SG178428A1 - Colored resin composition - Google Patents

Colored resin composition Download PDF

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Publication number
SG178428A1
SG178428A1 SG2012010526A SG2012010526A SG178428A1 SG 178428 A1 SG178428 A1 SG 178428A1 SG 2012010526 A SG2012010526 A SG 2012010526A SG 2012010526 A SG2012010526 A SG 2012010526A SG 178428 A1 SG178428 A1 SG 178428A1
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Singapore
Prior art keywords
group
acrylate
resin composition
meth
pigment
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Application number
SG2012010526A
Inventor
Satoru Kobayashi
Yutaka Ishii
Takaaki Kurata
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Nippon Kayaku Kk
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Publication of SG178428A1 publication Critical patent/SG178428A1/en

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • 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
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optical Filters (AREA)
  • Materials For Photolithography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

[Abstract][Problems to be solved] To provide a colored resin composition for forming highly reliable pixels of color filters which have high sharpness, high quality color characteristics, and improved resistance compared to conventional compositions. [Means for solving the problems] The colored resin composition for producing pixels of color filters of the invention is easily obtained by using a specific colorant compound added with a binder resin, a solvent, and a curing agent, etc. The pixels of the color filter produced contain a dye as a colorant compound and have high reliability with an excellent resistance including heat resistance.[Representative drawing] None

Description

DESCRIPTION
COLORED RESIN COMPOSITION
TECHNICAL FIELD
[0001]
The present invention relates to a colored resin composition for forming blue, red, and green pixels, a color filter produced by using the colored resin composition, and an electronic display device like a liquid crystal display device, an imaging device (CCD and CMOS), and an organic EL display that are produced by using the color filter.
BACKGROUND ART
[00C2]
A color filter is necessary for colorization of a liquid crystal display element used in a iiquid crystal display (LCD) such as a laptop PC, a liquid crystal television, a cellular phone, and the like, or for colorization of an imaging device (CCD, CMOS) used as an input device of a digital camera or a cclor printer. As amethod of manufacturing a color filter used for a liquid crystal display device or for a solid-state imaging element, there are many method such as a staining nethod, an electrode position method, a printing method, and a pigment dispersion method, and the like. In recent days the pigment dispersion method is mostly used. As a method of patterning, photolithography is the most representative method. According to the method, a color filter is produced by using a mixture of a photosensitive resin composition and a pigment dispersiocn.
Recently, a method of producing a color filter by directly applying a coloring ink to a substrate with an ink jet printer without using a mask is also performed.
[0003]
Improvements in color purity, chroma, brightness, and contrast, that are the characteristics required for a color filter, are particularly impertant. With an improvement in brightness, light amount of a backlight can be lowered and powar consumption can be suppressed to a low level, and therefore such an improvement is also an environmentally-required technology.
To improve cooler purity of a celor filter, it is necessary Lo increase the content of a coloring pigment or to choose a pigment having better spectral waveform. Meanwhile, since an improvement in brightness can be achieved by increasing the light transmittance, pigment concentration should be lowered or film thickness should be reduced. To satisfy these two contradicting characteristics at the same time, a pigment micronization is carried out. However, since resistance and dispersion stability approach certain limits as the micronization progresses, it isdifficult te improve resistance when brightness is increased at a current stage.
[0004]
As another apprecach to solve the problems described above, an investigation of a color filter employing a dye is carried out. When a dye is used, both the color purity and brightness can be obtained at the same time, which is difficult to achieve by using a pigment, and there is also an advantage that, not being a particle, it can suppress light scattering so that contrast can be also improved. However, for a display body like
TV which requires long term reliability, light resistance or heat resistance is particularly required. In this regard, many dyes, in particular blue dyes, have significantly lower resistance than pigments. For example, disclosed in Patent
Document 1 and 2 is a color filter wherein triphenylmethane compounds are used. However, the triphenylmethane compounds have significantly low light resistance or heat resistance, and therefore they cannot be used at practical level. Further, although it is disclosed in Patent Document 3 that xanthene compounds have excellent brightness, there is no description relating to resistance. For a color filter required to have high reliability, a colored resin composition containing colorant compounds with excellent resistances is waited for, but very few are practically usable. As such, as a next generation, a high quality color filter having excellent brightness and excellent resistance is in need.
CITATION LIST
PATENT DOCUMENTS :
[0005]
Patent Document 1: Japanese Patent Application
Laid-Open (JP-A) No. B8-94826
Patent Document 2: JP-A No. 2002-14222
Patent Document 3: JP-A Ne. 2010-32999
Patent Document 4: JP-A No. 63-172772
DISCLOSURE OF THE INVENTION PROBLEM TC BE SOLVED BY THE INVENTION
[0005]
An object of the invention is to provide a color filter having excellent color characteristics like brightness and ’ excellent heat resistance and light resistance.
MEANS FOR SOLVING PROBLEM
[0007]
The present inventeors have made extensive studies in order to solve the problems described above, and as a result, they have found that the problems canbe solved by using a colored resin composition containing a specific colorant compound for producing pixels of a color filter, and thus the invention has been achieved.
[0008]
Specifically, the invention relates to the following: (1) A colored resin composition for color filters comprising a colorant compound represented by the following formula (1), a binder resin, a sclvent, and a curing agent [Chemical Formula 1]
Ys Rj Ry 15 _N : 0 NT
ICL
Ro 7 Rs
Ry Re z® (1)
Xg 7 Xi
X4 Xs
Xs {wherein R; to Rg each independently represent a hydrogen atom, = halogen atom, a Cl1-Cl2 alkyl group, a Cl-Cl2 alkoxy group, a nitro group, a carboxyl group, or an alkoxycarbonyl group.
Y; to Ys each independently represent a hydrogen atom, a C1-Cl12 alkyl group, or an aryl group. X; to Xs each independently represent a hydrogen atom, a C1-Cl2 alkyl group, a Cl-Cl2 alkoxy group, a halogen atom, a nitro group, a phenoxy group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, a sulfo group, or a sulfamovyl group. Anion part Z° represents an aikylsulfonyl methide anion having a highly halogenated C1-C10 alkyl group), {2} The colored resin composition described in the above (1), in which Z° in the formula (1) is a tristrifluorcmethanesulfonyl methide anion, (3) The colored resin composition described in the above (1) or (2), which comprises a metal phthalocyanine pigment, (4) A colored cured film for color filters obtained by patterning of the colored resin composition described in any one of the above (1) to (3), (5) A color filter consisting of the colored cured film for color filters described in the above (4),
(6) A display device comprising the color filter described in the above {5}, and (7) A solid-state imaging device comprising the cclor filter described in the above (5).
EFFECT OF THE INVENTION
[0009]
According to the colored resin composition of the invention comprising a specific colorant compound, high quality color filters having excellent brightness and heat resistance can be provided.
