CN109960108A - Colored filter coloured composition and colored filter - Google Patents

Colored filter coloured composition and colored filter Download PDF

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Publication number
CN109960108A
CN109960108A CN201811569918.2A CN201811569918A CN109960108A CN 109960108 A CN109960108 A CN 109960108A CN 201811569918 A CN201811569918 A CN 201811569918A CN 109960108 A CN109960108 A CN 109960108A
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CN
China
Prior art keywords
parts
methyl
general formula
colored filter
pigment
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Pending
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CN201811569918.2A
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Chinese (zh)
Inventor
平佐美幸
饭田裕介
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongyang Yihuan Co Ltd
Toyocolor Co Ltd
Artience Co Ltd
Original Assignee
Dongyang Yihuan Co Ltd
Toyo Ink SC Holdings Co Ltd
Toyocolor Co Ltd
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Priority claimed from JP2017246440A external-priority patent/JP6432076B1/en
Priority claimed from JP2018132442A external-priority patent/JP6432077B1/en
Application filed by Dongyang Yihuan Co Ltd, Toyo Ink SC Holdings Co Ltd, Toyocolor Co Ltd filed Critical Dongyang Yihuan Co Ltd
Publication of CN109960108A publication Critical patent/CN109960108A/en
Pending legal-status Critical Current

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Classifications

    • 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
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B25/00—Quinophthalones
    • 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
    • G03F7/0005—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
    • 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

Abstract

The present invention provides a kind of colored filter coloured composition and colored filter that can form excellent heat resistance, lightness and contrast than high film.Colored filter coloured composition, it is the colored filter coloured composition containing colorant, resin and solvent, and the colorant includes quinophthalone compound (A1) represented by the following general formula (1), the resin includes acrylic block copolymer as alkaline dispersing agent (C).[changing 1] general formula (1)

Description

Colored filter coloured composition and colored filter
Present application is advocated with the Japan Patent Patent 2017-246440 to file an application on December 22nd, 2017 and 2018 Priority based on the Japan Patent Patent 2018-132442 to file an application July 12, and the full content disclosed draws For this.
Technical field
This announcement is to be related to a kind of colored filter coloured composition and colored filter.
Background technique
Liquid crystal display device is the polarisation journey that the liquid crystal layer control clamped by two panels polarizer passes through the light of the 1st polarizer It spends to control the display device shown by the light quantity of the 2nd polarizer, and uses twisted nematic (Twisted Nematic, TN) type liquid crystal type become mainstream.Liquid crystal display device can be by being arranged colored filter between two panels polarizer Mating plate and carry out colored display.Therefore, it is expanding and liquid crystal display device is used for television set or individual computer monitor use On the way.
As the mode of other representative liquid crystal display devices, exists and be set to a pair of electrodes on unilateral substrate And applies coplanar switching (In-Plane Switching, IPS) mode of electric field on the direction with substrate-parallel, makes to have and bear Dielectric anisotropy nematic liquid crystal vertical orientation vertical orientation (Vertically Alignment, VA) mode and Keep the optical axis of the phase difference film of uniaxiality orthogonal and carries out the optical compensation curved (Optically of optical compensation Compensated Bend, OCB) mode etc., and respectively carry out practical.
Typically, colored filter includes: on the surface for will be formed in the transparent substrates such as glass comprising red filter Optical filtering section (the filter of fine band (striped) shape of lamella (R), green filter lamella (G) and blue filter lamella (B) Segment) (pixel) parallel or cross-over configuration person, or the winner with the optical filtering section for being arranged fine fixed in length and breadth.Filter Fine to a few micrometers~hundreds of microns of light section, and each form and aspect to configure with providing marshalling.In addition, recently, also using Optical filtering comprising red filter lamella (R), green filter lamella (G), blue filter lamella (B) and Yellow filter lamella (Y) Section.
Usually by vapor deposition or sputter used in color liquid crystal display arrangement colorized optical filtering on piece formation to The transparent electrode of liquid crystal is driven, and then forms the alignment films be orientated liquid crystal on fixed-direction on the transparent electrodes.For The abundant performance for obtaining these transparent electrodes and alignment films, need usually 200 DEG C or more, be preferably 230 DEG C or more The formation process is carried out under high temperature, and heat resistance is required to colored filter.
As the important quality project required colored filter, contrast ratio and lightness can be enumerated.If using comparison Degree can then upset the polarization degree that liquid crystal is controlled than low colored filter, (OFF state) light leakage when that must cover light, When that light must be made to penetrate, (ON state) penetrates optical attenuation, therefore becomes fuzzy picture.Therefore, in order to realize the liquid crystal of high-quality Display device, indispensable is to improve contrast ratio.
In addition, if the colored filter low using lightness, the transmitance of light is low, therefore become dark picture, in order to set For bright picture, need to increase the quantity of the backlight as light source.For the viewpoint that may refrain from consumption electric power, colored filter High brightness chemical conversion be trend (trend).
In turn, as described above, color liquid crystal device becomes to be used in television set or individual computer monitor etc., thus it is right For colored filter, the requirement to high contrast, high brightness and wide color reproduction region or high reliability is also mentioned It is high.
In addition, with complementary metal oxide semiconductor (Complementary Metal Oxide Semiconductor, C-MOS: complementary metal oxide film semiconductor), charge coupled cell (Charge Coupled Device, CCD) etc. be representative Color image sensor be usually be separately equipped on its light receiving element with red filter lamella (R), green filter lamella (G) and the colored filter of the optical filtering section of the primary colors of the addition of blue filter lamella (B) mixing carries out color decomposition.In addition, being It obtains compared with higher sensitivity for the colored filter of primary colors, also commonly using with the benefit for being equivalent to red, green, blue The colored filter of the cyan of color, magenta, the optical filtering section of yellow (CMY).The colored filter of complementary color is mostly used for being difficult to benefit With in video cameras of secondary light sources such as flash of light etc..
In recent years, in the colored filter used in color image sensor, high transmittance, that is, lightness or high reliability Equal requirements also improve.
In the manufacture of green filter section, use yellow uitramarine as toning colorant, especially mainly uses C.I. Pigment yellow (pigment yellow) 138, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 185 etc..Wherein, For the aspect that can get high transmittance, mostly used as the C.I. pigment yellow 13 8 of quinophthalone compound.But C.I. face Although expecting that yellow 138 lightness are relatively excellent, it is expected further to improve lightness.In addition, in recent years, for the height of colored filter The expectation of contrast is strong, but C.I. pigment yellow 13 8 entertains contrast than low problem.In turn, C.I. pigment yellow 13 8 is also deposited In following problem: when applying 230 DEG C or more of heat, generating crystallization and be precipitated and poor heat resistance.Therefore, seek a kind of more previous C.I. for pigment yellow 13 8, lightness, contrast when superior yellow colorants of heat resistance.
It is such in order to solve the problems, such as, about quinophthalone compound, carry out various exploitations.For example, being disclosed in patent document 1 There is a kind of tinting strength, tinting power excellent and provides the structure of high brightness, contrast ratio as novel quinophthalone compound.In addition, patent document A kind of quinophthalone compound containing fluorine atom is recorded in 2.However, the colorant comprising these quinophthalone compounds and being discontented with Sufficient heat resistance and tinting strength, tinting power.
In addition, in order to reach higher lightness and wide color reproduction region, usually will in the manufacture of red filter section The yellow uitramarines such as red pigment and C.I. pigment yellow 13 8,139,185 are used as colorant (3~patent document of patent document 5).So And although such as 8 lightness of C.I. pigment yellow 13 it is relatively excellent, non-coloring power and entertain colorized optical filtering sector-meeting and being asked as thick film Topic.In contrast, though C.I. pigment yellow 13 9 is excellent in terms of tinting strength, tinting power, there are lightness or contrast than it is low the problems such as, and it is existing Truth condition is to be unable to fully reach all items to colored filter requirement.
In addition, disclosing the quinophthalone having used in a kind of coloring of high molecular material with naphthalene nucleus in patent document 6 Compound.But the quinophthalone compound obtained by the manufacturing method of patent document 6 is for the purpose of the coloring of plastics, And it is indefinite for the adaptive of colored filter purposes.
[existing technical literature]
[patent document]
[patent document 1] Japanese Patent Laid-Open 2012-226110 bulletin
[patent document 2] Japanese Patent Laid-Open 2016-145282 bulletin
[patent document 3] Japanese Patent Laid-Open 2006-307149 bulletin
[patent document 4] Japanese Patent Laid-Open 2007-133131 bulletin
[patent document 5] Japanese Patent Laid-Open 2011-095491 bulletin
[patent document 6] Japanese Patent Laid-Open No. Sho 51-147544 bulletin
Summary of the invention
[problem to be solved by the invention]
This announcement be designed to provide it is a kind of can form excellent heat resistance and lightness and contrast than high film coloured silk Colo(u)r filter coloured composition.
[technical means to solve problem]
The present inventor et al. makes great efforts to study repeatedly, as a result, it has been found that can be solved by following colored filter with coloured composition Certainly described problem, thereby completing the present invention, the colored filter are the quinophthalones that will have specific structure with coloured composition Compound combined with specific alkaline dispersing agent or by the quinophthalone compound with specific structure with have and its not The quinophthalone compound of same structure is composed.
That is, the 1st colored filter coloured composition in this announcement is the colored filter containing colorant, resin and solvent Mating plate coloured composition, and
The colorant includes quinophthalone compound (A1) represented by the following general formula (1),
The resin includes acrylic block copolymer as alkaline dispersing agent (C).
[changing 1]
General formula (1)
[in general formula (1), X1、X2、Y1Separately indicate halogen atom；N, m indicates that 0~6 integer, p indicate 0~5 Integer；It (n+m) is 1 or more]
In addition, the 2nd colored filter coloured composition in this announcement is the colour containing colorant, resin and solvent Optical filter coloured composition, and
The colorant include the following general formula (1) represented by quinophthalone compound (A1) with selected from by the following general formula (2), The quinophthalone compound (A2) of one or more of group composed by general formula (3) and general formula (4).
[changing 2]
General formula (1)
[in general formula (1), X1、X2、Y1Separately indicate halogen atom；N, m indicates that 0~6 integer, p indicate 0~5 Integer；It (n+m) is 1 or more]
[changing 3]
General formula (2)
[changing 4]
General formula (3)
[changing 5]
General formula (4)
[in general formula (2)~general formula (4), R18~R30、R31~R45、R46~R60Separately indicate that hydrogen atom, halogen are former Son, the alkoxy that can have substituent group, the aryl that can have substituent group, can have substituent group at the alkyl that can have substituent group Phthalimide methyl or the sulfamoyl that can have substituent group]
In one embodiment of the 2nd colored filter coloured composition, the content phase of quinophthalone compound (A1) It is 3 mass of mass %~90 % for quinophthalone compound (A1) and adding up to for quinophthalone compound (A2).
In one embodiment of the 1st colored filter coloured composition, the acrylic block copolymer tool Have comprising selected from by the repetitive unit represented by the following general formula (5), repetitive unit and the following general formula represented by the following general formula (6) (7) block of the repetitive unit of one or more of group composed by the repetitive unit represented by.
[changing 6]
General formula (5)
[in general formula (5), R1~R3It indicates hydrogen atom independently of each other or can have the chain or cricoid of substituent group Alkyl, R1~R3In two or more can be bonded each other and form cyclic structure；R4Indicate that hydrogen atom or methyl, X indicate that divalent connects Tie base, Y-Indicate counter anion]
[changing 7]
General formula (6)
[in general formula (6), R5And R6It indicates hydrogen atom independently of each other or can have the chain or cricoid of substituent group Alkyl, R5And R6It can be bonded each other and form cyclic structure；R4Indicate that hydrogen atom or methyl, X indicate bivalence linking base]
[changing 8]
General formula (7)
[in general formula (7), R7Indicate hydrogen atom, the alkyl of carbon number 1~18, the aryl of carbon number 6~20, carbon number 7~12 Aralkyl, acyl group, oxygen radical or OR12, R12Indicate hydrogen atom, the alkyl of carbon number 1~18, the aryl of carbon number 6~20, carbon number 7 ~12 aralkyl or acyl group, R8、R9、R10、R11Separately indicate methyl, ethyl or phenyl；R4Indicate hydrogen atom or first Base, X indicate bivalence linking base]
One embodiment of the 1st colored filter coloured composition and the 2nd colored filter coloured composition In, also contain pigment derivative, the pigment derivative includes the pigment derivative with acidic substituent.
One embodiment of the 1st colored filter coloured composition and the 2nd colored filter coloured composition In, the pigment derivative includes the quinophthalone compound (B) with sulfo group, the metal salt of sulfo group or alkylammonium salt.
One embodiment of the 1st colored filter coloured composition and the 2nd colored filter coloured composition In, the colorant includes selected from by phthalocyanine color, isoindoline system pigment, diketopyrrolo-pyrrole system pigment, anthraquinone system face Material, azo pigment are pigment, quinacridone pigment, in group composed by oxa- anthracene dye and cyanine based dye More than one.
One embodiment of the 1st colored filter coloured composition and the 2nd colored filter coloured composition In, also containing selected from one or more of optical polymerism list amount body (E) and Photoepolymerizationinitiater initiater (F).
In addition, this announcement provides a kind of colored filter, has on substrate and coloured by the 1st colored filter Composition or the 2nd colored filter are formed by optical filtering section with coloured composition.
[The effect of invention]
According to this announcement, it is possible to provide one kind can form excellent heat resistance and lightness and contrast are filtered than the colour of high film Mating plate coloured composition.
Specific embodiment
Hereinafter, sequentially to the 1st colored filter coloured composition, the 2nd colored filter coloured composition and colour Optical filter is described in detail.
Furthermore in this specification, it is being expressed as " (methyl) acryloyl group ", " (methyl) acrylic ", " (methyl) propylene In the case where acid ", " (methyl) acrylate " or " (methyl) acrylamide ", as long as no special instructions, then " propylene is respectively indicated Acyl group and/or methylacryloyl ", " acrylic and/or methacrylic acid group ", " acrylic acid and/or methacrylic acid ", " acrylate and/or methacrylate " or " acrylamide and/or Methacrylamide ".In addition, listed in this specification " C.I. " lifted refers to Colour Index (Colour Index, C.I.).
1. the 1st colored filter coloured composition
The 1st colored filter coloured composition in this announcement is the colorized optical filtering containing colorant, resin and solvent Piece coloured composition, and
The colorant includes quinophthalone compound (A1) represented by the following general formula (1),
The resin includes acrylic block copolymer as alkaline dispersing agent (C).
The excellent storage stability of the 1st colored filter coloured composition, and the heavily fortified points such as heat resistance, solvent resistance Jail property is excellent and available lightness and contrast are than high pixel.Therefore, when showing same color, the film thickness of pixel can be made to become It is thin.
The 1st colored filter coloured composition at least contains colorant, resin and solvent, optionally can also also contain There are other compositions.Hereinafter, being illustrated to each ingredient of such 1st colored filter coloured composition.
[colorant]
The colored filter coloured composition of this announcement at least contains quinophthalone compound (A1) represented by general formula (1) As colorant, it can also optionally contain other colorants.
< quinophthalone compound (A1) >
Firstly, quinophthalone compound (A1) represented by mutual-through type (1) is illustrated.
[changing 9]
General formula (1)
[in general formula (1), X1、X2、Y1Separately indicate halogen atom；N, m indicates that 0~6 integer, p indicate 0~5 Integer；It (n+m) is 1 or more]
X1、X2Indicate naphthalene nucleus substituent group.Y1Indicate quinoline ring substituents.
Herein, it as halogen atom, can enumerate: fluorine, chlorine, bromine, iodine.As halogen atom, preferably chlorine or bromine, wherein Particularly preferably chlorine.
In the quinophthalone compound (A1) of general formula (1), substitution radix n, m of halogen atom indicate 0~6, and (n+m's) is total It is 1 or more.It can be the mixture for the compound for replacing radix different, may be, for example, the compound that n is 3 and the compound that n is 4 Mixture.
The substitution radix (n+m) of halogen atom is 1~12.If (n+m) is more, when heat resistance optimizes contrast.With For color power, the viewpoint of lightness, preferably 2~7.Wherein, if m is 0 and n is 2~4, tinting strength, tinting power, lightness it is high and it is preferred that.
The integer for replacing radix p expression 0~5 of halogen atom.For tinting strength, tinting power, the viewpoint of lightness, preferably 0~2.
For lightness, the viewpoint of contrast ratio, halogen distribution is preferably 6 or less.Herein, so-called " halogen distribution Range " is the distribution of halogen number replaced in quinophthalone compound represented by general formula (1).About halogen distribution, Carry out quality analysis and in the mass spectrum that obtains, calculate and replace with halogen the corresponding each ingredient of number quinophthalone compound point Value (total peak value) obtained by son measures the signal strength (each peak value) of comparable molecular ion wave crest and adds up each peak value is right Each peak value is counted relative to the quantity for the wave crest that the ratio of total peak value is 1% or more, and is set as halogen distribution.
Quinophthalone compound (A1) can make 8- amidoquinaldine (8-Aminoquinaldine) represented by general formula (8) with 2,3- naphthalene dicarboxylic acids represented by 2,3- naphthalene dicarboxylic acids acid anhydride represented by general formula (9) and/or general formula (10) is reacted and is obtained.
[changing 10]
General formula (8)
[changing 11]
General formula (9)
[changing 12]
General formula (10)
[in general formula (8)~general formula (10), R61~R65、R66~R71、R72~R77Separately indicate hydrogen atom, halogen Atom]
Quinophthalone compound (A1) can also obtain (11) halogenation of following compounds.In addition, by compound (12) halogenation Afterwards, it is reacted with 2,3- naphthalene dicarboxylic acids represented by 2,3- naphthalene dicarboxylic acids acid anhydride represented by general formula (9) and/or general formula (10), thus The naphthalene dicarboxylic acids acid anhydride that structure can be made different is condensed in the amino side of 8- amidoquinaldine with methyl side.
[changing 13]
Compound (11)
[changing 14]
Compound (12)
It, can also be according to being recorded in Japanese Patent Laid-Open 2012-226110 bulletin in addition, about quinophthalone compound (A1) Synthetic method and after obtaining compound represented by general formula (13), and 2 represented by general formula (9), 3- naphthalene dicarboxylic acids acid anhydride and/or The reaction of 2,3- naphthalene dicarboxylic acids represented by general formula (10).
[changing 15]
General formula (13)
[in general formula (13), R78~R88Separately indicate hydrogen atom, halogen atom]
When synthesizing quinophthalone compound (A1) and its intermediate, halogenating agent is used.So-called halogenating agent refers to fluorization agent, chlorination Agent, bromating agent and iodating agent.For example, can enumerate as fluorization agent: fluorine aoxidizes fluoroform, fluorosulfuric acid caesium, acetyl group Fluorine monohydroxide Salt, N- fluorine sulfonamide, diethylaminosulfur trifluoride, N- fluorine pyridiniujm etc..It as chlorinating agent, can enumerate: chlorine (Cl2)、N- Chlorosuccinimide, chlorosulfuric acid (sulfuryl chloride), trichloroisocyanuric acid, sodium dichloroisocyanurate, 2,3,4,5, 6,6- chlordene -2,4- cyclohexadienone, 2,3,4,4,5,6- chlordene -2,5- cyclohexadienone, N- chlorine triethyl ammonium chloride, phenyl Selenium chloride (benzeneselenenyl chloride) etc..It as bromating agent, can enumerate: bromine (Br2), N- bromo succinyl it is sub- Amine, silver sulfate-bromine, tetramethyl tribromide ammonium, trifluoroacetyl group hypobromite, dibromo isocyanuric acid, 2,4,4,6- tetrabromo hexamethylene- 2,5- dienone, hydrogen bromide-dimethyl sulfoxide, N- bromo-succinimide-dimethylformamide, 2,4- diaminostilbene, 3- thiophene Azoles tribromide hydrogen, the bromo- 5,5- dimethyl hydantoin of 1,3- bis- etc..It as iodating agent, can enumerate: iodine (I2), 1,3- bis- iodo- 5, 5- dimethyl hydantoin, trifluoroacetyl group hypoiodite, iodo- periodic acid, ethylidene iodine chloride (ethylene Iodochloride), N- N-iodosuccinimide etc..
