylsulfamoyl base, N-Butylsulfamoyl base, N-isobutyl sulfamoyl, N-sec-butyl sulfamoyl, N-tert-butyl group sulfamoyl, N-amyl group sulfamoyl, N-(1-ethyl propyl) sulfamoyl, N-(1,1-dimethyl propyl) sulfamoyl, N-(1,2-dimethyl propyl) sulfamoyl, N-(2,2-dimethyl propyl) sulfamoyl, N-(1-methyl butyl) sulfamoyl, N-(2-methyl butyl) sulfamoyl, N-(3-methyl butyl) sulfamoyl, N-Cyclopentylsulfamoyl base, N-hexyl sulfamoyl, N-(1,3-dimethylbutyl) sulfamoyl, N-(3,3-dimethylbutyl) sulfamoyl, N-heptyl sulfamoyl, N-(1-methylhexyl) sulfamoyl, N-(Isosorbide-5-Nitrae-dimethyl amyl group) sulfamoyl, N-octyl group sulfamoyl, N-(2-ethylhexyl } sulfamoyl, N-(1,5-dimethyl) hexyl sulfamoyl, the N-1 such as N-(1,1,2,2-tetramethyl butyl) sulfamoyl replace sulfamoyl, and

N; N-DimethylsuIfamoyl, N; N-ethyl-methyl sulfamoyl, N, N-diethyl amino sulfonyl, N, N-hydroxypropyl methyl sulfamoyl, N; N-isopropyl methyl sulfamoyl, N; N-tertbutyl methyl sulfamoyl, N, N-butyl ethyl sulfamoyl, N, N-two (1-methyl-propyl) sulfamoyl, N; N, the N-2 such as N-hept-ylmethyl sulfamoyl replace sulfamoyl etc.

In addition, to expression R ⁹and R ¹⁰the saturated hydrocarbyl of 1 valency of carbon number 1 ~ 20, hydrogen atom contained in this saturated hydrocarbyl can be replaced by-OH or halogen atom ,-CH contained in this saturated hydrocarbyl ₂-can by-O-,-CO-,-NH-or-NR ⁸-replace.

R ⁹and R ¹⁰the heterocycle comprising 3 ~ 10 rings of nitrogen-atoms can be formed by bonding mutually, as this heterocycle, such as, can enumerate following material.

R ⁵preferably-CO ₂h ,-CO ₂r ⁸,-SO ₃ ^-,-SO ₃ ^-m ⁺,-SO ₃h or SO ₂nHR ⁹, more preferably SO ₃ ^-,-SO ₃ ^-m ⁺,-SO ₃h or SO ₂nHR ⁹.

M preferably 1 ~ 4, more preferably 1 or 2.

As R ⁶and R ⁷in the alkyl of carbon number 1 ~ 6, can enumerate in the above-mentioned alkyl enumerated, the alkyl of carbon number 1 ~ 6.

As R ¹¹in the aralkyl of carbon number 7 ~ 10, benzyl, phenethyl, phenyl butyl etc. can be enumerated.

M ⁺for ⁺n (R ¹¹) ₄, Na ⁺or K ⁺, be preferably ⁺n (R ¹¹) ₄.

As ⁺n (R ¹¹) ₄, at 4 R ¹¹in, preferably at least 2 is the saturated hydrocarbyl of 1 valency of carbon number 5 ~ 20.In addition, 4 R ¹¹total carbon atom number be preferably 20 ~ 80, more preferably 20 ~ 60.Exist in compound (1) ⁺n (R ¹¹) ₄when, R ¹¹during for above-mentioned group, the color filter of few foreign can be formed by the photosensitive composition of the present invention of inclusion compound (1).

As compound (1), compound shown in preferred formula (2) is (following, be sometimes referred to as " compound (2) "), as xanthene dye (Aa), more preferably the dyestuff of inclusion compound (2), compound (2) can be its dynamic isomer.When using compound (2), content preferably more than the 50 quality % of the compound (2) in xanthene dye (Aa), more preferably more than 70 quality %, further preferred more than 90 quality %.As xanthene dye (Aa), particularly preferably only use compound (2).

[in formula (2), R ²¹~ R ²⁴separately represent hydrogen atom ,-R ²⁶or the aromatic hydrocarbyl of 1 valency of carbon number 6 ~ 10, hydrogen atom contained in this aromatic hydrocarbyl can by-SO ₃ ^-,-SO ₃ ^-m ^a+,-SO ₃h ,-SO ₃r ²⁶or-SO ₂nHR ²⁶replace.

X ^arepresent halogen atom.

A1 represents the integer of 0 or 1.

Ml represents the integer of 0 ~ 5.When m1 is the integer of more than 2, multiple R ²⁵can be identical or different.

M ^a+represent ⁺n (R ²⁷) ₄, Na ⁺or K ⁺.

R ²⁵expression-SO ₃ ^-,-SO ₃ ^-m ^a+,-SO ₃h or-SO ₂nHR ²⁶.

R ²⁶represent the saturated hydrocarbyl of 1 valency of carbon number 1 ~ 20.

R ²⁷separately represent saturated hydrocarbyl or the benzyl of 1 valency of carbon number 1 ~ 20.

As R ²¹~ R ²⁴in the aromatic hydrocarbyl of 1 valency of carbon number 6 ~ 10, can enumerate and R ¹~ R ⁴in the identical group of the group enumerated as aromatic hydrocarbyl.

Wherein, as R ²¹~ R ²⁴combination, preferred R ²¹and R ²³for hydrogen atom and R ²²and R ²⁴for the aromatic hydrocarbyl of 1 valency of carbon number 6 ~ 10, hydrogen atom contained in this aromatic hydrocarbyl can by-SO ₃ ^-,-SO ₃ ^-m ⁺,-SO ₃h ,-SO ₃r ²⁶or-SO ₂nHR ²⁶replace.More preferably R ²¹and R ²³for hydrogen atom and R ²²and R ²⁴for the aromatic hydrocarbyl of 1 valency of carbon number 6 ~ 10, hydrogen atom contained in this aromatic hydrocarbyl can by-SO ₃ ^-m ⁺or-SO ₂nHR ²⁶replace.R ²¹~ R ²⁴during for above-mentioned group, the color filter of excellent heat resistance can be formed by the photosensitive composition of the present invention of inclusion compound (2).

As R ²⁶and R ²⁷in the saturated hydrocarbyl of 1 valency of carbon number 1 ~ 20, can enumerate and R ⁸~ R ¹¹in the identical group of the group enumerated as saturated hydrocarbyl.

At R ²¹~ R ²⁴for-R ²⁶when ,-R ²⁶be preferably separately hydrogen atom, methyl or ethyl.

As-SO ₃r ²⁶or-SO ₂nHR ²⁶in R ²⁶, the branched-chain alkyl of preferred carbon number 3 ~ 20, the more preferably branched-chain alkyl of carbon number 6 ~ 12, further preferred 2-ethylhexyl.At R ²⁶during for these groups, the photosensitive composition of inclusion compound (2) can form foreign matter and produce few color filter.

M ^a+for ⁺n (R ²⁷) ₄, Na ⁺or K ⁺, be preferably ⁺n (R ²⁷) ₄.

As ⁺n (R ²⁷) ₄, at 4 R ²⁷in, preferably at least 2 is the saturated hydrocarbyl of 1 valency of carbon number 5 ~ 20.In addition, 4 R ²⁷total carbon atom number be preferably 20 ~ 80, more preferably 20 ~ 60.Exist in compound (2) ⁺n (R ²⁷) ₄when, can by R ²⁷photosensitive composition of the present invention for the inclusion compound (2) of these groups forms foreign matter and produces few color filter.

M1 preferably 1 ~ 4, more preferably 1 or 2.

As compound (1), such as, can enumerate the compound shown in formula (1-1) ~ formula (1-30).In addition, in following formula, Ra represents the saturated hydrocarbyl of 1 valency of carbon number 1 ~ 20, the branched-chain alkyl of preferred carbon number 6 ~ 12, further preferred 2-ethylhexyl.Wherein, the quaternary ammonium salt of the sulfonamide compound of preferred C.I. acid red 289, the quaternary ammonium salt of C.I. acid red 289, the sulfonamide compound of C.I. acid violet 102 or C.I. acid violet 102.As such compound, such as, can enumerate formula (1-1) ~ formula (1-8), formula (1-11) or the compound etc. shown in formula (1-12).

In addition, as xanthene dye (Aa), the dyestuff of the compound (following, to be sometimes referred to as " compound (3) ") also more preferably shown in contained (3).Compound (3) also can be its dynamic isomer.When using compound (3), content preferably more than the 50 quality % of the compound (3) in xanthene dye (Aa), more preferably more than 70 quality %, further preferred more than 90 quality %.

[in formula (3), R ³¹and R ³²separately represent the alkyl of carbon number 1 ~ 10.R ³³and R ³⁴separately represent the alkyl sulphonyl of the alkyl of carbon number 1 ~ 4, the alkyl alkylthio base of carbon number 1 ~ 4 or carbon number 1 ~ 4.R ³¹and R ³³the ring comprising nitrogen-atoms can be formed together, R ³²and R ³³the ring comprising nitrogen-atoms can be formed together.

P and q represents the integer of 0 ~ 5 independently of each other.When p is more than 2, multiple R ³³can be identical, also can be different, when q is more than 2, multiple R ³⁴can be identical, also can be different.

As expression R ³¹and R ³²the alkyl of carbon number 1 ~ 10, can enumerate: methyl, ethyl, propyl group, butyl, isopropyl, isobutyl, sec-butyl, the tert-butyl group, hexyl, 2-ethylhexyl, nonyl, decyl etc.As expression R ³³and R ³⁴the alkyl of carbon number 1 ~ 4, in these groups, can enumerate: the group of carbon number to 4.

As expression R ³³and R ³⁴the alkyl alkylthio base of carbon number 1 ~ 4, can enumerate: methylsulfanyl, Ethylsulfanyl, Propylsulfanyl, butyl sulfanyl and isopropyl sulfanyl etc.

As expression R ³³and R ³⁴the alkyl sulphonyl of carbon number 1 ~ 4, can enumerate: methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, butyl sulfonyl and isopropelsulfonyl etc.

Preferred R ³¹and R ³²be methyl, ethyl, propyl group or isopropyl independently of each other.Preferred R ³³and R ³⁴for the alkyl of carbon number 1 ~ 4, be more preferably methyl.

Preferred p and q is the integer of 0 ~ 2 independently of each other, more preferably 1 or 2.

As compound (3), such as, can enumerate the compound shown in formula (1-31) ~ formula (1-43) respectively.Wherein, from the viewpoint of dissolubility excellence in organic solvent, the compound shown in preferred formula (1-31) ~ formula (1-40).

As xanthene dye (Aa), also commercially available xanthene dye (" Rhodamin6G " that " ChugaiAminolFastPinkR-H/C ", hilllock, field chemical industry (strain) that such as, middle tank formation (strain) is made are made etc.) can be used.In addition, using commercially available xanthene dye as initiation material, with Japanese Unexamined Patent Publication 2010-32999 publication for reference is synthesized.

As pigment (A2), organic pigment and inorganic pigment can be enumerated, the compound being classified as pigment in Colour Index (TheSocietyofDyersandColourists publication) can be enumerated.Wherein, preferred organic pigment.

