CN104698748A - Coloring composition, colored cured film and display device - Google Patents

Coloring composition, colored cured film and display device Download PDF

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Publication number
CN104698748A
CN104698748A CN201410721122.XA CN201410721122A CN104698748A CN 104698748 A CN104698748 A CN 104698748A CN 201410721122 A CN201410721122 A CN 201410721122A CN 104698748 A CN104698748 A CN 104698748A
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compound
ring
substituted
formula
methyl
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CN104698748B (en
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米田英司
川部泰典
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JSR Corp
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JSR Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Liquid Crystal (AREA)
  • Electroluminescent Light Sources (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

The invention provides a color composition containing a colorant (A), a bonding agent resin (B) and a polymer compound (C); the colorant (A) comprises a compound having a structure represented by formula (1) and a compound having a structure represented by a formula (2); the combined content of the compound having the structure represented by formula (1) and the compound having the structure represented by a formula (2) are above 0.001 mass percentage; in formula (1) and (2), loops Z1 to Z4 mutually independent so as to represent replace or non-replace heterocyclic rings; R1-R6 mutually independent so as to represent a hydrogen atom, a halogen atom or a replace or non-replace alkyl; if R1 to R5 are more than one, they can be same or different; p refers to 1 or 2, when p equal to 1, q refers to an integer above 2, when p=2, the q refers to an integer above 3.

Description

Coloured composition, color solidification film and display element
Technical field
The present invention relates to coloured composition, color solidification film and display element, more specifically, relate to coloured composition, the color solidification film using this coloured composition to be formed and the display element possessing this color solidification film for the formation of the color solidification film used in transmission-type or reflective color liquid crystal display device, solid-state imager, organic EL display element, Electronic Paper etc.
Background technology
When using the sensitivity composition of colored radiation to manufacture color filter, there will be a known coating pigment decentralized on substrate the sensitivity composition of colored radiation and after drying, radioactive ray are irradiated to dry coating (following to become desired pattern form, be called " exposure "), develop, thus obtain the method (for example, referring to patent documentation 1 ~ 2) of assorted pixel.In addition, also there will be a known the method (for example, referring to patent documentation 3) utilizing the optical polymerism composition being dispersed with carbon black to form black matrix".In addition, the colored resin composition that also there will be a known use pigment-dispersing type utilizes ink-jetting style to obtain the method (for example, referring to patent documentation 4) of assorted pixel.
For the coloured composition for the formation of color solidification film, for the object of color solidification film forming more high brightness, have studied and use dyestuff as colorant.Such as, in patent documentation 5, report by using cyanine dyes as colorant, thus obtain the film with excellent brightness.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2-144502 publication
Patent documentation 2: Japanese Unexamined Patent Publication 3-53201 publication
Patent documentation 3: Japanese Unexamined Patent Publication 6-35188 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2000-310706 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2009-235392 publication
Summary of the invention
But, according to the research of the present inventor etc., be aware of for containing cyanine dyes as colorant coloured composition for, the storage stability of coloured composition is sometimes insufficient.
Therefore, problem of the present invention be to provide containing cyanine dyes as colorant, storage stability is good and can form the coloured composition of the color solidification film of high brightness.In addition, problem of the present invention is to provide the color solidification film using this coloured composition to be formed and the display element possessing this color solidification film.
The present inventor etc. conduct in-depth research, and found that by using at least 2 kinds of cyanine compounds as colorant, and it are proportional to control containing of they, can solve above-mentioned problem.
Namely, the invention provides a kind of coloured composition, it is the coloured composition containing (A) colorant, (B) resin glue and (C) polymerizable compound, (A) colorant contains the compound with the structure that following formula (1) represents and the compound with the structure that following formula (2) represents, the content with the compound of the structure that following formula (2) represents is more than 0.001 quality % relative to the compound with the structure that following formula (1) represents and the total content of the compound with the structure that following formula (2) represents.
In addition, the invention provides a kind of colorant, containing having the compound of the structure that following formula (1) represents and having the compound of the structure that following formula (2) represents, the content with the compound of the structure that following formula (2) represents is more than 0.001 quality % relative to the compound with the structure that following formula (1) represents and the total content of the compound with the structure that following formula (2) represents.
(in formula (1),
Ring Z 1with ring Z 2represent substituted or non-substituted heterocycle independently of each other.
P represents 1 or 2.Wherein, when p is 2, multiple R 1and R 2can be the same or different.
R 1~ R 3represent hydrogen atom, halogen atom or substituted or non-substituted alkyl independently of each other.〕
(in formula (2),
Ring Z 3with ring Z 4represent substituted or non-substituted heterocycle independently of each other.
When p is 1, q represents the integer of more than 2, and when p is 2, q represents the integer of more than 3.
R 4~ R 6represent hydrogen atom, halogen atom or substituted or non-substituted alkyl independently of each other.Wherein, multiple R 4and R 5can be the same or different.〕
In addition, the invention provides the color solidification film using above-mentioned coloured composition to be formed and the display element possessing this color solidification film.At this, " color solidification film " refers to each color pixel, black matrix", black separator etc. that use in display element, solid-state imager.
The storage stability of coloured composition of the present invention is good.In addition, if use coloured composition of the present invention, the color solidification film of high brightness can be formed.
Therefore, coloured composition of the present invention is extremely applicable to make the solid-state imagers such as display element, cmos image sensor such as color liquid crystal display device, organic EL display element, Electronic Paper.
Embodiment
Below, the present invention is described in detail.
coloured composition
Below, the constituent of coloured composition of the present invention is described in detail.
-(A) colorant-
It is (following that coloured composition of the present invention contains the compound with the structure that following formula (1) represents, also referred to as " compound (1) ") and there is the compound (hereinafter also referred to as " compound (2) ") of the structure that following formula (2) represents as (A) colorant.
(in formula (1),
Ring Z 1with ring Z 2represent substituted or non-substituted heterocycle independently of each other.
P represents 1 or 2.Wherein, when p is 2, multiple R 1and R 2can be the same or different.
R 1~ R 3represent hydrogen atom, halogen atom or substituted or non-substituted alkyl independently of each other.〕
(in formula (2),
Ring Z 3with ring Z 4represent substituted or non-substituted heterocycle independently of each other.
When p is 1, q represents the integer of more than 2, and when p is 2, q represents the integer of more than 3.
R 4~ R 6represent hydrogen atom, halogen atom or substituted or non-substituted alkyl independently of each other.Multiple R 4and R 5can be the same or different.〕
Ring Z 1~ ring Z 4in heterocycle can be monocyclic type heteroaromatic, also can be polycyclic heterocycle.Heterocycle can be unsaturated ring also can be saturated rings, can have the heteroatoms (such as, nitrogen-atoms, oxygen atom, sulphur atom) of of the same race or different types of more than 2 in addition in ring.Such as can enumerate the nitrogenous ester ring type heterocycles such as pyrrolidine ring, pyrazoline ring, morpholine ring, thiomorpholine ring, piperidine ring, piperazine ring, homopiperazine ring, tetrahydropyrimidine ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, quinoline ring, isoquinoline ring, phthalazines ring, quinoxaline ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, benzothiazole ring, azoles ring, indole ring, indazole ring, benzimidazole ring, benzo the nitrogenous heteroaromatics such as azoles, phthalimide ring, other the heteroaromatic such as thiphene ring, furan nucleus, purine ring.Wherein, preferred nitrogenous heteroaromatic, more preferably indole ring, benzo azoles ring, benzothiazole ring, further preferred indole ring.
P represent 1 or 2, p be preferably 1.
When p is 1, q represents the integer of more than 2, but is preferably 2 or 3, is more preferably 2.In addition, when p is 2, q represents the integer of more than 3, but is preferably 3.
As the combination of p and q, preferred p is 1, and q is more than 2, and more preferably p is 1, and q is 2.
As R 1~ R 6in halogen atom, such as can enumerate fluorine atom, chlorine atom, bromine atoms.
As R 1~ R 6in alkyl, such as can enumerate aliphatic alkyl, ester ring type alkyl, aromatic hydrocarbyl.
Aliphatic alkyl can be saturated also can be unsaturated, such as, can enumerate alkyl, thiazolinyl, alkynyl.The carbon number of these aliphatic alkyls is preferably 1 ~ 30, is more preferably 1 ~ 24, is particularly preferably 1 ~ 20.In addition, these aliphatic alkyls can be straight-chain also can be branched.Specifically, as alkyl, such as, can enumerate methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, sec-butyl, the tert-butyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, 1-methyldecyl, dodecyl, 1-methyl dodecyl, 1-ethyl decyl, tridecyl, myristyl, tertiary dodecyl, pentadecyl, 1-heptyl octyl group, cetyl, octadecyl, heneicosane-1-base, docosane-1-base, tricosane-1-base, lignocerane-1-base etc.As thiazolinyl, such as can enumerate vinyl, 1-propenyl, 2-propenyl, 1-butenyl group, 2-butenyl group, 1,3-butadiene base, 1-pentenyl, 2-pentenyl, 1-hexenyl, 2-ethyl-2-butenyl group, 2-octenyl, (4-vinyl)-5-hexenyl, 2-decene base etc.In addition, as alkynyl, such as, can enumerate ethinyl, 1-propinyl, 1-butynyl, 1-pentynyl, 3-pentynyl, 1-hexin base, 2-ethyl-2-butynyl, 2-octyne base, (4-ethinyl)-5-hexin base, 2-decynyl etc.