(autofrettage of quinophthalone compound)
Quinophthalone compound (A1) can for example pass through Japanese Patent Laid-Open 4-226163, Japanese Patent Laid-Open 2012- The method recorded in No. 226110 bulletins manufactures, but is not limited to these methods.
As the concrete example of quinophthalone compound (A1) represented by general formula (1), following those shown can be enumerated, but and unlimited Due to these.
[changing 16]
[changing 17]
Quinophthalone compound (A1) represented by general formula (1) is that yellow person is presented in its form and aspect itself, by and with other Toner comes using can be made into the coloring compositions to form homochromy Yellow filter section and green filter section, red filter section Object.
Other colorants of < >
In addition to 1st colored filter is with coloured composition quinophthalone compound (A1) represented by the general formula (1), It can arbitrarily select to contain conventionally known various pigment and dyestuff as other colorants.It is exemplified below and can be used as other colorants Representative pigment and dyestuff.
Red pigment can for example be enumerated: C.I. paratonere (pigment red) 1,2,3,4,5,6,7,8,9,10,14,17, 22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,57:1,81,81:1,81:2,81:3,81:4, 83、88、90、105、112、119、122、123、144、146、149、150、155、166、168、169、170、171、172、175、 176、177、178、179、184、185、187、188、190、200、202、206、207、208、209、210、216、220、221、 224、226、242、246、254、255、264、270、272、273、274、276、277、278、279、280、281、282、283、 284,285,286,287 or Japanese patent special table 2011-523433 bulletin in record diketopyrrolo-pyrrole pigment, Japan The azopigment etc. recorded in open patent 2011-173971, but it is not particularly limited to these.In addition, it is possible to use oxa- The orchils such as anthracene system, azo system, bisazo system, anthraquinone system.It is specific enumerable: C.I. acid red (acid red) 52,87, 92, the salt-forming compound etc. of the xanthenes system acid dyes such as 289,338.
Orange pigment can for example be enumerated: C.I. pigment orange (pigment orange) 38,43,71 or 73 etc., but not special These are not defined in it.
Yellow uitramarine can for example be enumerated: C.I. pigment yellow (pigment yellow) 1,2,3,4,5,6,10,11,12,13, 14,15,16,17,18,20,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61, 62、63、65、73、74、77、81、83、86、93、94、95、97、98、100、101、104、106、108、109、110、113、 114、115、116、117、118、119、120、123、125、126、127、128、129、137、138、139、147、150、151、 152、153、154、155、156、161、162、164、166、167、168、169、170、171、172、173、174、175、176、 177,179,180,181,182,185,187,188,193,194,198,199,213,214,218,219,220,221 or Japanese The quinophthalone system pigment etc. recorded in No. 4993026 bulletin of patent, but it is not particularly limited to these.In addition, it is possible to use The welds such as quinoline system, azo system, bisazo system, methine system.
Viridine green can for example be enumerated: C.I. naphthol green (pigment green) 7,10,36,37,58, Japan Patent spy Open 2008-19383 bulletin, Japanese Patent Laid-Open 2007-320986 bulletin, Japanese Patent Laid-Open 2004-70342 bulletin ZnPc pigment recorded in etc., but it is not particularly limited to these.
Blue pigment can for example be enumerated: C.I. pigment blue (pigment blue) 1,1:2,9,14,15,15:1,15:2, 15:3,15:4,15:6,16,22,60,64, Japanese Patent Laid-Open 2004-333817 bulletin, Japanese Patent No. 4893859 Aluminium phthalocyanine color recorded in bulletin etc. etc., but it is not particularly limited to these.
In colorant, for the aspect of the relationship of the color characteristics with quinophthalone compound (A1), preferably individually make With a kind of any yellow uitramarine or it is applied in combination two or more.As yellow uitramarine, more preferably quinophthalone system pigment, different Yin Diindyl quinoline system's pigment and azo pigment.
It is excellent as the azo pigment as isoindoline system pigment, preferably C.I. pigment yellow 13 9,185 It is selected as C.I. pigment yellow 150.
In colorant, for the aspect of the relationship of the color characteristics with quinophthalone compound (A1), preferably individually make It with a kind of any phthualocyanine pigment or combines two or more in turn and is used as green coloring composition.
As the phthualocyanine pigment, preferably halogenated copper phthalocyanine pigment, zinc halide phthalocyanine color or aluminium phthalocyanine color.More Preferably C.I. pigment Green 7,36,58, No. 4893859 bulletins of Japanese Patent No., Japanese Patent Laid-Open 2016-153481, Japan The aluminium phthalocyanine color recorded in open patent 2017-197685 bulletin etc..
In addition, can also be combined with red pigment and be used as red colored composition.As red pigment, preferably diketone pyrrole Cough up simultaneously azole series pigment, anthraquione pigmentss and azo pigment.
As diketopyrrolo-pyrrole system pigment, preferably C.I. paratonere 254, Japanese patent special table 2011- The bromination diketopyrrolo-pyrrole pigment recorded in No. 523433 bulletins, as the anthraquione pigmentss, preferably C.I. pigment Red 177, as the azo pigment, preferably C.I. pigment orange 38, C.I. paratonere 176, C.I. paratonere 242, C.I. Paratonere 269, is recorded in Japanese Patent Laid-Open 2012-229344 bulletin Japanese Patent Laid-Open 2011-173971 bulletin Azo-compound.
(miniaturization of pigment)
Quinophthalone compound (A1) is preferably miniaturize and is used.Miniaturization method is not particularly limited, such as can It is ground using wet type, dry type is ground, solution modeling method is any.As described later, for example, using the one kind ground as wet type Kneader method come carry out salt mill (salt milling) processing etc. and miniaturize.Pigment it is micro- by penetration type electron Mirror (Transmission Electron Microscope, TEM) and the average primary particle diameter found out is preferably 5nm~90nm Range.For the viewpoint of dispersion, contrast ratio in organic solvent, preferred average primary particle diameter be 10nm~ The range of 70nm.
So-called salt mill processing is following processing: using kneader (kneader), twin-roll mill (two-rod roll Mill), three-roll mill (three-rod roll mill), ball mill (ball mill), grater (attritor), sand mill Kneading machines such as (sand mill) machine the mixture of pigment, water-soluble inorganic salt and water-miscible organic solvent on one side heat while After being kneaded to tool, water-soluble inorganic salt and water-miscible organic solvent are removed by washing.Water-soluble inorganic salt is as broken The broken auxiliary agent person of playing a role, salt make pigment broken using the height of the hardness of inorganic salts when grinding.By making to carry out salt to pigment Mill processing when constrained optimization, can get primary particle diameter it is very fine and also distribution narrow scope, with sharp grain Spend the pigment of distribution.
As water-soluble inorganic salt, sodium chloride, potassium chloride, sodium sulphate etc. can be used, for the aspect of price, preferably It uses sodium chloride (salt).For treatment effeciency and production efficiency these two aspects, (100 matter on the basis of the gross mass of pigment Measure %), water-soluble inorganic salt preferably uses the 50 mass % of mass %~2000, most preferably uses 300 mass %~1000 Quality %.
Water-miscible organic solvent is to play the actor for keeping pigment and water-soluble inorganic salt wet, if dissolution (mixing) in Inorganic salts person used in water and substantially insoluble, then be not particularly limited.Temperature rises when wherein, due to salt mill, at Hold evaporable state for solvent, so for the aspect of safety, preferably 120 DEG C of boiling point or more of high boiling solvent. Such as it can be used: 2-methyl cellosolve, butoxy ethanol, 2- (isoamoxy) ethyl alcohol, 2- (hexyloxy) ethyl alcohol, diethyl two Alcohol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, the polyethylene glycol of liquid, 1- first Oxygroup -2- propyl alcohol, 1- ethyoxyl -2- propyl alcohol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid poly- third Glycol etc..On the basis of the gross mass of pigment (100 mass %), water-miscible organic solvent preferably uses 5 mass %~1000 Quality % most preferably uses 50 mass of mass %~500 %.
When carrying out salt mill processing to pigment, resin can also be optionally added.The type of used resin has no special limit It is fixed, natural resin, modified natural resin, synthetic resin, the synthetic resin being modified through natural resin etc. can be used.Used tree Rouge is preferably solid and is water-insoluble at room temperature, and can preferably dissolve a part in the organic solvent in turn. On the basis of the gross mass of pigment (100 mass %), the usage amount of resin is preferably the range of 2 mass of mass %~200 %.
[pigment derivative]
The colored filter coloured composition of this announcement can also contain pigment derivative.Pigment derivative, which is for example used as, to be divided Scattered auxiliary agent functions.As pigment derivative, it can enumerate and be imported with alkalinity in organic pigment, anthraquinone, acridone or triazine Substituent group, acidic substituent or can have substituent group phthalimide methyl compound, such as can be used Japan specially Sharp tekiaki 63-305173 bulletin, Japan Patent examined patent publication 57-15620 bulletin, Japan Patent examined patent publication 59-40172 Bulletin, Japan Patent examined patent publication 63-17102 bulletin, Japanese Patent Laid-fair 5-9469 bulletin, Japanese Patent Laid-Open 2001-335717 bulletin, Japanese Patent Laid-Open 2003-128669 bulletin, Japanese Patent Laid-Open 2004-091497 public affairs Report, Japanese Patent Laid-Open 2007-156395 bulletin, Japanese Patent Laid-Open 2008-094873 bulletin, Japanese Patent Laid-Open 2008-094986 bulletin, Japanese Patent Laid-Open 2008-095007 bulletin, Japanese Patent Laid-Open 2008-195916 public affairs Recorded person in No. 4585781 report, Japanese Patent No. bulletins etc., these can be used alone or be used in mixed way two or more.
Wherein, for the viewpoint of the interaction with aftermentioned alkaline dispersing agent (C), it is however preferred to have acid functional groups Pigment derivative.The particularly preferably metal salt or amine salt of sulfonation pigment derivative or sulfonation pigment derivative.
As the metal for constituting metal salt, can enumerate: the various metals such as sodium, potassium, calcium, barium, iron, magnesium, aluminium, nickel, cobalt, strontium. In these, if it can get the separation property in not only manufacture using aluminium salt and the dispersibility as pigment dispersing agent be excellent, but also Low viscosity, flow behavior, through when the most excellent coloured composition of viscosity stability.
As the amine for constituting amine salt, can enumerate: ammonia, dimethyl amine, Trimethylamine, diethylamide, triethylamine, hydroxyl second Base amine, dihydroxy ethyl amine, 2- ethylhexylamine, N, N- dimethylaminopropyl amine, N, N- diethyl amino propyl amine, N, N- The low-grade amines such as dibutylamino propyl amine；Lauryl amine, oleyl amine, palmityl amine, stearic amine, dimethyl lauryl amine etc. The chain alkyl amine of alkyl with 2 or more carbon number；Lauryl ammonium, stearyl ammonium, lauryl trimethyl ammonium, dilauryl diformazan Base ammonium, stearyl trimethyl ammonium, distearyl dimethyl ammonium etc. have 12 or more carbon number alkyl chain alkyl level Four ammonium from Son.In these, if using the chain alkyl level Four ammonium ion of the alkyl with lauryl ammonium, stearyl ammonium etc. with 12 or more carbon number Salt, then can get that dispersion stabilization is most excellent and the extra high coloured composition of storage stability.
The importing number of sulfo group is preferably one to two relative to pigment skeleton.If becoming three or more, relatively In the organic solvent that can be suitable in colored filter, compatibility disappears, and dispersibility reduces.
As pigment derivative, it is however preferred to have the metal salt or alkylammonium salt person of sulfo group or sulfo group.Wherein, just with For the viewpoint of the interaction of quinophthalone compound, the pigment derivative is preferably the metal with sulfo group or sulfo group The quinophthalone compound (B) of salt or alkylammonium salt.
Quinophthalone compound (B) with sulfo group is illustrated.
So-called quinophthalone compound is the compound in the molecular structure with skeleton represented by following chemical formula (14) Skeleton.As the concrete example of the quinophthalone compound with sulfo group, it can enumerate and use well known method by C.I. Indian yellow (acid Yellow) the commercially available dyestuffs such as 3,5 and C.I. pigment yellow 13 8, C.I. solvent yellow (solvent yellow) 33,114,157, C.I. compound made of the commercially available pigment of disperse yellow (disperse yellow) 54,64,67 etc. and dyestuff sulfonation；Under and Those shown is stated, but is not limited to these.
[changing 18]
Chemical formula (14)
As the concrete example of quinophthalone compound (B), following those shown can be enumerated, but are not limited to these.Under in addition, Stating exemplary compounds can be using well known method simply by-SO3H back exchange is metal salt or alkylammonium salt.
[changing 19]
[changing 20]
On the basis of the total amount of colorant (100 mass %), the mass ratio with pigment derivative is preferably 1 mass %~40 Quality %, more preferably in the range of 3 mass of mass %~30 %.
That is, there are contrasts than low and high viscosity tendency, in pigment in the case where the ratio of pigment derivative is very few In the case that the ratio of derivative is excessive, tendency that and heat resistance low there are lightness is also deteriorated.
[resin]
The colored filter coloured composition of this announcement contains resin.In the 1st colored filter coloured composition, At least contain acrylic block copolymer as alkaline dispersing agent (C), optionally can also also contain other resins.
< alkaline dispersing agent (C) >
It includes acrylic block copolymer as basic dispersion that the 1st colored filter in this announcement, which uses coloured composition, Agent (C).The acrylic block copolymer has the structure of amino.The acrylic block copolymer is to include A block With the block copolymer of B block, the A block includes to be selected from the repetitive unit containing quarternary ammonium salt base represented by general formula (5) And one of repetitive unit of structure of amino containing level-one, second level or three-level represented by general formula (6), general formula (7) with On repetitive unit, the B block do not have the general formula (5), general formula (6), structure represented by general formula (7).A block and B The composition of block is not particularly limited, preferably A-B block, B-A-B block or A-B-A block, and A-B can be preferably used in turn Block, B-A-B block.
[changing 21]
General formula (5)
[in general formula (5), R1~R3It indicates hydrogen atom independently of each other or can have the chain or cricoid of substituent group Alkyl, R1~R3In two or more can be bonded each other and form cyclic structure；R4Indicate that hydrogen atom or methyl, X indicate that divalent connects Tie base, Y-Indicate counter anion]
[changing 22]
General formula (6)
[in general formula (6), R5And R6It indicates hydrogen atom independently of each other or can have the chain or cricoid of substituent group Alkyl, R5And R6It can be bonded each other and form cyclic structure；R4Indicate that hydrogen atom or methyl, X indicate bivalence linking base]
[changing 23]
General formula (7)
[in general formula (7), R7Indicate hydrogen atom, the alkyl of carbon number 1~18, the aryl of carbon number 6~20, carbon number 7~12 Aralkyl, acyl group, oxygen radical or OR12, R12Indicate hydrogen atom, the alkyl of carbon number 1~18, the aryl of carbon number 6~20, carbon number 7 ~12 aralkyl or acyl group, R8、R9、R10、R11Separately indicate methyl, ethyl or phenyl；R4Indicate hydrogen atom or first Base, X indicate bivalence linking base]
As the R in general formula (5)1~R3, can more preferably have the alkyl of the carbon number 1~4 of substituent group, can have substitution The aralkyl of the carbon number 7~16 of base, particularly preferably methyl, ethyl, propyl, butyl, benzyl.
As the R in general formula (6)5And R6, can more preferably have the alkyl of the carbon number 1~4 of substituent group, particularly preferably Methyl, ethyl, propyl, butyl.
R in general formula (7)7In, as the alkyl of carbon number 1~18, straight-chain, branch-like, cricoid alkyl can be enumerated, is had Body can be enumerated: methyl, ethyl, n-propyl, isopropyl, normal-butyl, tert-butyl, n-hexyl, cyclohexyl, n-octyl, cetyl Deng.
It as the aryl of carbon number 6~20, such as can enumerate: phenyl, 1- naphthalene, 2- naphthalene etc..
As the aralkyl of carbon number 7~12, such as the alkyl of carbon number 1~8 can be enumerated and be bonded on the aryl of carbon number 6~10 Made of base, it is specific enumerable: benzyl, phenethyl, α-methylbenzyl, 2- phenyl-propane -2- base etc..
In addition, the alkanoyl and aroyl of carbon number 2~8, specific enumerable acetyl group, benzoyl can be enumerated as acyl group Base etc..
Wherein, particularly preferably hydrogen atom, the alkyl of carbon number 1~5, oxygen radical, more preferably hydrogen atom, methyl, most Preferably methyl.
It in general formula (5), general formula (6) and general formula (7), as bivalence linking base X, such as can enumerate: methylene, carbon number 2 ~10 alkylidene, arlydene ,-CONH-R13-、-COO-R14(wherein, R13And R14For singly-bound, methylene, carbon number 2~10 The ether (alkoxyalkyl) of alkylidene or carbon number 2~10) etc., preferably-COO-R14-.In addition, in the formula (5), as Counter anion Y-, can enumerate: Cl-、Br-、I-、ClO4 -、BF4 -、CH3COO-、PF6 -Deng.
As long as A block has no special limit with either one or two of structure represented by general formula (5), general formula (6), general formula (7) It is fixed, it is preferably derived from the part-structure of the unsaturated single amount body of ethylene.
As the precursor portions structure for becoming general formula (5), the unsaturated singly amount body of the ethylene with quarternary ammonium salt base Concrete example, such as can enumerate: (methyl) acryloyloxyethyl trimethyl ammonium chloride, three second of (methyl) acryloyl-oxyethyl Ammonium chloride, (methyl) acryloyl-oxyethyl dimethyl benzyl ammonium chloride, (methyl) acryloxyethyl methyl morpholinyl (methyl) alkyl acrylate such as ammonium chloride system quarternary ammonium salt；(methyl) Acryloyl amino hydroxypropyltrimonium chloride, (first Base) alkyl such as Acryloyl amino ethyl triethyl ammonium chloride, (methyl) Acryloyl amino ethyl dimethyl benzyl ammonium chloride (methyl) acryloyl group amide system quarternary ammonium salt；Dimethyldiallylammonium Methylsulfate, trimethyl-ethylene base tetraphenylphosphonium chloride Ammonium etc..
As the precursor portions structure for becoming general formula (6), the unsaturated singly amount body of the ethylene with three-level amido Concrete example can be enumerated: (methyl) acrylic acid N, N- dimethylamino ethyl ester, (methyl) acrylic acid N, N- diethylamino ethyl ester, (methyl) acrylic acid N, N- dimethylamino propyl ester, (methyl) acrylic acid N, N- diethylamino propyl ester etc. have three-level amino (methyl) esters of acrylic acid；
N, N- dimethyl aminoethyl (methyl) acrylamide, N, N- diethylamino ethyl (methyl) acrylamide, N, N- dimethylaminopropyl (methyl) acrylamide and N, N- diethyl amino propyl (methyl) acrylamide etc. have tertiary amine (methyl) acrylic amide of base etc..