As pigment, such as, can enumerate: the yellow uitramarines such as C.I. pigment yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,137,138,139,147,148,150,153,154,166,173,194,214;

C.I. pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65,71, the orange pigments such as 73;

C.I. Pigment Red 9,97,105,122,123,144,149,166,168,175,176,177,180,192,209,215,216,224,242,254,255,264, the red pigments such as 265;

C.I. pigment blue 15,15:3,15:4,15:6,60, the blue pigments such as 80; C.I. pigment violet 1,19,23,29,32,36, the violet pigments such as 38;

C.I. pigment Green 7,36, the viridine greens such as 58;

C.I. the brown pigments such as bistre 23,25; And

C.I. the black pigment etc. such as pigment black 1,7.

Wherein, preferred C.I. pigment yellow 13 8,139,150, C.I. paratonere 177,209,242,254, C.I. pigment Violet 23, C.I. pigment blue 15: 3,15:6 and C.I. pigment Green 7,36,58.As the pigment used in photosensitive composition of the present invention, more preferably comprise and be selected from C.I. pigment blue 15: 6, C.I. paratonere 254, C.I, the pigment of at least one in the group that paratonere 242, C.I. paratonere 177, C.I. naphthol green 58, C.I. paratonere 150 and C.I. pigment yellow 13 8 are formed.By comprising above-mentioned pigment, the optimization of transmitted spectrum is easy, and chemical proofing is good

These pigment can be used alone, and also can mix two or more and use.

Pigment also can implement rosin process as required, employ the surface treatment of the pigment derivative that imported acidic-group or basic group etc., utilize the grafting process to surface of pigments of macromolecular compound etc., utilize the micronize process of sulfuric acid particles method etc. or utilize the cleaning treatment of organic solvent for removing impurity or water etc., the removing process etc. utilizing ion exchange process etc. of ionic impurity.

Pigment preferable particle size is even.By carrying out dispersion treatment containing pigment dispersing agent, the dispersible pigment dispersion that pigment is evenly dispersed in the state in solution can be obtained.

As above-mentioned pigment dispersing agent, such as, can enumerate: the surfactants etc. such as kation system, negative ion system, nonionic system, both sexes, Polyester, polyamine system, acrylic acid series.These pigment dispersing agents can be used alone, and also can combine two or more and use.As pigment dispersing agent, can enumerate: trade name KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system), Floren (common prosperity society chemistry (strain) system), Solsperse (Zeneca (strain) system), EFKA (CIBA Inc.), Ajisper (aginomoto fine chemistry (strain) system), Disperbyk (BYK-Chemie Inc.) etc.

When using spreading agent, its use amount is preferably 100 quality % relative to pigment (A2), is more preferably more than 5 quality % and below 50 quality %.The use amount of pigment dispersing agent, when above-mentioned scope, has the trend of the dispersible pigment dispersion that can obtain uniform disperse state.

When comprising pigment (A2), the content ratio of dyestuff (A1) and pigment (A2) in quality criteria preferably 1: 99 ~ 99: 1, more preferably 3: 97 ~ 90: 10.

By being set to such ratio, the easy optimization of transmitted spectrum, due to high-contrast, high brightness can be obtained, thus preferably.And then thermotolerance, chemical proofing are good.

Particularly when photosensitive composition of the present invention is prepared as blue-colored photosensitive polymer combination, as colorant (A), preferably comprise the colorant of xanthene dye (Aa) and blue pigment, preferably comprise xanthene dye (Aa) and C.I. pigment blue 15: the colorant of 6.Xanthene dye (Aa) and C.I. pigment blue 15: the content ratio of 6 in quality criteria preferably 3: 97 ~ 90: 10, more preferably 3: 97 ~ 70: 30, further preferably 3: 97 ~ 50: 50.

The content of colorant (A) is preferably 5 ~ 60 quality % relative to the solid constituent in photosensitive composition, is more preferably 8 ~ 55 quality %, more preferably 10 ~ 50 quality %.The content of colorant (A) is when above-mentioned scope, and colour saturation when making color filter is abundant, and contains resin and the polymerizable compound of necessary amounts in the composition, therefore, can form the sufficient pattern of physical strength.At this, solid constituent refers to the total amount of the composition deducting solvent from photosensitive composition of the present invention.The content of solid constituent and on the other hand each composition such as can measure by the known analytical approach such as liquid phase chromatography or vapor-phase chromatography.

Photosensitive composition of the present invention comprises resin (B).As resin (B), be not particularly limited, be preferably alkali soluble resin.

As resin (B), such as, can enumerate following resin [K1] ~ [K6] etc.

The monomer (a) that [K1] has the cyclic ether structure of carbon number 2 ~ 4 and ethene unsaturated link is (following, be sometimes referred to as " (a) ") and be selected from the multipolymer of at least one (b) (following, to be sometimes referred to as " (b) ") in the group that is made up of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides.

[K2] (a) and (b) and can (wherein, (a) and (b) is different with the monomer (c) of (a) copolymerization.) multipolymer of (following, be sometimes referred to as " (c) ").

The multipolymer of [K3] (b) and (c)

The resin that [K4] makes the copolymer reaction of (a) and (b) and (c) and obtain.

The resin that [K5] makes the copolymer reaction of (b) and (a) and (c) and obtain.

[K6] makes (b) and (a) copolymer reaction with (c), then the resin making itself and carboxylic acid anhydrides react and obtain.

A () such as refers to the polymerizable compound of cyclic ether structure (being such as selected from least a kind in the group of oxirane ring, oxetanes ring and tetrahydrofuran ring formation) and the ethene unsaturated link with carbon number 2 ~ 4.A () preferably has the cyclic ether of carbon number 2 ~ 4 and the monomer of (methyl) acryloxy.

In addition, in this manual, " (methyl) acrylic acid " represents at least a kind in the group being selected from acrylic acid and methacrylic acid formation." (methyl) acryloyl group " and " [(methyl) acrylate " etc. are recorded also has the identical meaning.

As (a), such as can enumerate: the monomer (a1) with Oxyranyle and ethene unsaturated link is (following, be sometimes referred to as " (a1) "), the monomer (a2) with oxetanyl and ethene unsaturated link is (following, be sometimes referred to as " (a2) "), there is the monomer (a3) (following, be sometimes referred to as " (a3) ") etc. of tetrahydrofuran base and ethene unsaturated link.

For (a1), such as can enumerate: the monomer (a1-1) with structure that straight-chain or branched unsaturated aliphatic hydrocarbon be at least partially epoxidized and ethene unsaturated link is (following, be sometimes referred to as " (a1-1) ") and there is the monomer (a1-2) (following, to be sometimes referred to as " (a1-2) ") of structure that ester ring type unsaturated hydrocarbon is at least partially epoxidized and ethylene unsaturated bond.

As (a1-1), can enumerate: (methyl) glycidyl acrylate, (methyl) propenoic acid beta-methylglycidyl esters, (methyl) propenoic acid beta-ethyl glycidyl ester, glycidyl vinyl ether, adjacent vinylbenzyl glycidyl base ether, between vinylbenzyl glycidyl base ether, to vinylbenzyl glycidyl base ether, Alpha-Methyl-adjacent vinylbenzyl glycidyl base ether, an Alpha-Methyl-vinylbenzyl glycidyl base ether, an Alpha-Methyl-vinylbenzyl glycidyl base ether, two (glycidyl oxy methyl) styrene of 2,3-, two (glycidyl oxy methyl) styrene of 2,4-, two (glycidyl oxy methyl) styrene of 2,5-, 2,6-pair (glycidyl oxy methyl } styrene, 2,3,4-tri-(glycidyl oxy methyl) styrene, 2,3,5-tri-(glycidyl oxy methyl) styrene, 2,3,6-tri-(glycidyl oxy methyl) styrene, 3,4,5-tri-(glycidyl oxy methyl) styrene, 2,4,6-tri-(glycidyl oxy methyl) styrene etc.

As (a1-2), single vinylcyclohexene oxide, 1,2-epoxy-4-vinyl cyclohexane (such as, CELLOXIDE2000 can be enumerated; Daicel chemical industry (strain) make), 3,4-epoxycyclohexyl-methyl (methyl) acrylate (such as, CyclomerA400; Daicel chemical industry (strain) make), 3,4-epoxycyclohexyl-methyl (methyl) acrylate (such as: CyclomerM100; Daicel chemical industry (strain) is made) and the compound shown in formula (I) and the compound etc. shown in formula (II).

[in formula (1) and formula (II), R ^aand R ^brepresent the alkyl of hydrogen atom or carbon number 1 ~ 4 independently of each other, hydrogen atom contained in this alkyl can be optionally substituted by a hydroxyl group.

X ¹and X ²represent singly-bound ,-R independently of each other ^c-, *-R ^c-O-,-R ^c-S-, *-R ^c-NH-.

R ^crepresent alkane two base of carbon number 1 ~ 6.

* the connecting key with O is represented.]

As the alkyl of carbon number 1 ~ 4, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group etc. can be enumerated.

As the alkyl that hydrogen atom is optionally substituted by a hydroxyl group, can enumerate: hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1 monohydroxy propyl group, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyl-1-Methylethyl, 2-hydroxyl-1-Methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl etc.

As R ^aand R ^b, preferably can enumerate: hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, can more preferably enumerate hydrogen atom, methyl.

As alkane two base, methylene, ethylidene, propane-1,2-bis-base, propane-1,3-bis-base, butane-Isosorbide-5-Nitrae-two base, pentane-1,5-bis-base, hexane-1,6-bis-base etc. can be enumerated.

As X ¹and X ², preferably can enumerate singly-bound, methylene, ethylidene, *-CH ₂-O-(* represents the connecting key with O) base, *-CH ₂cH ₂-O-base, more preferably can enumerate singly-bound, *-CH ₂cH ₂-O-base.

As the compound shown in (I), can enumerate: the compound etc. shown in formula (I-I) ~ formula (I-15).Can preferably enumerate: the compound shown in formula (I-I), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) ~ formula (I-15).More preferably formula (I-I), formula (X-7), formula (I-9) or the compound shown in formula (I-15) can be enumerated.

As the compound shown in formula (II), the compound etc. shown in formula (II-1) ~ formula (II-15) can be enumerated.Can preferably enumerate: formula [II-1), the compound shown in formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) ~ formula (II-15).More preferably formula (II-1), formula (II-7), formula (II-9) or the compound shown in formula (II-15) can be enumerated.

Compound shown in formula (I) and the compound shown in formula (II) can individually use, and in addition, these can mix with arbitrary ratio.When mixing, its mixture ratio is with molar ratio computing preferred formula (I): formula (II) is 5: 95 ~ 95: 5, more preferably 10: 90 ~ 90: 10, especially preferably 20: 80 ~ 80: 20.

As the monomer (a2) with oxetanyl and ethene unsaturated link, more preferably there is the monomer of oxetanyl and (methyl) acryloxy.As (a2), can enumerate: 3-methyl-3-methacryloxymethyl oxetanes, 3-methyl-3-acryloyloxymethyl oxetanes, 3-ethyl-3-methacryloxymethyl oxetanes, 3-ethyl-3-acryloyloxymethyl oxetanes, 3-methyl-3-methacryloxyethyl oxetanes, 3-methyl-3-acryloyl-oxyethyl oxetanes, 3-ethyl-3-methacryloxyethyl oxetanes, 3-ethyl-3-acryloyl-oxyethyl oxetanes etc.