As ester ring type alkyl, the ester ring type alkyl of preferred carbon number 3 ~ 30.Ester ring type alkyl can be saturated also can be unsaturated, such as, can enumerate naphthenic base, cycloalkenyl group, fused polycycle alkyl, bridged cyclic hydrocarbon group, volution alkyl, cyclic terpene alkyl etc.More specifically, the naphthenic base such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, tert-butylcyclohexyl, suberyl, ring octyl group can be enumerated; The cycloalkenyl groups such as 1-cyclohexenyl group; The fused polycycle alkyl such as three ring decyls, decahydro-2-naphthyl, adamantyl; Three ring [5.2.1.0 2,6] bridged cyclic hydrocarbon group such as decane-8-base, pentacyclopentadecandimethanol base, isobornyl, dicyclopentenyl, three cyclopentenyls; From volution alkyl such as the 1 valency groups that spiral shell [3,4] heptane, spiral shell [3,4] octane remove 1 hydrogen atom and obtain; From to the Meng alkane, sabinane, removing 1 hydrogen atom such as carane and the cyclic terpene alkyl etc. such as the 1 valency group that obtains.In above-mentioned naphthenic base and cycloalkenyl group, more preferably carbon number is 3 ~ 12.
As aromatic hydrocarbyl, the aromatic hydrocarbyl of preferred carbon number 6 ~ 20, the more preferably aromatic hydrocarbyl of carbon number 6 ~ 10.As aromatic hydrocarbyl, such as, aryl can be enumerated.At this, in this instructions, " aryl " refers to monocycle ~ three-ring type aromatic hydrocarbyl, specifically, can enumerate phenyl, benzyl, o-tolyl, a tolyl, p-methylphenyl, xylyl, naphthyl, naphthyl, anthryl, phenanthryl, Azulene base, 9-fluorenyl etc.
As ring Z 1~ ring Z 4heterocycle and R 1~ R 6the substituting group of alkyl, halogen atom, hydroxyl, cyano group, formoxyl, carboxyl, nitro, amino, dialkyl amido, ammonia diaryl base, alkoxy, aryloxy group, alkoxy carbonyl, alkyl sulfenyl, artyl sulfo, trialkylsilkl, sulfydryl, allyl, alkyl sulphonyl, alkylsulfamoyl group, aliphatic alkyl, heterocyclic radical, aromatic hydrocarbyl etc. can be enumerated.
The compound with the structure that formula (1) represents preferably has the compound of the structure that following formula (1A) represents (hereinafter also referred to as " compound (1A) ".In addition, the compound with the structure that formula (2) represents preferably has the compound of the structure that following formula (2A) represents (hereinafter also referred to as " compound (2A) ").
(in formula (1A),
R 1~ R 3identical with above-mentioned implication.
Ring Z 1Awith ring Z 2Arepresent substituted or non-substituted aromatic hydrocarbon ring independently of each other.
Q 1and Q 2represent-O-,-S-or-CR independently of each other 13r 14-.
R 11~ R 14represent substituted or non-substituted alkyl independently of each other.〕
(in formula (2A),
Q, R 4~ R 6identical with above-mentioned implication.
Ring Z 3Awith ring Z 4Arepresent substituted or non-substituted aromatic hydrocarbon ring independently of each other.
Q 3and Q 4represent-O-,-S-or-CR independently of each other 23r 24-.
R 21~ R 24represent substituted or non-substituted alkyl independently of each other.〕
As ring Z 1A~ ring Z 4Ain aromatic hydrocarbon ring, the aromatic hydrocarbon ring of preferred carbon number 6 ~ 20, more preferably the aromatic hydrocarbon ring of carbon number 6 ~ 10, particularly preferably phenyl ring.
As R 1~ R 6, preferred hydrogen atom.
Q preferably 2.
Q 1and Q 2preferably-O-,-CR 13r 14-.As R 13and R 14in alkyl, preferred aliphat alkyl, more preferably alkyl.As alkyl, the alkyl of preferred carbon number 1 ~ 8, the more preferably alkyl of carbon number 1 ~ 4, particularly preferably methyl, ethyl.
Q 3and Q 4preferably-O-,-CR 23r 24-.As R 23and R 24in alkyl, preferred aliphat alkyl, more preferably alkyl.As alkyl, the alkyl of preferred carbon number 1 ~ 8, the more preferably alkyl of carbon number 1 ~ 4, particularly preferably methyl, ethyl.
As R 11~ R 14and R 21~ R 24in alkyl, aliphatic alkyl, ester ring type alkyl, aromatic hydrocarbyl can be enumerated.As concrete example, can enumerate and R 1~ R 6alkyl in illustrative Compound Phase with example.Wherein, as R 11~ R 12and R 21~ R 22in alkyl, preferred aliphat alkyl, more preferably alkyl.The carbon number of alkyl is preferably 1 ~ 12, is more preferably 1 ~ 8, is particularly preferably 1 ~ 6.
When the structure that formula (1) represents and the structure that formula (2) represents are cationic, the compound with this structure can have negative ion to become electric neutrality.As negative ion, such as, can enumerate the negative ion etc. in halide ion, boron anion, phosphate anion, carboxylate anion, sulfate anion, organic sulfonic acid anion, nitrogen negative ion, methide anion, ligand with the transient metal complex of azo-compound.
As halide ion, fluoride ion, chloride ion, bromide ion, iodide ion can be enumerated.As boron anion, phosphate anion, nitrogen negative ion, the ion that (0037) ~ (0039) section such as can enumerating Japanese Unexamined Patent Publication 2012-173399 publication is recorded.As carboxylate anion, such as, can enumerate the carboxylate anion recorded in Japanese Unexamined Patent Publication 2009-265641 publication and Japanese Unexamined Patent Publication 2008-096680 publication.As sulfate anion, such as, sulfate anion, sulfite anion etc. can be enumerated.As organic sulfonic acid anion, such as, can enumerate the organic sulfonic acid anion recorded in Japanese Unexamined Patent Publication 2012-173399 publication, International Publication No. 2011/037195 pamphlet, International Publication No. 2011/162217 pamphlet, Japanese Patent No. 3736221 instructions and Japanese Unexamined Patent Publication 2011-070172 publication.As methide anion, such as, can enumerate the methide anion recorded in Japanese Unexamined Patent Publication 2011-145540 publication, United States Patent (USP) No. 5554664 instructions, Japanese Unexamined Patent Publication 2005-309408 publication, Japanese Unexamined Patent Publication 2004-085657 publication, Japanese Unexamined Patent Application Publication 2010-505787 publication etc.
As the negative ion of transient metal complex in ligand with azo-compound, such as, can enumerate the negative ion recorded in Japanese Unexamined Patent Publication 2009-163226 publication, Japanese Unexamined Patent Publication 2012-212089 publication.
In these negative ion, there is in preferred boron anion, nitrogen negative ion, ligand the negative ion of the transient metal complex of azo-compound, further preferred boron anion, nitrogen negative ion.
As the concrete example of boron anion, such as, BF can be enumerated 4 -, (CF 3) 4b -, (CF 3) 3bF -, (CF 3) 2bF 2 -, (CF 3) BF 3 -, (C 2f 5) 4b -, (C 2f 5) 3bF -, (C 2f 5) BF 3 -, (C 2f 5) 2bF 2 -, (CF 3) (C 2f 5) 2bF -, (C 6f 5) 4b -, [(CF 3) 2c 6h 3] 4b -, (CF 3c 6h 4) 4b -, (C 6f 5) 2bF 2 -, (C 6f 5) BF 3 -, (C 6h 3f 2) 4b -, B (CN) 4 -, B (CN) F 3 -, B (CN) 2f 2 -, B (CN) 3f -, (CF 3) 3b (CN) -, (CF 3) 2b (CN) 2 -, (C 2f 5) 3b (CN) -, (C 2f 5) 2b (CN) 2 -, (n-C 3f 7) 3b (CN) -, (n-C 4f 9) 3b (CN) -, (n-C 4f 9) 2b (CN) 2 -, (n-C 6f 13) 3b (CN) -, (CHF 2) 3b (CN) -, (CHF 2) 2b (CN) 2 -, (CH 2cF 3) 3b (CN) -, (CH 2cF 3) 2b (CN) 2 -, (CH 2c 2f 5) 3b (CN) -, (CH 2c 2f 5) 2b (CN) 2 -, (CH 2cH 2c 3f 7) 2b (CN) 2 -, (n-C 3f 7cH 2) 2b (CN) 2 -, (C 6h 5) 3b (CN)-, four (pentafluorophenyl group) borate anion etc.
In addition, as the concrete example of nitrogen negative ion, such as, can enumerate [(CN) 2n] -, [(FSO 2) 2n] -, [(FSO 2) N (CF 3sO 2)] -, [(FSO 2) N (CF 3cF 2sO 2)] -, [(FSO 2) N{ (CF 3) 2cFSO 2] -, [(FSO 2) N (CF 3cF 2cF 2sO 2)] -, [(FSO 2) N (CF 3cF 2cF 2cF 2sO 2)] -, [(FSO 2) N{ (CF 3) 2cFCF 2sO 2] -, [(FSO 2) N{CF 3cF 2(CF 3) CFSO 2] -, [(FSO 2) N{ (CF 3) 3cSO 2] -, [(CF 3sO 2) 2n] -deng.