The concrete example of the unsaturated single amount body of ethylene as the precursor portions structure for becoming general formula (7), such as can arrange Lift compound represented by following compounds (7-1)~compound (7-11) etc..
[changing 24]
[changing 25]
In compound (7-1)~compound (7-11), R4Indicate hydrogen or methyl.
In these, preferably methacrylic acid 2,2,6, the 6- tetramethyl piperidine esters (R in the compound (7-1)4For first The compound of base), the methacrylic acid 1,2,2,6,6- pentamethvl ester (R in the compound (7-2)4For the change of methyl Close object), particularly preferably methacrylic acid 1,2,2,6,6- pentamethvl esters.
Part-structure containing base represented by general formula (5), general formula (6), general formula (7) can be in an A block containing single It is solely one or more kinds of, containing two or more, can by random copolymerization or block copolymerization it is any in the form of contain.
In addition, the content of base represented by general formula (5), general formula (6), general formula (7) in A block be preferably 50 mass %~ 100 mass %, the more preferably 80 mass % of mass %~100, particularly preferably 95 mass of mass %~100 %.
On the other hand, as the Component units without base represented by general formula (5), general formula (6), general formula (7) in A block And B block is then not particularly limited if the polymer architecture for making copolymerizable single amount body copolymerization, can be suitable for depending on the application Selection.Copolymerizable single amount body described below.
Such as it can enumerate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) Isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) third Olefin(e) acid isopentyl ester, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) Acrylic acid cetyl, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) lauryl acrylate, (methyl) third Olefin(e) acid tridecane base ester, the different tetradecane base ester of (methyl) acrylic acid, (methyl) stearyl acrylate base ester, (methyl) acrylic acid are different hard The straight chained alkyls such as aliphatic radical ester (methyl) acrylate or branched alkyl groups (methyl) esters of acrylic acid；
(methyl) cyclohexyl acrylate, (methyl) t-butylcyclohexyl ester, (methyl) dicyclopentanyl acrylate, (first Base) cyclic alkyls (methyl) esters of acrylic acid such as acrylic acid dicyclopentenyl ester, (methyl) isobornyl acrylate；
(methyl) tetrahydrofurfuryl acrylate, (methyl) acrylic acid 3- methyl -3- oxa- ring butyl ester etc. have (the first of heterocycle Base) esters of acrylic acid；
(methyl) benzyl acrylate, (methyl) phenoxyethyl acrylate etc. have (methyl) acrylate of aromatic ring Class；
(methyl) acrylic acid 2- methoxy acrylate, (methyl) acrylic acid 2- ethoxy ethyl ester, (methyl) acrylic acid 2- methoxy Base propyl ester, diethylene glycol monomethyl ether (methyl) acrylate, diethylene glycol monoethyl ether (methyl) acrylate, diethylene glycol are mono- 2- ethylhexyl ether (methyl) acrylate, dipropylene glycol monomethyl ether (methyl) acrylate, triethylene glycol monomethyl ether (methyl) Acrylate, Triethylene glycol ethyl ether (methyl) acrylate, Tripropylene glycol monomethyl Ether (methyl) acrylate, tetraethylene glycol list Methyl ether (methyl) acrylate, poly glycol monomethyl ether (methyl) acrylate, polypropylene glycol monomethyl ether (methyl) acrylate, Polyethyleneglycol lauryl ether (methyl) acrylate, polyethyleneglycol stearyl ether (methyl) acrylate, the poly- second of octyloxy Glycol-polypropylene glycol (methyl) acrylate etc. (poly-) alkane glycol monoalkyl ether (methyl) esters of acrylic acid；
Phenoxy group diethylene glycol (methyl) acrylate, phenoxy group tetraethylene glycol (methyl) acrylate, six second of phenoxy group Glycol (methyl) acrylate, phenoxy group polyethylene glycol (methyl) acrylate, (methyl) acrylic acid to cumylphenoxy ethyl ester, To cumylphenoxy ethylene glycol (methyl) acrylate, to cumylphenoxy polyethylene glycol (methyl) acrylate, nonyl benzene oxygen Base polyethylene glycol (methyl) acrylate, Nonylphenoxy polypropylene glycol (methyl) acrylate, the poly- (second two of Nonylphenoxy Alcohol-propylene glycol) (poly-) alkane glycol (methyl) esters of acrylic acid with aromatic ring such as (methyl) acrylate；
3- methacryloxypropylmethyl dimethoxysilane, 3- methacryloxypropyl trimethoxy silicon Alkane, 3- methacryloxypropyl methyl diethoxysilane, 3- methacryloxypropyl and 3- Acryloyloxypropyltrimethoxysilane etc. has (methyl) esters of acrylic acid of alkoxysilane group；
(methyl) acrylic acid trifluoro ethyl ester, (methyl) acrylic acid octafluoro pentyl ester, (methyl) perfluoroethyl octyl ethyl ester and (methyl) fluoroalkyl base ester class such as (methyl) acrylic acid tetrafluoro propyl ester；
(methyl) acryloxy modified dimethyl polysiloxane (silicone polymeric monomer) class；
(methyl) acrylamide, dimethyl (methyl) acrylamide, N, N- diethyl (methyl) acrylamide, N- isopropyl N substituted type (methyl) acrylic amides such as (methyl) acrylamide, diacetone (methyl) acrylamide, acryloyl morpholine；(first Base) nitriles such as acrylonitrile etc..
In addition, can enumerate: the phenylethylenes such as styrene, α-methylstyrene；
Ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether, iso-butyl vinyl The vinyl ethers such as base ether；
Fatty acid ethylenes esters such as vinyl acetate, vinyl propionate etc..
In turn, can also and body be measured with the unsaturated list of carboxylic ethylene.As the unsaturated single amount of carboxylic ethylene Body can be enumerated: (methyl) acrylic acid, (methyl) acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, butenoic acid, adjacent benzene two Formic acid 2- (methyl) acryloyloxyethyl ester, phthalic acid 2- (methyl) acryloxy propyl ester, 2- (methyl) acryloyl-oxy Base ethyl hexahydrophthalic acid ester, 2- (methyl) acryloxypropyl hexahydrophthalic acid ester, (methyl) propenoic acid beta- Carboxyethyl, ω-carboxy-polycaprolactone (methyl) acrylate etc..
In addition, can also be in the range of not undermining effect and with containing represented by general formula (5), general formula (6), general formula (7) The unsaturated single amount body of the ethylene of amino other than base.
B block is preferably derived from the part-structure of the unsaturated single amount body of ethylene, and then is preferably selected from by (methyl) third Group composed by olefin(e) acid benzyl ester, (methyl) methyl acrylate, (methyl) ethyl acrylate and (methyl) Hydroxyethyl Acrylate In the unsaturated single amount body of ethylene.
(manufacture of block copolymer)
The acrylic block copolymer can for example be prepared using living polymerization as shown below.Herein, so-called Living polymerization is following polymerization: due to can inhibit generated side reaction in common free radical polymerization, and then equably Aggregation growth is carried out, so it is readily synthesized the resin of block polymer or molecular weight uniform.Pass through added polymerization when polymerization The loading ratio of initiator and vinyl monomer can freely control polymeric molecular weight or carry out the ratio of the monomer of block copolymerization Rate, and can be used for block polymer gradient polymer star polymer comb-shaped polymer and terminal-functional polymer Deng manufacture.
The acrylic block copolymer can be synthesized by well known radical living polymerization method, for example, can be used Documented method in Japanese Patent Laid-Open 2014-219665 etc..Not only with regard to the control of polymeric weight molecule amount distribution For the viewpoint of system, and just it is suitable for the aspect of single amount body of wide scope, the polymerization that can adapt to existing equipment can be used For the aspect of temperature, preferably Transfer Radical Polymerization (Atom Transfer Radical Polymerization method, ATRP method) and NO free radical regulation polymerization (Nitroxide mediated Polymerization method, NMP method), in turn, just without using the transition metal of factor etc. that can become coloring etc. For, more preferably NO free radical regulation polymerization (NMP method).
[Transfer Radical Polymerization (ATRP method)]
In Transfer Radical Polymerization, use the transition metal complexes such as copper, ruthenium, iron, nickel poly- as redox Catalyst is closed to carry out.As the concrete example of transition metal complex, the low valences such as copper chloride (I), copper bromide (I) can be enumerated Halogenated transition metal.
Organic ligand can be used in the transition metal complex.Organic ligand is to be able to realize in polymer solvent Solubility and redox polymerization catalyst reversible variation and use.As the coordination atom of transition metal, can enumerate: Nitrogen-atoms, oxygen atom, phosphorus atoms, sulphur atom etc..
As initiator used in atomic radicals polymerization, known person can be used, it is main to can be used reactivity high The organohalogen compounds with carbon-halogen bond, sulfonyl halide based compound etc..If particular instantiation, for isobutyl ethyl bromide, bromine For ethyl butyrate, chloro ethyl isobutyrate, chloro ethyl butyrate, paratoluensulfonyl chloride, 1- bromo ethyl phenenyl, Chloroethyl benzene Deng.It is used alone or and uses these.
[NO free radical regulates and controls polymerization (NMP method)]
Living radical polymerization via NO free radical (nitroxide) be using stable NO free radical (= N-O it) is carried out as free radical scavenger.It as stable NO free radical, is not particularly limited, such as can enumerate: 2, 2,6,6- tetramethyl -1- piperidyl oxygen radical (TEMPO), 2,2,6,6- tetraethyl -1- piperidyl oxygen radical, 2,2,6,6- Tetramethyl -4- oxo -1- piperidyl oxygen radical, 2,2,5,5- tetramethyl -1- pyrrolidinyl oxygen radical, 1,1,3,3- tetramethyl Base -2- iso-dihydro-indole-group oxygen radical, N, N- di-t-butyl amine oxygen radical etc..It can also replace NO free radical and use The stable free radicals such as ten thousand oxygroup of jar (unit of capacitance) (galvinoxyl) free radical.
The free radical scavenger can be used in combination with radical polymerization initiator.The two and be not particularly limited with ratio, Suitably relative to 1 mole of free radical scavenger and radical initiator be 0.1 mole~10 moles.
The radical polymerization initiator can be suitable for selection according to the weight average molecular weight (Mw) of synthesized resin, 1 mole of (methyl) acryloyl group when relative to synthetic copolymer in used single amount body and be 0.0001 mole~1 mole, Preferably 0.001 mole~0.1 mole of ratio.
It is then had no as radical polymerization initiator if the compound that can be generated free radicals under the conditions of polymerization temperature Known person may be selected in especially limitation.Such as it can enumerate: di-t-butyl peroxide, dicumyl peroxide, butyl-cumyl Peroxide, α, the equal dialkyl group of bis- (tert-butyl hydroperoxide-isopropyl) benzene of α ' -, (tert-butyl hydroperoxide) hexin -3 of 2,5- bis- Peroxide；
Tert butyl peroxy benzoate, tert-butyl hydroperoxide acetic acid esters, two (benzoyl mistake of 2,5- dimethyl -2,5- Oxidation) peroxyesters such as hexane；
The ketone peroxide such as Cyclohexanone peroxides, 3,3,5 trimethyl hexanone peroxide, methyl cyclohexanone peroxide Compound class；
Bis- (the 4,4- di-t-butyl peroxidating cyclohexyl) propane of 2,2-, bis- (tert-butyl hydroperoxide) the 3,3,5- front threes of 1,1- The peroxidating such as bis- (tert-butyl hydroperoxide) hexamethylenes of butylcyclohexane, 1,1-, bis- (tert-butyl hydroperoxide) valerates of normal-butyl -4,4- Ketal class；
Cumene hydroperoxide, diisopropyl benzene hydroperoxides, 2,5- dimethyl cyclohexane -2,5- dihydro-peroxidase Etc. hydroperoxide types；
Benzoyl peroxide, decanol peroxide, lauroyl peroxide, 2,4 dichloro benzene formoxyl peroxide The diacyl peroxides class such as compound；
The organic peroxides such as the peroxy dicarbonates such as bis- (tert-butylcyclohexyl) peroxy dicarbonates or these Mixture.
In addition, it is possible to use azo-compound is as radical polymerization initiator.Such as can enumerate: 2,2'- azo is double different The double fourths of 2, the 2'- such as butyronitrile (2,2'-azobisisobutyronitrile, AIBN), 2,2'- azo bis- (2- methylbutyronitriles) azo Nitrile；The 2,2'- such as 2,2'- azo bis- (4- methoxyl group -2,4- methyl pentane nitriles), 2,2'- azo bis- (2,4- methyl pentane nitriles) The double valeronitrile classes of azo；The double propionitrile classes of the 2,2'- such as 2,2'- azo bis- (2- hydroxymethyl propionitrile) azo；Bis- (the hexamethylenes of 1,1'- azo Alkane -1- formonitrile HCN) etc. double -1- alkane nitriles of 1,1'- azo etc..
In turn, it is such as reported in " macromolecular (Macromolecules) " 1995,28,2993 like that, instead of and with certainly The alkoxyamine represented by following compounds (N-1~N-4) can be used by base agent for capturing and the radical polymerization initiator Compound is as initiator.
[changing 26]
[changing 27]
[changing 28]
[changing 29]
Manufacture block copolymer process in, can it is solvent-free or optionally and use solvent.As solvent, such as can arrange It lifts: ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, dimethylbenzene, acetone, hexane, methyl ethyl ketone, cyclohexanone, third Glycol monomethylether acetate, dipropylene glycol monomethyl ether acetic acid esters, ethylene glycol monoethylether acetate, ethylene glycol monomethyl ether acetate, Diethylene glycol monoethyl ether acetic acid esters, butyl carbitol acetate etc., but be not particularly limited.These polymerization solvents can mix Using two or more.
Used quantity of solvent preferably 0 mass parts relative to single amount 100 mass parts of body comprising A block and B block ~300 mass parts, and then preferably 0 mass parts~100 mass parts.Used solvent can pass through distillation etc. after the completion of reaction It operates and removes, or can be directly as a part of the product of composition.
A block is preferably the 1 mass % of mass %~99 relative to the containing ratio of block copolymer solid component, and then preferably For the 20 mass % of mass %~50, particularly preferably 20 mass of mass %~30 %.In the A containing 20 mass of mass %~30 % In the case where block, the remaining 70 mass mass of %~80 % constitutes B block.Therefore, because of B block and the solvent as dispersion matchmaker It is affine, so be present in while pigment stabilizer can be made in dispersion matchmaker.
In addition, the amount of base represented by general formula (5), general formula (6), general formula (7) in acrylic block copolymer 1 g is excellent Be selected as 0.1mmol~5mmol, if in the range, then can further make lightness with dispersibility and deposit.
Though acrylic block copolymer also depend on general formula (5), general formula (6), structure represented by general formula (7) kind Class, but amine value is more preferably 30mgKOH/g~350mgKOH/g.If amine value is 30mgKOH/g or more, pigment dispersion glues Degree and viscosity stability are excellent, if 350mgKOH/g hereinafter, then lightness is excellent.
In addition, the molecular weight of acrylic block copolymer in terms of the weight average that polystyrene converts and preferably 1, 000 or more, 100,000 ranges below.If the molecular weight of acrylic block copolymer less than 1,000, then it is steady to there is dispersion Qualitative reduced tendency, if more than 100,000, then there is the tendency of developability reduction.
In 1st colored filter coloured composition, the acrylic block copolymer is used as dispersing agent, at this point, Various resins can also be added.
(other dispersing agents)
1st colored filter coloured composition can also and with other dispersing agents.It is specific to can be used as other dispersing agents The polycarboxylates such as polyurethanes, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (part) amine salt, polycarboxylic acid Ammonium salt, polycarboxylic acid alkylamine salt, polysiloxanes, long-chain polyaminoamide phosphate, the polycarboxylate of hydroxyl or changing for these Property object, by poly- (low-grade alkylidene imines) and the polyester with free carboxyl to react the amide to be formed or its salt etc. oily Property dispersing agent, (methyl) acrylic-styrene copolymer, (methyl) acrylic acid-(methyl) acrylate copolymer, styrene- The water-soluble resins such as maleic acid, polyvinyl alcohol, polyvinylpyrrolidone or water-soluble high-molecular compound, polyester System, modified polyacrylate system, ethylene oxide/propylene oxide additive compound, phosphate system etc., these can be used alone or mix It is two or more to close use, but is not limited to these.
It as commercially available resin type dispersing agent, can enumerate: chemical (BYK-Chemie Japan) the company manufacture of Japanese Bi Ke Di Sipabike (Disperbyk) -101,103,107,108,110,111,116,130,140,154,161,162,163, 164、165、166、170、171、174、180、181、182、183、184、185、190、2000、2001、2020、2025、2050、 2070,2095,2150,2155 or peace for safe draw (Anti-Terra)-U, 203,204 or BYK-P104, P104S, 220S, 6919 Or orange red is drawn to wash one's hair grace (Lactimon), orange red is drawn to wash one's hair grace (Lactimon)-WS or Bi Kemen (Bykumen) etc.；Japanese Lu Borun (Lubrizol) the Suo Lusi Paasche (SOLSPERSE) -3000 of company's manufacture, 9000,13000,13240,13650,13940, 16000、17000、18000、20000、21000、24000、26000、27000、28000、31845、32000、32500、 32550,33500,32600,34750,35100,36600,38500,41000,41090,53095,55000,76500 etc.；Day The Ai Fuka (EFKA) -46 of this BASF (BASF Japan) company manufacture, 47,48,452,4008,4009,4010,4015, 4020、4047、4050、4055、4060、4080、4400、4401、4402、4403、4406、4408、4300、4310、4320、 4330、4340、450、451、453、4540、4550、4560、4800、5010、5065、5066、5070、7500、7554、1101、 120,150,1501,1502,1503 etc.；The A Ji of aginomoto microtechnic (Ajinomoto Fine-Techno) company manufacture Si Pa (Ajisper)-PA111, PB711, PB821, PB822, PB824 etc..
The person that preferably has acidic substituent with the resin type dispersing agent of the acrylic block copolymer.As Acidic substituent, such as can enumerate: phosphate, sulfo group, carboxyl.Wherein, have aromatic carboxyl person due to preventing after dispersing The effect of colorant re-united is especially big, so it is preferred that.As the resin type dispersing agent with aromatic carboxyl, preferably under State (S1) or (S2).
(S1) as the polymeric hydroxyl, anti-with the anhydride group of tricarboxylic acid anhydride and/or tetracarboxylic dianhydride with hydroxyl Answer the resin type dispersing agent of product.
(S2) as following polymeric resin type dispersing agent, the condensate is the hydroxyl in the compound with hydroxyl Base, with make in the presence of the reaction product of the anhydride group of tricarboxylic acid anhydride and/or tetracarboxylic dianhydride the unsaturated single amount body of ethylene into Row is polymerized.