DETAILED DESCRIPTION OF THE INVENTION
[0010]
The colored resin composition of the invention comprises a binder resin, a solvent, a curing agent, and a specific colorant compound, and if necessary, an additional colorant compound like other pigments and dyes and various additives like a surface active agent, a photopolymerization initiator, a thermal polymerization initiator, a polymerization inhibitor, and a UV absorbing agent, but not limited thereto. As for the component other than the specific colorant compound, it can be used without specific limitation.
[0011]
As for the method for manufacturing pixels by using the colored resin composition of the invention, there are photolithography and an ink jet method, etc. For the former,
a light sensitive resin composition having excellent developability and using a photeopolymerization initiator is used. For the latter, the photopolymerization initiator is not necessarily required sc that a thermosetting resin composition is used.
[0012]
R; to Rg in the colorant compound represented by the formula (i) as used in the invention each independently represent a hydrogen atom, a halogen atom, a C1-Ci2 alkyl group, a Cl-Cl2 alkoxy group, a nitro group, a carboxyl group, or an alkoxycarbonyl group. Y; to Ys each independently represent a hydrogen atom, a Cl1-C12 aikyl group, or ah aryl group. X; to
Xs each independently represent a hydrogen atom, a C1-Cl2 alkyl group, a Cl-Cl2 alkoxy group, a halogen atom, a nitro group, a phenoxy group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, a sulfo group, or a sulfamoyl group. The anion part Z° represents a sulfonyl methide anion having a highly halogenated C1-Cl10 alkyl group.
[0013]
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. [C014]
Examples of the alkyl group include a C1-Ci2 alkyl group like methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, iso-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, and cyclohexyl. The alkyl group may have a substituent group, and examples of the alkyl group having a substituent group inciude a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a Z2-sulfoethyl group, a carboxyethyl group, a cyanoethyl group, a methoxyethyl group, an ethoxyethyl group, a butoxyethyl group, a trifluoromethyl group, and a pentafluoroethyl group. Further, examples of the substituent group which may be contained in the alkyl group include a carbamoyl group and a carboxyl group.
[0015]
Examples of the alkoxy group include an alkoxy group having C1-C12 alkyl group as described above. Examples of the alkoxycarbonyl group include the alkoxycarbonyl group having
Cl-Cl2 aikyl group as described above.
[0016]
Examples of the aryl group include an aromatic hydrocarbon residue like a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, and a benzopyrenyl group; and an aromatic heterocyclic residue like a pyridyl group, a pyrazyl group, a pyrimidyl group, a quinolyl group, an isodquinelyl group, a pyrrolyl group, an indolyl group, an imidazolyl group, a carbazolyl group, a thienyl group, and a furyl group. These aryl groups may have a substituent group and examples of the substituent group include an alkyl group, an alkoxy group, a halogen atom, a sulfo group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, and a cyano group.
[0017]
The phenoxy group may have a substituent grcup, and examples of the substituent group include a linear or branched
C1-C12 alkyl group, a halogen atom, an amino group, an alkylamino grcup, and a hydroxy group.
[0018]
Examples of the alkoxycarbonyl group include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, iscpropyloxycarbonyl, butyvloxycarbonyl, isobutyloxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclchexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, cctyloxycarbonyl, 2-ethylhexyloxycarbonyl, cyclococtyloxycarbonyl, nonyloxycarbonyl, decanyloxycarbonyl, tricyclodecanyioxycarbonyl, methoxypropyloxycarbonyl, ethoxypropyloxycarbonyl, hexyloxypropyloxycarbonvl,
Z-ethylhexyloxypropyloxycarbonyl, methoxyvhexyleoxycarbonyl, and benzyloxycarbonyl.
[0019]
The carbamoyl group may have a substituent group, and examples of the substituent group include a linear or branched, substituted or unsubstituted C1-C12 alkyl group, a phenvl group, a benzyl group, a tosyl group, and a pyrimidinyl group. Further, with respect to the carbamoyl group, two alkyl groups attached on the nitrogen may form, together with the nitrogen atom, a
C3-C12 cycloalkyl ring cor an aliphatic heterocycle having at least one heteroatom like nitrogen, oxygen, and sulfur.
[0020]
Examples of the sulfo group include methanesulfonyl,
ethanesulfonyl, hexanesulfonryl, and decanesulfonyl.
[0021]
Examples of the sulfamoyl group include sulfamoyl, methanesulfamoyl, ethanesulfamoyl, propanesulfamoyl, isopropanesulfamoyl, butanesulfamoyl, isobutanesulfamoyl, pentanesulfamoyl, isopentanesulfamoyl, neopentanesulfamoyl, cyclopentanesulfamoyl, hexanesulfamoyl, cyclchexanesulfamoyl, heptanesulfamoyl, cycloheptanesulfamoyl, octanesulfamoyl, 2-ethylhexanesul famoyl, 1,5-dimethylhexanesulfamoyl, cyclooctanesulfamoyl, nonanesulfamoyl, decanesulfameyli, tricyclodecanesul famoyl, methoxyprcpanesulfamoyl, ethoxypropanesulfamoyl, propoxypropanesulfamoyl, isopropoxypropanesulfamoyl, hexyloxypropanesulfamovl, 2-ethylhexyloxypropanesulfamoyl, methoxyhexanesulfamoyl, and 3-phenyl-i-methylpropanesulfamoyl.
[0022]
The anion part 2° in the formula (1) represents a sulfonyl methide anion having a highly halogenated Ci-ClC alkyl group, and a tristrifiuvoromethanesulfonyl methide anion is particularly preferable.
[0023]
The colorant compcund used for the colored resin composition of the invention is obtained according to a known synthetic method described in, for example, “Theoretical "Preduction, Dye Chemistry” by Hosoda Yutaka (published by
Gihodc Shuppan Co., Ltd., pp 373 to 375). However, it can be also synthesized by obtaining a commerical product in which the anion part Z7 is a chloride anion and adding a corresponding base or acid for salt-exchange.
[0024]
When the colorant compound of the invention is synthesized by salt-exchange, a cclorant compound in which the anion part Z7 is a chloride anion is dissolved in a reaction solvent (for example, water or a water-soluble pclar sclvent like methanol, ethanol, iscprcpancl, acetone,
N,N~dimethylformamide (herein below, abbreviated as DMF),
N-methyl-2-pyrrolidone (herein below, abbreviated as NMP), and the solvent may be used either singly or in a mixture thereof), a corresponding base or acid is added in an amount of 0.5 to 3 equivalents thereto, the mixture is stirred at a pre-determined temperature (for example 0 to 100°C), and precipitated crystals are filtered to easily obtain the target compound.
[0025]
Specific examples represented by the formula (1) above are given in the following Table 1-1 and Table 1-2, but the invention is net limited by them.