In coloured composition of the present invention, the content of compound (2) is required to be more than 0.001 quality % relative to the total content of compound (1) and compound (2).The present inventor etc. infer because compound (1) dissolubility is in a solvent low, easy crystallization and become foreign matter, so the storage stability of coloured composition is poor.And, infer the crystallization by can prevent compound (1) together with compound (1) containing compound (2) more than ormal weight, improve the storage stability of coloured composition.From the viewpoint of improving storage stability further, the content of compound (2) is relative to the total content of compound (1) and compound (2), be preferably more than 0.003 quality %, be more preferably more than 0.005 quality %, more preferably more than 0.008 quality %, is particularly preferably more than 0.01 quality %.In addition, from the viewpoint of forming the higher color solidification film of brightness, be preferably below 1 quality %, be more preferably below 0.4 quality %, more preferably below 0.1 quality %, more preferably below 0.09 quality %, is further preferably below 0.08 quality %, is further preferably below 0.07 quality %.The content of compound (2) is relative to the total content of compound (1) and compound (2), be preferably 0.001 ~ 1 quality %, be more preferably 0.003 ~ 0.4 quality %, more preferably 0.005 ~ 0.1 quality %, further be preferably 0.01 ~ 0.1 quality %, be particularly preferably 0.01 ~ 0.08 quality %.
Coloured composition of the present invention can also contain the colorant (hereinafter also referred to as " other colorant ") beyond compound (1) and compound (2).As other colorant, be not particularly limited, can suitably select color, material according to purposes, the pigment beyond compound (1) and compound (2) and dyestuff all can use.Wherein, in the meaning obtaining brightness and the high color solidification film of colour purity, preferred organic pigment, organic dyestuff.
As above-mentioned organic pigment, such as, can enumerate color index (C.I.; The Society of Dyersand Colourists corporation issues) in be classified into the compound of pigment.Wherein, preferred C.I. paratonere 166, C.I. paratonere 177, C.I. pigment red179, C.I. paratonere 224, C.I. paratonere 242, C.I. paratonere 254, C.I. paratonere 264, C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 58, C.I. pigment blue 15: 6, C.I. alizarol saphirol 80, C.I. pigment yellow 83, C.I. pigment Yellow 12 9, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 180, C.I. pigment yellow 185, C.I. pigment yellow 211, C.I. pigment yellow 215, C.I. pigment orange 38, C.I. pigment Violet 23 etc.In addition, the bromination diketo-pyrrolo pyrrole pigments that the mordant pigment also recorded in preferred Japanese Unexamined Patent Publication 2001-081348 publication, Japanese Unexamined Patent Publication 2010-026334 publication, Japanese Unexamined Patent Publication 2010-191304 publication, Japanese Unexamined Patent Publication 2010-237384 publication, Japanese Unexamined Patent Publication 2010-237569 publication, Japanese Unexamined Patent Publication 2011-006602 publication, Japanese Unexamined Patent Publication 2011-145346 publication etc., the formula (Ic) of Japanese Unexamined Patent Application Publication 2011-523433 publication represent.In mordant pigment, preferred triarylmethane system mordant pigment, xanthene system mordant pigment, azo system mordant pigment, more preferably triarylmethane system mordant pigment and xanthene system mordant pigment.
In the present invention, when using the colorant of pigment as other, also can be refined pigment by recrystallization method, reprecipitation method, solvent wash method, sublimed method, vaccum heating method or their combination and use.In addition, pigment can carry out modification to use to its particle surface with resin as required.As the resin particle surface of pigment being carried out to modification, such as, can enumerate the resin of vehicle resin or the commercially available various pigment dispersions recorded in Japanese Unexamined Patent Publication 2001-108817 publication.As the resin-coated method of carbon blacksurface, such as, the method recorded in Japanese Unexamined Patent Publication 9-71733 publication, Japanese Unexamined Patent Publication 9-95625 publication, Japanese Unexamined Patent Publication 9-124969 publication etc. can be adopted.In addition, organic pigment can utilize so-called salt mill to make primary particle miniaturization to use.As the method for salt mill, such as, method disclosed in Japanese Unexamined Patent Publication 8-179111 publication can be adopted.
In the present invention, when using the colorant of pigment as other, can also be made it further containing known spreading agent and dispersing aid.As known spreading agent, such as can enumerate polyurethane series spreading agent, polyethyleneimine system spreading agent, polyoxyethylene alkyl ether system spreading agent, polyoxyethylene alkyl phenyl ether system spreading agent, polyethylene glycol di system spreading agent, sorbitan fatty acid ester system spreading agent, Polyester spreading agent, dispersant containing acrylic etc., as dispersing aid, pigment derivative etc. can be enumerated.
Such spreading agent can obtain commercially, such as, as dispersant containing acrylic, can enumerate Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (being BYK-Chemie (BYK) Inc. above), as polyurethane series spreading agent, can enumerate Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182, Disperbyk-2164 (being BYK-Chemie (BYK) Inc. above), Solsperse 76500 (Lubrizol (strain) Inc.), as polyethyleneimine system spreading agent, Solsperse24000 (Lubrizol (strain) Inc.) can be enumerated, as Polyester spreading agent, AdisperPB821 can be enumerated, Adisper PB822, Adisper PB880, Adisper PB881 (being Ajinomoto Fine-Techno Inc. above), in addition also has BYK-LPN21324 (nonvolatile component is 40 quality %) (BYK-Chemie (BYK) Inc.) etc.
In addition, as pigment derivative, specifically, the sulfonic acid etc. of copper phthalocyanine, diketopyrrolopyrrolecocrystals, quinophthalone can be enumerated.
In the present invention, other colorant may be used singly or as a mixture of two or more.
Coloured composition of the present invention is preferred for forming red pixel or green pixel.
During for the formation of red pixel, as (A) colorant, preferably together with compound (1) containing at least a kind of colorant as other in the red pigment, orchil, violet pigment, cudbear, yellow uitramarine, weld and the orange pigment that are selected from beyond compound (1).During for the formation of green pixel, as (A) colorant, preferably together with compound (1) containing at least a kind of colorant as other in the viridine green, green colouring material, yellow uitramarine and the weld that are selected from beyond compound (1).
As above-mentioned red pigment, the diketo-pyrrolo pyrrole pigments of the pigment represented such as formula (Ic) of preferred C.I. paratonere 177 and C.I. paratonere 254, C.I. paratonere 264, Japanese Unexamined Patent Application Publication 2011-523433 publication.As above-mentioned violet pigment, preferred C.I. pigment Violet 23.As above-mentioned yellow uitramarine, preferred C.I. pigment Yellow 12 9, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 185.As above-mentioned orange pigment, preferred C.I. pigment orange 38.As above-mentioned viridine green, the phthalocyanine color of preferred C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 58 etc.
As above-mentioned orchil, cudbear, preferred xanthene based dye.
Even if from the viewpoint of being formed also excellent with low exposure colorimetric properties and not easily producing the pixel of defect or black matrix", the black separator of light-proofness excellence, in the solid constituent of coloured composition, (A) content of colorant is generally 5 ~ 70 quality %, be preferably 10 ~ 60 quality %, be more preferably 15 ~ 40 quality %.At the composition that this solid constituent is beyond solvent described later.
In addition, when using other colorant, the proportional total content relative to colorant that contains of other colorant is preferably below 99 quality %, is more preferably below 95 mass parts.Lower limit is not particularly limited, as long as be more than 0.01 quality %.
-(B) resin glue-
As (B) resin glue in the present invention, be not particularly limited, but preferably there is the resin of the acidic functionality such as carboxyl, phenolic hydroxyl group.Wherein, the polymkeric substance preferably with carboxyl is (following, also referred to as " carbonyl bearing polymer "), the ethylenically unsaturated monomers such as can enumerating the carboxyl with more than 1 is (following, also referred to as " unsaturated monomer (b1) ") with other can the multipolymer of ethylenically unsaturated monomers (hereinafter also referred to as " unsaturated monomer (b2) ") of copolymerization.
As above-mentioned unsaturated monomer (b1), such as can enumerate (methyl) acrylic acid, maleic acid, maleic anhydride, mono succinate (2-(methyl) acryloyl-oxyethyl) ester, ω-carboxy-polycaprolactone list (methyl) acrylate, to vinyl benzoic acid etc.
These unsaturated monomers (b1) may be used singly or as a mixture of two or more.
In addition, as above-mentioned unsaturated monomer (b2), such as, can enumerate:
As the N-position substituted maleimide amine of N-phenylmaleimide, N-N-cyclohexylmaleimide and so on;
As styrene, α-methyl styrene, vinyltoluene, 4-Vinyl phenol, to hydroxy-alpha-methyl styrene, aromatic ethenyl compound to vinylbenzyl glycidyl ether, acenaphthylene and so on;
As (methyl) methyl acrylate, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, polyglycol (degree of polymerization 2 ~ 10) methyl ether (methyl) acrylate, polypropylene glycol (degree of polymerization 2 ~ 10) methyl ether (methyl) acrylate, single (methyl) acrylate of polyglycol (degree of polymerization 2 ~ 10), single (methyl) acrylate of polypropylene glycol (degree of polymerization 2 ~ 10), (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, (methyl) acrylic acid dicyclopentenyl ester, glycerine list (methyl) acrylate, (methyl) acrylic acid 4-hydroxylphenyl ester, ethylene-oxide-modified (methyl) acrylate of p-cumylphenol, (methyl) glycidyl acrylate, 3,4-epoxycyclohexyl-methyl (methyl) acrylate, (methyl) acrylic acid 3,4-epoxy three ring [5.2.1.0 2,6] decane-8-base ester, (methyl) acrylic acid 3,4-epoxy three ring [5.2.1.0 2,6] decane-9-base ester, 3-((methyl) acryloyloxymethyl) oxetanes, 3-((methyl) acryloyloxymethyl)-3-Ethyloxetane and so on (methyl) acrylate,
As the vinyl ether of cyclohexyl vinyl ether, isobornyl vinyl ether, three rings [5.2.1.02,6] decane-8-base vinyl ether, pentacyclopentadecandimethanol base vinyl ether, 3-(ethene yloxymethyl)-3-Ethyloxetane and so on;
There is at the end of the polymer molecular chain of such as polystyrene, poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate, polysiloxane and so on the macromonomer etc. of list (methyl) acryloyl group.