As the monomer (a3) with tetrahydrofuran base and ethene unsaturated link, more preferably there is the monomer of tetrahydrofuran base and (methyl) acryloxy.

As (a3), specifically, acrylic acid tetrahydrofuran ester (such as, ViscoatV#150, Osaka Organic Chemical Industry (strain) system) and THFMA etc. can be enumerated.

As (a), from the viewpoint of making, the reliability of the thermotolerance of the color filter obtained, chemical proofing etc. is higher, is preferably (a1).And then, from the viewpoint of the excellent storage stability of photosensitive composition, more preferably (a1-2).

As (b), specifically, such as can enumerate: acrylic acid, methacrylic acid, crotonic acid, neighbour, to unsaturated monocarboxylic classes such as vinyl benzoic acids;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2, the unsaturated dicarboxylic classes such as 3,6-tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid, Isosorbide-5-Nitrae-cyclohexene dicarboxylic acid;

Methyl-5-norborene-2, the carboxylic dicyclo unsaturated compound class such as 3-dicarboxylic acid, 5-carboxyl dicyclo [2.2.1] hept-2-ene", 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene"s, 5-carboxyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-6-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-6-ethyl dicyclo [2.2.1] hept-2-ene";

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic acid acid anhydride, 4-vinylphthalic acid acid anhydride, 3,4,5,6-tetrabydrophthalic anhydride, 1,2, the unsaturated dicarboxylic class acid anhydrides such as 3,6-tetrabydrophthalic anhydride, dimethyl tetrahydro phthalic anhydride, 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene"s (carbic anhydride);

Unsaturated list [(methyl) acryloxyalkyl] the ester class of the polyvalent carboxylic acid more than divalents such as mono succinate [2-(methyl) acryloyl-oxyethyl] ester, phthalic acid list [2-(methyl) acryloyl-oxyethyl]; And

The unsaturated esters of acrylic acid etc. containing hydroxyl and carboxyl in same a part as α-(hydroxymethyl) acrylic acid.

Wherein, consider in deliquescent aqueous alkali of copolyreaction aspect and the resin that obtains, preferred acrylic acid, methacrylic acid, maleic anhydride etc.

As (c), such as, can enumerate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) dodecylacrylate, (methyl) lauryl acrylate, (methyl) aliphatic acrylate, (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methyl cyclohexyl, three ring [5.2.1.0 ^2.6] decane-8-base (methyl) acrylate (in this technical field, as trivial name, is called as dicyclopentenyl (methyl) acrylate.), dicyclopentenyl oxygen base ethyl (methyl) acrylate, three ring [5.2.1.0 ^2.6] decene-8-base (methyl) acrylate is (in this technical field, as trivial name, be called as dicyclopentenyl (methyl) acrylate), (methyl) esters of acrylic acid such as (methyl) isobornyl acrylate, (methyl) acrylic acid adamantane esters, (methyl) allyl acrylate, (methyl) propargylacrylate, (methyl) phenyl acrylate, (methyl) acrylic acid naphthalene ester, (methyl) benzyl acrylate;

(methyl) esters of acrylic acid of the hydroxyls such as (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester;

The dicarboxylic diesters such as diethyl maleate, DEF, diethyl itaconate;

Dicyclo [2.2.1] hept-2-ene", 5-methyl bicycle [2.2.1] hept-2-ene", 5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxyl dicyclo [2.2.1] hept-2-ene", 5-hydroxymethyl dicyclo [2.2.1] hept-2-ene", 5-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5-methoxyl dicyclo [2.2.1] hept-2-ene", 5-ethoxy dicyclo [2.2.1] hept-2-ene", 5.6-dihydroxy dicyclo [2.2.1] hept-2-ene", 5,6-bis-(hydroxymethyl) dicyclo [2.2.1] hept-2-ene", 5,6-bis-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5,6-dimethoxy dicyclo [2.2.1] hept-2-ene", 5,6-diethoxy dicyclo [2.2.1] hept-2-ene", 5-hydroxy-5-methyl base dicyclo [2.2.1] hept-2-ene", 5-hydroxy-5-methyl base dicyclo [2.2.1] hept-2-ene", 5-hydroxymethyl-5-methyl bicycle [2,2,1] hept-2-ene", 5-tert-butoxycarbonyl dicyclo [2.2.1] hept-2-ene", 5-cyclohexyloxy carbonyl dicyclo [2.2.1] hept-2-ene", 5-phenyloxycarbonyl dicyclo [2.2.1] hept-2-ene", two (tert-butoxycarbonyl) dicyclo [2.2.1] hept-2-ene" of 5,6-, the dicyclo unsaturated compound classes such as two (cyclohexyloxy carbonyl) dicyclo [2.2.1] hept-2-ene"s of 5,6-,

The dicarbonyl imides derivant classes such as N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, N-succimide base-3-maleimidobenzoyl ester, N-succimide base-4-malimidobutanoate, N-succimide base-6-maleimide valerate, N-succimide base-3-maleimidopropionic acid ester, N-(9-acridinyl) maleimide;

Styrene, α-methyl styrene, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxy styrene, vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene etc.

Wherein, from the viewpoint of copolyreaction and thermotolerance, optimization styrene, vinyltoluene, N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, dicyclo [2.2.1] hept-2-ene" etc.

In resin [K1], stem from the ratio of the structural unit of each material, in the general construction unit forming resin [K1], preferably in following scope.

Be derived from the structural unit of (a); 50 ~ 98 % by mole (more preferably 60 ~ 90 % by mole)

Be derived from the structural unit of (b); 2 ~ 50 % by mole (more preferably 10 ~ 40 % by mole)

When the ratio of the structural unit of resin [K1] is in above-mentioned scope, there is the tendency that the solvent resistance of the storage stability of photosensitive composition, developability and color filter becomes good.

Resin [K1] can be such as with reference to manufacturing with the citing document described in described method in document " experimental method of Polymer Synthesizing " (grand row work sale room (strain) chemistry in large Tianjin is with the distribution on March 1st, 1972 of people's the 1st edition the 1st brush) and the document.

Specifically, following methods can be enumerated: put in reaction vessel by (a) and (b) of ormal weight, polymerization initiator and solvent etc., such as by nitrogen displace oxygen, form deoxidation atmosphere thus, carry out heating and being incubated while carry out stirring limit.In addition, polymerization initiator used herein and solvent etc. are not particularly limited, and also can use any one in normally used material in this field.Such as, as polymerization initiator, can enumerate: azo-compound [2,2 '-azoisobutyronitrile, 2,2 '-azo two (2,4-methyl pentane nitrile) etc.) or organic peroxide (benzoyl peroxide etc.), as solvent, as long as the material of each monomer of solubilized, as the solvent (F) of photosensitive composition of the present invention, solvent described later etc. can be used.

In addition, the multipolymer obtained can directly use reacted solution, also can use the solution after concentrated or dilution, can also use the material taken out with the form of solid (powder) by the method such as precipitating again.Particularly when carrying out this polymerization, as solvent, solvent contained in the photosensitive composition of the application of the invention, reacted solution can be directly used in the preparation of photosensitive composition of the present invention thus, therefore, the manufacturing process of photosensitive composition of the present invention can be simplified.

In resin [K2], be derived from the ratio of the structural unit of respective material, in the general construction unit forming resin [K2], preferably in following scope.

Be derived from the structural unit of (a); 2 ~ 95 % by mole (more preferably 5 ~ 80 % by mole)

Be derived from the structural unit of (b); 4 ~ 45 % by mole (more preferably 10 ~ 30 % by mole)

Be derived from the structural unit of (c); 1 ~ 65 % by mole (more preferably 5 ~ 60 % by mole)

The ratio of the structural unit of resin [K2], when above-mentioned scope, has the trend that the solvent resistance of the storage stability of photosensitive composition, developability and color filter, thermotolerance and physical strength become good.

In resin [K2], such as, manufacture in the same manner as the method can recorded with the manufacture method as resin [K1].

Specifically, following methods can be enumerated: join in reaction vessel by (a), (b) and (c) of ormal weight, polymerization initiator and solvent, such as form deoxidation atmosphere by nitrogen displace oxygen, carry out heating and being incubated while carry out stirring limit.The polymkeric substance obtained can directly use, and also can use solution that is concentrated or dilution, can also use the material taken out with the form of solid (powder) by the method such as precipitating again.

In resin [K3], the ratio being derived from the structural unit of each material in the general construction unit forming resin [K3], preferably in following scope.

(b) 2 ~ 50 % by mole, more preferably 5 ~ 40 % by mole

(c) 50 ~ 98 % by mole, more preferably 60 ~ 95 % by mole

Manufacture in the same manner as the method that resin [K3] such as can be recorded with the manufacture method as resin [K1].

Resin [K4] can by obtaining (b) and (c) multipolymer and the cyclic ether of the carbon number 2 ~ 4 making (a) have adds and is formed in carboxyl or carboxylic acid anhydrides that (b) have and obtains.

First, the multipolymer of (b) and (c) is manufactured in the same manner as the method recorded as the manufacture method of [K1].Now, the ratio being derived from the structural unit of each material in the general construction unit of multipolymer forming (b) and (c), preferably in following scope.

(b) 5 ~ 50 % by mole, more preferably 10 ~ 45 % by mole

(c) 50 ~ 95 % by mole, more preferably 55 ~ 90 % by mole

Then, the part being derived from carboxyl contained in the structural unit of (b) and/or carboxylic acid anhydrides in the cyclic ether of the carbon number 2 ~ 4 (a) being had and above-mentioned multipolymer is reacted.

Then the manufacture of the multipolymer of (b) and (c), atmosphere in beaker is replaced into air by nitrogen, (a), the catalysts of carboxyl and cyclic ether and polymerization inhibitor are joined in beaker, react 1 ~ 10 hour at such as 60 ~ 130 DEG C, thus, resin [K4] can be obtained.As above-mentioned catalysts, such as, can enumerate three (dimethylaminomethyl) phenol etc.The use amount of above-mentioned catalysts, preferably relative to the total amount of (a) ~ (e), is 0.001 ~ 5 quality %.As above-mentioned polymerization inhibitor, such as, quinhydrones etc. can be enumerated.The use amount of above-mentioned polymerization inhibitor is preferably 0.001 ~ 5 quality % relative to the total amount of (a) ~ (c).The reaction conditionss such as feeding method, temperature of reaction and time can consider the thermal value etc. that manufacturing equipment and polymerization produce and suitable adjustment.It should be noted that, same with polymerizing condition, also can consider that the thermal value etc. that manufacturing equipment and polymerization produce is suitable for adjusting feed process and temperature of reaction.

The use amount of (a) now, is preferably 5 ~ 80 moles relative to (b) 100 moles, is more preferably 10 ~ 75 moles, more preferably 15 ~ 70 moles.By being set in this scope, the balance of the solvent resistance of the storage stability of photosensitive composition, developability and sensitivity and color filter, thermotolerance and physical strength is had to become excellent trend.

For resin [K5], as the first stage, obtain the multipolymer of (a) and (c) in the same manner as the manufacture method of above-mentioned resin [K1].As described above, the multipolymer obtained can directly use reacted solution, also can use solution that is concentrated or dilution, can also use the material taken out with the form of solid (powder) by the method such as precipitating again.