[0026] [Table 1]
Table 1-1
Compound No. Chemical formula ge Et
N >
Et” a =1
I
F3C0;5..280,CF,
COOH S0,CFy
H H
. ] oS Oy 3 we INP F360;9..9,.80,CF, or SO,CF; & Et at i o Hy
Fit0;5.8.80,0F,
COE 80,CF, & Et yE ee Sem
FiC0.5.0.50,CF, 1 ore S04CF,
Et Et ©
Bt NN Ne i F105. 980:CFs {
CONH: SOLF
ZY <7) Fs nH H , n &
Et” o Moet , FiC0:5. 2. 80,CF,
COOEL SO,CF;
H H
N o Ne
Et” “Et : 1 FaC0z5. 2, 80:CF; 1 1 : 50,CFy " 5
N He
HW CH, he 0g s0icrs
COOEL S0,CFy
Table 1-2
Compound No. Chemical formula
H el @
WN BN i ; ! :
HyC ANF FiC0iS-g-S0:CR . ~~ COO B0,CFy
NG
Et Et i | 5 ge RO ogy — Pe i FiCO:8. 8. SO. CF,
H
CONHY S0,CF. nA ~ oH ®
Et;N 0) Q NEt; pe
H FiC08. 9 S0,0F
N
9g ° he SO.CFs ®
EtN ® oc NEL,
DG
FaC0;5..2_S0,CF,
NY 50,0F;
L_NH @
Et;N ® 0 NEt,
XO
FyC0,5, © BO,CF cl COOK 2 Se” LF cl iQ cl SO,CF, cl a
ELN OC O NEt, 7 8 FiCO;S. © .SO.CF,
OH
C] 0 SO,CF, cl Ci
Ql @
Et;N o NEt; ® LJ FiCO,5. © .50,CF; 0 « ¢ ag SO,CF,
[0027]
The colored resin compositien of the invention is a composition which contains the colorant compound represented by the formula (1) in an amcunt of preferably 1 fo 60 parts by weight, and more preferably 5 to 30 parts by weight compared to the total solidmatter (indicating the total amount of a solid matter consisting of a colorant compound, a binder resin, and a curing agent, etc., and the same shall apply herein below).
When the content is above the range, problems like precipitation and aggregation occur and adhesiveness to a substrate may decrease due to insufficient curing. On the other hand, when it is below the range, there is a tendency that sufficient color purity cannot be obtained as color characteristics, although it may not cause a big problem.
[0028]
When the colorant compound represented by the formula (1) has a poor solubility in the colored resin composition, it can be dispersed with an aid of a dispersant, similar to a pigment as an optional component described below. The colorant compound represented by the formula (1) may be used either singly or in combination of two or more, and it may be also mixed with other dye or pigment. As the invention mostly relates to blue pixels or red pixels, it is preferable that a known blue dve, violet dye, red dye or yellow dye, or blue pigment, violet pigment, red pigment, or vellow pigment is admixed therewith.
[0029]
The binder resin used in the invention is preferably scluble in an alkali developing solution used for a development prccess for producing a color filter according to photelithographic design and has a sufficient curing property with a photopolymerization initiator or a photopolymerizable monomer to form favorable fine patterns. It is also reguired for the pigment dispersant resin composition to have good compatibility with a constitutional material like photopoliymerization initiator, photopolymerizable monomer, and pigment dispersion and geod stability not to cause any precipitation or aggregation. In an ink jet method, alkali solubility is not particularly required, and therefore a resin having good compatibility with other colorant compound or additives can be selected.
[0030]
Any resin known in the art can be used as a binder resin.
However, it is preferably a copolymer ¢f an ethylenically unsaturated monomer having at least one carboxyl group or a hydroxy group cr an ethylenically unsaturated monomer having other copclymerizable aromatic hydrocarbon group or aliphatic hydrocarbon group as described below. Further, a resin having an epoxy group in a side chain cr terminal or an epoxy acrylate resin added with acrylate can be also used. The monomer may be used either singly or in combination of two or more.
[0031]
Examples of the ethylenically unsaturated monomer having carboxyl group that can be used in the invention include unsaturated monocarboxylic acids like acrylic acid,
methacrylic acid, crotonic acid, o-chleoroacrylic acid, ethacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids (anhydride) like maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; unsaturated polycarboxylic acids (anhydride) having valency of 3 or more, 2— (meth)acryloyloxyethyl hexahydrophthalic acid,
Z2-methacryloyloxyethyl-2-hydroxypropylphthalate, and 2~acryloyloxyethyl —2-hydroxyethyl phthalic acid. They may be used either singly or in combination of two or more.
[0032]
Examples of the ethylenically unsaturated monomer having hydroxy group that can be used in the invention include 2-hydroxyethyl (meth)acrylate, Z-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth})acrylate, b5-hydroxypentyl {(meth)acrylate, 4-hydroxypentyl (meth) acrylate, 3-hydroxypentyl (meth)acrylate, o-hydroxyhexyl (meth)acrylate, 5-hydrexyhexyl (meth)acrylate, 4d-hydroxyhexyl (meth)acrylate, 5-hydroxy-3-methyl-pentyl {meth)acrylate, cyclohexane-1,4~dimethanocl mono (meth) acrylate, 2-(Z-hydroxyethyioxy)ethyl {meth}acrylate, glycerin monomethacrylate, and polyalkylene glvcol mono (meth)acrylate having terminal hydroxy group like polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, and poly(ethylene glycol-propylene glycol)monomethacrylate. They may be used either singly or in combination of twec or more.