These unsaturated monomers (b2) may be used singly or as a mixture of two or more.
In these unsaturated monomers (b2), preferably comprise the ethylenically unsaturated monomers as having epoxy ethyl, there is the ethylenically unsaturated monomers with the cyclic ether structure of carbon number 2 ~ 4 of the ethylenically unsaturated monomers of oxetanylmethoxy, the ethylenically unsaturated monomers with tetrahydrofuran base and so on, more preferably comprise the ethylenically unsaturated monomers with epoxy ethyl.As the ethylenically unsaturated monomers with epoxy ethyl, preferably (methyl) acrylic acid 3,4-epoxycyclohexanecarboxylate, (methyl) acrylic acid 3,4-epoxy three ring [5.2.1.0 2,6] decane-8-base ester, (methyl) acrylic acid 3,4-epoxy three ring [5.2.1.0 2,6] decane-9-base ester.
In the multipolymer of unsaturated monomer (b1) with unsaturated monomer (b2), the copolymerization ratios of the unsaturated monomer (b1) in this multipolymer is preferably 5 ~ 50 quality %, more preferably 10 ~ 40 quality %.By making unsaturated monomer (b1) copolymerization with such scope, the coloured composition of alkali development and excellent storage stability can be obtained.
As the concrete example of unsaturated monomer (b1) with the multipolymer of unsaturated monomer (b2), such as, can enumerate multipolymer disclosed in Japanese Unexamined Patent Publication 7-140654 publication, Japanese Unexamined Patent Publication 8-259876 publication, Japanese Unexamined Patent Publication 10-31308 publication, Japanese Unexamined Patent Publication 10-300922 publication, Japanese Unexamined Patent Publication 11-174224 publication, Japanese Unexamined Patent Publication 11-258415 publication, Japanese Unexamined Patent Publication 2000-56118 publication, Japanese Unexamined Patent Publication 2004-101728 publication etc.
In addition; in the present invention; such as, the carbonyl bearing polymer at side chain with polymerism unsaturated links such as (methyl) acryloyl groups this disclosed in Japanese Unexamined Patent Publication 5-19467 publication, Japanese Unexamined Patent Publication 6-230212 publication, Japanese Unexamined Patent Publication 7-207211 publication, Japanese Unexamined Patent Publication 9-325494 publication, Japanese Unexamined Patent Publication 11-140144 publication, Japanese Unexamined Patent Publication 2008-181095 publication etc. can also be used as resin glue.
Resin glue in the present invention is (following with gel permeation chromatography, economize slightly GPC) (eluting solvent: tetrahydrofuran) weight-average molecular weight (Mw) of polystyrene conversion of measuring is generally 1000 ~ 100000, is preferably 3000 ~ 50000.By becoming this mode, residual film ratio, pattern form, thermotolerance, electrical characteristics, the resolution of tunicle can be improved further, the generation of dry foreign matter when being coated with can be suppressed in addition with high level.
In addition, the weight-average molecular weight (Mw) of the resin glue in the present invention is preferably 1.0 ~ 5.0 with the ratio (Mw/Mn) of number-average molecular weight (Mn), is more preferably 1.0 ~ 3.0.Should illustrate, refer to the number-average molecular weight of the polystyrene conversion measured with GPC (eluting solvent: tetrahydrofuran) at this said Mn.
Resin glue in the present invention can utilize known method manufacture, and such as method disclosed in Japanese Unexamined Patent Publication 2003-222717 publication, Japanese Unexamined Patent Publication 2006-259680 publication, International Publication No. 07/029871 pamphlet etc. also can be utilized to control its structure, Mw, Mw/Mn.
In the present invention, resin glue may be used singly or as a mixture of two or more.
In the present invention, (B) content of resin glue is relative to (A) colorant 100 mass parts, is generally 10 ~ 1000 mass parts, is preferably 20 ~ 500 mass parts, be more preferably 50 ~ 200 mass parts, more preferably 80 ~ 150 mass parts.By becoming this mode, alkali development, the storage stability of coloured composition, pattern form, colorimetric properties can be improved further.
-(C) polymerizable compound-
In the present invention, polymerizable compound refers to the compound of the polymerisable group with more than 2.As polymerisable group, such as, can enumerate ethylenic unsaturated group, epoxy ethyl, oxetanylmethoxy, N-alkoxy methyl amino etc.In the present invention, as polymerizable compound, the compound of the compound preferably with (methyl) acryloyl group of more than 2 or the N-alkoxy methyl amino with more than 2.
As the concrete example of compound of (methyl) acryloyl group with more than 2, can enumerate and aliphatic polyhydroxy compound and (methyl) acrylic acid be reacted and multifunctional (methyl) acrylate of obtaining, by multifunctional (methyl) acrylate of caprolactone modification, by multifunctional (methyl) acrylate of alkylene oxide modification, make to have polyfunctional carbamate (methyl) acrylate that (methyl) acrylate of hydroxyl and polyfunctional isocyanate react and obtain, make to have (methyl) acrylate of hydroxyl and anhydride reaction and multifunctional (methyl) acrylate etc. with carboxyl obtained.
At this, as aliphatic polyhydroxy compound, such as, can enumerate the aliphatic polyhydroxy compound of 2 yuan as ethylene glycol, propylene glycol, polyglycol, polypropylene glycol and so on; As the aliphatic polyhydroxy compound of more than 3 yuan of glycerine, trimethylolpropane, pentaerythrite, dipentaerythritol and so on.As above-mentioned (methyl) acrylate with hydroxyl, such as, can enumerate (methyl) acrylic acid 2-hydroxy methacrylate, trimethylolpropane two (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, glycerol dimethacrylate etc.As above-mentioned polyfunctional isocyanate, such as, can enumerate toluene diisocyanate, hexamethylene diisocyanate, MDI, isophorone diisocyanate etc.As acid anhydrides, such as can enumerate the acid anhydrides of the dibasic acid as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride and so on, the tetra-atomic acid dianhydride of pyromellitic acid anhydride, bibenzene tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride and so on.
In addition, as by multifunctional (methyl) acrylate of caprolactone modification, such as, the compound recorded in (0015) ~ (0018) section of Japanese Unexamined Patent Publication 11-44955 publication can be enumerated.As above-mentioned by multifunctional (methyl) acrylate of alkylene oxide modification, bisphenol-A two (methyl) acrylate of at least a kind of modification be selected from oxirane and epoxypropane can be enumerated, be selected from isocyanuric acid three (methyl) acrylate of at least a kind of modification in oxirane and epoxypropane, be selected from trimethylolpropane tris (methyl) acrylate of at least a kind of modification in oxirane and epoxypropane, be selected from pentaerythrite three (methyl) acrylate of at least a kind of modification in oxirane and epoxypropane, be selected from pentaerythrite four (methyl) acrylate of at least a kind of modification in oxirane and epoxypropane, be selected from dipentaerythritol five (methyl) acrylate of at least a kind of modification in oxirane and epoxypropane, be selected from dipentaerythritol six (methyl) acrylate etc. of at least a kind of modification in oxirane and epoxypropane.
In addition, as the compound of N-alkoxy methyl amino with more than 2, such as, the compound etc. with melamine structure, benzoguanamine structure, urea structure can be enumerated.Should illustrate, melamine structure, benzoguanamine structure refer to that the triazine ring with more than 1 or phenyl replace the chemical constitution of triazine ring as basic framework, are the concepts comprising melamine, benzoguanamine or their condensation product.As the concrete example of compound of N-alkoxy methyl amino with more than 2, N can be enumerated, N, N ', N ', N ", N "-six (alkoxy methyl) melamine, N, N, N ', N '-four (alkoxy methyl) benzoguanamine, N, N, N ', N '-four (alkoxy methyl) glycoluril etc.
In these polymerizable compounds, preferably make the aliphatic polyhydroxy compound of more than 3 yuan and (methyl) acrylic acid react and obtain multifunctional (methyl) acrylate, by multifunctional (methyl) acrylate of caprolactone modification, polyfunctional carbamate (methyl) acrylate, there is multifunctional (methyl) acrylate, the N of carboxyl, N, N ', N '; N "; N "-six (alkoxy methyl) melamine, N, N, N ', N '-four (alkoxy methyl) benzoguanamine.High from the intensity of dyed layer, the surface smoothness of dyed layer is excellent, and not easily dirt is produced on the substrate in unexposed portion He on light shield layer, the viewpoint that film remains etc. is considered, in multifunctional (methyl) acrylate obtained making the aliphatic polyhydroxy compound of more than 3 yuan and (methyl) acrylic acid react, particularly preferably trimethylolpropane triacrylate, pentaerythritol triacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate, in multifunctional (methyl) acrylate with carboxyl, particularly preferably make the compound that pentaerythritol triacrylate and succinic anhydride react and obtain, make the compound that Dipentaerythritol Pentaacrylate and succinic anhydride react and obtain.
In the present invention, (C) polymerizable compound may be used singly or as a mixture of two or more.
The content of (C) polymerizable compound in the present invention is relative to (A) colorant 100 mass parts, be preferably 10 ~ 1000 mass parts, be more preferably 20 ~ 700 mass parts, more preferably 50 ~ 500 mass parts, be further preferably 80 ~ 250 mass parts.The content of (C) polymerizable compound is relative to (B) resin glue 100 mass parts in addition, is preferably 50 ~ 300 mass parts, is more preferably 70 ~ 200 mass parts, more preferably 100 ~ 150 mass parts.By becoming this mode, curability, alkali development can be improved further, suppressing on the substrate in unexposed portion or on light shield layer, to produce dirt with high level, film remains.