The ratio being derived from the structural unit of (a) and (c) preferably relative to the total molal quantity of the general construction unit of above-mentioned formation multipolymer respectively in following scope.

Be derived from the structural unit of (a); 5 ~ 95 % by mole (more preferably 10 ~ 90 moles)

Be derived from the structural unit of (c); 5 ~ 95 % by mole (more preferably 10 ~ 90 % by mole)

And then, the cyclic ether being derived from (a) that the multipolymer of the carboxylic acid (b) being had by same with the manufacture method of resin [K4] condition or carboxylic acid anhydrides and (a) and (c) has reacts, and can obtain resin [K5] thus.

The use amount of carrying out (b) that react in above-mentioned multipolymer is preferably 5 ~ 80 moles relative to (a) 100 moles.The reactivity of cyclic ether is high, (a) of not easily remained unreacted, therefore, as (a) that use in resin [K5], preferably (a1), further preferably (a1-1).

Resin [K6] is the resin further carboxylic acid anhydrides and resin [K5] being reacted.Carboxylic acid anhydrides is reacted with the hydroxyl being reacted by cyclic ether and carboxylic acid or carboxylic acid anhydrides and produced.

As carboxylic acid anhydrides, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic acid acid anhydride, 4-vinylphthalic acid acid anhydride, 3 can be enumerated, 4,5,6-tetrabydrophthalic anhydride, 1,2,3,6-tetrabydrophthalic anhydride, dimethyl tetrahydro phthalic anhydride, 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene" acid anhydrides etc.

As resin (B), specifically, can enumerate: 3,4-epoxycyclohexyl-methyl (methyl) acrylate/(methyl) acrylic copolymer, 3,4-epoxy three ring [5.2.1.0 ^2.6] resin [K1] such as decyl acrylate/(methyl) acrylic copolymer, (methyl) glycidyl acrylate/(methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) glycidyl acrylate/styrene/(methyl) acrylic copolymer, 3,4-epoxy three ring [5.2.1.0 ^2.6] decyl acrylate/(methyl) acrylic acid/N-N-cyclohexylmaleimide multipolymer, 3,4-epoxy three ring [5.2.1.0 ^2.6] resin [K2] such as decyl acrylate/(methyl) acrylic acid/vinyl toluene copolymer, 3-methyl-3-(methyl) acryloyloxymethyl oxetanes/(methyl) acrylic acid/styrol copolymer, methyl) resin [K3] such as benzyl acrylate/(methyl) acrylic copolymer, styrene/(methyl) acrylic copolymer, (methyl) glycidyl acrylate is added be formed in the resin of (methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) glycidyl acrylate is added be formed in the resin of three ring decyl (methyl) acrylate/styrene/(methyl) acrylic copolymer, (methyl) glycidyl acrylate is added and is formed in the resins [K4] such as the resin of three ring decyl (methyl) acrylate/benzyl (methyl) acrylate/(methyl) acrylic copolymer, the resin making the multipolymer of (methyl) acrylic acid and dicyclopentenyl (methyl) acrylate/(methyl) glycidyl acrylate carry out reacting, the multipolymer of (methyl) acrylic acid and dicyclopentenyl (methyl) acrylate/styrene/(methyl) glycidyl acrylate is made to carry out the resins [K5] such as the resin reacted, tetrabydrophthalic anhydride is made to carry out the resins such as the resin reacted [K6] etc. with the resin making the multipolymer of (methyl) acrylic acid and dicyclopentenyl (methyl) acrylate/glycidyl (methyl) acrylate carry out reacting further.Wherein, preferred resin [K1] and resin [K], more preferably resin [K1], further preferred 3,4-epoxy three ring [5.2.1.0 ^2.6] decyl acrylate/(methyl) acrylic copolymer.When resin (B) is for comprising the resin of the structural unit being derived from (a), the reliabilities such as the thermotolerance of the color filter obtained, chemical proofing can be made higher.

The weight-average molecular weight of the polystyrene conversion of resin (B) is preferably 3,000 ~ 100,000, is more preferably 5,000 ~ 50,000, more preferably 5,000 ~ 35,000, be particularly preferably 6,000 ~ 30,000, be especially preferably 7,000 ~ 28,000.Molecular weight when above-mentioned scope, have that hardness of film improves, residual film ratio also high, relative to the favorable solubility of the developer solution in unexposed portion and the trend that improves of resolution.

The molecular weight distribution [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] of resin (B) is preferably 1.1 ~ 6, is more preferably 1.2 ~ 4.

The acid number of resin (B) is preferably 50 ~ 150mg-KOH/g, is more preferably 60 ~ 135mg-KOH/g, more preferably 70 ~ 135mg-KOH/g.At this, acid number be as in and the amount (mg) of the necessary potassium hydroxide of resin 1g and determined value, such as can carry out titration to try to achieve by using potassium hydroxide aqueous solution.

The content of resin (B) is preferably 7 ~ 65 quality % relative to the solid constituent of photosensitive composition, is more preferably 13 ~ 60 quality %, more preferably 17 ~ 55 quality %.The content of resin (B), when above-mentioned scope, has and can form colored pattern, in addition, and the trend that resolution and residual film ratio improve.

Photosensitive composition of the present invention comprises polymerizable compound (C).Polymerizable compound (C) is the compound that the living radical that produced by polymerization initiator (D) and acid etc. can be utilized to be polymerized, such as can enumerate: the compound etc. with the ethene unsaturated link of polymerism, preferably can enumerate (methyl) acrylate compounds.

Wherein, as polymerizable compound (C), preferably there is the polymerizable compound of more than 3 ethene unsaturated links.As such polymerizable compound, such as can enumerate: pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, tripentaerythritol eight (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, tetrapentaerythritol ten (methyl) acrylate, tetrapentaerythritol nine (methyl) acrylate, three (2-(methyl) acrylyl oxy-ethyl) isocyanuric acid ester, glycol-modified pentaerythrite four (methyl) acrylate, glycol-modified dipentaerythritol six (methyl) acrylate, propylene glycol modified pentaerythrite four (methyl) acrylate, propylene glycol modified dipentaerythritol six (methyl) acrylate, caprolactone modification pentaerythrite four (methyl) acrylate, and caprolactone modification dipentaerythritol six (methyl) acrylate etc.Wherein, can preferably enumerate: dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc.Polymerizable compound can be used alone, and also can combine two or more and use.

The weight-average molecular weight of polymerizable compound (C) is preferably more than 150 and 2, less than 900, is more preferably 250 ~ 1, less than 500.

The content of polymerizable compound (C) is preferably 7 ~ 65 quality % relative to the solid constituent of photosensitive composition of the present invention, is more preferably 13 ~ 60 quality %, more preferably 17 ~ 55 quality %.When the content of above-mentioned polymerizable compound (C) is in above-mentioned scope, have cause solidification fully, residual film ratio in development improves, undercutting not easily enters into colored pattern and adaptation becomes good trend, therefore preferably.

Photosensitive composition of the present invention comprises polymerization initiator (D).

As above-mentioned polymerization initiator (D), as long as produce living radical, acid etc. by the effect of light or heat and can the compound of initiated polymerization just be not particularly limited, known polymerization initiator can be used.

As polymerization initiator (D), preferably by the compound of the dissociation produces active free radical of light, more preferably benzene alkyl ketone compound, triaizine compounds, acylphosphine oxideization are containing thing, oxime compound and united imidazole.

Above-mentioned benzene alkyl ketone compound is for having the compound of the part-structure shown in the part-structure shown in formula (d2) or formula (d3).In these part-structures, phenyl ring also can have substituting group.

As the compound with the part-structure shown in formula (d2), such as, can enumerate: 2-methyl-2-morpholinyl-1-(4-methylsulfanyl phenyl) propane-1-ketone, 2-dimethylamino-1-(4-morpholino phenyl)-2-benzyl butane-1-ketone and 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl] butane-1-ketone etc.Also the commercially available products such as IRGACURE (registered trademark) 369,907 and 379 (more than, BASF AG's system) can be used.

As the compound with the part-structure shown in formula (d3), such as can enumerate: oligomer, α, α-diethoxy acetophenone and the benzyl dimethyl ketal etc. of 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl] propane-1-ketone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenyl phenyl) propane-1-ketone.

From the viewpoint of sensitivity, as benzene alkyl ketone compound, preferably there is the compound of the part-structure shown in formula (d2), more preferably 2-methyl 2-morpholinyl-1-(4-methylsulfanyl phenyl) propane-1-ketone and 2-dimethylamino-1-(4-morpholino phenyl)-2-benzyl butane-1 ketone.

As above-mentioned triaizine compounds, can 2 be enumerated, two (the trichloromethyl)-6-(4-methoxyphenyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl naphthyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-piperonyl-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(5-methylfuran-2-base) vinyl]-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(furans-2-base) vinyl]-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-1 of 4-, 3, 5-triazine, 2, two (trichloromethyl)-6-[2-(3 of 4-, 4-Dimethoxyphenyl) vinyl]-1, 3, 5-triazine etc.

As above-mentioned acylphosphine oxide compound, can enumerate: 2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc.Also the commercially available products such as IRGACURE (registered trademark) 819 (BASF AG's system) can be used.

Above-mentioned oxime compound is for having the compound of the part-structure shown in formula (d1).

Below, * represents connecting key.

As above-mentioned oxime compound, can enumerate: N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) butane-1-ketone-2-imines, N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) octane-1-ketone-2-imines, N-benzoyloxy-1-(4-Phenylsulfanyl phenyl)-3-cyclopentyl propane-1-ketone-2-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-{2-methyl-4-(3, 3-dimethyl-2, 4-dioxa cyclopentenyl methoxyl) benzoyl } 9H-carbazole-3-base] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-3-cyclopentyl propane-1-imines, N-benzoyloxy-1-[9-ethyl-6-{2-methyl benzoyl)-9H-carbazole-3-base]-3-cyclopentyl propane-1-ketone-2-imines etc.Also the commercially available products such as IRGACURE (registered trademark OXE01, OXE02 (more than, BASF AG's system), N-1919 (ADEKA Inc.) can be used.Wherein, N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) butane-1-ketone-2-imines, N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) octane-1-ketone-2-imines and N-benzoyloxy-1-(4-Phenylsulfanyl phenyl)-3-cyclopentyl propane-1-ketone-2-imines.During for these compounds, when photosensitive composition of the present invention is prepared into blue-colored photosensitive polymer combination, there is the tendency that the brightness of the color filter obtained uprises.

As united imidazole, can enumerate: 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2,3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline is (for example, referring to Japanese Unexamined Patent Publication 6-75372 publication and Japanese Unexamined Patent Publication 6-75373 publication.), 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxaline, 2,2 '-bis-(2-chlorphenyl)-4,4 ' 5,5 '-four (alkoxyl phenyl) bisglyoxaline, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxaline is (for example, referring to Japanese Patent Publication 48-38403 publication and Japanese Laid-Open Patent Publication 62-174204 publication etc.), 4,4 ' 5, the imidazolium compounds (for example, referring to Japanese Unexamined Patent Publication 7-10913 publication etc.) etc. that the phenyl of 5 '-position is replaced by alkoxy carbonyl group.Can preferably enumerate: 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2,3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline.