[0033]
Examples of an ethylenically unsaturated monomer that is copolymerizable other than those described above include an aromatic vinyl compound like styrene, o-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, and p—methoxysiyrene; unsaturated carboxylic acid esters like methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, sec-butyl {meth)acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth)acrylate, paracumyl phenoxyethylene glycol {meth)acrylate, 2-hydroxy=-3-phenoxypropyl {(meth)acrylate, o-phenylphenol glycidyl ether (meth)acrylate, hydroxyethyl-c-phenyiphenol (meth)acrylate, and phenoxyethyl (meth)acrylate; alicyclic skeletons like cyclopentyl (meth)acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, norbornyl (meth)acrylate, norbornylmethyl (meth)acrylate, phenyinorbornyl (meth)acrylate, cyanconorbornyl (meth)acrylate, iscbornyl (meth)acrylate, bornyl (meth}acrylate, menthyl {meth)acrylate, pentyl (meth)acrylate, adamantyl (meth)acrylate, dimethyladamantyl (meth)acrylate, tricyclo[5.2.1.02,6]deca-8-yl=(meth)acrylate, tricyclo[5.2.1.02,6]deca-4-methyl=(meth)acrylate, cyclodecyl (meth)acrylate,
2-{meth)acryloyloxyethylhexahydrophthalic acid, and t-butylcyclohexyl (meth)acrylate; polyalkylene glycol mono (meth) acrylates having a terminal hydroxy group like polyethylene glycol monc{meth)acrylate, polypropylene glycol mono (meth)acrylate, and poly(ethylene glycol-propylene glycol)monomethacrylate; polyalkylene glycol mono (meth)acrylates having a terminal alkyl group like methoxypolyethylene glycel monomethacrylate, lauroxypolyethylene glycol mono (meth)acrylate, octoxypolyethylene glycol polypropylene glycol mono (meth)acrylate, nonylphenoxypolyethylene glyccl mono acrylate, nonylphenoxypolypropylene glycol mono acrylate, and arylexypclyethylene giycel pelypropylene glycol mono (meth}acrylate; unsaturated carboxylic acid aminoalkyl esters like Z2-aminoethyl acrylate, 2-aminoethyl methacrylate,
Z2-aminopropyl acrylate, Z-aminopropyl methacrylate, . 3—aminopropyl acrylate, and 3-aminopropyl methacrylate; unsaturated carboxylic acid glycidyl esters like glycidyl acrylate, glycidyl methacrylate, 3, 4-epoxybutyl {(meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate glycidyl ether; carboxylic acid vinyl esters like vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ethers like vinyl methyl ether, vinyl ethyl ether, aryl glycidyl ether, and methallyl glycidyl ether; cyano vinyl compounds like acrylonitrile, methacrylonitrile, a-chloroacrylonitrile, and cyano vinylidene; unsaturated amides or unsaturated imides like acrylamide, methacrylamide, o-chlorcacrylamide, N-phenyl maleimide, N-cyclohexyl maleimide,
N- (meth) acryloylphthalimide, N-(2-hydroxyethyl)acrylamide,
N-{2-hydroxyethyl)methacrylamide, and maleimide; aliphatic conjugated dienes like 1,3-butadiene, isoprene, and chlorcprene, and; macromonomers having a monoacryloyl group or a monomethacryloyl group at the terminal of a polymer molecular chain like polystyrene, polymethyl acrylate, polymethyl methacrylate, poly n-butyl acrylate, poly n-butyl methacrylate, and pelysilicone. They may be used either singly or in combination of two or more.
[0034]
Further, a polymer having an additional unsaturated double bond in the copolymer side chain is also useful.
Examples therecf include a compound which is obtained by reaction of a maleic anhydride part of a copolymer between maleic anhydride and a copolymerizable styrene, vinyl phenol, acrylic acid, acrylic acid ester, cr acrylamide with an acrylate having an alcoholic hydroxy group like hydroxyethyl acrylate or an acrylate having an epoxy group like glycidyl methacrylate followed by half-esterification, or a compound which is obtained by reacting acrylic acid with a hydroxy group of a cepolymer between acrylic acid or acrylic acid ester and an acrylate having an alcoholic hydroxy group like hydroxyethyl acrylate. Further, a urethane resin, a polyamide resin, a polyimide resin, a polyester resin, and commercially available
ACA-200M (trade name, manufactured by Daicel Corporation),
ORGA-3060 (trade name, manufactured by OSAKA ORGANIC CHEMICAL
INDUSTRY LTD.) , AX3-BNX0Z (trade name, manufactured by NIPPON
SHOKUBAI CO., LTD.), UXE-3024 (trade name, manufactured by
NIPPON KAYAKU CQ,, LTD.}), UXE-3000 {trade name, manufactured by NIPPON KAYAKU CO., LTD.) , ZGA~287H {trade name, manufactured by NIPPON KAYAKU CO., LTD.), TCR-1338H (trade name, manufactured by NIPPON KAYAKU CO., LTD.) , ZXR-1722H (trade name, manufactured by NIPPON KAYAKU CO., LTD.) , ZFR-1401H (trade name, manufactured by NIPPON KAYAKU CO., LTD.), and ZCR-1642 (trade name, manufactured by NIPPON KAYAKU CO., LTD.) can be also used.
[0035]
For dispersing a pigment, a dispersant or a dispersant aid is generally used, and there is a pigment-based dispersant, a resin-based dispersant, or a surface active agent which has a good adsorptivity to a pigment. With respect to the pigment-based dispersant, a method of mixing a sulfonate or a metal salt of a pigment with a pigment as disclosed in Patent
Document 4 or a method of mixing with a substituted aminomethyl derivative is known, for example. As for the resin-based dispersant, there is a non-polar and non-ionic dispersant.
However, a polymer resin with an acid value or an amine value to give a good pigment adsorptivity is more general. Examples thereof include an acryl resin, a polyurethane resin, polycarboxylic acid, a pclyamide resin and a polyester resin.
Specific examples thereof include ED211 (trade name, manufactured by Kusumoto Chemicals, Ltd.), AJISPER-PB321 {trade name, manufactured by Ajinomoto Fine-Technho Co., Inc.)
and SOLSPERSE 71000 (trade name, manufactured by Avecia).
[0036]
For producing the binder resin (i.e., copolymer) that is used in the invention, a polymerization initiator is used.
Specific examples of the polymerization initiator that is used for synthesis of a copolymer include o,a’ -azobis (iscbutyronitrile), 2,2’-azobis(2-methylbutyronitrile), t-butyl percctoate, di-t-butyl percxide peroxo benzoyl methyl ethyl ketone peroxide. Use ratio of the peclymerization initiator is 0.01 to 25 parts by weight compared to the total of monomers used for synthesis of a copolymer. Further, it is preferable to use an organic sclvent explained belcw for synthesis of a copolymer. However, a sclvent having sufficient dissolving power for a monofunctional monomer or a polymerization initiator should be emplcyed. The reaction temperature for synthesis of a copolymer is preferably 50 to 120°C, and particularly preferably 80 to 100°C. Further, the reaction time is preferably 1 to €0 hours, and more preferably 3 to 20 hours. The preferred acid value of the copolymer is to 300 (mgKOH/g), and the preferred hydroxy value is 10 to 200 (mgKOH/g). When the acid value or the hydroxy value is 10 or less, the developability is impaired. The weight average molecular weight (Mw) of the copolymer is preferably 2000 to 400000, and more preferably 3000 to 100000. When the weight average molecular weight is less than or equal to 2000 or more than or equal to 400000, the sensitivity and the developability, etc. are impaired.
[C037]
According to the invention, the binder resin may be used either singly or in combination of two or more. The content of the binder resin of the invention is generally 0.5 to 99 parts by weight, and preferably 5 to 50 parts by weight compared to the 100 parts by weight of the total solid matter in the colored resin composition. When the content of the binder resin is less than 0.5 parts by weight, problems may arise that alkali developability is impaired or surface contamination or film residue occurs in an area other than a pixel-forming part.