[resin type dispersing agent (S1)]
Resin type dispersing agent (S1) is using WO2008/007776 bulletin, Japanese Patent Laid-Open 2008-029901 public affairs The well known method of report, Japanese Patent Laid-Open 2009-155406 bulletin etc. manufactures.Condensate (p) with hydroxyl is preferred To have the condensate of hydroxyl in end, for example, can following polymeric form obtain, the condensate is with hydroxyl Compound (q) in the presence of so that unsaturated single amount body (r) of ethylene is polymerized.As the compound with hydroxyl (q), preferably in the molecule with the compound of hydroxyl and mercapto.The hydroxyl of end is preferably several, therefore, wherein can It is suitable to use the compound (q1) having in the molecule there are two hydroxyl and a mercapto.
That is, an example more preferably single end tool there are two the condensates of hydroxyl can following condensate (p1) Form obtains, and the condensate (p1) is the presence for having the compound (q1) there are two hydroxyl and a mercapto in the molecule Under, so that unsaturated single amount body (r) of the ethylene comprising single amount body (r1) is polymerized.Condensate (p) with hydroxyl Hydroxyl reacts with the anhydride group of tricarboxylic acid anhydride and/or tetracarboxylic dianhydride and forms ester bond, on the other hand, no water ring open loop and Generate carboxylic acid.
[resin type dispersing agent (S2)]
Resin type dispersing agent (S2) is using Japanese Patent Laid-Open 2009-155406 bulletin, Japanese Patent Laid-Open 2010- Method well known to No. 185934 bulletins, Japanese Patent Laid-Open 2011-157416 bulletin etc. manufactures, such as can pass through such as lower section Formula obtains: reacting production in the hydroxyl of the compound (q) with hydroxyl, with the anhydride group of tricarboxylic acid anhydride and/or tetracarboxylic dianhydride In the presence of object, it polymerize unsaturated single amount body (r) of ethylene.Wherein, preferably in the molecule tool there are two hydroxyl with The reaction product of the anhydride group of the hydroxyl and tricarboxylic acid anhydride and/or tetracarboxylic dianhydride of the compound (q1) of one mercapto is deposited Under, make the condensate being polymerized comprising unsaturated single amount body (r) of single ethylene for measuring body (r1).
(S1) with (S2) the difference is that: first carry out or after carry out unsaturated single amount body (r) of ethylene polymerize and At polymerization body region importing.Though molecular weight etc. has several differences due to all conditions, but as long as raw material is identical as reaction condition, It then theoretically can be identical.
Resin type dispersing agent is relative to colorant total amount and preferably with the use of 5 mass parts~200 mass parts degree, just For the viewpoint of film forming, more preferably with the use of 5 mass parts~100 mass parts degree.
< adhesive resin >
The 1st colored filter coloured composition in this announcement can also contain adhesive resin.Adhesive resin is to make Colorant dispersion is dyed or the person of being impregnated with, and can enumerate thermoplastic resin etc..In addition, with alkali developable coloring resist material In the case that form uses coloured composition, it is preferable to use will be made of the unsaturated single amount body copolymerization of the ethylene containing acidic groups Alkali-soluble vinylite.In addition, in order to further increase photo sensitivity, it is possible to use the work with ethylene unsaturated double-bond Property energy line hardening resin.
In particular, by side chain there is the active energy ray hardening resin of ethylene unsaturated double-bond to be used for alkali developable Colour in resist material, thus be exposed using active energy ray and when forming film, resin carry out it is three-dimensional cross-linked, thus Colorant is fixed, and heat resistance becomes well, and can inhibit colorant because of the colour fading (evil of dichroism caused by heat Change).Further, it may have following effect: in developing procedure, the cohesion of coloring agent component also being inhibited to be precipitated.
As adhesive resin, it is divided preferably in all wavelengths region of 400nm~700nm of visible light region saturating The rate of mistake is preferably the resin of 80% or more, more preferably 95% or more.
For the aspect for dispersing colorant preferably, the weight average molecular weight (Mw) of adhesive resin is preferably 10,000~100,000, more preferably 10,000~80,000.In addition, number average molecular weight (Mn) be preferably 5,000~ 50,000, Mw/Mn value is preferably 10 or less.
In the case where the coloured composition of this announcement is used as colored filter photosensitive coloring composition, about viscous Mixture resin, carboxyl that the solvable base of alkali when adsorbing base and development as colorant plays a role are carried with as colorant The balance of the compatibility base fatty group to play a role and aromatic series base of body and solvent for colorant dispersibility, be impregnated with It is important for property, developability and durability, the preferably resin of acid value 20mgKOH/g~300mgKOH/g.If acid value is less than 20mgKOH/g then is difficult to form fine pattern for the dissolubility difference of developer solution.If will not be stayed more than 300mgKOH/g Lower fine pattern.
About adhesive resin, for film forming and the good aspect of all patience, preferably relative to the total of colorant 100 mass parts of quality and be 20 mass parts or more, for colorant concentration is high and can show the aspect of good color characteristics, Preferably 1000 below the mass.
It as thermoplastic resin used in adhesive resin, such as can enumerate: acrylic resin, butyral resin, benzene Ethylene maleic acid copolymer, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-acetate base ester copolymer, gathers haloflex Vinyl-acetic ester, polyester resin, vinylite, alkyd resin, polystyrene resin, gathers polyurethanes system resin Amide resin, rubber series resin, thermoprene system resin, cellulose family, polyethylene (high density polyethylene (HDPE) (High Density Polyethylene, HDPE), low density polyethylene (LDPE) (Low Density Polyethylene, LDPE)), polybutadiene and poly- Imide resin etc..Wherein, preferably acrylic resin.
Ethylene system alkali soluble resin made of being copolymerized as the ethylene unsaturated monomer that will contain acidic groups, such as can arrange Lift the resin with acidic groups such as carboxyl, hydroxyl, sulfo groups.
It is specific enumerable as alkali soluble resin: acrylic resin, alpha-olefin/maleic acid (acid anhydride) with acidic groups Copolymer, styrene/Styrene Sulfonic Acid Copolymer, ethylene/(methyl) acrylic copolymer or isobutene/maleic acid (acid anhydride) copolymerization Object etc..Wherein, selected from acidic groups acrylic resin and at least one of styrene/Styrene Sulfonic Acid Copolymer tree Rouge, particularly acrylic resin with acidic groups are since heat resistance, the transparency are high, so can be suitable for using.
As the active energy ray hardening resin with ethylene unsaturated double-bond, such as can enumerate using as shown below (i) or (ii) method and imported the resin of unsaturated ethylene double bond.
[method (i)]
As method (i), such as there are as below methods: for by making there is epoxy group unsaturated ethylene list amount body, With it is other more than one single amount body copolymerization and the side links oxygroup of copolymer that obtains, addition reaction have unsaturated ethylene The carboxyl of the unsaturated monoacid of property double bond, and then react hydroxyl generated with multi-anhydride, to import unsaturated ethylene Alkene double bond and carboxyl.
As the unsaturated ethylene list amount body with epoxy group, such as can enumerate: (methyl) glycidyl acrylate, (methyl) acrylic acid methylglycidyl esters, (methyl) acrylic acid 2- glycidoxypropyl ethyl ester, (methyl) acrylic acid 3,4- ring Oxygen butyl ester and (methyl) acrylic acid 3,4- epoxy cyclohexyl, these can be used alone, can also and with two or more.Just with next work For the reactive viewpoint of the unsaturated monoacid of sequence, preferably (methyl) glycidyl acrylate.
It as unsaturated monoacid, can enumerate: (methyl) acrylic acid, butenoic acid, adjacent vinyl benzoic acid, vinyl benzene Formic acid, the position the α halogenated alkyl to vinyl benzoic acid, (methyl) acrylic acid, alkoxy, halogen, nitro, cyano replace body etc. single Carboxylic acid etc., these can be used alone, can also and with two or more.
It as multi-anhydride, can enumerate: tetrabydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, amber Amber acid anhydrides, maleic anhydride etc., these can be used alone, can also and with two or more.The quantity etc. of carboxyl can also be increased, optionally Using tricarboxylic acid anhydrides such as trimellitic anhydrides or using tetracarboxylic dianhydrides such as pyromellitic acid anhydrides come by remaining anhydride group water Solution.In addition, as multi-anhydride, if using the tetrabydrophthalic anhydride or maleic anhydride with unsaturated ethylene double bond, Unsaturated ethylene double bond can then be increased in turn.
As the similar approach of method (i), such as there are as below methods: for the unsaturated ethylene by making to have carboxyl Single amount body, with it is other more than one single amount body copolymerization and a part of the side chain carboxyl group of copolymer for obtaining, addition reaction Unsaturated ethylene list amount body with epoxy group, to import unsaturated ethylene double bond and carboxyl.
[method (ii)]
As method (ii), there are as below methods: making the isocyanic acid of the unsaturated ethylene list amount body with isocyanate group Ester group and by using the unsaturated ethylene list amount body with hydroxyl and with other unsaturated monoacid with carboxyl The pendant hydroxyl group of single amount body or other single copolymers measuring body copolymerization and obtaining is reacted.
It as the unsaturated ethylene list amount body with hydroxyl, can enumerate: (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) Acrylic acid 2- hydroxy propyl ester or (methyl) acrylic acid 3- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl or (methyl) acrylic acid 3- hydroxybutyl or (methyl) acrylic acid 4- hydroxybutyl, (methyl) glycerol acrylate or cyclohexanedimethanol list (methyl) third Olefin(e) acid ester etc. (methyl) hydroxyalkyl acrylates class, these can be used alone, can also and with two or more.In addition, can also make With to made of (methyl) the hydroxyalkyl acrylates addition polymerization ethylene oxide, propylene oxide and/or epoxy butane etc. Polyethers list (methyl) acrylate or addition (poly-) gamma-valerolactone, (poly-) 6-caprolactone and/or (poly-) 12- hydroxy stearic acid etc. Made of (poly-) ester list (methyl) acrylate.For the viewpoint that film foreign matter inhibits, preferably (methyl) acrylic acid 2- hydroxyl Base ethyl ester or (methyl) glycerol acrylate.
As the unsaturated ethylene list amount body with isocyanate group, it is different that 2- (methyl) acryloyl-oxyethyl can be enumerated Cyanate or 1, bis- [(methyl) acryloxy] ethyl isocyanates of 1- etc., but be not particularly limited, can also and with two kinds with On.
< thermosetting compound >
The coloured composition of this announcement can also contain thermosetting compound.Thermosetting compound is not particularly limited, With regard to chemical-resistant, solvent resistance viewpoint for, preferably epoxide.
(epoxide)
As long as epoxide be the compound with epoxy group, can be low molecular compound, can also for resin that The high-molecular weight compounds of sample.
Particularly preferably polyfunctional epoxy resin, function radix are preferably two functions or more, more preferably trifunctional with On.It, can be with adhesive resin or dispersing agent in the calcining as colored filter production process by containing epoxy resin Carboxyl carries out heat cross-linking and obtains the high coloring film of crosslink density.
Thermosetting compound be epoxy resin in the case where, preferred weight average molecular weight be 1500 or more, 100,000 or less.Preferred molecular weight is 1750 or more, 10,000 hereinafter, being in turn preferably 2000 or more, 7000 or less.
Colored filter is preferably 5 mass of mass %~20 % with the content of the epoxide in coloured composition.If For 5 mass % or more, then the improvement of solvent resistance is excellent, if 20 mass % hereinafter, can then prevent by the Huang after toasting The quality of colored filter caused by change etc. reduces, and the ageing stability of coloured composition also becomes good.
As the epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, cresol novolak type can be used Epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin etc. it is any.
As two functional epoxy resins, can enumerate: grand (EPICLON) 830 in Chinese mugwort library of DIC (DIC) company manufacture, 840,850,860,1050,2050,3050,4050,7050,HM-091,101；Long rapids chemical conversion (Nagase ChemteX) manufacture Pellet receive EX-211,212,252,711,721 Cauer (Denacol) etc..
As polyfunctional epoxy resin more than trifunctional, phenolic resin varnish type epoxy resin, ester ring type asphalt mixtures modified by epoxy resin can be enumerated Rouge etc..
Phenolic resin varnish type epoxy resin is compound represented by the following general formula (15), and is classified as phenol novolacs Type epoxy resin, cresol novolak type epoxy resin.
[changing 30]
General formula (15)
R1 in general formula (15) is separately methyl or hydrogen atom, the integer that q is 2~100.
It is specific enumerable as phenolic resin varnish type epoxy resin: EOCN-1020, EOCN-102S, EOCN-103S, EOCN- 104S, EOCN-4500, EOCN-4600, XD-1000, XD-1000-L, XD-1000-2L, NC-3000, NC-3000-H (more than It is made for Japanese chemical drug corporation)；YDPN-638,YDCN-700-2,YDCN-700-3,YDCN-700-5,YDCN-700-7, YDCN-700-10, YDCN-704, YDCN-704A (the above are the manufactures of chemical company, Nippon Steel)；N-660,N-665,N-670,N- 673, (the above are enlightening love by N-680, N-690, N-695, N-665-EXP, N-672-EXP, N-655-EXP-S, N-662-EXP-S Raw (DIC) company manufacture) etc..
Alicyclic epoxy resin is, for example, compound represented by the following general formula (16).It, can as alicyclic epoxy resin Enumerate EHPE3150 (manufacture of Daicel (Daicel) chemical industrial company) etc..
[changing 31]
General formula (16)
In general formula (16), j, k, l are respectively 1~30 integer.
As the polyfunctional epoxy resin more than trifunctional other than described, can enumerate: the epoxy resin as trifunctional Cruel cyclopentadienyl (Techmore) VG3101 of Thailand (general woods technology (Printech) company manufactures), as tetrafunctional epoxy resin Thailand Ladd (TETRAD)-C, Tai Lade (TETRAD)-X (the above are the manufactures of gas chemical company, Mitsubishi) etc..
In addition, can enumerate: the pellet of long rapids chemical conversion (Nagase ChemteX) manufacture receive Cauer (Denacol) EX-313, 314,321,411,421,512,521,611,612,614,614B, 622 etc..
In addition, JER1031S, 1302H60 of Mitsubishi Chemical Ind's manufacture, 604,630,630LSD etc. can be enumerated.
(other thermosetting compounds)
It as other thermosetting compounds, such as can enumerate: benzoguanamine compound/resin, Abietyl modified maleic acid The thermosettings compounds such as resin, Abietyl modified fumaric resin, melamine compound/resin, carbamide resin and phenol resin, or Monomer and oligomer before the heating polymerization of these thermosetting resins.
[solvent]
The colored filter coloured composition of this announcement contains solvent.By containing solvent, to be easy to make colorant It is fully dispersed, be impregnated in color carrier, and on the substrates such as such as glass substrate with dry film thickness become 0.2 μm~5 μm Mode be coated to form optical filtering section.In addition to the coating for considering coloured composition is good, it is also contemplated that coloured composition Solvent is selected in the dissolubility of each ingredient and safety.
It as solvent, such as can enumerate: ethyl lactate, benzyl alcohol, 1,2,3- trichloropropanes, 1,3-BDO (1,3- Butanediol), 1,3 butylene glycol diacetate esters, 1,4- dioxanes, 2-HEPTANONE, 2- methyl-1,3-propanediol, 3,5,5- front three Base -2- cyclohexene -1- ketone, 3,3,5- trimethylcyclohexanone, 3- ethoxyl ethyl propionate, 3- methyl-1,3- butanediol, 3- methoxy Base -3- methyl-1-butanol, 3- methoxyl group -3- Methylbutyl acetate, 3- methoxybutanol, 3- methoxybutyl acetic acid esters, 4- Heptanone, meta-xylene, diethylbenzene, m-dichlorobenzene, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, normal-butyl alcohol, N-butylbenzene, n-propyl acetate, N-Methyl pyrrolidone, ortho-xylene, ortho-chlorotolu'ene, adjacent diethylbenzene, o-dichlorohenzene, to chlorine Toluene, p-diethylbenzene, sec-butylbenzene, tert-butyl benzene, gamma-butyrolacton, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, second Dibutyl ether, ethyleneglycol monopropylether, ethylene glycol monoethyl ether, ethylene glycol monoethylether acetate, the tertiary butyl ether of ethylene glycol list, second two Alcohol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol ether, ethylene glycol monohexylether, glycol monoethyl ether, ethylene glycol list first Ether acetic acid ester, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol list isopropyl ether, diethylene glycol list Ether acetate, diethylene glycol monobutyl ether, butyl carbitol acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol second Acid esters, cyclohexanone, dimethyl ether, dipropylene glycol methyl ether acetic acid esters, dipropylene glycol monoethyl ether, Dipropylene glycol mono-n-butyl Ether, Dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, glyceryl triacetate, Tri(propylene glycol)butyl ether,mixture of isomers, tripropylene glycol list Methyl ether, propylene-glycol diacetate, propylene glycol phenylate, dihydroxypropane single-ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, Propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monomethyl ether propionate, benzylalcohol, methyl tert-butyl Base ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester Deng.
These solvents can be used alone, or is optionally used in mixed way with arbitrary ratio two or more.
The content of solvent is 100 mass parts~10000 mass relative to 100 mass parts of colorant in coloured composition Part, preferably 500 mass parts~5000 mass parts.
[any ingredient]
The coloured composition of this announcement at least contains colorant, resin and solvent, but optionally can also be containing various any Ingredient.Hereinafter, being illustrated to any ingredient other than the pigment derivative.
< photopolymerizable compound >
The coloured composition of this announcement can also contain photopolymerizable compound.Comprising by ultraviolet in photopolymerizable compound Line or heat etc. and harden and generate the monomer or oligomer of transparent resin.
It as by ultraviolet light or the equal hardening of heat and generating the monomer of transparent resin, oligomer, such as can enumerate: (first Base) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) cyclohexyl acrylate, (methyl) P-carboxy ethyl acrylates, polyethylene glycol two (methyl) acrylate, 1,6-HD Two (methyl) acrylate, triethylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, trihydroxy methyl third Alkane three (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, 1,6- oneself two Alcohol diglycidyl ether two (methyl) acrylate, bisphenol A diglycidyl ether two (methyl) acrylate, neopentyl glycol two contract Water glycerin ether two (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylic acid Ester, (methyl) acrylic acid tristane base ester, ester acrylate, methylolated melamine (methyl) acrylate, epoxy Various acrylate and the methacrylates such as (methyl) acrylate, propenoic methyl carbamate；(methyl) acrylic acid, benzene second Alkene, vinyl-acetic ester, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythrite trivinyl ether, (methyl) third Acrylamide, N- hydroxymethyl (methyl) acrylamide, N- vinyl formamide, acrylonitrile etc., but be not particularly limited.
These photopolymerizable compounds can be used alone one kind, or optionally with arbitrary ratio be used in mixed way two kinds with On.
The content of photopolymerizable compound preferably 5 mass parts~500 mass parts relative to 100 mass parts of colorant, For the viewpoint of photo-hardening and developability, more preferably 10 mass parts~400 mass parts.
< Photoepolymerizationinitiater initiater >
The coloured composition of this announcement can also contain Photoepolymerizationinitiater initiater.In order to make coloring compositions by ultraviolet light irradiation Object, which hardens, simultaneously forms optical filtering section using photoetching process, and adds Photoepolymerizationinitiater initiater and photosensitive with solvent development type or alkali developable It is prepared by the form of property coloured composition.