-(D) Photoepolymerizationinitiater initiater-
Can make in coloured composition of the present invention containing Photoepolymerizationinitiater initiater.Thereby, it is possible to it is sensitivity to give radioactive ray to coloured composition.The Photoepolymerizationinitiater initiater used in the present invention produces the compound that can cause the spike of the polymerization of above-mentioned polymerizable compound by the exposure of the radioactive ray such as luminous ray, ultraviolet, far ultraviolet, electron beam, X ray.
As such Photoepolymerizationinitiater initiater, such as can enumerate thioxanthone compounds, acetophenone compound, united imidazole, triaizine compounds, O-acyl oxime compound, salt compound, benzoin compound, benzophenone cpd, α-dione compounds, polynucleation quinone compound, diazo-compounds, acid imide sulfonate compound etc.
In the present invention, Photoepolymerizationinitiater initiater may be used singly or as a mixture of two or more.As Photoepolymerizationinitiater initiater, be preferably selected from least a kind in thioxanthone compounds, acetophenone compound, united imidazole, triaizine compounds, O-acyl oxime compound.
In the present invention in preferred Photoepolymerizationinitiater initiater, as the concrete example of thioxanthone compounds, thioxanthones, CTX, 2-methyl thioxanthones, ITX, ITX, 2 can be enumerated, 4-bis-clopenthixal ketone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropylthioxanthone etc.
In addition, as the concrete example of above-mentioned acetophenone compound, 2-methyl isophthalic acid-(4-(methyl mercapto) phenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) butane-1-ketone, 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morphlinophenyl) butane-1-ketone etc. can be enumerated.
In addition, as the concrete example of above-mentioned united imidazole, can 2 be enumerated, 2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4,6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.
Should illustrate, when using united imidazole as Photoepolymerizationinitiater initiater, preferred and use hydrogen donor from the viewpoint of sensitivity can be improved.Referring at this said " hydrogen donor " can to the compound by exposing the free radical supply hydrogen atom produced by united imidazole.As hydrogen donor, such as, can enumerate 2-mercaptobenzothiazole, 2-sulfydryl benzo the mercaptan hydrogen donors such as azoles, the amine hydrogen donors such as 4,4 '-bis-(dimethylamino) benzophenone, 4,4 '-bis-(diethylamino) benzophenone.In the present invention, hydrogen donor may be used singly or as a mixture of two or more, but from the viewpoint of improving sensitivity further, preferably the mercaptan hydrogen donor of more than a kind and the amine hydrogen donor of more than a kind is combinationally used.
In addition, as the concrete example of above-mentioned triaizine compounds, can 2 be enumerated, 4, 6-tri-(trichloromethyl)-s-triazine, 2-methyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-(2-(5-methylfuran-2-base) vinyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(2-(furans-2-base) vinyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(2-(4-diethylamino-2-aminomethyl phenyl) vinyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(2-(3, 4-Dimethoxyphenyl) vinyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-methoxyphenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-ethoxystyrene base)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-n-butoxyphenyl)-4, two (the trichloromethyl)-s-triazine of 6-etc. have the triaizine compounds of halogenated methyl.
In addition, as the concrete example of O-acyl oxime compound, 1-(4-(thiophenyl) phenyl)-1 can be enumerated, 2-octanedione 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-ethyl ketone 1-(O-acetyl oxime), 1-(9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9H-carbazole-3-base)-ethyl ketone 1-(O-acetyl oxime), 1-(9-ethyl-6-{2-methyl-4-(2, 2-dimethyl-1, 3-dioxolanyl) methoxybenzoyl base }-9H-carbazole-3-base)-ethyl ketone 1-(O-acetyl oxime) etc.As the commercially available product of O-acyl oxime compound, NCI-831, NCI-930 (above is Inc. of Asahi Denka Co., Ltd.) can also be used, DFI-020, DFI-091 (being Daitochemix Co., Ltd. system above) etc.
In the present invention, when using the Photoepolymerizationinitiater initiater beyond the united imidazole such as acetophenone compound, can also and use sensitizer.As such sensitizer; such as can enumerate 4; 4 '-bis-(dimethylamino) benzophenone, 4; 4 '-bis-(diethylamino) benzophenone, 4-diethyl amino benzoylformaldoxime, 4-dimethylamino propiophenone, EDMAB, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, 2,5-two (4-diethylamino benzal) cyclohexanone, 7-diethylamino-3-(4-diethylamino benzoyl) cumarin, 4-(diethylamino) chalcone etc.
In the present invention, (D) content of Photoepolymerizationinitiater initiater is relative to (C) polymerizable compound 100 mass parts, is preferably 0.01 ~ 120 mass parts, is more preferably 1 ~ 100 mass parts, more preferably 5 ~ 50 mass parts, are particularly preferably 10 ~ 30 mass parts.By becoming this mode, curability can be improved further, by membrane property.
-(E) solvent-
Other composition that coloured composition of the present invention contains above-mentioned (A) ~ (C) composition and adds arbitrarily, coordinates solvent to be prepared into fluid composition usually.
As (E) solvent, as long as dispersion or dissolve and form (A) ~ (C) composition, other the composition of coloured composition, and do not react with these compositions, there is suitable volatility, just can suitably choice for use.
In such solvent, such as, can enumerate:
Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list positive propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, DPE, dipropylene glycol list positive propyl ether, dipropylene glycol mono-n-butyl ether, Tripropylene glycol monomethyl Ether, (gathering) alkylene glycol monoalkyl ethers such as tripropylene glycol list ether,
The lactic acid alkyl ester such as methyl lactate, ethyl lactate class;
(ring) alkyl alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, isopropyl alcohol, isobutyl alcohol, the tert-butyl alcohol, octanol, 2-Ethylhexyl Alcohol, cyclohexanol;
The ketols such as diacetone alcohol;
(gathering) alkylene glycol monoalkyl ether acetate classes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetic acid esters, 3-methoxybutyl acetic acid esters, 3-methyl-3-methoxybutyl acetic acid esters;
Other the ethers such as diethylene glycol dimethyl ether, diethylene glycol ethylmethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
The ketones such as MEK, cyclohexanone, 2-HEPTANONE, 3-heptanone;
The diacetate esters classes such as propylene-glycol diacetate, 1,3-BDO diacetate esters, 1,6-hexanediol diacetate esters;
The alkoxyl carboxylate classes such as 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, 3-methyl-3-methoxybutyl propionic ester; Other the ester class such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, 2-Oxobutyric acid ethyl ester;
Toluene, dimethylbenzene etc. are aromatic hydrocarbon based;
Acid amides or the lactams etc. such as DMF, DMA, 1-METHYLPYRROLIDONE.
In these solvents, from dissolubility, pigment-dispersing, the viewpoints such as coating are considered, preferably (gathering) alkylene glycol monoalkyl ethers, lactic acid alkyl ester class, (gathering) alkylene glycol monoalkyl ether acetate class, other ethers, ketone, diacetate esters class, alkoxyl carboxylate class, other ester class, particularly preferably propylene glycol monomethyl ether, dihydroxypropane single-ether, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetic acid esters, diethylene glycol dimethyl ether, diethylene glycol ethylmethyl ether, cyclohexanone, 2-HEPTANONE, 3-heptanone, 1,3-BDO diacetate esters, 1,6-hexanediol diacetate esters, ethyl lactate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, 3-methyl-3-methoxybutyl propionic ester, n-butyl acetate, isobutyl acetate, formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, ethyl pyruvate etc.
In the present invention, solvent may be used singly or as a mixture of two or more.
(E) content of solvent is not particularly limited, and the total concentration of each composition except the solvent of coloured composition preferably becomes the amount of 5 ~ 50 quality %, more preferably becomes the amount of 10 ~ 40 quality %.By becoming this mode, coloured composition dispersiveness, the colorant dispersion had good stability and coating can be obtained, having good stability.
-adjuvant-
Coloured composition of the present invention can also contain various adjuvant as required.
As adjuvant, such as, can enumerate the filling agent such as glass, aluminium oxide, the macromolecular compounds such as polyvinyl alcohol (PVA), poly-(fluoroalkyl base ester) class, the surfactant such as fluorine surfactant, organic silicon surfactant, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, APTES, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl dimethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane, the closely sealed promoter such as 3-mercaptopropyi trimethoxy silane, 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-DI-tert-butylphenol compounds, pentaerythrite four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], 3, two [the 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl)-propionyloxy]-1 of 9-, 1-dimethyl ethyl]-2,4,8, the antioxidants such as 10-tetra-oxa-s-spiral shell [5.5] undecane, thiodiethylene two [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl) ultraviolet light absorber such as-5-chlorobenzotriazole, alkoxy benzophenone class, the deflocculants such as sodium polyacrylate, malonic acid, hexane diacid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-ethylaminoethanol, 3-amino-1-propyl alcohol, 5-amino-1-amylalcohol, 3-amino-1,2-propylene glycol, 2-amino-1, the residue improvers such as amino-1, the 2-butanediol of ammediol, 4-, the developability improvers etc. such as mono succinate (2-(methyl) acryloyl-oxyethyl) ester, phthalic acid list (2-(methyl) acryloyl-oxyethyl) ester, ω-carboxy-polycaprolactone list (methyl) acrylate.