[0038]
In case of radical polymerization, examples of the curing agent used in the invention include a photopolymerization monomer. In case of ion curing, examples include an epoxy resin as wells as a melamine curing agent. Specific examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth)acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth)acrylate, triethylene glycol (meth}acrylate, tetraethylene glycol (meth)acrylate, trimethylol prcpane tri (meth)acrylate, pentaerythritol di (meth)acrylate, pentaerythritol tri (meth)acrylate, pentaerythritol tetra {meth)acrylate, dipentaerythritol hexa{meth)acrylate, glycerol (meth) acrylate, bisphenol-A type epoxy di(meth)acrylate, bisphenol-F type epoxy di (meth)acrylate, bisphenol-fluorene type epoxy di (meth)acrylate, ethoxylated trimethylol propane tri (meth)acrylate, propoxylated trimethylol propane tri (meth)acrylate, ethoxylated glycerin tri (meth}acrylate, ethoxylated isocyanuric acid tri (meth)acrylate, ditrimethylol propane tetra (meth)acrylate, ethoxylated pentaerythritol tetra (meth)acrylate, 9,8-bis[4- (2-acryloyloxyethoxy) phenyl] fluorene, Kayarad
RP-1040 (trade name, manufactured by NIPPON KAYAKU CO., LTD.},
Kayarad DPCA-30 (trade name, manufactured by NIPPON KAYAKU CO.,
LTD.), UA-33H (trade name, manufactured by Shin Nakamura
Chemical Co., Ltd.), UA-53H (trade name, manufactured by Shin
Nakamura Chemical Co., Ltd. ), M~8060 {trade name, manufactured by TOAGOSEI CO., LTD.); as a thiol-based monomer for polymerization, TEMPIC (trade name, manufactured by Sakai
Chemical Industry Co., Ltd.), TMMP (trade name, manufactured by Sakai Chemical Industry Co., Ltd.), PEMP {trade name, manufactured by Sakai Chemical Industry Co., Ltd.), and DPMP (trade name, manufactured by Sakai Chemical Industry Co.,
Ltd.) ; as an epoxy resin, NC-6000, NC-3000, EQCN-1020, XD-1000,
EPPN-501H, BREN-S, and NC-7300L, all manufactured by NIPPON
KAYAKU CO., LTD., CELLOXIDE 2021%, EHPE3150, CYCLOMER M100, and
EPOLEAD PB3600, all manufactured by Daicel Corporation, EPICOAT 828, EPICOAT YX8000, and EPICOAT YX4000, all manufactured by
Japan Epoxy Resins Co., Ltd., Sila-Ace S510 (trade name, manufactured by Chisso Corporation), and TEPIC (trade name, manufactured by Nissan Chemical Industries, Ltd.), etc., and; as a melamine curing agent, methylolated melamine and Mw=-30C (trade name, manufactured by SANWA Chemical Co., Ltd.). They may be used either singly or in combination of twe or more. The content is 1 to 80 parts by weight, and preferably 5 to 30 parts by weight compared to the 100 parts by weight of the total solid matter in the colored resin compesition.
[0039]
The pigment which can be used in combination with the essential components of the colored resin composition of the invention preferably has spectral characteristics that are suitable for color filters. It may be suitably selected from a dye, an organic pigment and an inorganic pigment. If necessary, it may be used either singly or in combination of two or more. The content is 0 to 60 parts by weight, and preferably 5 to 30 parts by weight compared to the 100 parts by weight of the total solid matter in the colcred resin composition. Various pigments and dyes are described herein under.
[0040]
The organic pigment that can be used in combination with the essential components of the colored resin composition of the invention is not specifically limited, and the examples thereof include a pigment like an anthraquinone-based pigment, a phthalocyanine-based pigment, a triphenylmethane-based pigment, a benzimidazolone-based pigment, a guinacridone-based pigment, an azo chelate-based pigment, an azo-based pigment, an iscindoline-based pigment, an isoindolinone-based pigment, a pyranthrone-based pigment, an indanthrone-based pigment, an anthrapyrimidine-based pigment, a dibromoanthanthrone-based pigment, a flavanthrone-based pigment, a perylene-based pigment, a perinone-based pigment, a quinophthalone-based pigment, a thioindigo-based pigment, a dioxadine-based pigment, a quinarcridone-based pigment, and a xanthene-based pigment, and; a lake pigment and a dyed lake pigment which are cbtained by insclubilization of an acidic dye, abasic dye, or adirect dyewith a precipitating agent therefor.
More specific examples include, in terms of Color Index, Pigment
Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, ¢€6, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, Pigment Violet 3, 4, 27, 39, Pigment Red 7, 14, 41, 48:1, 48:2, 48:3, 48:4, 57:1, 81, 81:1, 81:2, 81:3, 81:4, 81:5, 122, 146, 168, 177, 178, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, 279,
Pigment Orange 43, 71, 73, Pigment Yellow 1, 2, 3, 4, 5, &, 10, 12, 13, 14, 15, le, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 54, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, leé6, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, isc, 181, 182, 185, 187, 188, 193, 194, 198, 1%9, 213, 214, and
Pigment Green 7, 36, 58. Of these, metal phthalccyanine pigments like Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, le, 17, 75, 76, 79, Pigment Violet 23, Pigment Red 177, 254, and Pigment Yellow 83, 138, 139, 150 which have good color and resistance, etc., are preferable. Pigment Blue 15:6 as a copper phthalocyanine pigment is particularly preferable.
[0041]
Examples of the inorganic pigment that can used in combination with the essential components of the colored resin composition of the invention are not specifically limited, and the examples thereof include a metal oxide, a metal sulfide, a sulfate salt, a metal hydroxide, and a metal carbonate like complex metal oxide pigment, carbon black, lowly oxidized black titan, titan oxide, barium sulfate, zinc oxide, lead sulfate, yvellow-colored lead, bengara, deep navy, navy, chromium oxide, antimony white, black iron, red lead, zinc sulfide, cadmium yellow, cadmium red, zinc, manganese purple, cobalt purple, barium sulfate, and magnesium carbonate.
[0042]
The dye which can be used in combination with the essential components of the colored resin composition of the invention is not specifically limited and examples thereof include an acidlc dye, a basic dye, a direct dye, a sulfur dye, a dye for dry-dyeing, a naphthol dye, a reactive dye and a dispersion dye.
Of these, any dye soluble in an crganic solvent can be suitably used. However, a dye insoluble in an organic solvent can be also suitably used after it is prepared as a dispersicn. It is well known that a dye inscluble in an organic solvent, for example an acidic dye, can be modified to an amine salt dye by reacting it with an organic amine compound (for example, n-preopylamine and ethylhexyl propionic acid amine) or to a dye having a sulfonamide group by reacting the sulfonic acid group with the same organic amine compound. The amine-medified dyes can be also used for the colored resin composition of the invention. More specific examples of the dye include, in terms of Color Index Number, Basic Blue 7, Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 80, 83, 86, 87, 20, 92, 96, 103, 1iz, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 249, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324, 335, 340, Basic Blue 7, 11, 15, 26, Solvent Blue 2, 3, 4, 5, 6, 23, 25, 35, 37, 38, 43, 55, 59, 67, 72, 124, Basic Violet 10, Acid Viclet 17, 49, Solvent Violet 4, 5, 14, Basic Red 1, 10, 29, Acid Red 91, 92, 97, 114, 138, 151, 289, Solvent Red 45, 49, 127, Acid Yellow 17, 23, 25, 29, 38, 40, 42, 76, Solvent
Yellow 4, 14, 15, 24, 76, 81, 82, 94, 98, 162, Solvent Orange 2, 1, 11, 15, 26, 56, and, Acid Green 9, 16.