It as Photoepolymerizationinitiater initiater, can enumerate: 4- phenoxydichloroacetophenone, 4- tert-butyl-dichloroacetophenone, diethoxy Benzoylformaldoxime, 1- (4- isopropyl phenyl)-2- hydroxy-2-methyl propane-1- ketone, 1- hydroxycyclohexylphenylketone, 2- methyl-1- [4- (methylsulfany) phenyl] -2- morpholinopropane -1- ketone, 2- (dimethylamino) -2- [(4- aminomethyl phenyl) methyl] -1- The benzene such as [4- (4- morpholinyl) phenyl] -1- butanone, 2- benzyl -2- dimethylamino -1- (4- morpholino phenyl)-butane -1- ketone Ethyl ketone based compound；The styraxes such as styrax, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal Based compound；Benzophenone, benzoyl benzoic acid, benzoyl methyl benzoate, 4- phenyl benzophenone, hydroxy benzophenone Ketone, acrylated benzophenone, 4- benzoyl -4'- dimethyl diphenyl sulfide, 3,3', (the tert-butyl hydroperoxide carbonyl of 4,4'- tetra- Base) benzophenone based compounds such as benzophenone；Thioxanthone, 2- chlorothiaxanthenone, 2- methyl thioxanthone, isopropyl thioxanthone The thioxanthones based compounds such as anthrone, 2,4- diisopropyl thioxanthone, 2,4- diethyl thioxanthone；2,4,6- tri- is chloro- Bis- (the trichloromethyl)-s-triazine of triazine, 2- phenyl -4,6-, bis- (the trichloromethyl)-s-triazine of 2- (p-methoxyphenyl) -4,6-, Bis- (the trichloromethyl)-s-triazine of 2- (p-methylphenyl) -4,6-, bis- (the trichloromethyl)-s-triazine of 2- piperonyl -4,6-, 2,4- are bis- (trichloromethyl) -6- styryl-s-triazine, bis- (the trichloromethyl)-s-triazine of 2- (naphthalene -1- base) -4,6-, 2- (4- methoxyl group - Naphthalene -1- base) bis- (the trichloromethyl)-s-triazine of -4,6-, 2,4- trichloromethyl-(piperonyl) -6- triazine, 2,4- trichloromethyl - The triazine based compounds such as (4'- methoxyl-styrene) -6- triazine；1,2- acetyl caproyl, 1- [4- (phenylsulfartyl)-, 2- (O- benzene Formoxyl oxime)], the oximes ester such as O- (acetyl group)-N- (1- phenyl -2- oxo -2- (4'- methoxy-naphthyl) ethylidene) hydroxylamine Based compound；Bis- (2,4,6- trimethylbenzoyl) phenylphosphine oxides, 2,4,6- trimethylbenzoyldiphenyl oxygen The phosphines based compound such as compound；The oxime-based compounds such as 9,10- phenanthrenequione, camphorquinone, ethyl hydrazine；Borate based compound；Carbazole system Compound；Imidazole compound；Titanocenes based compound etc..
These Photoepolymerizationinitiater initiaters can be used alone one kind, or is optionally used in mixed way with arbitrary ratio two or more.
The content of Photoepolymerizationinitiater initiater preferably 1 mass parts~500 mass parts relative to 100 mass parts of colorant, just For the viewpoint of photo-hardening and developability, more preferably 5 mass parts~400 mass parts.
< sensitizer >
In turn, the colored filter coloured composition of this announcement can also contain sensitizer.
It as sensitizer, can enumerate: chalcone (chalcone) derivative or dibenzalacetone (dibenzalacetone) etc. the 1,2- derovatives of unsaturated ketones, benzil or camphorquinone etc., Benzoin derivative, Fluorene derivative, naphthoquinone derivatives, anthraquinone derivative, xanthene derivative, thia anthracene derivant, xanthone derivative, thia Anthracyclinone derivatives, coumarin derivative, ketocoumarin derivative, Cyanine derivative object, Merocyanine derivatives, oxonols derivative Equal polymethines pigment, acridine derivatives, azine derivatives, thiazine derivative, oxazines derivative, indoline derivative object, Azulene spread out Derivative, derivatives of porphyrin, Tetraphenyl porphyrin derivative, triaryl in biology, Azulene (azulenium) derivative, side are sour Methane Derivatives, Tetrabenzoporphyrin derivative, four pyrazines and porphyrazine (tetrapyrazinoporphyrazine) derivative, Phthalocyanine derivates, four azepine porphyrazine (tetraazaporphyrazine) derivatives, four quinoxalines and seaweed oxazine derivatives, naphthalene Phthalocyanine derivates, sub- phthalocyanine derivates, pyran derivate, thiapyran (thiopyrylium) derivative, four films (tetraphyrin) derivative, annulene (annulene) derivative, spiropyran derivatives, spirooxazine derivative, thio spiro-pyrans Derivative, metal-arene complex, organic ruthenium complex, michaelis ketone (Michler's ketone) derivative etc..
These sensitizers can be used alone one kind, or is optionally used in mixed way with arbitrary ratio two or more.
In turn, concrete example can enumerate " pigment handbook " (1986, talk about society), the great river original letter that great river original letter et al. is write Et al. bright et al. " the specific function material " write of " functional pigmented chemistry " (1981, CMC) write, Chi Senzhong tri- The sensitizer recorded in (1986, CMC), but it is not limited to these.In addition, furthermore can also contain to ultraviolet near infrared region The light in domain shows the sensitizer of absorption.
In the sensitizer, as particularly suitable sensitizer, can enumerate: thioxanthone derivative, Michaelis ketone derivatives, Carbazole derivates.In turn, 2,4- diethyl thioxanthone, 2- chlorothiaxanthenone, 2,4-, bis- chlorothiaxanthenone, 2- specifically can be used Bis- (dimethylamino) hexichol of the chloro- 4- propoxyl group thioxanthone of isopropyl thioxanthone, 4- isopropyl thioxanthone, 1-, 4,4'- Bis- (diethylamino) benzophenone of ketone, 4,4'-, bis- (ethylmethylamino) benzophenone of 4,4'-, N- ethyl carbazole, 3- Benzoyl-N-ethyl carbazole, 3,6- dibenzoyl-N- ethyl carbazole etc..
The content of sensitizer preferably 3 matter relative to 100 mass parts of Photoepolymerizationinitiater initiater contained in coloured composition Measure part~60 mass parts, with regard to photo-hardening, developability viewpoint for, more preferably 5 mass parts~50 mass parts.
< multi-functional thiol >
Multi-functional thiol can also be contained in the colored filter coloured composition of this announcement.Multi-functional thiol is with two The compound of a above mercaptan (SH) base.
Radical polymerization process of the multi-functional thiol by being used together with the Photoepolymerizationinitiater initiater, after light irradiation In, it plays a role as chain-transferring agent, and generate the Thiyl Radical (thiyl for being not easily susceptible to that polymerization hinders as caused by oxygen Radical), therefore colored filter obtained with coloured composition is high sensitivity.Particularly preferably SH base is bonded to methylene Multifunctional aliphatic mercaptan on the fatty groups such as base, ethylidene.
It as multi-functional thiol, such as can enumerate: the double propane thioic acids of hexanedithiol, decanedithiol, 1,4-butanediol The double thioglycolic acid esters of ester, 1,4- butanediol, the double thioglycolic acid esters of ethylene glycol, ethylene glycol double thiopropionates, trihydroxy methyl The thio ethyl glycolate of propane three, trimethylolpropane tris thiopropionate, trimethylolethane trimethacrylate (3- mercaptobutylate), three hydroxyls Methylpropane three (3- mercaptobutylate), trimethylolpropane tris (3-thiopropionate), pentaerythrite tetrathio ethyl glycolate, Pentaerythrite tetrathio propionic ester, pentaerythrite four (3-thiopropionate), dipentaerythritol six (3-thiopropionate), three mercaptos Base propionic acid three (2- hydroxyethyl) isocyanuric acid ester, 1,4- dimethyl sulfydryl benzene, 2,4,6- tri-thiol-s-triazine, 2- (N, N- bis- Butylamino) -4,6- dimercapto-s-triazine etc..
These multi-functional thiols can be used alone one kind, or is optionally used in mixed way with arbitrary ratio two or more.
The content of multi-functional thiol preferably 0.05 mass parts~100 mass parts relative to 100 mass parts of colorant, more Preferably 1.0 mass parts~50.0 mass parts.
By using multi-functional thiols more than 0.05 mass parts, more good resistance to developability can get.Using mercaptan (SH) in the case where the simple function mercaptan that base is one, the raising of such resistance to developability can not be obtained.
< levelling agent >
In the coloured composition of this announcement, in order to keep the levelability of the composition on transparent substrate good, preferably add Levelling agent.As levelling agent, preferably there is the dimethyl siloxane of polyether structure or polyester construction in main chain.As in main chain The concrete example of dimethyl siloxane with polyether structure can be enumerated: beautiful DOW CORNING (the Toray Dow Corning) company in east The BYK-333 etc. of chemical (BYK-Chemie) the company manufacture of FZ-2122, Bi Ke of manufacture.There is polyester construction as in main chain Dimethyl siloxane concrete example, can enumerate: Bi Ke chemistry (BYK-Chemie) company manufacture BYK-310, BYK-370 Deng.Can also and be used in dimethyl siloxane of the main chain with polyether structure, in dimethyl silica of the main chain with polyester construction Alkane.The content of levelling agent relative to coloured composition 100 mass parts of gross mass and preferably 0.003 mass parts~1.0 mass Part.
As levelling agent, particularly preferred person is the so-called surfactant in the molecule with hydrophobic group and hydrophilic group One kind, though and have containing dissolubility of the hydrophilic group for water it is small, in the case where making an addition in coloured composition, surface Tension reduces the low feature of ability, in turn, also good to the wetability of glass plate even if surface tension reduction effectiveness is low.It is such Levelling agent can be not in sufficiently to inhibit charging property under the additive amount by the caused paint film defect that blisters.As with such The levelling agent of preferred characteristics can enumerate the dimethyl polysiloxane with polyalkylene oxide units.As polyalkylene oxide units, can arrange Lift polyalkylene oxide unit, polypropylene oxide unit.Dimethyl polysiloxane can also have polyalkylene oxide unit simultaneously and gather Propylene oxide units.
In addition, polyalkylene oxide units can be bonded to two with the bond form of dimethyl polysiloxane for polyalkylene oxide units The end of side position (pendant) type, the end for being bonded to dimethyl polysiloxane in the repetitive unit of methyl polysiloxane changes Property type, with dimethyl polysiloxane alternately repeat bond straight-chain block copolymer type it is any.With polyalkylene oxide The dimethyl polysiloxane of unit is commercially available by beautiful DOW CORNING (the Toray Dow Corning) limited liability company in east, such as It can enumerate: FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ-2207, but it is not limited to this A bit.
Anionic property, cationic, nonionic or the surfactant of both sexes can also be auxiliarily added in levelling agent.Table Face activating agent can be used in mixed way two or more.
It as the anionic surfactant auxiliarily made an addition in levelling agent, can enumerate: polyoxyethylene alkyl ether sulphur Hydrochlorate, dodecyl benzene sulfonic acid sodium salt, the alkali salt of Styrene-acrylic copolymer, Negel, alkyl diphenyl base ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, triethanolamine lauryl sulfate, Texapon Special, stearic acid monoethanolamine, stearic acid Sodium, NaLS, the monoethanolamine of Styrene-acrylic copolymer, polyoxyethylene alkyl ether phosphate etc..
As the cationic surfactant auxiliarily made an addition in levelling agent, can enumerate alkyl quarternary ammonium salt or these Ethylene oxide adduct.As the nonionic surfactant auxiliarily made an addition in levelling agent, can enumerate: polyoxyethylene Oleyl ether, polyoxyethylene lauryl ether, ethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene are de- The ethers such as water sorbitan monostearate, polyethylene glycol monolaurate system surfactant；Alkyl dimethyl amion acetic acid sweet tea The amphoteric surfactantes such as the alkyl betaines such as dish alkali, alkyl imidazoline；And the surfactant of fluorine system or silicone-based.
< ultraviolet absorbing agent, polymerization inhibitor >
Ultraviolet absorbing agent or polymerization inhibitor can also be contained in the colored filter coloured composition of this announcement.Pass through Containing ultraviolet absorbing agent or polymerization inhibitor, the shape and analyticity of controllable pattern.
It as ultraviolet absorbing agent, such as can enumerate: 2- [4- [(2- hydroxyl -3- (dodecyl and tritriacontyl) oxygroup propyl) Oxygroup] -2- hydroxy phenyl] bis- (2,4- the 3,5-dimethylphenyl) -1,3,5- triazines of -4,6-, 2- (2- hydroxyl -4- [1- carbonyl octyloxy Ethyoxyl] phenyl) the hydroxyphenyltriazinuvs system such as bis- (4- phenyl) -1,3,5- triazines of -4,6-；2- (5- methyl -2- hydroxy benzenes Base) benzotriazole, bis- (1- methyl-1-phenylethyl) phenol of 2- (2H- benzotriazole-2- base)-4,6-, 2- (3- tert-butyl-5- Methyl -2- hydroxy phenyl) enumerate BTA systems such as -5- chlorobenzotriazole；2,4 dihydroxyl benzophenone, 2- hydroxyl -4- octyloxy Benzophenone, 2,2', the benzophenone series such as 4,4'- tetrahydroxybenzophenone；Phenyl salicylate, p-t-butylphenyl salicylate etc. Salicylate system；The cyanoacrylates systems such as acrylic acid ethyl -2- cyano -3,3'- diphenyl ester；2,2,6,6 ,-tetramethyl piperidine- 1- oxygroup (tri acetylacetonate-amine-n-oxygroup), bis- (2,2,6,6- tetramethyl -4- piperidyl)-sebacates, it is poly- [[6- [(1,1,3, The 3- tetrabutyl) amino] -1,3,5- triazine -2,4- diyl] hindered amines such as [(2,2,6,6- tetramethyl -4- piperidyl) imino group] System etc..
These ultraviolet absorbing agents can be used alone one kind, or is optionally used in mixed way with arbitrary ratio two or more.
It as polymerization inhibitor, such as can enumerate: methyl hydroquinone, tert-butyl hydroquinone, 2,5- di-t-butyl pair Hydroquinone derivatives and the phenolate such as benzenediol, 4- benzoquinones, 4- metoxyphenol, 4- methoxyl group -1- naphthols, tert-butyl catechol Close object；The amine compounds such as phenthazine, double-(1- dimethyl benzyl) phenthazine, 3,7- dioctyl phenthazine；Two sulphur ammonia first of dibutyl Compound nantokites and the manganese such as sour copper, diethyl-dithiocarbamate copper, diethyl-dithiocarbamate manganese, Diphenyl disulfide ammonia formic acid manganese Salt compound；4- nitrosophenol, N- nitrosodiphenylamine int he, N- nitrous butylcyclohexyl hydroxylamine, N- nitroso phenyl hydroxyl The nitroso compounds such as amine and its ammonium salt or aluminium salt etc..
These polymerization inhibitors can be used alone one kind, or is optionally used in mixed way with arbitrary ratio two or more.
Ultraviolet absorbing agent and polymerization inhibitor are 0.01 matter relative to 100 mass parts of colorant in coloured composition Measure part~20 mass parts, preferably 0.05 mass parts~10 mass parts amount.
By using ultraviolet absorbing agents or polymerization inhibitor more than 0.01 mass parts, more good parsing can get Degree.
< antioxidant >
In order to improve the transmitance of film, the colored filter coloured composition of this announcement can contain antioxidant.It is anti- Oxidant prevents Photoepolymerizationinitiater initiater contained in colored filter coloured composition because of thermmohardening or tin indium oxide (indium Tin oxide, ITO) annealing when thermal process and aoxidize xanthochromia, therefore the transmitance of film can be improved.
As antioxidant it is preferred that person can enumerate hindered phenolic antioxidant, amine antioxidant of being obstructed, phosphorus system antioxygen Agent or thioether antioxidant etc..In addition, more preferably hindered phenolic antioxidant, amine antioxidant of being obstructed or phosphorus system are anti- Oxidant.
These antioxidants can be used alone one kind, or is optionally used in mixed way with arbitrary ratio two or more.
As hindered phenolic antioxidant, can enumerate: 2,4- bis- [(lauryl sulfenyl) methyl]-o-cresols, 1,3,5- tri- (3,5- di-t-butyl -4- hydroxybenzyl), 1,3,5- tri- (4- tert-butyl -3- hydroxyl -2,6- dimethyl benzyl) and 2,4- it is bis- - (n-octyl sulfenyl) -6- (4- hydroxyl -3,5- di-t-butyl anilino-) -1,3,5- triazine, the [3- (3,5- bis--of pentaerythrite four Tert-butyl-hydroxy phenyl) propionic ester etc..
It as amine antioxidant of being obstructed, can enumerate: bis- (2,2,6,6- tetramethyl -4- piperidyl) sebacates, bis- (N- Methyl -2,2,6,6- tetramethyl -4- piperidyl) sebacate, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,6- six of N'- Methylene diamine, 2- methyl -2- (2,2,6,6- tetramethyl -4- piperidyl) amino-N- (2,2,6,6- tetramethyl -4- piperidyl) Propionamide, four (2,2,6,6- tetramethyl -4- piperidyl) -1,2,3,4- butane tetracarboxylic acid esters, poly- [{ 6- (1,1,3,3- tetramethyl Butyl) imino group -1,3,5- triazine -2,4- diyl } { (2,2,6,6- tetramethyl -4- piperidyl) imino group } hexamethyl (2,2, 6,6- tetramethyl -4- piperidyl) imino group], poly- [(6- morpholinyl -1,3,5- triazine -2,4- diyl) { (2,2,6,6- tetramethyl Base -4- piperidyl) imino group six methines { (2,2,6,6- tetramethyl -4- piperidyl) imino group }], dimethyl succinate with The condensation polymer, N of 1- (2- hydroxyethyl) -4- hydroxyl -2,2,6,6- tetramethyl piperidine, the N'-4,7- tetra- [bis- { N- butyl-N- of 4,6- (1,2,2,6,6- pentamethyl -4- piperidyl) amino } -1,3,5- triazine -2- base] -4,7- diaza decane -1,10- diamines etc..
It as phosphorous antioxidant, can enumerate: three [2- [[2,4,8,10- tetra- (1,1- dimethyl ethyl) dibenzo [d, f] [1,3,2] miscellaneous English in the heptan -6- base of dioxathion] oxygroup] ethyl] amine, three [2- [(tetra--tert-butyl of 4,6,9,11- dibenzo [d, f] [1, 3,2] miscellaneous English in the heptan -2- base of dioxathion) oxygroup] ethyl] amine, bis- (the 2,4- di-t-butyl -6- aminomethyl phenyl) esters of phosphorous acid ethyl.
It as thioether antioxidant, can enumerate: 2,2- thio-di ethylene bis [3- (3,5- di-t-butyl -4- hydroxyls Phenyl) propionic ester], bis- [(octylthio) the methyl]-o-cresols of 2,4-, bis- [(lauryl sulfenyl) methyl]-o-cresols of 2,4- etc..
The content of antioxidant is preferred in total 100 mass % of the solid component of colored filter coloured composition For 0.1 mass of mass %~5 %.
In the case where antioxidant is less than 0.1 mass %, the effect that transmitance improves is few, in the feelings for being more than 5 mass % Under condition, hardness declines to a great extent, in addition, the sensitivity of colored filter coloured composition is greatly reduced.
< other compositions >
In order to improve the adaptation with transparent substrate, the colored filter coloured composition of this announcement can be even containing silane The closely sealed enhancer such as mixture.In addition, the colored filter coloured composition of this announcement, which contains to have, makes the molten oxygen deposited also The amine compound etc. of former effect.