In addition, when coloured composition of the present invention uses both dyestuff and pigment as colorant, disclosed in Japanese Unexamined Patent Publication 2010-132874 publication, following preparation method can be adopted: make dye solution by after the 1st filtrator, dye solution by the 1st filtrator is mixed with the dispersible pigment dispersion etc. prepared in addition, the coloured composition obtained is prepared by the 2nd filtrator.In addition, following preparation method can be adopted: by dyestuff, above-mentioned (B) ~ (C) composition and other the component dissolves that uses as required in solvent, make the solution obtained by after the 1st filtrator, solution by the 1st filtrator is mixed with the dispersible pigment dispersion prepared in addition, the coloured composition obtained is prepared by the 2nd filtrator.In addition, also following preparation method can be adopted: make dye solution by after the 1st filtrator, by by the dye solution of the 1st filtrator and above-mentioned (B) ~ (C) composition and other the composition mixed dissolution that uses as required, make the solution obtained by the 2nd filtrator, again the solution by the 2nd filtrator is mixed with the dispersible pigment dispersion prepared in addition, the coloured composition obtained is prepared by the 3rd filtrator.
color solidification film and its formation method
Color solidification film of the present invention uses coloured composition of the present invention to be formed, and specifically, refers to each color pixel, black matrix", black separator etc. that form color filter.
Below, the color solidification film used in the color filter to formation display element, solid-state imager and its formation method are described.
As the method manufacturing color filter, the first, following method can be enumerated.First, light shield layer (black matrix") is formed in the mode marking off the part forming pixel as required on a surface of a substrate.Then, after being coated with the liquid composition of the such as red sensitivity coloured composition of radioactive ray of the present invention on the substrate, carrying out preliminary drying and solvent is evaporated, form film.Then, after via photomask this film being exposed, use alkaline-based developer to develop, dissolve the unexposed portion of removing film.Thereafter, by rear baking, form the pel array of the red pattern of pixels (color solidification film) that is arranged specified.
Then, use the sensitivity coloured composition of each radioactive ray of green or blueness, carry out the coating of the sensitivity coloured composition of each radioactive ray, preliminary drying, exposure, development and rear baking as described above, form green pel array and blue pel array on the same substrate successively.Thus, the color filter being configured with redness, green and this trichromatic pel array blue on substrate is obtained.Wherein, in the present invention, the order forming each color pixel is not limited to said sequence.
Above-mentioned black matrix" can utilize photoetching process to make to become desired pattern by metallic films such as the chromium of sputtering, evaporation and film forming and be formed, and the sensitivity coloured composition of the radioactive ray being dispersed with black colorant also can be used to be formed in the same manner as the situation of the above-mentioned pixel of formation.
As the substrate used when forming color filter, such as, can enumerate glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamidoimide, polyimide etc.
In addition, can also implement to utilize the pre-treatment that the agent treated of silane coupling agent etc., Cement Composite Treated by Plasma, ion plating, sputtering, gas-phase reaction method, vacuum evaporation etc. are suitable to these substrates as required.
When substrate is coated with radioactive ray sensitivity coloured composition, spraying process, rolling method, spin-coating method (spin coat method), slit mould can be adopted to be coated with the suitable rubbing method such as method (slit coating method), stick coating method, particularly preferably to adopt spin-coating method, slit mould to be coated with method.
Preliminary drying normally combines drying under reduced pressure and heat drying carries out.Drying under reduced pressure proceeds to 50 ~ 200Pa usually.In addition, the condition of heat drying is generally 70 ~ 110 DEG C, about 1 ~ 10 minute.
Coating thickness, with dried film thickness gauge, is generally 0.6 ~ 8 μm, is preferably 1.2 ~ 5 μm.
As the light source of the radioactive ray used when forming at least a kind of being selected from pixel and black matrix", such as can enumerate the lamp source such as xenon lamp, Halogen lamp LED, tungsten lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, the LASER Light Source etc. such as argon laser, YAG laser, XeCl excimer laser, N_2 laser.As exposure light source, also ultraviolet LED can be used.Optimal wavelength is at the radioactive ray of the scope of 190 ~ 450nm.
The exposure of radioactive ray is generally preferably 10 ~ 10000J/m 2.
In addition, as above-mentioned alkaline-based developer, such as, preferred sodium carbonate, sodium bicarbonate, NaOH, potassium hydroxide, Tetramethylammonium hydroxide, choline, 1, the aqueous solution of 8-diazabicyclo-[5.4.0]-7-undecylene, 1,5-diazabicyclo-[4.3.0]-5-nonene etc.
Also the such as water-miscible organic solvent such as methyl alcohol, ethanol can be added in right amount in alkaline-based developer, surfactant etc.Should illustrate, after alkaline development, usually wash.
As development treatment method, spray development method, spray development method, dipping (dip) development method, puddle (puddle) development method etc. can be applied.The preferred normal temperature of development conditions 5 ~ 300 seconds.
The condition of rear baking normally 180 ~ 280 DEG C, about 10 ~ 60 minutes.
The thickness of the pixel of such formation is generally 0.5 ~ 5 μm, is preferably 1 ~ 3 μm.
In addition, as the second method manufacturing color filter, can adopt disclosed in Japanese Unexamined Patent Publication 7-318723 publication, Japanese Unexamined Patent Publication 2000-310706 publication etc. and utilize ink-jetting style to obtain the method for assorted pixel.In the method, first, the next door also having shade function concurrently is formed on a surface of a substrate.Then, after utilizing jetting system to spray the liquid composition of such as red Thermocurable coloured composition in the next door formed, carry out preliminary drying and solvent is evaporated.Then, after exposing this film as required, make it solidify by rear baking, form blue pattern of pixels.
Then, each Thermocurable coloured composition of green or blueness is used to form green pattern of pixels and blue pattern of pixels as described above on the same substrate successively.Thus, the color filter being configured with redness, green and this trichromatic pattern of pixels blue on substrate is obtained.Wherein, in the present invention, the order forming assorted pixel is not limited to above-mentioned order.
Should illustrate, shade function is not only played in next door, also plays the function of the Thermocurable coloured composition not colour mixture making to be ejected into the colors in septal area, so compared with the black matrix" used in above-mentioned first method, thickness is thick.Therefore, next door uses the sensitivity composition of black radioactive ray to be formed usually.
The substrate used when forming color filter, the light source of radioactive ray and preliminary drying, the method for rear baking, condition are identical with the first above-mentioned method.The thickness of pixel formed by ink-jetting style like this and the height in next door are equal extent.
After the pattern of pixels obtained like this forms diaphragm as required, form nesa coating by sputtering.After forming nesa coating, separator can also be formed further and make color filter.Separator uses the sensitivity composition of radioactive ray to be formed usually, but also can form the separator (black separator) with light-proofness.In this situation, use the sensitivity coloured composition of radioactive ray being dispersed with the colorant of black, but coloured composition of the present invention is also applicable to form this black separator.
The sensitivity coloured composition of radioactive ray of the present invention is applicable to and forms in above-mentioned color filter any one color solidification film of each color pixel, black matrix", black separator etc. that use.
The brightness comprising the color filter of color solidification film of the present invention of such formation and colour purity high, therefore exceedingly useful in color liquid crystal display device, colour pick-up tube element, color sensor, organic EL display element, Electronic Paper etc.Should illustrate, as long as the color solidification film that the sensitivity coloured composition of use radioactive ray of the present invention that display element described later possesses more than at least 1 is formed.
display element
Display element of the present invention possesses color solidification film of the present invention.As display element, color liquid crystal display device, organic EL display element, Electronic Paper etc. can be enumerated.
The color liquid crystal display device possessing color solidification film of the present invention can be transmission-type also can be reflective, can adopt suitable structure.Such as, can adopt and form color filter on the substrate different from the driving substrate being configured with thin film transistor (TFT) (TFT), driving substrate and the substrate that is formed with color filter are across the opposed structure of liquid crystal layer.In addition, the substrate that is formed with color filter on the surface of the driving substrate being configured with thin film transistor (TFT) (TFT) and the substrate being formed with ITO (indium oxide doped with tin) electrode can also be adopted across the opposed structure of liquid crystal layer.The structure of the latter has can significantly improve aperture opening ratio, obtain bright and the advantage that the liquid crystal display cells of fine is such.Should illustrate, when adopting the structure of the latter, black matrix", black separator can be formed in the substrate-side and either party being formed in the substrate-side of ITO electrode being formed with color filter.
The color liquid crystal display device possessing color solidification film of the present invention is except possessing cold cathode fluorescent tube (CCFL:Cold Cathode Fluorescent Lamp), and also possessing with White LED is the backlight unit of light source.As White LED, such as display predetermined colors in combination LED can be enumerated, green LED and blue led obtain the White LED of white light by colour mixture, combined blue LED, red LED and green-emitting phosphor obtain the White LED of white light by colour mixture, combined blue LED, red light-emitting phosphor and green-emitting phosphor body obtain the White LED of white light by colour mixture, the White LED of white light is obtained by the colour mixture of blue led and YAG system fluorophor, combined blue LED, orange luminescence fluorophor and green-emitting phosphor body obtain the White LED of white light by colour mixture, combination ultraviolet LED, red light-emitting phosphor, green-emitting phosphor body and blue-light-emitting fluorescent material obtain the White LED etc. of white light by colour mixture.
The color liquid crystal display device possessing color solidification film of the present invention can adopt TN (Twisted Nematic, twisted-nematic) type, STN (Super Twisted Nematic, supertwist to row) type, IPS (In-Planes Switching, in face switch) type, VA (VerticalAlignment, vertical orientated) liquid crystal mode that type, OCB (Optically Compensated Birefringence, optical compensation curved arrangement) type etc. are suitable.
In addition, the organic EL display element possessing color solidification film of the present invention can adopt suitable structure, such as, can enumerate structure disclosed in Japanese Unexamined Patent Publication 11-307242 publication.
In addition, the Electronic Paper possessing color solidification film of the present invention can adopt suitable structure, such as, can enumerate structure disclosed in Japanese Unexamined Patent Publication 2007-41169 publication.