And then, as polymerization initiator (D), the benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether can be enumerated; Benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl thioether, 3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 2, the benzophenone cpds such as 4,6-tri-methyl benzophenone; The naphtoquinone compounds such as 9,10-phenanthrenequione, 2-EAQ, camphorquinone; 10-butyl-2-chloro-acridine ketone, benzyl, phenylglyoxalates methyl esters, two cyclopentadiene titanium compounds etc.These preferably cause auxiliary agent (D1) (particularly amine) combinationally use with described later polymerizations.

As by the acidic acid agent of light, such as, can enumerate: salt and nitrobenzyl tosylate class and the benzoin toluenesulfonic acid salts etc. such as 4-hydroxy phenyl dimethyl disulfide tosilate, 4-hydroxy phenyl dimethyl disulfide hexafluoro antimonate, 4-acetoxyl group phenyl dimethyl disulfide tosilate, 4-acetoxyl group phenyl methyl dibenzylsulfide hexafluoro antimonate, triphenyl sulphur tosilate, triphenyl sulphur hexafluoro antimonate, diphenyl iodine tosilate, diphenyl iodine hexafluoro antimonate.

The content of polymerization initiator (D) is preferably 0.1 ~ 30 mass parts relative to total amount 100 mass parts of resin (B) and polymerizable compound (C), is more preferably 1 ~ 20 mass parts.When the content of Photoepolymerizationinitiater initiater is in above-mentioned scope, can high-sensitivity be realized and shorten the time shutter thus improve throughput rate.

Photosensitive composition of the present invention can also comprise polymerization and cause auxiliary agent (D1).Polymerization causes auxiliary agent (D1) in order to promote the compound that the polymerization of the polymerizable compound of the initiated polymerization by polymerization initiator uses or sensitizer, usually can combinationally use with polymerization initiator (D).

Cause auxiliary agent (D1) as polymerization, amines, alkoxy anthracene compound, thioxanthone compounds, carboxylic acid compound etc. can be enumerated.

As amines, triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl esters, EDMAB, 4-dimethylaminobenzoic acid isopentyl ester, benzoic acid 2-dimethylamino ethyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, N can be enumerated, N-dimethyl-p-toluidine, 4,4 '-bis-(dimethylamino) benzophenone (being commonly called as michler's ketone), 4,4 '-bis-(diethylamino) benzophenone, 4,4 '-bis-(ethylmethylamino) benzophenone etc.Wherein, preferred 4,4 '-bis-(diethylamino) benzophenone.The commercially available products such as EAB-F (hodogaya chemical industry (strain) system) can be used.

As alkoxy anthracene compound, can enumerate: 9,10-dimethoxy anthracene, EDMO, 9,10-diethoxy anthracenes, 2-ethyl-9,10-diethoxy anthracene, 9,10-dibutoxy anthracenes, 2-ethyl-9,10-dibutoxy anthracene etc.

As thioxanthone compounds, can enumerate: ITX, ITX, 2,4-diethyl thioxanthones, 2,4-bis-clopenthixal ketones, the chloro-4-propoxythioxanthone of 1-etc.

As carboxylic acid compound, can enumerate: Phenylsulfanyl acetic acid, methyl phefzylsulfanyl acetic acid, ethylphenyl sulfanyl acetic acid, Methylethyl phenyl sulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenyl sulfanyl acetic acid, Dimethoxyphenyl sulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenyl sulfanyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthio acetic acid, N-naphthyl glycocoll, naphthoxy acetic acid etc.

Polymerization causes auxiliary agent and can be used alone, and also can combine two or more and use.

When using polymerization to cause auxiliary agent (D1), its use amount preferably relative to total amount 100 mass parts of resin (B) and polymerizable compound (C), is 0.1 ~ 30 mass parts, is more preferably 1 ~ 20 mass parts.When the amount of polymerization initiation auxiliary agent (D1) is within the scope of this, has and can form pattern with high sensitivity further, make the trend that the throughput rate of pattern improves.

Photosensitive composition of the present invention comprises ultraviolet light absorber (E).Comprise ultraviolet light absorber by photosensitive composition, film or the pattern of excellent heat resistance can be formed with high-contrast.As ultraviolet light absorber (E), preferably there is between 250 ~ 450nm the ultraviolet light absorber of the maximal value of absorbance, be preferably dissolved in the ultraviolet light absorber of organic solvent further.

As ultraviolet light absorber (E), such as, can enumerate: benzophenone series ultraviolet light absorber, benzoic ether system ultraviolet light absorber, benzotriazole system ultraviolet light absorber, triazine system ultraviolet light absorber and acrylic acid cyano group ester system ultraviolet light absorber.

Benzophenone series ultraviolet light absorber is the compound with benzophenone structural, such as, be the compound shown in formula (a).

[in formula (a), Q ¹and Q ²represent halogen atom, hydroxyl, carboxyl, sulfo group ,-Q independently of each other ³,-OQ ³,-SO ₂q ³,-CO-OQ ³, amino or-NQ ³q ⁴.

P represents the integer of 0 ~ 5.When P is more than 2, multiple Q ¹can be identical or different.

Q ³the alkyl that expression can have substituent carbon number 1 ~ 20, the aryl can with substituent carbon number 6 ~ 10 maybe can have the aralkyl of substituent carbon number 7 ~ 10.

Q ⁴represent hydrogen atom, the alkyl of substituent carbon number 1 ~ 20 can be had, the aralkyl that the aryl of substituent carbon number 6 ~ 10 maybe can have substituent carbon number 7 ~ 10 can be had.

Q represents the integer of 0 ~ 4.When q is more than 2, multiple Q ²can be identical or different.]

As halogen atom, can enumerate: fluorine atom, chlorine atom, bromine atoms, atomic iodine etc.

As the alkyl of carbon number 1 ~ 20, can enumerate: methyl, ethyl, propyl group, isopropyl, butyl, hexyl, octyl group, decyl, dodecyl, octadecyl, eicosyl etc.

As the aryl of carbon number 6 ~ 10, can enumerate: phenyl, tolyl, xylyl, sym-trimethyl benzene base, ethylphenyl, butyl phenyl etc.

As the aralkyl of carbon number 7 ~ 10, can enumerate: benzyl, phenylethyl, phenyl butyl etc.

As-OQ ³, can enumerate: methoxyl, ethoxy, propoxyl group, isopropoxy, butoxy, own oxygen base, octyloxy, the last of the ten Heavenly stems oxygen base, dodecyloxy, octadecane oxygen base, the alkoxy such as eicosane oxygen base; The aryloxy group such as phenoxy group, toloxyl, xylyloxy; The aralkoxies etc. such as benzyloxy, phenyl ethoxy base.

As-SO ₂q ³, can enumerate: methyl sulphonyl, ethylsulfonyl, decyl sulfonyl, phenyl sulfonyl, benzylsulphonyl etc.

As-CO-OQ ³, can enumerate: methoxycarbonyl, ethoxy carbonyl, hexyloxy carbonyl, carbonyl octyloxy, phenyloxycarbonyl, benzyloxycarbonyl etc.

As-NQ ³q ⁴, can enumerate: dimethylamino, diethylamino, phenyl amino, benzylamino etc.

As the substituting group that abovementioned alkyl, above-mentioned aryl and above-mentioned aralkyl can have, can enumerate: the alkoxy of hydroxyl, carboxyl, carbon number 1 ~ 6, the acyloxy etc. of carbon number 2 ~ 6.

As the acyloxy of carbon number 2 ~ 6, can enumerate: acetoxyl group, propionyloxy, penta acyloxy, acryloxy, methacryloxy.

As Q ¹and Q ², preferred hydroxyl ,-OQ ³, more preferably-OQ ³.

As benzophenone series ultraviolet light absorber, such as, can enumerate the compound shown in following formula.

[in formula, Q ¹⁰⁰⁰represent the alkyl of hydrogen atom or carbon number 1 ~ 20.]

As benzophenone series ultraviolet light absorber, such as, can enumerate: 2,4-DihydroxyBenzophenone, ESCALOL 567, 2-hydroxyl-4-octyloxybenzophenone, 2-hydroxyl-4-oxygen in last of the ten Heavenly stems base benzophenone, 2-hydroxyl-4-dodecyloxy benzophenones, 2-hydroxyl-4-behzyloxybenzophenone, 2-hydroxyl-4-(2-hydroxy-3-methyl acryloxy propoxyl group) benzophenone, 2-hydroxyl-4-methoxyl-5-diphenylsulfone ketone trihydrate, 2-hydroxyl-4-methoxyl-2 '-carboxyl benzophenone, 2-hydroxyl-4-octadecane oxygen base benzophenone, 2-hydroxyl-4-diethylamino-2 '-hexyloxy carbonyl benzophenone, 2,2 '-dihydroxy-4-methoxy benzophenones, BP-2, 2,2 '-dihydroxy-4,4 '-dimethoxy-benzophenone, 2-hydroxyl-4-octyloxybenzophenone, 2-hydroxyl-4-methoxyl-5-diphenylsulfone ketone, hexyl-2-(4-diethylamino-2-hydroxy benzoyl) benzoic ether and Isosorbide-5-Nitrae-bis-(4-benzoyl-3-hydroxyphenoxy) butane.In addition, as the commercially available product of 2,4-DihydroxyBenzophenone, can enumerate: ASL-23 (Xiang Nan chemical company system), Seesorb100 (shiraishi calcium Inc.), ジスライザ mono-O (tri-Association changes into Inc.), Sumisorb100 (sumitomo chemical company system), DHBP (Eastman Chemical's system), Biosorb100 (common drug company system), Uvinul-400 (BASF AG's system) etc., as the commercially available product of ESCALOL 567, can enumerate: ASL-23 (Xiang Nan chemical company system), CyasorbUV-9 (Cytec Inc.), ジスライザ mono-M (tri-Association changes into Inc.), Sumisorb100 (sumitomo chemical company system), Seesorb101 (shiraishi calcium Inc.), Biosorb110 (common drug company system), Uvinul-M-40 (BASF AG's system), Eusolex4360 (MerckJapan Inc.), as the commercially available product of 2-hydroxyl-4-octyloxybenzophenone, can enumerate: CyasorbUV-531 (Cytec Inc.), Seesorb102 (shiraishi calcium Inc.), ジスライザ mono-E (tri-Association changes into Inc.), Sumisorb130 (sumitomo chemical company system), Seesorb130 (shiraishi calcium Inc.), Biosorb130 (common drug company system), Advastab-46, Adecastab1413 (Adeca Inc.), as the commercially available product of 2-hydroxyl-4-dodecyloxy benzophenones, DOPB (Eastman Chemical's system) can be enumerated, as 2, the commercially available product of 2 '-dihydroxy-4-dimethoxy-benzophenone, can enumerate CyasorbUV-24 (Cytec Inc.).As 2; 2 '-dihydroxy-4; the commercially available product of 4 '-methoxy benzophenone; can enumerate: ASL-40 (Xiang Nan chemical company system), Uvinul-D-49 (BASF AG's system); as the commercially available product of 2-hydroxyl-4-methoxyl-5-diphenylsulfone ketone; Uvinu1-MS-40 (BASF AG's system) can be enumerated; as the commercially available product of two (2-methoxyl-4-hydroxyl-5-benzoylphenyl) methane, AdecastabLA-51 (Adeca Inc.) can be enumerated.

Benzoic ether system ultraviolet light absorber is the compound with phenylamino benzoic acid ester structure, such as, be the compound shown in formula (b).