[0043]
As for the photopelymerization initiator used for the colored resin composition of the invention, that is used for photography method, an initiator having sufficient sensitivity toward UV light emitted from a ultrahigh pressure mercury lamp generally used as a light source for exposure is preferable.
Examples thereof include a radical polymerizable photoradical initiator and an ion curable photo-acid generator or a photo-base generator. For the photopolymerization, a polymerization promoter component, which is called as a sensitizer to cause curing even with small exposure energy, can be used in combination. Examples of the photopolymerization initiator that can be used include, although not specifically limited, benzil, benzoin ether, benzoin butyl ether, benzoin propyl ether, benzophenone, 3,3" -dimethyl-4-methoxybenzophenone, benzovl benzoate, ester product of benzoyl benzoate, 4-benzoyi-4'-methyl diphenyl sulfide, benzyl dimethyl ketal,
Z-butoxyethyl-4d-methylaminobenzoate, chlorothioxanthone, methyl thioxanthone, ethyl thioxanthone, isopropyl thioxanthone, dimethyl thioxanthcne, diethyl thioxanthoeone, diisopropyl thioxanthone, dimethylaminomethylbenzoate, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, l1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-{4-isopropylphenyl)-2-hydroxy-2-methylpropan-1l-one, methylbenzoyl formate, 2-methyl-1~{(4-methylthiophenyl)-2-morphoclinopropan-1l-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)-butanone-1, 2,4-bis(trichloromethyl)-6- (4-methoxyphenyl)-1,3,5-s~triazi ne, 2,4,é-tris(trichloromethyl)-1,3,5-s-triazine, 2,4-bis (tribromomethyl)-6- (4 -methoxyphenyl)-1, 3, 5-s-triazi ne, 2,4,6-tris(tribromomethyl)-1,3,5-s-triazine, 2,4-bis(trichlorcomethyl)-6-(1,3-benzodioxoclan-5-yl}-1,3, 5-5 —~triazine, benzophencne, benzoyl benzoate, 1-{4-phenylsulfanylphenyl}butane-1, 2-dion-2-cxime-o-benzoat
Cy : 1-{d-methylsulfanylphenyl)bufane-1,2-dion-2-oxime-c-acetate, 1-(4d-methylsulfanylphenyl)butan-l-cnoxime-o—-acetate,
4,4" -bis{diethylamino} benzophenone, p-dimethylamino benzoic acid iscamyl ester, p-dimethylamino benzoic acid ethyl ester, 2,2’ -bis({o-chlorophenyl)-4,4’,5,5" -tetraphenyl-1,2"-biimida zcle, diazonaphthoquinone-based initiatcr, and commercially avallable Kayacure-DMBI, Kayacure-BDMK, Kayacure-BP-100,
Kayacure-BMEI, Kayacure-DETX-5, Kayacure-EPA (trade names, all manufactured by NIPPON KAYAKU CO., LTD.), Darocure 1173 and
Darocure 1116 (trade names, all manufactured by Merck Japan Co.
Ltd.), Irgacure S07 , Trgacure 369 (trade name, manufactured by BASF Japan Ltd.) , Irgacure 379 EG ( (trade name, manufactured by BASF Japan Ltd.), Irgacure OXE-01 (trade name, manufactured by BASF Japan Ltd.), Irgacure OXE-02 (trade name, manufactured by BASF Japan Ltd.), Irgacure PAGl103 (trade name, manufactured by BASF Japan Ltd.) , TME-triazine (trade name, manufactured by
SANWA Chemical Co., Ltd.), biimidazole (manufactured by
Kurogane Kasei Co., Ltd.}, and STR-110 and STR-1 (trade names, all manufactured by Respe Chemical Co., Ltd.).
[0044]
For a thermosetting resin composition for use in an ink jet method, etc., a thermo-polymerization initiator is generally used. However, if necessary, a photopolymerization initiator can be also used in combination. Examples of the thermo-polymerization initiator include an azo-based compound and an organic peroxide compound and specific examples thereof include 2,2'-azobisisobutyronitrile, 2,2" -azokis(2,4-dimethylvalerconitrile), : 2,2" —azobis (2-methylbutyronitrile), di-t-butyl peroxide,
dibenzeoyl peroxide, and cumyl peroxynecdecanoate.
[0045]
The polymerization initiator may be used either singly or in combination of two or more, if necessary. The content is 0.5 to 50 parts by weight, and preferably 1 to 25 parts by weight compared to the 100 parts by weight of the total solid matter in the colored resin composition.
[0046]
As for the organic solvent used in the invention, a solvent having sufficient solubility for the constitutional components of the colored resin composition, such as. a binder resin, a photopolymerizable monomer, and a photopeolymerization initiator, and also for the monofunctional monomer or the polymerization initiator used for the synthesis of a binder resin can be used. In addition, a solvent capable of maintaining the dispersion stability even when a pigment dispersion is prepared can be used.
[0047]
The organic solvent used in the invention is not specifically limited, as long as it is usable. Specific examples thereof include benzenes like benzene, toluene, and xylene; cellosolves like methyl cellosolve, ethyl cellosolve, and butyl cellosolve; cellosclve acetic acid esters like methyl cellosolve acetate, ethyl cellosclve acetate, and butyl cellosolve acetate; propylene glycol monoalkyl ether acetic acid esters like propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate; propionic acid esters like methyl methoxyprepionic acid, ethyl methoxypropionic acid, methyl ethoxypropionic acid, and ethyl ethoxypropionic acid; lactic acid esters like methyl lactate, ethyl lactate, and butyl lactate; diethylene glycols like diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; acetic acid esters like methyl acetate, ethyl acetate, and butyl acetate; ethers like dimethyl ether, diethyl ether, tetrahydrofuran, and dioxane; ketones like acetone, methyl ethyl ketone, methyl butyl ketone, and cyclohexanone, and; alcohols like methanol, ethanol, butanol, isopropyl alcohol, and benzyl alcohol.
[0048]
It may be used either singly or in combination of two or more. The use amount of the organic solvent is preferably 40 to 1000C parts by weight, and preferably 100 to 1000 parts by weight compared to the 100 parts by weight of the total solid matter in the colored resin composition.
[0049]
The colored resin compesition of the invention is produced bymixing and stirring of abinder resin, a curing agent, a specific colorant compound, and an crganic sclvent, etc. using a dissolver or a homomixer. In addition, other pigments or dyes can be added, if necessary. However, a pigment or a dye having low solubility is first converted into a dispersion by using an appropriate dispersant with a disperser like paint shaker, and then added and mixed with the colored resin composition.
[0050]
To the colored resin composition of the invention, various additives, for example, a filler, a surface active agent, a photopolymerization initiator, a thermal polymerization initiator, a polymerization inrhibitcr, an adhesion promoter, an anti-oxidant, a UV absorbing agent, and an aggregation inhibitor, can be further added, if necessary. Further, to remove foreign impurities, etc., the colored resin composition of the invention may be subjected to microfiltration using a filter, etc. after producticn.