Embodiment
Below, enumerate embodiment to be specifically described further embodiments of the present invention.But the invention is not restricted to following embodiment.
The synthesis > of < colorant
Synthesis example 1
To be equipped with stirrer 300mL eggplant type flask in add 2,3,3-tri-methyl indole quinoline 9.7g, 1-iodomethane 25.9g and acetonitrile 85mL, while add hot reflux limit to stir 10 hours.After being cooled to room temperature, reaction solution being joined in Di Iso Propyl Ether 425mL, carry out ice-cold, leave standstill 30 minutes.Thereafter, leach precipitate by suction strainer, the solid that drying under reduced pressure obtains 16.1g pale pink is carried out to the solid obtained.Pass through 1the analysis of H-NMR and MS spectrum, the solid confirming to obtain is the compound (A1) that above-mentioned formula represents.
Synthesis example 2
To be equipped with stirrer 100mL eggplant type flask in add compound (A1) 8.1g and ethyl orthoformate 12.0g and pyridine 24mL that obtain in synthesis example 1,120 DEG C stir 5 hours.After being cooled to room temperature, with Rotary Evaporators, reduced pressure concentration is carried out to reaction solution.Thereafter, add 20mL acetone, stir 30 minutes at 40 DEG C.Thereafter, join in Di Iso Propyl Ether 200mL, carry out ice-cold, leave standstill 30 minutes.Thereafter, leach precipitate by suction strainer, drying under reduced pressure is carried out to the solid obtained and obtains the purpureal solid of 6.3g.Pass through 1the analysis of H-NMR and LC-MS, the solid confirming to obtain is the potpourri of the compound that the compound that represents of above-mentioned formula (A2-1) and above-mentioned formula (A2-2) represent.Using this compound as colorant (A-2).
Synthesis example 3
Following method is utilized to make colorant (A-2) recrystallization.That is, to be equipped with stirrer 300mL eggplant type flask in add obtain in synthesis example 2 colorant (A-2) 5.0g, ethanol containing 10 quality % ion exchange water 100g, stir 2 hours at 80 DEG C.Thereafter, solution is cooled, leave standstill an evening at 5 DEG C.Leach precipitate by suction strainer, drying under reduced pressure is carried out to the solid obtained and obtains the purpureal solid of 4.6g.Using this compound as colorant (A-3).
Synthesis example 4
Following method is utilized to make colorant (A-3) recrystallization.That is, to be equipped with stirrer 300mL eggplant type flask in add obtain in synthesis example 3 colorant (A-3) 5.0g, ethanol containing 10 quality % ion exchange water 100g, stir 2 hours at 80 DEG C.Thereafter, solution is cooled, leave standstill an evening at 5 DEG C.Leach precipitate by suction strainer, drying under reduced pressure is carried out to the solid obtained and obtains the purpureal solid of 4.3g.Using this compound as colorant (A-4).
Synthesis example 5
To be equipped with stirrer 300mL eggplant type flask in add colorant (A-2) 3.0g obtained in synthesis example 2, two trifluoromethanesulfonimide lithium 2.7g, acetonitrile 24mL, ethyl acetate 36mL and ion exchange water 30mL, stir 2 hours.Thereafter, be separated removing water layer, with ion exchange water 30mL, 3 times cleaned to organic layer.Then with Rotary Evaporators, reduced pressure concentration is carried out to organic layer, late 50 DEG C of vacuum drying one, obtain the bolarious solid of 4.0g.Pass through 1the analysis of H-NMR and LC-MS, the solid confirming to obtain is the potpourri of the compound that the compound that represents of above-mentioned formula (A5-1) and above-mentioned formula (A5-2) represent.Using this compound as colorant (A-5).
Synthesis example 6
In synthesis example 5, colorant (A-3) is used to replace colorant (A-2), in addition, carry out the operation same with synthesis example 5, obtain the potpourri of compound that above-mentioned formula (A5-1) represents and the compound that above-mentioned formula (A5-2) represents.Using the compound that obtains as colorant (A-6).
Synthesis example 7
In synthesis example 5, colorant (A-4) is used to replace colorant (A-2), in addition, carry out the operation same with synthesis example 5, obtain the potpourri of compound that above-mentioned formula (A5-1) represents and the compound that above-mentioned formula (A5-2) represents.Using the compound that obtains as colorant (A-7).
Synthesis example 8
In synthesis example 5, use and two trifluoromethanesulfonimide lithium 2.7g is replaced to (ethenylphenyl) trifluoromethanesulfonimide triethylenetetraminehexaacetic acid amine salt 2.4g, in addition, carry out the operation same with synthesis example 5.Pass through 1the analysis of H-NMR and LC-MS, the solid confirming to obtain is the potpourri of the compound that the compound that represents of above-mentioned formula (A8-1) and above-mentioned formula (A8-2) represent.Using the compound that obtains as colorant (A-8).
Synthesis example 9
In synthesis example 8, colorant (A-3) is used to replace colorant (A-2), in addition, carry out the operation same with synthesis example 8, obtain the potpourri of compound that above-mentioned formula (A8-1) represents and the compound that above-mentioned formula (A8-2) represents.Using the compound that obtains as colorant (A-9).
Synthesis example 10
In synthesis example 8, colorant (A-4) is used to replace colorant (A-2), in addition, carry out the operation same with synthesis example 8, obtain the potpourri of compound that above-mentioned formula (A8-1) represents and the compound that above-mentioned formula (A8-2) represents.Using the compound that obtains as colorant (A-10).
Synthesis example 11
In synthesis example 1, use 1-iodopropane 30.9g to replace 1-iodomethane 25.9g, in addition, carry out the operation same with synthesis example 1, obtain the compound (A11) that above-mentioned formula represents.
Synthesis example 12
In synthesis example 2, use compound (A11) 8.8g obtained in synthesis example 11 to replace compound (A1) 8.1g, in addition, carry out the operation same with synthesis example 2.Pass through 1the analysis of H-NMR and LC-MS, the compound confirming to obtain is the potpourri of the compound that the compound that represents of above-mentioned formula (A12-1) and above-mentioned formula (A12-2) represent.Using this compound as colorant (A-12).
Synthesis example 13
In synthesis example 3, use colorant (A-12) 5g to replace colorant (A-2) 5g, in addition, carry out the recrystallization operation same with synthesis example 3.Using the compound that obtains as colorant (A-13).
Synthesis example 14
In synthesis example 4, use colorant (A-13) 5g to replace colorant (A-3) 5g, in addition, carry out the recrystallization operation same with synthesis example 4.Using the compound that obtains as colorant (A-14).
Synthesis example 15
In synthesis example 5, colorant (A-12) 3.3g is used to replace colorant (A-2) 3.0g, in addition, carry out the operation same with synthesis example 5, obtain the potpourri of compound that above-mentioned formula (A15-1) represents and the compound that above-mentioned formula (A15-2) represents.Using the compound that obtains as colorant (A-15).
Synthesis example 16
In synthesis example 5, colorant (A-13) 3.3g is used to replace colorant (A-2) 3.0g, in addition, carry out the operation same with synthesis example 5, obtain the potpourri of compound that above-mentioned formula (A15-1) represents and the compound that above-mentioned formula (A15-2) represents.Using the compound that obtains as colorant (A-16).
Synthesis example 17
In synthesis example 5, colorant (A-14) 3.3g is used to replace colorant (A-2) 3.0g, in addition, carry out the operation same with synthesis example 5, obtain the potpourri of compound that above-mentioned formula (A15-1) represents and the compound that above-mentioned formula (A15-2) represents.Using the compound that obtains as colorant (A-17).
purity confirms
Prepare the acetonitrile solution (colorant concentration 1000ppm) of colorant (A-5) ~ (A-10) and (A-15) ~ (A-17) respectively, utilize high performance liquid chromatography to carry out the quantitative of purity according to following analysis condition.Measure the compound (2) in each colorant, namely there is the concentration of the compound of the structure that formula (2) represents, calculate the content of the compound (2) of the total content relative to compound (1) and compound (2).Show the result in table 1.
(analysis condition)
Device: high performance liquid chromatography (Smartline (PDA SYSTEM) LC SYSTEM, KNAUER Inc.)
Detecting device: Smartline PDA Detector 2850
Solvent: acetonitrile/0.1% trifluoroacetic acid aqueous solution=7/3 (v/v) mixed solvent
Post: CAPCELLPAK C18 MG (5 μ 150x4.6mm, Shiseido Inc.)
Column oven design temperature: 40 DEG C
Sample injection rate IR: 10 μ L
Flow: 0.5mL/min
Table 1
The concentration of the compound (2) in colorant shown in table 1 (A-7), (A-10) and (A-17) is lower than the detectability in high performance liquid chromatography.
The preparation > of < dispersible pigment dispersion
Preparation example 1
The C.I. paratonere 254 of 15 mass parts is used as colorant, the BYK-LPN21116 (BYK-Chemie (BYK) Inc.) of 12.5 mass parts (solid component concentration 40 quality %) is used as spreading agent, the propylene glycol methyl ether acetate of 72.5 mass parts is used as solvent, utilize ball mill to process, prepare dispersible pigment dispersion (a-1).
The preparation > of < colourant solution
Preparation example 2
By colorant (A-5) 10 mass parts and the mixing of propylene glycol monomethyl ether 90 mass parts, prepare colourant solution (A-5).
Preparation example 3 ~ 10
In preparation example 2, the kind of change colorant as shown in table 2, in addition, prepares colourant solution (A-6) ~ (A-10) and (A-15) ~ (A-17) in the same manner as preparation example 2.