[in formula (b), Q ⁵~ Q ⁹represent the alkyl of hydrogen atom or carbon number 1 ~ 8 independently of each other

As the alkyl of carbon number 1 ~ 8, can enumerate: methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, sec-butyl, the tert-butyl group, hexyl, 1-methyl amyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, octyl group, iso-octyl, tertiary octyl group, 2-ethylhexyl etc., preferred branched-chain alkyl, the more preferably tert-butyl group.

As benzoic ether system ultraviolet light absorber, such as, can enumerate: 2,4-di-tert-butyl-phenyl 3,5-di-tert-butyl-4-hydroxybenzoic acid ester.As commercially available product, can enumerate: Tinuvin120 (CibaJapan Inc.), Sumisorb400 (sumitomo chemical company system).

As benzotriazole system ultraviolet light absorber, such as can enumerate: 2-(2H-benzotriazole-2-base)-4, two (1-methyl isophthalic acid-phenylethyl) phenol of 6-, 2-(5-methyl-2-hydroxy phenyl) benzotriazole, 2-(3, 5-di-t-butyl-2-hydroxy phenyl) benzotriazole, 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, 2-(3, 5-di-t-butyl-2-hydroxy phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-5-octyl phenyl) benzotriazole, 2-(3, 5-bis-tertiary pentyl-2-hydroxy phenyl) benzotriazole, 2-[2-hydroxyl-3, two (the α of 5-, α-dimethylbenzyl) phenyl]-2H-benzotriazole, and [methyl-3-[the 3-tert-butyl group-5-(2H-benzotriazole-2-base)-4-hydroxy phenyl] propionic ester-polyglycol] condensation product etc.

As triazine system ultraviolet light absorber, such as can enumerate: 2, 4-diphenyl-6-(2-hydroxyl-4-methoxyphenyl)-1, 3, 5-triazine, 2, 4-diphenyl-6 '-(2-hydroxyl-4-ethoxyl phenenyl)-1, 3, 5-triazine, 2, 4-diphenyl-(2-hydroxyl-4-propoxyphenyl)-1, 3, 5-triazine, 2, 4-diphenyl-(2-hydroxyl-4-butoxy phenyl)-1, 3, 5-triazine, 2, 4-diphenyl-6-(2-hydroxyl-4-butoxy phenyl)-1, 3, 5-triazine, 2, 4-diphenyl-6-(2-hydroxyl-4-Hexyloxy-phenyl)-1, 3, 5-triazine, 2, 4-diphenyl-6-(2-hydroxyl-4-octyloxyphenyl)-1, 3, 5-triazine, 2, 4-diphenyl-6-(2-hydroxyl-4-dodecyloxy phenyl)-1, 3, 5-triazine, 2, 4-diphenyl-6-[2-hydroxyl-4-benzyloxy-phenyl)-1, 3, 5-triazine, and 2, 4-diphenyl-6-(2-hydroxyl-4-Butoxyethoxy)-1, 3, 5-triazine etc.

As acrylic acid cyano group ester system ultraviolet light absorber, such as, can enumerate: 2-ethylhexyl-2-cyano group-3,3 '-diphenylacrylate ester and ethyl-2-cyano group-3,3 '-diphenylacrylate ester etc.

As ultraviolet light absorber (E), preferred benzophenone series ultraviolet light absorber and benzoic ether system ultraviolet light absorber.During for these ultraviolet light absorbers, can form film or the pattern of excellent heat resistance with high-contrast, in addition, the foreign matter of generation is also few.

The content of ultraviolet light absorber (E) is preferably more than 0.1 mass parts relative to total amount 100 mass parts of resin (B) and polymerizable compound (C) and below 20 mass parts, be more preferably more than 0.5 mass parts and below 15 mass parts, be more preferably more than 1 mass parts and below 10 mass parts.The content of ultraviolet light absorber, when above-mentioned scope, has the trend that the contrast of film while the developability that maintenance is good is also high, therefore preferably.

Preferred photosensitive composition of the present invention comprises solvent (F).

Solvent (F) is not particularly limited, and can be used in the normally used solvent in this field.Such as can from ester solvent (comprise-COO-structure and do not comprise the solvent of-O-structure in molecule), ether solvents (comprise-O-structure and do not comprise the solvent of-COO-structure in molecule), ether-ether solvent (comprising the solvent of-COO-structure and-O-structure in molecule), ketone solvent (comprise-CO-structure and do not comprise the solvent of-COO-structure in molecule), alcoholic solvent (comprises OH base and does not comprise-O-structure in molecule, the solvent of-CO-structure and-COO-structure), aromatic hydrocarbon solvents, amide solvent, choice for use in dimethyl sulfoxide (DMSO) etc.

As ester solvent, can enumerate: methyl lactate, ethyl lactate, butyl lactate, 2-hydroxy-methyl isobutyl acid, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, adnoral acetate, gamma-butyrolacton etc.

As ether solvents, can enumerate: glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxyl-n-butyl alcohol, 3-methoxyl-3-methyl butanol, tetrahydrofuran, oxinane, 1, 4-diox, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol MEE, diethylene glycol dipropyl ether, dibutyl ethylene glycol ether, methyl phenyl ethers anisole, phenetol, methylanisole etc.

As ether-ether solvent, can enumerate: methoxy menthyl acetate, ethyl methoxyacetate, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, 2-methoxy methyl propionate, 2-methoxypropionate, 2-methoxy propyl propyl propionate, 2-ethoxypropanoate, 2-ethoxyl ethyl propionate, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester, 3-methoxybutyl acetic acid esters, 3-methyl-3-methoxybutyl acetic acid esters, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetic acid esters, butyl carbitol acetate etc.

As ketone solvent, can enumerate: 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-HEPTANONE, 3-heptanone, 4-heptanone, 4-methyl-2 pentanone, cyclopentanone, cyclohexanone, isophorone etc.

As alcoholic solvent, can enumerate: methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerine etc.

As aromatic hydrocarbon solvents, can enumerate: benzene,toluene,xylene, sym-trimethyl benzene etc.

As amide solvent, can enumerate: DMF, DMA, 1-METHYLPYRROLIDONE etc.

These solvents can be used alone, and also can combine two or more and use.

In above-mentioned solvent, from the viewpoint of coating, drying property, the boiling point preferably under 1atm is more than 120 DEG C and the organic solvent of less than 180 DEG C.Wherein, preferred propylene glycol methyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxyl ethyl propionate, glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetic acid esters, 3-methoxyl-n-butyl alcohol, 4-hydroxy-4-methyl-2-pentanone, N, dinethylformamide etc., more preferably propylene glycol methyl ether acetate, ethyl lactate, 4-hydroxy-4-methyl-2-pentanone, 3-methoxybutyl acetic acid esters, 3-methoxyl-n-butyl alcohol, 3-ethoxyl ethyl propionate etc.

The content of the solvent (F) in photosensitive composition, relative to the total amount of photosensitive composition of the present invention, is generally 70 ~ 95 quality %, is preferably 75 ~ 92 quality %.In other words, the solid constituent of photosensitive composition is preferably 5 ~ 30 quality %, is more preferably 8 ~ 25 quality %.The content of solvent (F), when above-mentioned scope, has following trend: flatness during coating becomes good, and in addition, because the colour saturation when forming color filter can be abundant, therefore, display characteristic becomes good.

Surfactant (G) can also be comprised at photosensitive composition of the present invention.As surfactant (G), can enumerate: silicone-based surfactant, fluorine system surfactant and there is the silicone-based surfactant etc. of fluorine atom.These also can have polymerizable group on side chain.

As silicone-based surfactant, the surfactant etc. with siloxane bond can be enumerated.Specifically, can enumerate: ToraySilicone (trade name) DC3PA, ToraySiliconeSH7PA, ToraySiliconeDCIIPA, ToraySiliconeSH21PA, ToraySiliconeSH28PA, ToraySiliconeSH29PA, ToraySiliconeSH30PA, ToraySilicone8400 (eastern beautiful DOW CORNING (strain) system), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (PerformanceMaterialJapan contract Inc.) etc.

As above-mentioned fluorine system surfactant, the surfactant etc. with fluorocarbon chain can be enumerated.Specifically, can enumerate: Fluorad (registered trademark) FC430, FluoradFC431 (Sumitomo 3M strain) makes), Megafac (registered trademark) F142D, MegafacF171, MegafacF172, MegafacF173, MegafacF177, MegafacF183, MegafacF554, MegafacR30, MegafacRS-718-K (DIC (strain) system), Ftop (registered trademark) EF301, FtopEF303, FtopEF351, FtopEF352 (Mitsubishi Materials electronics changes into (strain) system), Surflon (registered trademark) S381, SurflonS382, SurflonSC101, SurflonSC105 (Asahi Glass (strain) system), E5844 ((strain) (research of great Jin fine chemistry is made) etc.

As the above-mentioned silicone-based surfactant with fluorine atom, the surfactant etc. with siloxane bond and fluorine carbon can be enumerated.Specifically, can enumerate: Megafac (registered trademark) R08, MegafacBL20, MegafacF475, MegafacF477, MegafacF443 (DIC (strain) system) etc.

These surfactants can be used alone, and also can combine two or more and use.

The content of surfactant (G) is preferably more than 0.001 quality % and below 0.2 quality % relative to the total amount of photosensitive composition of the present invention, be preferably more than 0.002 quality % and below 0.1 quality %, be more preferably more than 0.01 quality % and below 0.05 quality %.In addition, this content does not comprise the content of above-mentioned pigment dispersing agent.When the content of surfactant (G) is in above-mentioned scope, the flatness of color filter can be made good.

Photosensitive composition of the present invention also can comprise the known various adjuvant (following, to be sometimes referred to as " other composition ") in this technical field such as filling agent, other macromolecular compound, closely sealed promoter, antioxidant, light stabilizer, chain-transferring agent as required.

Photosensitive composition of the present invention such as can pass through mixed colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D) and ultraviolet light absorber (E) and prepared by polymerization initiation auxiliary agent (D1) used as required, solvent (F), surfactant (G) and other composition.

When comprising pigment (A2), preferably pigment (A2) being mixed with the solvent (F) of part or all in advance, re-using the degree that mean grain size that ball mill etc. carries out being dispersed to pigment is less than 0.2 μm.Now, part or all of above-mentioned pigment dispersing agent, resin (B) can also be coordinated as required.In the dispersible pigment dispersion obtained, mix remaining composition etc. with the concentration specified, target coloration photosensitive polymer combination can be prepared.

Dyestuff (A1) is preferably dissolved in the solvent (F) of part or all in advance prepares solution.Preferably use this solution of metre filter in about 0.01 ~ 1 μm, aperture.

Preferably with the photosensitive composition that the metre filter in about 0.01 ~ 10 μm, aperture is as above mixed with.

As the method utilizing photosensitive composition of the present invention to form the pattern of color filter, can enumerate: the method etc. of photoetching process and use ink-jet apparatus.Photoetching process is such as following method: be coated on substrate by photosensitive composition of the present invention, by making its drying form coloring compositions nitride layer except modes such as desolventizing volatile ingredients, via photomask, exposure is carried out to this coloring compositions nitride layer again, develop.

After development, heat as required, thus, can colored pattern be formed.In above-mentioned photoetching process, by not using photomask when exposing and/or do not develop, the solidfied material of above-mentioned coloring compositions nitride layer can be formed, i.e. painted film.Therefore, the colored pattern obtained and painted film can be made color filter.