[0051]
Herein below, a method of producing a cured product from - the colored resin composition of the invention is explained.
First, the colored resin composition of the invention is coated on a substrate like a glass substrate and a silicon plate to the film thickness of 0.1 to 20 pm, and preferably 0.5 to 5 um according to a method such as a spin coating, a roll coating, a slit and spinning, a die coating, and a bar coating. Then drying under reduced pressure is carried out according to the drying condition under the temperature of 23 to 150°C for 1 to 60 min, more preferably the temperature of 60 to 120°C for 1 to 10min, in a reduced pressure chamber, if necessary. Further, a pre-baking treatment is carried out by using a hot plate or a cleanoven, etc. to forma film. Next, radiation (for example, electronic beam or UV light can be considered, and UV light is preferable) is applied thrcugh a certain mask pattern by a commonly-used photolithography method, and development using an aqueous solution of surface active agent, an aqueous alkali solution, or an aqueous mixture solution of a surface active agent and an alkali agent is carried out. Development method includes a dipping method, a spraying method, a shower method, a paddle method, and an ultrasonication method, and a combination thereof canbe also employed. The non-exposed area is removed by development process, and rinsed with water. The curable film undergoes post-baking treatment, for example, at the temperature of 130 to 300°C for 1 to 120 min, and more preferably at the temperature of 150 te 250°C for 1 to 30 min to obtain the pixels consisting of the colored curable film of the invention.
[0052]
Examples of the surface active agent that can be used include polyoxyethylene alkyl ether and polyoxyalkylene alkyl ether. Examples of the alkali agent that can be used include sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, diethanolamine, and tetramethylammonium hydroxide. In the invention, use of an aqueous solution containing both the alkali agent and surface active agent is preferable. Development process is typically carried cut at the treatment temperature of 10 to 50°C, preferably 20 to 40°C, for treatment time of 30 to 600 sec, more preferably 30 to 120 sec.
[0053]
The cured product of the colored resin composition of the invention is useful for color filters of a liquid crystal display device, an organic EL display, or a solid-state imaging device used in a digital camera, etc. and the color filters have patterned pixels consisting of the colored resin composition of the invention that is produced as described above.
[0054]
Among the display devices of the invention, the liquid crystal display device is produced to have a structure in which a back light, a polarizing film, a display electrode, a liquid crystal, analignment film, a common electrode, the color filter of the invention, and a polarizing film are laminated in this order. The organic EL display is produced by disposing the ceclor filter of the invention either above or below a multilayered organic light emitting device. For example, the solid-state imaging device is produced by forming the coler filter layer of the inventicn on a silicon wafer on which a transport electrode and a photcdiode are formed, and then © laminating a micro lens thereon.
Examples
[0055]
The invention is explained in greater detail in view of the following Examples, but the invention is not limited by the
Examples. As spectroscopic characteristics, spectral transmission ratio was measured by using a spectrophotometer “Shimadzu Corporation UV-3150”7 and chromaticity was estimated based on the XYZ Color System. Accordingly, the resistance of the colored material was evaluated. [00561
Synthetic Example 1
To & 100 mL beaker, 1 g of Rhodamine B (manufactured by
Tokyo Chemical Industry Co., Ltd.) of the following formula {1C0) and 20 g of water were added and stirred at room temperature for 30 min. Then, a solution in which 1 g of tristrifluoromethanesulfonyl methide (TFSM) cesium salt is dissolved in 1 g of DMF was added dropwise thereto and stirred for 3 hours. The precipitated dye was filtered, washed with water, and dried to obtain 0.7 g TFSM salt of Rhodamine B (Compound No. 1). Maximum absorption wavelength: 560 nm {cyclohexanone) [Chemical Formula 2]
Et Et “Cr poe ’
Cl $ COOH
[0057]
Synthetic Example 2
To a 100 mL beaker, 1 g of Rhodamine 6G (manufactured by
Tokyo Chemical Industry Co., Ltd.) of the following formula (101) and 20 g of water were added and stirred at room temperature for 30 min. Then, a solution in which 1 g of tristriflucromethanesulfonyl methide cesium salt is dissolved in 1 g of DMF was added dropwise thereto and stirred for 3 hours.
The precipitated dye was filtered, washed with water, and dried to obtain 0.8 g TFSM salt of Rhodamine 6G (Compound No. 2).
Maximum absorption wavelength: 531 nm (cyclohexanone) [Chemical Formula 3] ! “COO rr co 0) COOEt
[0058]
Synthetic Example 3 (production of binder resin (copolymer) )
To a 500 mL four neck flask, 160 g cf methyl ethyl ketone, g of methacrylic acid, 33 g of benzyl methacrylate, and 1 gof o,a’-azoblis (isobutyronitrile) were added and nitrogen gas was introduced to the flask for 30 min under stirring. The temperature was then raised to 80°C and the stirring was continued for four hours at 80 to 85°C. Once the reaction is completed, the mixture was cooled to the room temperature to obtain a colorless, transparent, and homogenecus copolymer solution. The copolymer solution was then precipitated in.1 : 1 mixture solution containing isopropyl alcohol and water and filtered. The sclid matter was extracted and dried to obtain the copolymer (A). Weight average molecular weight of the copclymer (A) as converted to polystyrene was 18000 and the acid value was 152,
[0059]
Example 1 5.49 of the copolymer (A) as a binder resin, 6 g of Kavarad
DPHA (trade name, manufactured by NIPPON KAYAKU CO., LTD.) as a photopolymerizable monomer, 1.5 g of Irgacure 907 (trade name, manufactured by BASF Japan Ltd.) and 0.6 g of Kavacure-DETX~-S (trade name, manufactured by NIPPON KAYAKU CO., LTD.) as a photopolymerization initiator, 0.6 g of the Compound No. 1 obtained from the Synthetic Example 1 as a dye, and 20 g of cyclohexanone and 8.6 g of propylene glycol monomethyl ether acetate as a solvent were admixed with one another to chtain the colored resin composition of the invention with violet color. 10060]
Examples 2 and 3 were performed as follows.
Example 2: The colored resin composition with red color - was obtained with the same composition as the Example 1 except that the Compound No. 1 of the Synthetic Example 1 is changed to the Compound No. 2 of the Synthetic Example 2.
Example 3: After mixing with composition ratio of C. I.
Pigment Blue 15:6/AJISPER-PB821/SOLSPERSE 50C0/PGMEA = 15.0/6.0/2.0/78.0 (weight ratio), 400 g of zirconia beads (0.3 mm) were added. After treating for 60 min using a paint shaker followed by filtration, the pigment dispersion 1 was obtained.
To the Example 1, 19 g of the pigment dispersion 1 was added to obtain the colored resin composition of the invention.