It as silane coupling agent, such as can enumerate: vinyl three ('beta '-methoxy ethyoxyl) silane, vinyl oxethyl silicon The vinyl silanes class such as alkane, vinyltrimethoxysilane；γ-methacryloxypropyl trimethoxy silane etc. (methyl) Acrylic silanes；β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane, β-(3,4- epoxycyclohexyl) methyl trimethoxy Oxysilane, β-(3,4- epoxycyclohexyl) ethyl triethoxysilane, β-(3,4- epoxycyclohexyl) methyltriethoxy silane The epoxy silanes such as alkane, γ-glycidoxypropyltrimewasxysilane, γ-glycidoxypropyl triethoxysilane Class；N- β (amino-ethyl) gamma-amino propyl trimethoxy silicane, N- β (amino-ethyl) γ aminopropyltriethoxy silane, N- β (amino-ethyl) gamma-amino hydroxypropyl methyl diethoxy silane, γ aminopropyltriethoxy silane, gamma-amino propyl Trimethoxy silane, N- phenyl-gamma-amino propyl trimethoxy silicane, N- phenyl-γ aminopropyltriethoxy silane etc. Amino silicone alkanes；The Thiosilicanes such as γ mercaptopropyitrimethoxy silane, γ-Mercaptopropyltriethoxysilane (thiosilane) class etc..
The content of silane coupling agent is 0.01 mass parts~10 relative to 100 mass parts of colorant in coloured composition Mass parts, preferably 0.05 mass parts~5 mass parts.
It as amine compound, can enumerate: triethanolamine, methyl diethanolamine, triisopropanolamine, 4- dimethylamino benzene Methyl formate, ethyl 4-dimethylaminobenzoate, 4- dimethylaminobenzoic acid isopentyl ester, benzoic acid 2- dimethylaminoethyl Ester, 4- dimethylaminobenzoic acid 2- ethylhexyl, N, N- dimethyl-p-toluidine etc..
The manufacturing method > of < colored filter coloured composition
The colored filter of this announcement can manufacture as follows (colorant dispersion) with coloured composition: using pinching Conjunction machine, twin-roll mill, three-roll mill, ball mill, horizontal sand Mill, longitudinal type sand mill, ring-like ball mill or grater etc. are various Decentralized institution is imperceptibly dispersed colorant in resin and/or solvent using dispersing agent together with other compositions optionally. At this point, can two or more colorants be mixed and be dispersed, respective dispersion can also prepared for every kind of colorant After mixed.
In addition, the colored filter of this announcement coloured composition is used as photosensitive coloring composition (resist material) In the case where, it can be used as solvent development type or alkali developable coloured composition and prepare.Solvent development type or alkali developable coloring Composition contains the colorant dispersion, optical polymerism list amount body and/or Photoepolymerizationinitiater initiater, other pigment point optionally Powder and additive etc..Photoepolymerizationinitiater initiater can also can make an addition to afterwards made in the stage addition for preparing coloured composition In standby coloured composition.
(dispersing aid)
It can be suitable for containing dispersing aiies such as pigment derivative, surfactants when dispersing colorant.Dispersing aid is anti- The effect of colorant after only dispersing re-united is big, thus using dispersing aid dispersed colorant in color carrier and At coloured composition lightness and viscosity stability become good.
It as surfactant, can enumerate: NaLS, polyoxyethylene alkyl ether sulfate salt, dodecyl benzene sulfonic acid Sodium, the alkali salt of Styrene-acrylic copolymer, odium stearate, Negel, alkyl diphenyl base ether sodium disulfonate, laurel Base diethanolamine, triethanolamine lauryl sulfate, Texapon Special, stearic acid monoethanolamine, Styrene And Chloroalkyl Acrylates are total The anionic surfactants such as monoethanolamine, the polyoxyethylene alkyl ether phosphate of polymers；Polyoxyethylene oleyl ether, polyoxy Ethylene lauryl ether, ethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan list are hard The nonionic surfactants such as resin acid ester, polyethylene glycol monolaurate；Alkyl quarternary ammonium salt or these ethylene oxide add At cationic surfactants such as objects；The alkyl betaines such as alkyl dimethyl oxyneurine, alkyl imidazoline etc. two Property surfactant, these can be used alone or be used in mixed way two or more, but may not be defined in these.
In the case where adding surfactant, content preferably 0.1 mass parts relative to 100 mass parts of colorant ~55 mass parts, and then preferably 0.1 mass parts~45 mass parts.In the feelings of less than 0.1 mass parts of the content of surfactant Under condition, it is difficult to obtain the effect of addition, if content is more than 55 mass parts, cause shadow to dispersion because of superfluous dispersing agent sometimes It rings.
The removal > of < oversize grain
The coloured composition of this announcement preferably by centrifuge separation, utilize the filtering of sintered filter or membrane filter Etc. means carry out 5 μm or more of oversize grain, preferably 1 μm or more of oversize grain and then preferably 0.5 μm or more coarse Particle and mixed dust removal.The coloured composition of this announcement is preferably the particle for not including 0.5 μm or more substantially, 0.3 μm or more of particle is not included more preferably.
2. the 2nd colored filter coloured composition
The 2nd colored filter coloured composition in this announcement is the colorized optical filtering containing colorant, resin and solvent Piece coloured composition, and
The colorant includes quinophthalone compound (A1) represented by general formula (1) and is selected from by general formula (2), general formula (3) And the quinophthalone compound (A2) of one or more of group composed by general formula (4).
According to the 2nd colored filter coloured composition, lightness, tinting strength, tinting power, contrast, heat resistance and electricity can be formed The film of excellent.
The 2nd colored filter coloured composition at least contains colorant, resin and solvent, optionally can also also contain There are other compositions.Hereinafter, be illustrated to each ingredient of such 2nd colored filter coloured composition, about with the described 1st The common person of colored filter coloured composition referring to the record in the 1st colored filter coloured composition, and omits Explanation herein.
[colorant]
< quinophthalone compound (A1) >
Quinophthalone compound (A1) and the 1st colored filter coloured composition are common, therefore omit saying herein It is bright.
< quinophthalone compound (A2) >
Quinophthalone compound (A2) represented by mutual-through type (2)~general formula (4) is illustrated.
[changing 32]
General formula (2)
[changing 33]
General formula (3)
[changing 34]
General formula (4)
[in general formula (2)~general formula (4), R18~R30、R31~R45、R46~R60Separately indicate that hydrogen atom, halogen are former Son, the alkoxy that can have substituent group, the aryl that can have substituent group, can have substituent group at the alkyl that can have substituent group Phthalimide methyl or the sulfamoyl that can have substituent group]
Herein, identical as person illustrated by the substituent group of mutual-through type (1) as halogen atom.
As the alkyl with substituent group in general formula (2)~general formula (4), such as can enumerate: methyl, ethyl, propyl, The straight chained alkyls such as isopropyl, butyl, isobutyl group, tert-butyl, neopentyl, n-hexyl, n-octyl, stearyl, 2- ethylhexyl or Branched alkyl groups and trichloromethyl, trifluoromethyl, 2,2,2- trifluoroethyls, 2,2- dibromoethyl, 2,2,3,3- tetra- fluoropropyls, 2- ethoxyethyl group, 2- butoxyethyl group, 2- nitropropyl, diethylamino ethyl, benzyl, 4- methylbenzyl, 4- tert-butyl Benzyl, 4- methoxy-benzyl, 4- nitrobenzyl, 2,4- dichloro benzyl etc..
It as the alkoxy that can have substituent group, such as can enumerate: methoxyl group, ethyoxyl, propoxyl group, isopropoxy, just Butoxy, isobutoxy, tert-butoxy, neopentyl oxygen, 2,3- dimethyl -3- amoxy, positive hexyloxy, n-octyloxy, tristearin The unbranched alkoxies such as oxygroup, 2- ethyl hexyl oxy or branch's alkoxy and trichloromethoxy, trifluoromethoxy, 2,2,2- tri- Fluorine ethyoxyl, 2,2,3,3- tetrafluoro propoxyl group, 2,2- di-trifluoromethyl propoxyl group, 2- ethoxy ethoxy, 2- butoxy ethoxy Base, 2- nitro propoxyl group, benzyloxy etc..
As the aryl that there can be substituent group, such as can enumerate: the aryl such as phenyl, naphthalene, anthryl, and to methylbenzene Base, p-bromophenyl, p-nitrophenyl, p-methoxyphenyl, 2,4 dichloro benzene base, pentafluorophenyl group, 2- aminophenyl, 2- methyl- 4- chlorphenyl, 4- hydroxyl -1- naphthalene, 6- methyl -2- naphthalene, the chloro- 2- naphthalene of 4,5,8- tri-, anthraquinonyl, 2- amino anthracene quinonyl etc..
As the phthalimide methyl (C that can have substituent group6H4(CO)2N-CH2) and can have a substituent group Sulfamoyl (H2NSO2) in " substituent group ", can enumerate: the halogen atom, the alkyl that can have substituent group can have and take The alkoxy of Dai Ji, the aryl that can have substituent group etc..
Wherein, quinophthalone compound (A2) is more preferably general formula (2)~general formula (4) R18~R30、R31~R45、R46~R60 For hydrogen atom or halogen atom.
The concrete example of quinophthalone compound used in coloured composition as this announcement (A2) can enumerate following institutes The person of showing, but it is not limited to these.
[changing 35]
[changing 36]
[changing 37]
In the 2nd colored filter coloured composition, for lightness, tinting strength, tinting power, the viewpoint of contrast ratio, quinophthalone The content of compound (A1) preferably 3 mass % relative to quinophthalone compound (A1) and adding up to for quinophthalone compound (A2) ~90 mass %, more preferably 10 mass of mass %~70 %.The ratio of quinophthalone compound (A1) is more, and heat resistance and electricity are special Property is more excellent.
The quinophthalone compound (A2) being used together with quinophthalone compound (A1) is if select at quinophthalone compound (A1) Absorption spectrum two maximum absorption wavelengths between tool there are two the maximum absorption waves of the long wavelength side in maximum absorption wavelength Elder, then tinting strength, tinting power and lightness improve and it is preferred that.
(autofrettage of quinophthalone compound (A2))
The quinophthalone compound (A2) can for example pass through Japanese Patent Laid-Open 4-226163, Japanese Patent Laid-Open The method recorded in 2012-226110 bulletin manufactures, but is not limited to these methods.
Quinophthalone compound (A1), quinophthalone compound (A2) be its form and aspect itself present yellow person, by and use other Colorant come using, can be made into formed homochromy Yellow filter section and green filter section, red filter section colour cell Close object.
Other colorants of < >
2nd colored filter coloured composition can also contain other colorants.Other colorants can be used and the described 1st The identical colorant of person illustrated in colored filter coloured composition, therefore omit explanation herein.
[pigment derivative]
2nd colored filter coloured composition can also contain pigment derivative.Pigment derivative can be used and the described 1st The identical pigment derivative of person illustrated in colored filter coloured composition, therefore omit explanation herein.
[resin]
The colored filter coloured composition of this announcement contains resin.As resin, adhesive resin, resin can be enumerated Type dispersing agent etc. optionally can also also contain other resins.
< adhesive resin >
2nd colored filter coloured composition can also contain adhesive resin.Adhesive resin can be used and the described 1st The identical adhesive resin of person illustrated in colored filter coloured composition, therefore omit explanation herein.
< resin type dispersing agent >
2nd colored filter coloured composition can also contain resin type dispersing agent.Resin type dispersing agent can be from the described 1st Colored filter is used with being suitable for selection in the resin type dispersing agent and alkaline dispersing agent (C) illustrated in coloured composition, Therefore explanation herein is omitted.
[solvent]
2nd colored filter coloured composition contains solvent.Solvent can be used to be coloured with the 1st colored filter The identical solvent of person illustrated in composition.
In the 2nd colored filter coloured composition, as solvent, with regard to the dispersibility, impregnability and coloring of colorant For the good aspect of the coating of composition, wherein preferably using ethyl lactate, propylene glycol methyl ether acetate, the third two The ethyl glycol acetates class such as alcohol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate；Benzyl alcohol, two The ketones such as the alcohols such as pyruvic alcohol or cyclohexanone.
In addition, in the 2nd colored filter coloured composition, so that it may coloured composition is adjusted to viscosity appropriate, And formed for the aspect of the coloring film of the homogeneous film thickness as target, solvent is preferably relative to 100 mass parts of colorant With the use of 500 mass parts~4000 mass parts amount.
[any ingredient]
2nd colored filter coloured composition at least contains colorant, resin and solvent, can also optionally contain various Any ingredient.Any ingredient can be used with the 1st colored filter coloured composition illustrated in person it is identical arbitrarily at Point, therefore omit explanation herein.
3. colored filter
Then, the colored filter of this announcement is illustrated.The colored filter of this announcement is red to have on substrate Color optical filtering section, green filter section and blue filter section person can also be and then have magenta optical filtering section, cyan optical filtering section or yellow Optical filtering section person, at least one described optical filtering section are used by the 1st colored filter coloured composition or the 2nd colored filter Coloured composition is formed.
The manufacturing method > of < colored filter
The colored filter of this announcement can be manufactured using print process or photoetching process.About the optical filtering section using print process It is formed, the printing and drying for only repeating the coloured composition prepared as printing ink can realize patterning, therefore As colored filter autofrettage and be low cost and production it is excellent.In turn, can be had because of the development of printing technology There is the printing of the fine pattern of high dimensional accuracy and smoothness.In order to be printed, be preferably set as in galley or Composition as blanket (blanket) curing ink will not be dried, is cured.In addition, the control of the mobility of the ink on printing machine System is also important, and dispersing agent or extender pigment can also be used to carry out the adjustment of ink viscosity.
In the case where forming optical filtering section using photoetching process, spraying coating or rotary coating, slot coated, roller coating are utilized The coating methods such as cloth, by the coloured composition prepared as the solvent development type or alkali developable coloring resist material with dry Dry film thickness is coated on transparent substrate as 0.2 μm~5 μm of mode.For optionally dried film, by with institute Film contact or discontiguous state and the mask with predetermined pattern that is arranged are stated to carry out ultraviolet exposure.Thereafter, it is impregnated in In solvent or alkaline-based developer, or using spraying etc. unhardened portion is removed and forms desired figure come spray development liquid After case, identical operation is repeated to other colors and colored filter can be manufactured.In turn, in order to promote colour resist material Polymerization, can also optionally be heated.It, can the high colored filter of the accuracy of manufacture print process according to photoetching process.
When development, as alkaline-based developer, the aqueous solution of sodium carbonate, sodium hydroxide etc. can be used, it is possible to use dimethyl The organic bases such as benzyl amine, triethanolamine.In addition, defoaming agent or surfactant can also be added in developer solution.
, can also be after dry by coloring resist material coating furthermore in order to improve ultraviolet exposure sensitivity, it will be water-soluble Property or buck soluble resin, such as polyvinyl alcohol or water soluble acrylic resin be coated with drying, formation prevent from being drawn by oxygen After the film that the polymerization risen hinders, ultraviolet exposure is carried out.
In addition to the method, electrodeposition process, transfer printing, ink-jet method etc. is can also be used to make in the colored filter of this announcement It makes, the coloured composition of this announcement can also be used in either method.Furthermore electrodeposition process is following method: using being formed in base Transparent conductive film on plate, using the electrophoresis of colloidal particle, electro-deposition forms assorted optical filtering section on nesa coating, thus Manufacture colored filter.In addition, transfer printing is following method: pre- on the surface of the transfer substrate (base sheet) of fissility It is initially formed optical filtering section, and the optical filtering section is transferred on desired substrate.
Black matrix" can be pre-formed before forming assorted optical filtering section on the substrates such as transparent substrate or reflection substrate. As black matrix", the inoranic membrane of chromium or chromium/chromium oxide multilayer film, titanium nitride etc. can be used or be dispersed with the tree of opacifier Adipose membrane, but it is not limited to these.In addition, thin film transistor (TFT) can also be pre-formed on the transparent substrate or reflection substrate (Thin Film Transistor, TFT), is subsequently formed assorted optical filtering section.In addition, in the colorized optical filtering on piece of this announcement, depending on Need to form outer film or transparent conductive film etc..
Optical filtering section and the dry film thickness of black matrix" are preferably 0.2 μm~10 μm, more preferably 0.2 μm~5 μm.Make to apply When cloth film is dry, pressure Reduction Dryer, convection oven, infrared ray (Infrared, IR) baking oven, hot plate etc. can be used.
Colored filter is bonded with opposite substrate using sealant and injects liquid crystal from the inlet for being set to sealing, Inlet is sealed later, and light polarizing film or phase difference film are optionally fitted in the outside of substrate, thus manufactures liquid crystal display Panel.
The liquid crystal display panel can be in twisted nematic (Twisted Nematic, TN), STN Super TN (Super Twisted Nematic, STN), coplanar switching (In-Plane Switching, IPS), vertical orientation (Vertically Alignment, VA), optical compensation curved (Optically Compensated Bend, OCB) etc. using colored filter and Used in the liquid crystal display mode of colorization.
As transparent substrate, the glass plate of soda-lime glass, low alkali Pyrex, alkali-free aluminium Pyrex etc. can be used, or The resin plate of polycarbonate, polymethyl methacrylate, polyethylene terephthalate etc..In addition, for the liquid after panelization Crystalline substance driving, can also form the transparent electrode comprising indium oxide, tin oxide etc. on the surface of glass plate or resin plate.
[embodiment]
Based on examples illustrate the present invention, but the present invention is not so limited.Furthermore in example, " part " and " % " Respectively indicate " mass parts " and " quality % ".In addition, " PGMAc " refers to propylene glycol methyl ether acetate.
Hereinafter, being divided into two embodiment groups to be illustrated.Following 1st embodiment groups and the 1st colored filter are used Coloured composition is associated.In addition, following 2nd embodiment groups are associated with the 2nd colored filter coloured composition.Respectively Embodiment group is respectively independent person, and sometimes between embodiment group, identical symbol is marked to different ingredients, to identical component Mark different symbols.
[the 1st embodiment group]
(weight average molecular weight (Mw) of resin)
The weight average molecular weight (Mw) of resin is using TSKgel tubing string (manufacture of Tosoh (Tosoh) company) and to utilize dress Have gel permeation chromatograph (Gel Permeation Chromatograph, GPC) (Tosoh (Tosoh) public affairs of RI detector Department's manufacture, HLC-8120GPC), and gathered using what tetrahydrofuran (tetrahydrofuran, THF) was measured as expansion solvent The weight average molecular weight (Mw) of styrene conversion.
(acid value of resin)
Acetone 80ml and water 10ml is added in 0.5 part~1.0 parts of resin solution, is stirred and is made its uniform dissolution, Using the KOH aqueous solution of 0.1mol/L as titrating solution, use automatic titration device (" COM-555 ", the manufacture of Ping Zhao industry companies) It is titrated, to measure the acid value of resin solution.Then, the solid component according to the acid value of resin solution and resin solution is dense It spends to calculate the acid value of the per unit solid component of resin.
(average molecular weight of block copolymer)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of block copolymer are using HLC-8320GPC (manufacture of Tosoh (Tosoh) limited liability company) is used as device, uses SUPER-AW3000 as tubing string, uses 30mM triethyl group The number for the polystyrene conversion that the N,N-dimethylformamide solution of amine and 10mM lithium bromide (LiBr) is measured as eluent Measure average molecular weight (Mn) and weight average molecular weight (Mw).