As substrate, quartz glass, pyrex, alumina silicate glass, the glass plate such as soda-lime glass be coated with by surface silica dioxide or polycarbonate, polymethylmethacrylate, pet resin plate, silicon can be used, on aforesaid substrate, form the substrate of aluminium, silver, silver/copper/palldium alloy film etc.These substrates also can be formed other color filter layer (such as utilizing the color filter layer etc. that photosensitive composition is formed on substrate), resin bed, transistor, circuit etc.

The thickness of the pattern made is not particularly limited, and according to the suitable adjustment such as material, purposes used, such as, can be 0.1 ~ 30 μm, be preferably 1 ~ 20 μm, more preferably 1 ~ 6 μm.

Specifically, the known methods such as photoetching technique each pixel on glass substrate 21 is utilized to form multiple TFT22 (with reference to Fig. 1).TFT22 by glass substrate 21, such as utilize molybdenum (Mo) to be formed and form the gate electrode 22a of a part for gate line, formed on this gate electrode 22a by such as nitride film (SiN _x) and oxide film (SiO ₂) stacked film form gate insulating film 22b, this gate insulating film 22b on formed polysilicon film 22c, by such as oxide film (SiO ₂) and nitride film (SiN _x) stacked film formed diaphragm 22d form.The region opposed with the gate electrode 22a of polysilicon film 22c is the channel region of TFT22, and in addition, the region of the both sides of this channel region is source region or drain region.The source region of polysilicon film 22c is electrically connected with utilizing the signal wire 27 that such as aluminium (Al) is formed via connecting hole (contacthole) set on diaphragm 22d.In addition, the drain region of polysilicon film 22C is electrically connected with pixel electrode 24 via connecting hole (contact hole) 201 as described later.

When on glass substrate 21, every pixel forms multiple TFT22, while glass substrate 21 forms TFT22, formation alignment mark [not shown).This alignment mark is the benchmark of the contraposition as described later in the formation process of color filter layer 23.In addition, these alignment marks also can be also used as the mark of the benchmark becoming the laminating driving substrate and counter substrate.When alignment mark forms the metal levels such as distribution or polysilicon layer in the manufacturing process of TFT22, at least utilize its one deck and formed in same operation.

Then, TFT22 and be formed with alignment mark glass substrate 21 on be coated with photosensitive composition of the present invention, remove the volatile ingredients such as desolventizing by heat drying (prebake) and/or drying under reduced pressure and make it dry, forming coloring compositions nitride layer.

As coating process, spin-coating method, slot coated method, slit and spin-coating method etc. can be enumerated.

Carry out the temperature preferably 30 ~ 120 DEG C during heat drying, more preferably 60 ~ 110 DEG C.In addition, as the heat time, be preferably 10 seconds ~ 60 minutes, be more preferably 30 seconds ~ 30 minutes.

When carrying out drying under reduced pressure, preferably carry out under the pressure of 50 ~ 150Pa, under the temperature range of 20 ~ 25 DEG C.

Then, via photomask (not shown) facing to colour cell compound layer irradiation ultraviolet radiation, recycling developer solution selectivity removes unwanted part (unexposed portion), thus, obtaining being formed with the laggard row washing of coloring compositions nitride layer formed thereby in the pixel of the connecting hole (contact hole) 201 of the drain region arriving polysilicon film 22c.

By development, the unexposed portion of coloring compositions nitride layer is dissolved in developer solution and is removed.As developer solution, such as, can enumerate: the aqueous solution of the alkali compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethyl ammonium hydroxide.Concentration in the aqueous solution of these alkali compounds is preferably 0.01 ~ 10 quality %, more preferably 0.03 ~ 5 quality %.And then developer solution also can comprise surfactant.

Developing method can be any one in paddle method, infusion process and spraying etc.And then, substrate can be tilted to arbitrarily angled when developing.

Then, flow again (backflow) to make the coloring compositions nitride layer being formed with connecting hole (contact hole) 201 and/or to make in coloring compositions nitride layer contained curability composition (polymerizable compound etc.) solidification, such as 100 ~ 300 DEG C, preferably at the temperature of 150 ~ 230 DEG C, heat such as 1 ~ 120 minute, preferably 10 ~ 60 minutes.Therefore, the photosensitive composition layer 23A as colored pattern is formed.23A is corresponding with color filter of the present invention for this photosensitive composition layer.

Repeat this operation, photosensitive composition layer 23A is formed respectively by red colored photosensitive polymer combination, green coloring photosensitive polymer combination and blue-colored photosensitive polymer combination, thus, each photosensitive composition layer 23A becomes the color filter layer 23 (with reference to Fig. 2) that comprise Red lightscreening plate 23a, green color filter 23b and blue color filter 23c corresponding with each pixel column.Region between each optical filter of color filter layer 23 becomes the Mixed Zone of adjacent color, but this region is the lightproof area opposed with signal wire 27, therefore, particularly no problem in quality.In addition, the region between this each optical filter also can not be colored.

Next, in order to such as utilize spin-coating method to cover color filter layer 23, the photosensitive resin film 29 as the such as diaphragm of thickness 0.3 ~ 2.0 μm is formed.Then, via photomask (not shown) to photosensitive resin film 29 irradiation ultraviolet radiation, and then, utilize developer solution selectivity to remove the region corresponding with connecting hole 201 and unwanted part, wash after the connecting hole (contact hole) 202 forming the drain region arriving polysilicon film 22c thus.Then, in order to make photosensitive resin film 29 flow again (backflow), preferably the scope of 100 ~ 300 DEG C temperature, such as heat at 200 DEG C.Then, in order to remove residue and the organism such as the dyestuff of accumulation in contact hole 202, the etching utilizing oxygen plasma is carried out, and then, in order to remove the oxide film utilizing oxygen plasma to be formed, utilize such as rare fluoric acid to etch.

Then, photosensitive resin film 29 utilize such as sputtering method form transparent conductive material, such as ITO (Indium-TinOxide: the oxide hybrid films of indium and tin), utilize photoetching technique and etching to carry out patterning to this ito film, form transparent pixel electrode 24 (with reference to Fig. 3).In addition, this pixel electrode 24 also can pass through the device of making and utilize the metal such as aluminium (Al) or silver (Ag) to be formed.Then, after forming alignment film by known method, by carrying out the laminating of this driving substrate and counter substrate, liquid crystal indicator can be manufactured.

According to photosensitive composition of the present invention, the color filter of particularly contrast excellence can be made.This color filter is useful as the color filter used in display device (such as liquid crystal indicator, organic el device and solid-state imager etc.).

Embodiment

Below, by embodiment, photosensitive composition of the present invention is described in more detail.

" % " and " part " in example unless otherwise specified, is quality % and mass parts.

In following synthesis example, compound is by ultimate analysis (VARlO-EL; (Elementar (strain) system)) identify.

[synthesis example 1]

15 parts, the potpourri (middle tank formation system) of the compound shown in throw-in type (A0-1) and the compound shown in formula (A0-2), chloroform 150 parts and N in the flask having condenser pipe and stirring apparatus, dinethylformamide 8.9 parts, limit under agitation maintains 20 DEG C to be added dropwise to thionyl chloride 10.9 parts below.After dropping terminates, be warming up to 50 DEG C, within 5 hours, react in synthermal lower maintenance, then, be cooled to 20 DEG C.While cooled reaction solution is under agitation maintained 20 DEG C to be added dropwise to the mixed liquor of 2-DEHA 12.5 parts and triethylamine 22.1 parts below.Then, within 5 hours, react in synthermal lower stirring.Then, after the reaction mixture rotary evaporation column distillation removing obtained is dissolved, add a small amount of methyl alcohol and carry out high degree of agitation.This potpourri is joined while stirring in the mixed liquor of ion exchange water 375 parts, make crystallization.Filter out the crystallization of precipitation, fully clean with ion exchange water, at 60 DEG C, carry out drying under reduced pressure, obtain dyestuff A1 (dyestuff A1) (potpourri of the compound shown in formula (A1-1) ~ formula (A1-8)) 11.3 parts.

[synthesis example 2)

Compound shown in hybrid under dark conditions (1x) 20 parts and N-methyl ortho-aminotoluene (pharmaceutical worker industry (strain) system pure with light) 200 parts, stir the solution obtained 6 hours at 110 DEG C.After the reactant liquor obtained is cooled to room temperature, is added in the mixed liquor of 800 parts, water, 35% hydrochloric acid 50 parts and also at room temperature stirs 1 hour, result, crystallization.Carry out drying after the crystallization of precipitation being obtained with the form of the residue of suction filtration, obtain the compound shown in formula (1-31) 24 parts.Yield is 80%.

The structure of the compound shown in formula (1-31) is by quality analysis (LC; Agilent system 1200 type, MASS; Agilent LC/MSD type) confirm.

(quality analysis) ionization mode=ESI+:m/z=[M+H] ⁺603.4

ExactMass：602.2

[synthesis example 3]

Use N-propyl group-2,6-xylidin to replace N-ethyl-ortho-toluidine, in addition, obtain the compound shown in formula (1-39) in the same manner as synthesis example 1.

The qualification of the compound shown in formula (1-39)

(quality analysis) ionization mode=ESI+:m/z=[M+H] ⁺659.9

ExactMass：658.9

[synthesis example 4)

In the beaker having reflux condenser, titration funnel and stirring machine, form nitrogen atmosphere with 0.02L/ minute flowing nitrogen, add 3-methoxyl-n-butyl alcohol 200 mass parts and 3-methoxybutyl acetic acid esters 105 mass parts, be heated to 70 DEG C while stirring.Then, methacrylic acid 60 mass parts, 3,4-epoxy three ring [5.2.1.0 are dissolved in ^2.6] prepare solution in decyl acrylate (with the compound shown in mol ratio 50: 50 hybrid (1-1) and the compound shown in formula (II-1)) 240 mass parts and 3-methoxybutyl acetic acid esters 140 mass parts, being used by this solution titration funnel to be added drop-wise to insulation through 4 hours is in the beaker of 70 DEG C.

On the other hand, will dissolve polymerization initiator 2, two (2,4-methyl pentane nitrile) 30 mass parts of 2 '-azo, in the solution of 3-methoxybutyl acetic acid esters 225 mass parts, use other titration funnel to be added drop-wise in beaker through 4 hours.After the dropping of the solution of polymerization initiator terminates, keep 4 hours at 70 DEG C, then, be cooled to room temperature, obtaining weight-average molecular weight Mw is 1.3 × 10 ⁴, molecular weight distribution is 2.5, solid constituent is 33 quality %, solution acid number is 34mg-KOH/g resin B 1 solution.Calculated by above-mentioned solid constituent and solution acid number, the solid constituent acid number of resin B 1 is 100mg-KOH/g.Resin B 1 has following shown structural unit.

[synthesis example 5]

Having stirring machine, thermometer, reflux condensing tube, propylene glycol methyl ether acetate 182g is imported in the beaker of titration funnel and nitrogen ingress pipe, after atmosphere in beaker is become nitrogen from air, be warming up to 100 DEG C, by benzyl methacrylate 70.5g (0.40 mole), methacrylic acid 43.0g (0.5 mole), drip in the potpourri that dicyclopentenyl methyl acrylate (Hitachi changes into (strain) FA-513M processed) 22.0g (0.10 mole) and propylene glycol methyl ether acetate 136g is formed and be added with 2, the solution of 2 '-azobis isobutyronitrile 3.6g, continue again to stir at 100 DEG C.