Table 2
Preparation example Colorant Colourant solution
2 (A-5) (A-5)
3 (A-6) (A-6)
4 (A-7) (A-7)
5 (A-8) (A-8)
6 (A-9) (A-9)
7 (A-not 0) (A-10)
8 (A-15) (A-15)
9 (A-16) (A-16)
10 (A-17) (A-17)
The synthesis > of < (B) resin glue
Synthesis example 18
In the flask possessing cooling tube and stirring machine, drop into propylene glycol methyl ether acetate 100 mass parts and carry out nitrogen displacement.Be heated to 80 DEG C, at such a temperature, propylene glycol methyl ether acetate 100 mass parts, methacrylic acid 20 mass parts, styrene 10 mass parts, benzyl methacrylate 5 mass parts, 2-hydroxyethyl methacrylate 15 mass parts, 2-Ethylhexyl Methacrylate 23 mass parts, N-phenylmaleimide 12 mass parts, mono succinate (2-acryloyl-oxyethyl) ester 15 mass parts and 2 is dripped with 1 hour, 2 '-azo two (2,4-methyl pentane nitrile) mixed solution of 6 mass parts, keep this temperature to carry out polymerization in 2 hours.Thereafter, by the temperature to 100 of reaction solution DEG C, then carry out polymerization in 1 hour, obtain resin glue solution (B1) (solid component concentration 33 quality %) thus.The Mw of the resin glue obtained is 12200, Mn is 6500.
Synthesis example 19
According to the method recorded in the synthesis example 6 of Japanese Unexamined Patent Publication 2013-203955 publication, obtain the solution containing the resin with following structural unit.Then, add propylene glycol methyl ether acetate and solid component concentration is adjusted to 33 quality %, obtain resin glue solution (B2) (solid component concentration 33 quality %).
the preparation of coloured composition
Embodiment 1
Will as the dispersible pigment dispersion of (A) colorant (a-1) 30.5 mass parts, colourant solution (A-5) 23.0 mass parts, as resin glue solution (B1) 26.3 mass parts of (B) resin glue, as the dipentaerythritol acrylate of (C) polymerizable compound and potpourri (Nippon Kayaku K. K's system of Dipentaerythritol Pentaacrylate, trade name KAYARADDPHA) 9.9 mass parts, as 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) butane-1-ketone (the trade name IRGACURE 369 of Photoepolymerizationinitiater initiater, Ciba SpecialtyChemicals Inc.) 1.8 mass parts and NCI-930 (Inc. of Asahi Denka Co., Ltd.) 0.1 mass parts, as fluorine system surfactant MEGAFAC F-554 (Dainippon Ink Chemicals's system) 0.05 mass parts and mix as the propylene glycol methyl ether acetate of solvent, prepare the coloured composition (S-1) that solid component concentration is 20 quality %.
the evaluation of colorimetric properties
After using spin coater to be coated with the coloured composition obtained on the glass substrate, carry out 10 minutes preliminary dryings with the hot plates of 80 DEG C and form film.The rotating speed changing spin coater forms 3 different films of thickness by same operation.
Then, after these substrates are cooled to room temperature, high-pressure sodium lamp is used, without photomask with 2000J/m 2exposure the exposure of each film is comprised to the radioactive ray of each wavelength of 365nm, 405nm and 436nm.Thereafter, with developer pressure 1kgf/cm 2(nozzle diameter 1mm) sprays the developer solution be made up of 0.04 quality % potassium hydroxide aqueous solution of 23 DEG C to these substrates, carries out spray development in 90 seconds.Thereafter, clean this substrate with ultrapure water, after air-dry, dry after carrying out 30 minutes further in the dustless baking oven of 200 DEG C, form the color solidification film evaluated.
Color analyzer (Otsuka Electronics Co., Ltd. MCPD2000 is used to the 3 color solidification films obtained), in illuminant-C, 2 degree of visual fields, measure the chromaticity coordinate value (x, y) in CIE color system and values (Y).According to measurement result, chromaticity coordinate value x when obtaining chromaticity coordinate value y=0.329 and values (Y).Evaluation result is shown in table 3.Should illustrate, more high brightness is higher can to say values (Y).
foreign matter is evaluated
Spin coater is used to be formed with the SiO preventing sodion stripping on surface 2after leaving standstill the coloured composition (S-1) of 3 days at the soda-lime glass substrate of the 10cm × 10cm of film is coated with 5 DEG C, carry out 4 minutes preliminary dryings with the hot plates of 90 DEG C, form the film that pre-baked thickness becomes 2.5 μm.With the substrate that observation by light microscope obtains, if do not observe the generation of foreign matter on film, be designated as "○", if the generation number of the foreign matter on film is 1 ~ 10, be designated as " △ ", if the generation number observing the foreign matter on film is more than 11, be designated as "×".Evaluation result is shown in table 3.Should illustrate, the storage stability of foreign matter fewer expression coloured composition is more excellent.
Embodiment 2 ~ 4 and comparative example 1,2
In embodiment 1, the kind of change colourant solution as shown in table 3, in addition, prepares coloured composition similarly to Example 1.Then evaluate similarly to Example 1.Show the result in table 3.
Embodiment 5,6 and comparative example 3
In embodiment 1, the kind of change colourant solution as shown in table 3 and resin glue, in addition, prepares coloured composition similarly to Example 1.Then evaluate similarly to Example 1.Show the result in table 3.
Table 3

Claims (7)

1. a coloured composition, containing (A) colorant, (B) resin glue and (C) polymerizable compound,
(A) colorant contains the compound with the structure that following formula (1) represents and the compound with the structure that following formula (2) represents, the content with the compound of the structure that following formula (2) represents is more than 0.001 quality % relative to the compound with the structure that following formula (1) represents and the total content of the compound with the structure that following formula (2) represents
In formula (1),
Ring Z 1with ring Z 2represent substituted or non-substituted heterocycle independently of each other,
P represents 1 or 2, wherein, when p is 2, and multiple R 1and R 2can be the same or different,
R 1~ R 3represent hydrogen atom, halogen atom or substituted or non-substituted alkyl independently of each other,
In formula (2),
Ring Z 3with ring Z 4represent substituted or non-substituted heterocycle independently of each other,
When p is 1, q represents the integer of more than 2, and when p is 2, q represents the integer of more than 3,
R 4~ R 6represent hydrogen atom, halogen atom or substituted or non-substituted alkyl independently of each other, wherein, multiple R 4and R 5can be the same or different.
2. coloured composition according to claim 1, for the formation of red pixel or green pixel.
3. coloured composition according to claim 1 and 2, wherein, the described compound with the structure that formula (1) represents is the compound with the structure that following formula (1A) represents, the described compound with the structure that formula (2) represents is the compound with the structure that following formula (2A) represents
In formula (1A),
R 1~ R 3with the R in claim 1 1~ R 3implication is identical,
Ring Z 1Awith ring Z 2Arepresent substituted or non-substituted aromatic hydrocarbon ring independently of each other,
Q 1and Q 2represent-O-,-S-or-CR independently of each other 13r 14-,
R 11~ R 14represent substituted or non-substituted alkyl independently of each other,
In formula (2A),
Q, R 4~ R 6with q, the R in claim 1 4~ R 6implication is identical,
Ring Z 3Awith ring Z 4Arepresent substituted or non-substituted aromatic hydrocarbon ring independently of each other,
Q 3and Q 4represent-O-,-S-or-CR independently of each other 23r 24-,
R 21~ R 24represent substituted or non-substituted alkyl independently of each other.
4. coloured composition according to claim 1 and 2, wherein, the compound that the content described in the compound of the structure that formula (2) represents has a structure that formula (1) represents relative to described and the described total content with the compound of the structure that formula (2) represents are 0.001 ~ 1 quality %.
5. a color solidification film, containing there is the compound of the structure that following formula (1) represents and there is the compound of the structure that following formula (2) represents, the content with the compound of the structure that following formula (2) represents is more than 0.001 quality % relative to the compound with the structure that following formula (1) represents and the total content of the compound with the structure that following formula (2) represents
In formula (1),
Ring Z 1with ring Z 2represent substituted or non-substituted heterocycle independently of each other,
P represents 1 or 2, wherein, when p is 2, and multiple R 1and R 2can be the same or different,
R 1~ R 3represent hydrogen atom, halogen atom or substituted or non-substituted alkyl independently of each other,
In formula (2),
Ring Z 3with ring Z 4represent substituted or non-substituted heterocycle independently of each other,
When p is 1, q represents the integer of more than 2, and when p is 2, q represents the integer of more than 3,
R 4~ R 6represent hydrogen atom, halogen atom or substituted or non-substituted alkyl independently of each other, wherein, multiple R 4and R 5can be the same or different.
6. a display element, possesses color solidification film according to claim 5.
7. a colorant, containing there is the compound of the structure that following formula (1) represents and there is the compound of the structure that following formula (2) represents, the content with the compound of the structure that following formula (2) represents is more than 0.001 quality % relative to the compound with the structure that following formula (1) represents and the total content of the compound with the structure that following formula (2) represents
In formula (1),
Ring Z 1with ring Z 2represent substituted or non-substituted heterocycle independently of each other,
P represents 1 or 2, wherein, when p is 2, and multiple R 1and R 2can be the same or different,
R 1~ R 3represent hydrogen atom, halogen atom or substituted or non-substituted alkyl independently of each other,
In formula (2),
Ring Z 3with ring Z 4represent substituted or non-substituted heterocycle independently of each other,
When p is 1, q represents the integer of more than 2, and when p is 2, q represents the integer of more than 3,
R 4~ R 6represent hydrogen atom, halogen atom or substituted or non-substituted alkyl independently of each other, wherein, multiple R 4and R 5can be the same or different.
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KR20150064679A (en) 2015-06-11
KR102373077B1 (en) 2022-03-11

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