(amine value of block copolymer)
The amine value of block copolymer is according to American Society for Testing Materials (American Society for Testing Materials, ASTM) D 2074 method by total amine value (mgKOH/g) solid component measured conversion obtained by value.
< contains the manufacturing method > of the alkaline dispersing agent (C) of acrylic block copolymer
(Production Example of block copolymer (EB-1): AB type block polymer)
Methacrylic acid is packed into the reaction unit for being equipped with gas introduction tube, condenser, stirring blade and thermometer 60 parts of methyl esters, 20 parts of n-BMA, as 13.2 parts of tetramethylethylenediamine of catalyst. while flowing into nitrogen It is stirred 1 hour at 50 DEG C, to progress nitrogen displacement in system.Then, it is loaded as the isobutyl ethyl bromide 9.3 of initiator Part, 5.6 parts of the stannous chloride as catalyst, 133 parts of acetic acid methoxyl group propyl ester are warming up to 110 DEG C and open under stream of nitrogen gas The polymerization for the first block (B block) that begin.After polymerization in 4 hours, samples polymeric solution and carry out solid component measurement, according to non-volatile Ingredient converts, and confirming polymerisation conversion is 98% or more.Then, acetic acid methoxy propyl is put into the reaction unit 61 parts of ester, as 20 parts of dimethylaminoethyl methacrylate of the second block (A block) monomer, keep 110 DEG C of nitrogen It is stirred in the state of under compression ring border, continues reaction.By 2 hours from putting into dimethylaminoethyl methacrylate Afterwards, it samples polymeric solution and carries out solid component measurement, converted according to nonvolatile component, confirming the second block, (A is embedding Section) polymerisation conversion be 98% or more, and reaction solution is cooled to room temperature and stops polymerizeing.The result of GPC measurement is poly- Close Mw9900, the molecular weight distribution mw/mn 1.2, reaction conversion ratio 98.5% of object.In this way, obtaining per unit solid component Amine value be 71.4mgKOH/g acrylic block copolymer (EB-1).After being cooled to room temperature, resin solution about 2g is sampled, Heat drying 20 minutes at 180 DEG C, and measure nonvolatile component, the addition the third two in the block copolymer solution synthesized before Alcohol methyl ether acetate is so that nonvolatile component becomes 50 mass %, so that it is molten to prepare acrylic block copolymer (EB-1) Liquid.
(manufacture of block copolymer (EB-2~EB-8, EB-10))
Using raw material recorded in table 1 and charge weight, in addition to this, synthesis is carried out similarly with block copolymer (EB-1) And obtain the solution of block copolymer (EB-2)~block copolymer (EB-8), block copolymer (EB-10).
(Production Example of block copolymer (EB-9): BAB type block polymer)
Methacrylic acid is packed into the reaction unit for being equipped with gas introduction tube, condenser, stirring blade and thermometer 20 parts of methyl esters, 15 parts of n-BMA, 13.2 parts of tetramethylethylenediamine exist while flowing into nitrogen and stir at 50 DEG C 1 hour, to progress nitrogen displacement in system.Then, 9.3 parts of isobutyl ethyl bromide, 5.6 parts of stannous chloride, acetic acid first are packed into 133 parts of oxygroup propyl ester, under stream of nitrogen gas, it is warming up to the polymerization of 110 DEG C and beginning the first block (B block).It polymerize within 3 hours Afterwards, it samples polymeric solution and carries out solid component measurement, converted according to nonvolatile component, confirming polymerisation conversion is 98% or more.
Then, 30 parts of acetic acid methoxyl group propyl ester is put into the reaction unit, as the second block (A block) monomer 25 parts of dimethylaminoethyl methacrylate, be stirred in the state of keeping under 110 DEG C of nitrogen environments, make reaction after It is continuous.From putting into dimethylaminoethyl methacrylate after 2 hours, samples polymeric solution and carry out solid component survey It is fixed, it is converted according to nonvolatile component, the polymerisation conversion for confirming the second block (A block) is 98% or more.
Then, 31 parts of acetic acid methoxyl group propyl ester is packed into the reaction unit, as third block (B block) monomer 25 parts of methyl methacrylate, 15 parts of n-BMA, 110 DEG C are warming up under stream of nitrogen gas and makes the first block (B Block) polymerization continue.From putting into third block (B block) monomer after 4 hours, samples polymeric solution and carry out solid Composition measurement converts according to nonvolatile component, will confirm that polymerisation conversion is that 98% or more reaction solution is cooled to Room temperature and stop polymerizeing.
After being cooled to room temperature, sample resin solution about 2g, heat drying 20 minutes at 180 DEG C, and measure it is non-volatile at Point, propylene glycol methyl ether acetate is added so that nonvolatile component becomes 50 matter in the block copolymer solution synthesized before % is measured, to prepare block copolymer (EB-9) solution.
The amine value of each block copolymer, weight average molecular weight in table 1 as recording.
MMA: methyl methacrylate
NBA: n-butyl acrylate
HEMA: hydroxyethyl methacrylate
DM: dimethylaminoethyl methacrylate
DE: diethyl aminoethyl methacrylate
LA-82: methacrylic acid 1,2,2,6,6- pentamethvl ester
DMC: methacryloxyethyl benzyl chloride
DMAPMA:N, N- dimethyl aminoethyl (methyl) acrylamide
The manufacturing method > of other resin type dispersant solutions of <
(preparation of resin type dispersant solution 1)
In the reaction vessel for having gas introduction tube, thermometer, condenser, blender be packed into 10 parts of methacrylic acid, 90 parts of methyl methacrylate, 50 parts of ethyl acrylate, 50 parts of tert-butyl acrylate, are replaced using nitrogen.Reaction is held Be heated to 80 DEG C in device, and add 0.1 part of 2,2'- azobis isobutyronitrile is dissolved in 3- sulfydryl -10 parts of 1,2-PD and At solution, react 10 hours.95% is confirmed by solid component measurement to be reacted.Additional pyromellitic dianhydride 20 Part, 200.0 parts of acetic acid methoxyl group propyl ester, as catalyst 1,8-, bis- azo it is bicyclic -0.40 part of [5.4.0] -7- hendecene, It is reacted 7 hours at 120 DEG C.98% or more acid anhydrides is confirmed through half-esterification by the measurement of acid value, and reaction was completed and obtains The polyester dispersants of acid value 77mgKOH/g, number average molecular weight 8500.Thereto with by solid component measure solid at The mode for being divided into 50% adds acetic acid methoxyl group propyl ester, to obtain the resin type dispersant solution 1 with aromatic carboxyl.
(preparation of resin type dispersant solution 2)
3- sulfydryl -1,2- the third two is packed into the reaction vessel for having gas introduction tube, thermometer, condenser, blender 6.5 parts of alcohol, 4.0 parts of pyromellitic dianhydride, 0.01 part of dimethyl benzyl amine, 41.8 parts of acetic acid methoxyl group propyl ester, using nitrogen into Line replacement.It will be heated to 100 DEG C in reaction vessel, and react 7 hours.98% or more acid is confirmed by the measurement of acid value Acid anhydride is cooled to 70 DEG C after half-esterification, by the temperature in system, be packed into 67 parts of methyl methacrylate, 5.0 parts of methacrylic acid, 16.0 parts of tert-butyl acrylate, methacrylic acid (3- Ethyloxetane -3- base) 10.0 parts of methyl esters, ethyl acrylate 2.0 Part, and 60.0 parts of 0.10 part of 2,2'- azobis isobutyronitrile and acetic acid methoxyl group propyl ester are added, it reacts 10 hours.By solid at Divide measurement and confirm 95% and polymerize, reaction was completed, to obtain acid value 47mgKOH/g, number average molecular weight 15000 polyester dispersants.Acetic acid first is added in a manner of measuring solid component by solid component to become 50% thereto Oxygroup propyl ester, to obtain the resin type dispersant solution 2 with aromatic carboxyl.
The manufacture > of < adhesive resin (F)
(adhesive resin (F-1) solution)
In being equipped with thermometer, cooling tube, nitrogen ingress pipe, drop tube and agitating device in detachable four-hole boiling flask Reaction vessel in be packed into 196 parts of cyclohexanone, be warming up to 80 DEG C, in reaction vessel carry out nitrogen displacement after, spend 2 hours from drip Add pipe that 20.0 parts of benzyl methacrylate, 17.2 parts of n-BMA, 2-hydroxyethyl methacrylate 12.9 is added dropwise (East Asia synthesizes limited liability company's manufacture for part, 12.0 parts of methacrylic acid, the ethylene-oxide-modified acrylate of p -cumylphenol " Aronix (Aronix) M110 ") 20.7 parts, 1.1 parts of 2,2'- azobis isobutyronitrile of mixture.After completion of dropwise addition, in turn Continue to react for 3 hours, to obtain the solution of acrylic resin.
After being cooled to room temperature, sample about 2 parts of resin solution, heat drying 20 minutes at 180 DEG C, and measure it is non-volatile at Point, PGMAc is added so that nonvolatile component becomes 20 mass %, to prepare adhesive tree in the resin solution synthesized before Rouge (F-1) solution.Weight average molecular weight (Mw) is 26,000.
(adhesive resin (F-2) solution)
In being equipped with thermometer, cooling tube, nitrogen ingress pipe, drop tube and agitating device in detachable four-hole boiling flask Reaction vessel in be packed into 207 parts of cyclohexanone, be warming up to 80 DEG C, in reaction vessel carry out nitrogen displacement after, spend 2 hours from drip Add pipe that 20 parts of methacrylic acid, 20 parts of benzyl methacrylate, the ethylene-oxide-modified acrylate (East Asia of p -cumylphenol is added dropwise Aronix (Aronix) M110 of Synesis Company's manufacture) 20 parts, 25 parts of methyl methacrylate, methacrylic acid 2- hydroxyl second 8.5 parts of ester and 1.33 parts of 2,2'- azobis isobutyronitrile of mixture.After completion of dropwise addition, and then continue to react for 3 hours, from And obtain copolymer resin lipoprotein solution.Then, relative to copolymer solution total amount obtained, stop nitrogen and inject 1 hour and do Pathogenic dryness body, while after being stirred, after being cooled to room temperature, spend 3 hours dropwise addition 2- methacryloxyethyls different at 70 DEG C 6.5 parts of cyanate (Ka Lunzi (Karenz) MOI of Showa electrician company manufacture), 0.08 part of dibutyl tin laurate, cyclohexanone 26 parts of mixture.After completion of dropwise addition, and then continue to react for 1 hour, to obtain the solution of acrylic resin.It is cooled to After room temperature, about 2 parts of resin solution of sampling, heat drying 20 minutes at 180 DEG C, and nonvolatile component is measured, it is synthesized before Resin solution in add cyclohexanone so that nonvolatile component become 20 mass %, to prepare adhesive resin (F-2) solution. Weight average molecular weight (Mw) is 18,000.
(adhesive resin (F-3) solution)
Propylene glycol is imported in the flask for having blender, thermometer, reflux cooling tube, addition funnel and nitrogen ingress pipe Methyl ether acetate 182g is warming up to 100 DEG C after environment in flask is set as nitrogen from air, then spends 2 hours from leakage is added dropwise Bucket will include benzyl methacrylate 70.5g (0.40 mole), methacrylic acid 43.0g (0.5 mole), tricyclodecane skeleton Monomethacrylates (FA-513M that Hitachi is melted into (stock) manufacture) 22.0g (0.10 mole) and propylene glycol monomethyl ether acetic acid Solution made of azobis isobutyronitrile 3.6g is added in the mixture of ester 136g to be added dropwise in flask, in turn, is continued at 100 DEG C Stirring 5 hours.Then, environment in flask is set as air from nitrogen, [0.25 rubs by glycidyl methacrylate 35.5g You, (relative to the methacrylic acid used in this reaction carboxyl and be 50 moles of %)], three-dimethylaminomethyl benzene Phenol 0.9g and hydroquinone 0.145g are put into flask, after continuing reaction in 6 hours at 110 DEG C, sample resin solution about 2 Part, heat drying 20 minutes at 180 DEG C, and nonvolatile component is measured, cyclohexanone is added in the resin solution synthesized before So that nonvolatile component becomes 20 mass %, to obtain adhesive resin (F-3) solution.Weight average molecular weight is 13, 000, molecular weight distribution (Mw/Mn) is 2.1, and solid component acid value is 79mgKOH/g.
(adhesive resin (F-4) solution)
Hold in the reaction for being equipped with thermometer, cooling tube, nitrogen ingress pipe, agitating device in detachable four-hole boiling flask It is put into 100 parts of propylene glycol methyl ether acetate in device, injects nitrogen into container on one side, is heated to 120 DEG C on one side, in the temperature Under degree, 2.5 hours are spent from drop tube, 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, methacrylic acid two is added dropwise The mixture of 41.0 parts of ring pentyl ester, 1.0 parts of azobis isobutyronitrile carries out polymerization reaction.
Then, to air displacement is carried out in flask, three-dimethylaminomethyl phenol are put into 17.0 parts of acrylic acid 0.3 part and 0.3 part of hydroquinone, continue to react for 5 hours at 120 DEG C, in solid component acid value=0.8mgKOH/g Moment point, reaction was completed, to obtain the resin solution that weight average molecular weight is about 1,2000 (utilizing the measurement of GPC).
In turn, 30.4 parts of tetrabydrophthalic anhydride, 0.5 part of triethylamine are added, is reacted 4 hours at 120 DEG C, is added Propylene glycol methyl ether acetate is so that nonvolatile component becomes 20%, to prepare adhesive resin (F-4) solution.
The manufacturing method > of < colorant
(manufacture of colorant (P-1))
Using with the identical system of blue colorant (PB-1) recorded in the embodiment of No. 4893859 bulletins of Japanese Patent No. It makes method and obtains the colorant (P-1) as aluminium phthalocyanine color.
(manufacture of colorant (P-2))
109 parts of sulfonic acid chloride, 131 parts of aluminium chloride, 18 parts of sodium chloride, 30 parts of ZnPc, bromine 52 are packed into 300mL flask Part.It spends 40 hours and is warming up to 130 DEG C, after taking out into water, green thick pigment is obtained and being filtered.It will be obtained green 20 parts of the thick pigment of color, 1.8 parts of 32 parts of 140 parts of sodium chloride, diethylene glycol, the dimethylbenzene loadings through crushing to 1L dual-arm kneader In, it is kneaded 6 hours at 100 DEG C.After mixing take out into 80 DEG C of water 2kg, stirring 1 hour after, be filtered, hot water wash, Dry, crushing, thus to obtain colorant (P-2).Colorant (P-2) obtained is following zinc halide phthalocyanine color, the halogen It is 12.69 average that change ZnPc pigment, which be the halogen atom number in a molecule according to x-ray fluorescence analysis, wherein bromine is former Subnumber is averagely 8.54, amount of chlorine atom is 4.16 average.
(manufacture of colorant (P-3))
Using identical as phthalocyanine color (P-10) recorded in the embodiment of Japanese Patent Laid-Open 2017-197685 bulletin Manufacturing method and obtain the colorant (P-3) as aluminium phthalocyanine color.
(manufacture of colorant (P-4))
Using with phthalocyanine color (PCY-9) phase for being recorded in the embodiment of Japanese Patent Laid-Open 2016-153481 bulletin With manufacturing method and obtain the colorant (P-4) as aluminium phthalocyanine color.
(manufacture of colorant (P-5))
Utilize manufacturing method identical with the azopigment 1 recorded in the embodiment of No. 5187326 bulletins of Japanese Patent No. And obtain colorant (P-5).
The manufacturing method > of < pigment derivative
(synthesis of quinophthalone compound (B-1))
Using with the quinophthalone compound (QL-c- that is recorded in the embodiment of Japanese Patent Laid-Open 2015-172732 bulletin 1) identical manufacturing method and obtain quinophthalone compound (B-1).
[changing 38]
Quinophthalone compound (B-1)
(synthesis of quinophthalone compound (B-15))
It obtains according to the synthetic method recorded in No. 4585781 bulletins of Japanese Patent No. as quinophthalone compound (B- 2) quinophthalone compound (B-15) of Al salt.
[changing 39]
Quinophthalone compound (B-15)
(synthesis of quinophthalone compound (B-16))
Using identical with the quinophthalone compound (B-3) recorded in the embodiment of No. 6160061 bulletins of Japanese Patent No. Manufacturing method and obtain the quinophthalone compound (B-16) as the lauryl trimethyl ammonium salt of quinophthalone compound (B-3).
[changing 40]
Quinophthalone compound (B-16)
(synthesis of quinophthalone compound (B-4))
Using with the quinophthalone compound (QL-f- that is recorded in the embodiment of Japanese Patent Laid-Open 2015-172732 bulletin 1) identical manufacturing method and obtain quinophthalone compound (B-4).
[changing 41]
Quinophthalone compound (B-4)
(synthesis of pigment derivative 5)
By (" the Pa Liao root Huang (Paliogen Yellow) of BASF (BASF) company manufacture of C.I. pigment yellow 185 D1155 ") 30 parts be dissolved in 300 parts of 101% sulfuric acid, stirred 8 hours at 70 DEG C, carry out sulfonating reaction.The terminal of reaction is set For measure sulfuric acid solution spectrophotometric spectra when can't see spectrum variation point.Then, the reaction solution is injected into ice water In 3000 parts, to the sulfonation pigment derivative being precipitated be filtered separation, washing and obtain the paste of sulfonation pigment derivative.It will The paste of sulfonation pigment derivative obtained is redispersed in 10000 parts of water (pH value 2.5).Then, water-soluble using sodium hydroxide Liquid is adjusted to pH value 11 and is dissolved, and 278 parts of aluminum sulfate aqueous solution (liquid aluminium sulfate) is slowly added in the solution.From The position being added dropwise gradually appears precipitate, and with addition, pH value is reduced, at the end of addition, pH value 3.6, and do not observe Exudation.Separation, washing are filtered to the slurry comprising the precipitate, to obtain the sulfonation as C.I. pigment yellow 185 The pigment derivative 5 of the aluminium salt of derivative.
[changing 42]
(pigment derivative 5)
(synthesis of pigment derivative 6)
At room temperature, by (the Pa Liao of BASF (BASF) company manufacture of C.I. pigment yellow 13 9 while being stirred Special Shandong Huang (Paliotol Yellow) D1819) 5 parts make an addition in 28 65 parts of mass % oleums.Stirring 19 is small at 90 DEG C Shi Hou is injected into the mixed liquor of 80 parts of ice, 15 parts of water, 30 parts of isopropanol.In ice bath, after suspension is stirred 30 minutes, Wet cake is obtained by suction filtration.Stirring and washing, progress four in 40 parts of isopropanol of room temperature by wet cake obtained After the operation of secondary suction filtration, wet cake is dried in vacuo and is crushed at 80 DEG C, thus to obtain as C.I. pigment yellow The pigment derivative 6 of 139 sulfonated derivative.
[changing 43]
(pigment derivative 6)
(identification method of quinophthalone compound (A1))
The substance assistant laser desorpted ionized flight time is used in the identification of quinophthalone compound used in the present invention Mass spectrum (Matrix-Assisted Laser Desorption/Ionization Time of Flight Mass Spectrometry, MALDI TOF-MS) spectrum.MALDI TOF-MS spectrum is using Brooker dalton (Bruker- Daltonics) the MALDI quality analysis apparatus autoflexIII of company's manufacture, is based on mass spectrographic molecular ion wave obtained Compound obtained is identified with by calculating the consistent of the mass number obtained at peak.