Then, atmosphere in beaker is become air from nitrogen, glycidyl methacrylate 35.5g [0.25 mole, (be 50 % by mole relative to the carboxyl of methacrylic acid used in this reaction)], three dimethylaminomethyl phenol 0.9g and quinhydrones 0.145g are put in beaker, at 110 DEG C, continue reaction, obtain resin B 2 solution that solid constituent is 29%, solid constituent acid number is 79mgKOH/g.The weight-average molecular weight of the polystyrene conversion measured by GPC is 30,000.

[synthesis example 6]

In the beaker having reflux condenser, titration funnel and stirring machine, form nitrogen atmosphere with 0.02L/ minute flowing nitrogen, add ethyl lactate 305 mass parts, be heated to 70 DEG C while stirring.Then, acrylic acid 46 mass parts, 3,4-epoxy radicals three ring [5.2.1.0 are dissolved in ^2.6] decyl acrylate (with the compound shown in mol ratio 50: 50 hybrid (1-1) and the compound shown in formula (11-1)) 240 mass parts and ethyl lactate 185 mass parts and prepare solution, being used by this solution titration funnel to be added drop-wise to insulation through 4 hours is in the beaker of 70 DEG C.

On the other hand, by solvent polymerization initiating agent 2, the two solution of (2,4-methyl pentane nitrile) 30 mass parts in ethyl lactate 225 mass parts of 2 '-azo uses other titration funnel to be added drop-wise in beaker through 4 hours.After the dropping of the solution of polymerization initiator terminates, keep 4 hours at 70 DEG C, then, be cooled to room temperature, obtaining weight-average molecular weight Mw is 9.1 × 10 ³, molecular weight distribution is 2.1, solid constituent is 26 quality %, solid constituent acid number is 120mg-KOH/g resin B 3 solution.Resin B 3 has following shown structural unit.

The weight-average molecular weight (Mw) of the resin obtained in synthesis example and the mensuration of number-average molecular weight (Mn) use GPC method to carry out in following condition.

Device: K2479 ((strain) Shimadzu Seisakusho Ltd. system)

Chromatographic column: SHIMADZUShim-packGPC-80M

Chromatogram column temperature; 40 DEG C

Solvent: THF (tetrahydrofuran >

Flow velocity: 1.0mL/min

Detecting device; RI

Correction standard substance: TSKSTANDARDPOLYSTYRENEF-40, F-4, F-288, A-2500, A-500 (eastern Cao (strain) system)

Using the ratio (Mw/Mn) of the weight-average molecular weight of polystyrene conversion obtained above and number-average molecular weight as molecular weight distribution.

[embodiment 1]

(preparation of photosensitive composition)

By (A) colorant: C.1. pigment blue 15: 633 parts

Acrylic acid series pigment dispersing agent 5 parts

Propylene glycol methyl ether acetate 137 parts mixes, and uses ball mill that pigment is fully disperseed, then, and will

(A) colorant: dyestuff A15 part

(B) resin: resin B 1 solution 150 parts

(C) polymerizable compound: dipentaerythritol acrylate

((KAYARAD (registered trademark) DPHA; Japan's chemical drug (strain) system) 50 parts

(D) polymerization initiator: N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) octane-1-ketone-2-imines

(IRGACURE (registered trademark) OXE01; BASFJapan Inc.) 15 parts

(E) compound shown in ultraviolet light absorber=formula (E1)

(Sumisorb (registered trademark) 130; Sumitomo Chemical (strain) is made) 3 parts

(F) solvent: ethyl lactate 289 parts carries out mixing

Obtain photosensitive composition.

The making > of < colored pattern

At the glass substrate (Eagle2000 that 5cm is square; Corning Inc.) on spin-coating method coating photosensitive composition coating after, at 100 DEG C, prebake obtains coloring compositions nitride layer in 3 minutes.After letting cool, the interval of the substrate and quartz glass photomask that are formed with this coloring compositions nitride layer is set to 100 μm, uses exposure machine (TME-150RSK; Topcon (strain) makes), under air atmosphere, with 150mJ/cm ³exposure (365nm benchmark) carry out illumination and penetrate.As photomask, use the photomask being formed with 100 μm of lines and intermittent pattern, after illumination is penetrated, by postradiation for light coloring compositions nitride layer in the water system developer solution comprising nonionic system surfactant 0.12% and potassium hydroxide 0.04% at 23 DEG C immersion development 80 seconds, after washing, in an oven, at 225 DEG C, carry out prebake 20 minutes, obtain colored pattern.

< determining film thickness >

The thickness of the colored pattern obtained is used determining film thickness device (DEKTAK3; Japan's vacuum technique (strain) system)) measure.Show the result in table 1.

< chromaticity evaluation >

Use colour examining machine (OSP-SP-200; Olympus (strain) makes) light splitting is measured to the pattern obtained, use the characteristic function of illuminant-C to measure the xy chromaticity coordinate (Bx, By) in the XYZ color specification system 1 of CIE and tristimulus values Y.The value larger expression brightness of Y is higher.Show the result in table 1.

< contrast evaluates >

Using photomask when exposing, in addition, operating in the same manner as the making of colored pattern, making painted film.Use contrast meter (CT-1; Hu Ban Motor Corporation system, color evaluating BM-5A; Topcon Inc., light source; F-10, light polarizing film; Kettle slope motor (strain) is made) and blank value is set to 30000 to the painted film mensuration contrast obtained.If the contrast in painted film is high, even if then can say in colored pattern to be high-contrast too.Show the result in table 1.

< Evaluation of Heat Tolerance >

By the film that obtains in an oven, heat 2 hours at 230 DEG C, as described above colourity and brightness are measured.Aberration Δ Eab* is calculated by the colourity before and after heating and lightness.Eab* is less for aberration Δ, and represent that before heating, look change is less, thermotolerance is better.The value of the aberration Δ Eab* tried to achieve is shown in table 1.

[embodiment 2]

The content of (E) ultraviolet light absorber is replaced with 5 parts, in addition, obtains photosensitive composition similarly to Example 1.To the evaluation that this photosensitive composition carries out similarly to Example 1.Show the result in table 1.

[embodiment 3)

The content of (E) ultraviolet light absorber is replaced with 7 parts, in addition, obtains photosensitive composition similarly to Example 1.To the evaluation that this photosensitive composition carries out similarly to Example 1.Show the result in table 1.

[embodiment 4]

Compound (Sumisorb (registered trademark) 400 shown in use formula (E2); Sumitomo Chemical (strain) is made) 3 parts replace the compound shown in formula (E1), in addition, obtain photosensitive composition similarly to Example 1, to the evaluation that this photosensitive composition carries out similarly to Example 1.Show the result in table 1.

[embodiment 5]

The content of (E) ultraviolet light absorber is replaced with 5 parts, in addition, obtains photosensitive composition similarly to Example 4.To the evaluation that this photosensitive composition carries out similarly to Example 1.Show the result in table 1.

[embodiment 6]

The content of (E) ultraviolet light absorber is replaced with 7 parts, in addition, obtains photosensitive composition similarly to Example 4.To the evaluation that this photosensitive composition carries out similarly to Example 1.Show the result in table 1.

[comparative example 1]

By (A) colorant: C.I. pigment blue 15: 620 parts

Acrylic acid series pigment dispersing agent 5 parts

Propylene glycol monomethyl ether 137 parts

Mix, use ball mill that pigment is fully disperseed, then,

By (A) colorant: dyestuff A13.5 part

(B) resin: resin B 2 solution 157 parts

(C) photopolymerizable compound: dipentaerythritol acrylate

(Japanese chemical drug (strain) system) 50 parts

(D) Photoepolymerizationinitiater initiater: OXE-01 (BASFJapan Inc.) 15 parts

(E) solvent: 4-hydroxy-4-methyl-2-pentanone 289

Carry out being obtained by mixing photosensitive composition.To the evaluation that this photosensitive composition carries out similarly to Example 1.Show the result in table 1.

Table 1

[embodiment 7 ~ 19]

Carry out each composition operated similarly to Example 1 with the composition mixing shown in table 2 and table 3, obtain photosensitive composition.

Table 2

Table 3

In table 2 and table 3, (A-1) ¹⁾use and dispersant containing acrylic and (F-1) ³⁾the propylene glycol methyl ether acetate mixing of the amount that hurdle is recorded, the material disperseed in advance.In addition, (F-1) ²⁾hurdle represents the total amount of the propylene glycol methyl ether acetate in the photosensitive composition of preparation.

In addition, in table 2 and table 3, the material that each composition is expressed as follows.

Colorant (A); (A-1); C.I. pigment blue 15: 6 (pigment)

Colorant (A); (1-31); Compound (xanthene dye) shown in formula (1-31)

Colorant (A); (A-3); C.I. acid red 52 (Tokyo changes into industry (strain) system) (xanthene dye)

Colorant (A); (1-39); Compound (xanthene dye) shown in formula (1-39)

Resin (B); (B-3); Resin B 3 represents the mass parts that solid constituent converts in showing.

Polymerizable compound (C); (C-1); Dipentaerythritol acrylate (KAYARAD (registered trademark) DPHA; Japan's chemical drug (strain) system)

Polymerization initiator (D); (D-1); N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) octane-1-ketone-2-imines (IRGACURE (registered trademark) OXE01; BASF society system)

Ultraviolet light absorber (E); (E-1); Compound (Sumisorb130 shown in formula (E1); Sumitomo Chemical (strain) is made)

Ultraviolet light absorber (E); (E-2); Compound (Sumisorb400 shown in formula (E2); Sumitomo Chemical (strain) is made)

Surfactant (G); (G-2) polyether modified silicone oil (ToraySiliconeSH8400; The beautiful DOW CORNING in east (strain) system)

Solvent (F); (F-1); Propylene glycol methyl ether acetate

Solvent (F): (F-2); Ethyl lactate

To the evaluation that the photosensitive composition of embodiment 7 ~ 19 carries out similarly to Example 1.Show the result in table 4 and table 5.

Table 4

Table 5

Can be confirmed by the above results, the color filter display high-contrast utilizing photosensitive composition of the present invention to be formed.

Industrial utilizability

Claims

1. a photosensitive composition, it comprises dyestuff, resin, polymerizable compound, polymerization initiator and ultraviolet light absorber,

Described ultraviolet light absorber is be selected from least one in the group that is made up of benzophenone series ultraviolet light absorber and benzoic ether system ultraviolet light absorber.

2. photosensitive composition as claimed in claim 1, wherein,

The content of described ultraviolet light absorber is below more than 0.1 mass parts 20 mass parts relative to total amount 100 mass parts of resin and polymerizable compound.

3. photosensitive composition as claimed in claim 1, wherein,

Described dyestuff is xanthene dye.

4. photosensitive composition as claimed in claim 1, wherein,

Described photosensitive composition also comprises pigment.

5. photosensitive composition as claimed in claim 1, wherein,

Described resin is alkali soluble resin.

6. photosensitive composition as claimed in claim 1, wherein,

Described polymerizable compound is (methyl) acrylate.

7. a color filter, it utilizes the photosensitive composition described in claim 1 to be formed.

8. a display device, it comprises color filter according to claim 7.