[0061]
Comparative Example 1: The colcred resin composition with violet color was obtained with the same composition as the
Example 1 except that the Compound No. 1 of the Synthetic Example 1 is changed to Rhodamine B.
Comparative Example 2: The colored resin composition with red color was obtained with the same composition as the Example 1 except that the Compound No. 1 of the Synthetic Example 1 is changed tc Rhodamine 6G.
Comparative Example 3: The colored resin composition with blue color was obtained with the same compcsition as the Example 1 except that the Compound No. 1 of the Synthetic Example 1 is changed to Basic Blue 7.
[0062]
Evaluation of patterning
The colored resin composition obtained from the above (Examples 1 to 3) was coated on the substrate and subjected to pre-baking under condition of 80°C x 100 sec. After that, it was cured by light exposure through a mask, developed with an aqueous alkali solution containing a surface active agent, rinsed with water, and heated at 200°C to obtain a colored pattern. The colored pattern obtained is a line and space pattern with resolution of 5 pum and no residues or peeling of pixels was identified.
[0063]
Evaluation of heat resistance
Similar to those described above, the substrate for evaluation of heat resistance was prepared by coating each composition on a glass substrate, carrying out whole exposure,
and treating the substrate at 200°C for 5 min for post-baking.
Thereafter, each evaluation was carried out as described below.
First, for determinaticn of heat resistance, spectral transmission ratio of the substrate for evaluation was measured by using a spectrophotometer. Thereafter, the substrate for evaluation was treated at 200°C for 120 min and spectral transmission ratic was measured again. Finally, the color difference (AEab) was estimated. Results of heat resistance are given in the Table 2.
[0064] [Table 2]
Table 2 Evaluation results of heat resistance
AEab il 374
Cuampl omparative —
In the Comparative Example 1, discoloration of the dyes occurred during post-baking befcre heat treatment, and heat resistance was significantly low.
[0065]
According to the Table 2 in which results of the heat resistance evaluation are given, it was found that the Examples 1 to 3 of the invention show significantly improved results compared to those of the conventional dyes of the Comparative
Examples 2 and 3. The Example 3, in which a mixture with a pigment is used in combination, also showed good results without yielding any precipitation even when the colorant compound of the invention having various color characteristics like blue color and red color is mixed with a pigment.
[0066]
Based on the results obtained above, it was found that the colored resin composition of the inventicn in which a specific colorant compound can be used for producing a color filter, wherein the color filter produced includes a dye and has sufficient resistance, and therefore it can be used for obtaining sharp pixels with high quality and high reliability.
Further, depending on specific use, it can be also easily mixed and used with a pigment or other dyes. Thus, it is found to be industrially very useful.

Claims (7)

CLATMS
1. A colored resin composition for color filters comprising a colorant compound represented by the following formuia (1), a binder resin, a solvent, and a curing agent [Chemical Formula 1) Yi Rj Ra Ty _N 0 NS BeSoN Ry Z Rs R; Rg 7© (1) Xs 2) X; X; X, X3 (wherein R; to Re each independently represent a hydrogen atom, a halogen atom, a C1-Cl2 alkyl group, a Cl1-Cl2 alkoxy group, a nitro group, a carboxyl group, or an alkoxycarbonyl group: Y; tc Y4 each independently represent a hydrogen atom, a Cl1-Cl2 alkyl group, or an aryl group; X; to Xs each independently represent a hydrogen atom, a C1-C12 alkyl group, a C1-Cl2 alkoxy group, a halogen atom, a nitro group, a phenoxy group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, a sulfo group, or a sulfamoyl group; and anion part Z represents a sulfonyl methide anion having a highly halogenated C1-C10 alkyl group).
z2. The colecred resin composition according to Claim 1, wherein 2° in the formula (1) is a tristrifluoromethanesulfonyl methide anion.
3. The colored resin composition according to Claim 1 or 2, which comprises a metal phthalocyanine pigment.
4. A colcred cured film for color filters obtained by patterning of the colored resin composition according to any one of Claims 1 to 3.
5. A color filter comprising the colored cured £ilm for color filters according to Claim 4.
0. A display device comprising the color filter according to Claim 5.
7. A solid-state imaging device comprising the color filter according te Claim 5.
SG2012010526A 2010-06-15 2011-06-10 Colored resin composition SG178428A1 (en)

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JP2010243009 2010-10-29
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US20160154303A1 (en) * 2013-09-06 2016-06-02 Fujifilm Corporation Colored composition, cured film, color filter, color-filter manufacturing method, solid-state imaging element, image display device, polymer, and xanthene dye
US10175574B2 (en) 2014-01-31 2019-01-08 Fujifilm Corporation Coloring composition, and cured film, color filter, pattern forming method, method for manufacturing color filter, solid-state imaging device, image display device, and dye multimer, each using the coloring composition

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JP5932435B2 (en) * 2012-03-29 2016-06-08 サカタインクス株式会社 Blue pigment dispersion composition for color filter and blue pigment dispersion resist composition for color filter containing the same
KR101361679B1 (en) * 2012-03-30 2014-02-12 (주)경인양행 Xanthene dye compounds, colored resin composition comprising the same for color filter and color filter using the same
KR20150134191A (en) * 2014-05-21 2015-12-01 제일모직주식회사 Photosensitive resin compositionand color filter using the same
KR102455993B1 (en) * 2015-01-30 2022-10-18 스미또모 가가꾸 가부시키가이샤 Colored photosensitive resin composition
KR102162610B1 (en) * 2016-08-19 2020-10-07 주식회사 엘지화학 Compound, colorant composition comprising the same and resin composition comprising the same

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JP4937742B2 (en) * 2003-08-21 2012-05-23 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング Cyanoborate, fluoroalkylphosphate, fluoroalkylborate or imide dye
JP2008088426A (en) * 2006-09-06 2008-04-17 Nippon Kayaku Co Ltd New cyanine compound and use of the same
JP2008242311A (en) * 2007-03-28 2008-10-09 Sumitomo Chemical Co Ltd Colored photosensitive resin composition, and color filter array using the same, and solid state imaging device
JP5504627B2 (en) * 2008-07-01 2014-05-28 住友化学株式会社 Colored photosensitive resin composition

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Publication number Priority date Publication date Assignee Title
US20160154303A1 (en) * 2013-09-06 2016-06-02 Fujifilm Corporation Colored composition, cured film, color filter, color-filter manufacturing method, solid-state imaging element, image display device, polymer, and xanthene dye
US10191369B2 (en) * 2013-09-06 2019-01-29 Fujifilm Corporation Colored composition, cured film, color filter, color-filter manufacturing method, solid-state imaging element, image display device, polymer, and xanthene dye
US10175574B2 (en) 2014-01-31 2019-01-08 Fujifilm Corporation Coloring composition, and cured film, color filter, pattern forming method, method for manufacturing color filter, solid-state imaging device, image display device, and dye multimer, each using the coloring composition

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JP5750045B2 (en) 2015-07-15
KR20130048129A (en) 2013-05-09

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