The average value of the substitution number of halogen atom is to obtain in the following way: firing pigment using oxygen burning flask method It burns, by ion chromatograph (the ICS-2000 chromatography of ions, Dai An (DIONEX) company manufacture) come to inhaling the comburant Liquid made of closing in water is analyzed and is quantified to halogen quantity, and the substitution number for being scaled halogen atom is averaged Value.
(the halogen distribution of quinophthalone compound (A1))
It is calculated and each ingredient about halogen distribution using MALDI TOF-MS spectrum and in mass spectrum obtained The signal strength (each peak value) of comparable molecular ion wave crest and by each peak value it is accumulative obtained by value (total peak value), to each peak value The quantity for the wave crest that ratio relative to total peak value is 1% or more is counted, and is set as halogen distribution.
(synthesis of quinophthalone compound (A1-1))
150 parts of 2,3- naphthalene dicarboxylic acids acid anhydride and 230 parts of trichloroisocyanuric acid are added in 1200 parts of 98% sulfuric acid, at 80 DEG C Reaction 4 hours.Reaction solution is injected into 9000 parts of agitated ice water, to precipitate generated to filter, wash, 1% Sodium hydrate aqueous solution cleaning, the sequence washed are handled, and are dried and obtain 220 parts of intermediate (a1-1).For Intermediate (a1-1), calculates chlorine substituent number, and result is 3.5 average.By 190 parts of intermediate obtained (a1-1), 8- ammonia 45 parts of base quinaldine, 60 parts of benzoic acid make an addition in 280 parts of methyl benzoate, heating stirring 6 hours at 180 DEG C.It is cooled to After room temperature, reaction mixture is put into 3000 parts of acetone, is stirred at room temperature 1 hour.Separation is filtered to product, benefit It is cleaned and is dried with methanol, to obtain 203 parts of quinophthalone compound (A1-1).Quality is carried out using TOF-MS Analysis, is as a result accredited as quinophthalone compound (A1-1).In addition, halogen distribution is 5.
[changing 44]
Quinophthalone compound (A1-1)
(synthesis of quinophthalone compound (A1-2))
Compound (12) are obtained according to the synthetic method recorded in Japanese Patent Laid-Open 2012-226110 bulletin.? (12) 105 parts of compound, 150 parts of the intermediate (a1-1), 100 parts of benzoic acid are added in 500 parts of methyl benzoate, are heated to It stirs for 180 DEG C and progress 4 hours.In turn, after being cooled to room temperature, reaction mixture is put into 5000 parts of acetone, in room temperature Lower stirring 1 hour.Separation is filtered to product, carries out methanol cleaning and drying, to obtain 183 parts of quinophthalone compound (A1-2).Quality analysis is carried out using TOF-MS, is as a result accredited as quinophthalone compound (A1-2).In addition, halogen distribution It is 3.
[changing 45]
Compound (12)
[changing 46]
Quinophthalone compound (A1-2)
(synthesis of quinophthalone compound (A1-3))
150 parts of 2,3- naphthalene dicarboxylic acids acid anhydride and 220 parts of N- chlorosuccinimide are added in 1200 parts of 98% sulfuric acid, 50 It is reacted 4 hours at DEG C.Reaction solution is injected into 9000 parts of agitated ice water, precipitate is filtered and separates and is subject to water Wash and be washed to filtrate ratio conductivity become 50 μ S/cm or less until, thus to obtain water paste.Water obtained is pasted at 80 DEG C Lower drying 24 hours and obtain 220 parts of intermediate (a1-3).For intermediate (a1-3), chlorine substituent number is calculated, result is flat Equal 2.220 parts of intermediate obtained (a1-3), 45 parts of 8- amidoquinaldine, 60 parts of benzoic acid are made an addition into methyl benzoate In 300 parts, heating stirring 6 hours at 180 DEG C.After being cooled to room temperature, reaction mixture is put into 3000 parts of acetone, It stirs 1 hour at room temperature.Separation is filtered to product, is cleaned and is dried using methanol, to obtain 170 parts Quinophthalone compound (A1-3).Quality analysis is carried out using TOF-MS, is as a result accredited as quinophthalone compound (A1-3).In addition, Halogen distribution is 3.
[changing 47]
Quinophthalone compound (A1-3)
(synthesis of quinophthalone compound (A1-4))
In the synthesis of intermediate (a1-1), N- bromo-succinimide 244 is changed to by 230 parts of trichloroisocyanuric acid Part, in addition to this, is synthesized using identical method and obtain intermediate (a1-4).For intermediate (a1-4), calculates bromine and take For radix, result is 1.5 average.By 225 parts of intermediate obtained (a1-4), 45 parts of 8- amidoquinaldine, benzoic acid 60 Part makes an addition in 300 parts of methyl benzoate, heating stirring 6 hours at 180 DEG C.After being cooled to room temperature, reaction mixture is thrown Enter into 3000 parts of acetone, is stirred at room temperature 1 hour.Separation is filtered to product, cleaned using methanol and is carried out It is dry, to obtain 204 parts of quinophthalone compound (A1-4).Quality analysis is carried out using TOF-MS, is as a result accredited as quinoline phthalein Ketone compound (A1-4).In addition, halogen distribution is 3.
[changing 48]
Quinophthalone compound (A1-4)
(synthesis of quinophthalone compound (A1-5))
150 parts of 2,3- naphthalene dicarboxylic acids and 600 parts of sodium dichloroisocyanurate are added in 1200 parts of 98% sulfuric acid, at 80 DEG C Reaction 4 hours.Reaction solution is injected into 9000 parts of agitated ice water, to precipitate generated to filter, wash, 1% Sodium hydrate aqueous solution cleaning, the sequence washed are handled, and are dried and obtain 255 parts of intermediate (a1-5).For Intermediate (a1-5), calculates chlorine substituent number, and result is 4 average.Then, in the synthesis of quinophthalone compound (A1-2), It is changed to 165 parts of intermediate (a1-5) by 150 parts of intermediate (a1-1), in addition to this, is synthesized and is obtained using identical method Obtain 187 parts of quinophthalone compound (A1-5).Quality analysis is carried out using TOF-MS, is as a result accredited as quinophthalone compound (A1- 5).In addition, halogen distribution is 2.
[changing 49]
Quinophthalone compound (A1-5)
(synthesis of quinophthalone compound (A1-6))
In the synthesis of intermediate (a1-1), bromo- 5, the 5- dimethyl second of 1,3- bis- is changed to by 230 parts of trichloroisocyanuric acid 100 parts of interior uride is synthesized using identical method in addition to this and obtains intermediate (a1-6).For intermediate (a1-6), Bromine substituent number is calculated, result is 3.8 average.By 225 parts of intermediate obtained (a1-6), 45 parts of 8- amidoquinaldine, 60 parts of benzoic acid make an addition in 300 parts of methyl benzoate, heating stirring 6 hours at 180 DEG C.After being cooled to room temperature, it will react Mixture is put into 3000 parts of acetone, is stirred at room temperature 1 hour.Separation is filtered to product, is carried out using methanol clear It washes and is dried, to obtain 204 parts of quinophthalone compound (A1-6).Quality analysis is carried out using TOF-MS, is as a result reflected It is set to quinophthalone compound (A1-6).In addition, halogen distribution is 6.
[changing 50]
Quinophthalone compound (A1-6)
(synthesis of quinophthalone compound (A1-7))
In the synthesis of quinophthalone compound (A1-1), intermediate (a1-5) 210 is changed to by 190 parts of intermediate (a1-1) Part, in addition to this, 156 parts of quinophthalone compound (a1-7) is synthesized and obtained using identical method.
According to the synthetic method recorded in Japanese Patent Laid-Open 2008-81566 bulletin, by quinophthalone compound (a1-7) 155 parts are used as raw material and obtain (17) 91 parts of compound.By (17) 90 parts of compound obtained, 80 parts of 2,3- naphthalene dicarboxylic acids, 50 parts of benzoic acid make an addition in 400 parts of methyl benzoate, heating stirring 5 hours at 160 DEG C.After being cooled to room temperature, it will react Mixture is put into 4000 parts of acetone, is stirred at room temperature 1 hour.Separation is filtered to product, is carried out using methanol clear It washes and is dried, to obtain 121 parts of quinophthalone compound (A1-7).Quality analysis is carried out using TOF-MS, is as a result reflected It is set to quinophthalone compound (A1-7).In addition, halogen distribution is 2.
[changing 51]
Compound (17)
[changing 52]
Quinophthalone compound (A1-7)
(synthesis of quinophthalone compound (A1-8))
In the synthesis of quinophthalone compound (A1-2), intermediate (a1-6) 250 is changed to by 150 parts of intermediate (a1-1) Part, in addition to this, 208 parts of quinophthalone compound (A1-8) is synthesized and obtained using identical method.Using TOF-MS into As a result row quality analysis is accredited as quinophthalone compound (A1-8).In addition, halogen distribution is 3.
[changing 53]
Quinophthalone compound (A1-8)
(synthesis of quinophthalone compound (A1-9))
50 parts of 8- amidoquinaldine, 115 parts of intermediate (a1-1), benzoic acid 140 are added in 200 parts of methyl benzoate Part, it is stirred 4 hours at 120 DEG C.Then, 143 parts of intermediate (a1-4) is added in turn in the reactive mixture, is heated to 180 DEG C, water is distilled remove on one side, carries out stirring for 4 hours on one side.After being cooled to room temperature, reaction mixture is put into acetone 2000 In part, it is stirred at room temperature 1 hour.Separation is filtered to product, is cleaned and is dried using methanol, to obtain 167 parts of quinophthalone compound (A1-9).Quality analysis is carried out using TOF-MS, is as a result accredited as quinophthalone compound (A1- 9).In addition, halogen distribution is 4.
[changing 54]
Quinophthalone compound (A1-9)
(synthesis of quinophthalone compound (A1-10))
(12) 100 parts and 54 parts of N- bromo-succinimide of compound are added in 700 parts of n,N-Dimethylformamide, It is reacted 3 hours at 85 DEG C.Reaction solution is injected into 6000 parts of agitated methanol, is stirred at room temperature 1 hour.To product into Row is separated by filtration, and is cleaned and is dried using methanol, to obtain (18) 105 parts of compound.In methyl benzoate 400 (18) 100 parts of compound, 115 parts of intermediate (a1-1), 30 parts of benzoic acid are added in part, are heated to 180 DEG C, are on one side distilled water Removal, carries out stirring for 4 hours on one side.After being cooled to room temperature, reaction mixture is put into 4000 parts of acetone, is stirred at room temperature It mixes 1 hour.Separation is filtered to product, is cleaned and is dried using methanol, to obtain 159 parts of quinophthalone It closes object (A1-10).Quality analysis is carried out using TOF-MS, is as a result accredited as quinophthalone compound (A1-10).In addition, halogen point Cloth range is 3.
[changing 55]
Compound (18)
[changing 56]
Quinophthalone compound (A1-10)
The manufacturing method > of < yellow colorants
(manufactures of yellow colorants (Y-1))
100 parts of quinophthalone compound (A1-1), 1200 parts of sodium chloride and 120 parts of diethylene glycol are packed into stainless steel 1 In gallon kneader (manufacture of Jing Shang manufacturing company), it is kneaded 8 hours at 60 DEG C.Then, the mixture is put into temperature In water, 1 hour being stirred while being heated to about 70 DEG C and pulp-like is made, repeated filtration is washed to remove sodium chloride and two After ethylene glycol, a drying for one day night at 80 DEG C, to obtain 97 parts of yellow colorants (Y-1).
(manufactures of yellow colorants (Y-2~Y-18))
Hereinafter, as shown in table 2, change composition, blending amount obtain yellow in the same manner as yellow colorants (Y-1) in addition to this Chromatic colorant agent (Y-2~Y-18).
(manufactures of yellow colorants (Y-19))
(11) 100 parts of compound, 1200 parts of sodium chloride and 120 parts of diethylene glycol are packed into 1 gallon of stainless steel and are mediated In machine (manufacture of Jing Shang manufacturing company), it is kneaded 8 hours at 60 DEG C.Then, the mixture is put into warm water, on one side 70 DEG C are heated to about to stir 1 hour on one side and pulp-like is made, repeated filtration is washed come after removing sodium chloride and diethylene glycol, A drying for one day night at 80 DEG C, to obtain 95 parts of yellow colorants (Y-19).
[changing 57]
Compound (11)
[table 2]
Yellow colorants Composition
Production Example 1 Y-1 A1-1
Production Example 2 Y-2 A1-2
Production Example 3 Y-3 A1-3
Production Example 4 Y-4 A1-4
Production Example 5 Y-5 A1-5
Production Example 6 Y-6 A1-6
Production Example 7 Y-7 A1-7
Production Example 8 Y-8 A1-8
Production Example 9 Y-9 A1-9
Production Example 10 Y-10 A1-10
Production Example 11 Y-11 A1-1/B-1=90/10
Production Example 12 Y-12 A1-1/B-15=90/10
Production Example 13 Y-13 A1-1/B-16=90/10
Production Example 14 Y-14 A1-2/B-1=90/10
Production Example 15 Y-15 A1-2/B-15=90/10
Production Example 16 Y-16 A1-2/B-16=90/10
Production Example 17 Y-17 A1-2/ pigment derivative 5=90/10
Production Example 18 Y-18 A1-10/B-15=90/10
Comparison manufacturing example 1 Y-19 Compound (11)
The manufacturing method > of < coloured composition
[embodiment 1A]
(yellow coloring composition (YP-1))
After following mixtures being stirred in a manner of becoming uniform, use the zirconium oxide bead and benefit of diameter 0.5mm With Chinese mugwort lattice grinding machine (eiger mill) (" mini (mini model) M- that Chinese mugwort lattice (Eiger Japan) company, Japan manufactures 250MKII ") after dispersion 3 hours, being filtered using 5.0 μm of the filter in aperture and make nonvolatile component is 20 mass % Yellow coloring composition (YP-1).
Yellow colorants (Y-1): 10.8 parts
Quinophthalone compound (B-1): 1.2 parts
Adhesive resin (F-4) solution: 25.0 parts
Propylene glycol methyl ether acetate (PGMAc): 57.0 parts
Acrylic block copolymer (EB-1): 6.0 parts
[embodiment 2A~embodiment 38A, comparative example 1A~comparative example 2A]
(yellow coloring composition (YP-2~YP-40))
Hereinafter, being changed to composition shown in table 3, in addition to this, Huang is prepared as with yellow coloring composition (YP-1) Chromatic colorant composition (YP-2~YP-40).
[table 3]
The evaluation > of < yellow coloring composition
About the evaluation of yellow coloring composition, film is made using yellow coloring composition, and to its lightness, film thickness And contrast ratio (Contrast Ratio, CR) is measured, and is thus evaluated.In addition, to the guarantor of yellow coloring composition Stability is deposited also to be evaluated.Evaluation method described below.
(lightness evaluation)
Yellow coloring composition is coated on the glass substrate of 100mm × 100mm, 1.1mm thickness using spin coater, It is heated 20 minutes at 230 DEG C, thus to obtain film.At this point, the film thickness about film, after 230 DEG C of heat treatment, with C light Mode under source as x=0.440 changes application conditions (revolving speed of spin coater, time) in due course to be coated.It uses Microspectrophotometer " OSP-SP100 " of manufacture (Olympus (Olympus) Optical Co., Ltd) measures film obtained Lightness (Y), and determine according to following benchmark.
◎: 90.0 or more (very good)
Zero: 89.0 or more~less than 90.0 (good)
△: 87.5 or more~less than 89.0 (implementable)
×: less than 87.5 (bad)
(tinting strength, tinting power evaluation)
Using film identical with lightness estimator is carried out, film thickness when to the coloration for showing x=0.440 is measured, And determine according to following benchmark.The film thickness for providing the coloration of x=0.440 is smaller, indicates that tinting strength, tinting power is bigger, can be described as excellent.
◎: less than 1.0 [μm] (very good)
Zero: 1.0 or more~less than 1.3 [μm] (good)
△: 1.3 or more~less than 1.6 [μm] (implementable)
×: 1.6 or more [μm] (bad)
(contrast ratio (CR) evaluation)
Come from the light of liquid crystal display back light unit by polarizer by polarisation, thus by being coated on glass substrate On coloured composition film, reach another polarizer.At this point, light is saturating if polarizer is parallel with the plane of polarisation of polarizer Polarizer is crossed, but in the case where plane of polarisation is orthogonal, light is interdicted by polarizer.But pass through by the light of polarizer polarisation When the film of color composition, if generating scattering etc. because of colorant particle, and offset is generated in a part of plane of polarisation, then inclined When tabula rasa is parallel, the light quantity of transmission is reduced, and when polarizer is orthogonal, a part of light is penetrated.The light that penetrates is measured as polarisation Brightness on plate, calculate polarizer it is parallel when brightness with it is orthogonal when brightness ratio as contrast ratio.
(contrast ratio)=(brightness when parallel)/(brightness when orthogonal)
Therefore, if generating scattering because of the colorant in film, brightness when parallel is reduced, and it is orthogonal when brightness increase Add, therefore contrast ratio is lower.
Furthermore as luminance meter, using color luminance meter (" BM-5A " that opens up the manufacture of Pu Kang (Topcon) company), as Polarizer uses polarizer (" NPF-G1220DUN " of the manufacture of Dong electrician company).When measurement, it is interposed between determination part and is separated by The black mask in the hole of 1cm square is measured.Using film identical with lightness estimator is carried out, and according to following benchmark To determine.
◎: 3000 or more (very good)
Zero: 2500 or more~less than 3000 (good)
△: 2000 or more~less than 2500 (implementable)
×: less than 2000 (bad)
(storage stability test method)
Using E type viscosimeter (the TUE-20L type of Dong Ji industry companies manufacture), existed with revolving speed 20rpm to coloured composition Viscosity at 25 DEG C is measured.It is saved according to the initial viscosity on the day of the production of coloured composition in 40 DEG C of thermostatic chamber The viscosity measured after 7 days calculates rate of change in viscosity (%) (=(viscosity-initial viscosity after saving 7 days at 40 DEG C)/first Beginning viscosity × 100), and evaluate storage stability with following benchmark.
◎: rate of change in viscosity less than 10% (extremely good)
Zero: rate of change in viscosity is 10% or more, less than 20% (good)
△: rate of change in viscosity is 20% or more, less than 50% (bad)
×: rate of change in viscosity is 50% or more (extremely bad)
By yellow coloring composition made in Examples and Comparative Examples evaluation result is shown in table in 4.
[table 4]
As shown in table 4, using the coloring of quinophthalone compound and the alkaline dispersing agent containing acrylic block copolymer Composition is good result in terms of the lightness of film, tinting strength, tinting power, contrast when storage stability.In addition, with use In the case that the coloured composition (comparative example 2A) of Y-19 is compared, by importing halogen, disperse because of steric hindrance more steady It is fixed, therefore observe the raising of quality.It is relatively good using the system of dimethylaminoethyl methacrylate in block copolymer It is good.In addition, especially by and with acidic resins type dispersing agent or acidic dye derivative, in lightness, tinting strength, tinting power, contrast ratio And good result is obtained in terms of storage stability.Especially by and with quinophthalone skeleton acidic dye derivative, obtain The good result of storage stability.
The production > of < green coloring composition
(green coloring composition (GP-1): colorant (P-1))
After following mixtures being stirred in a manner of becoming uniform, use the zirconium oxide bead and benefit of diameter 0.5mm With Chinese mugwort lattice grinding machine (eiger mill) (" mini (mini model) M- that Chinese mugwort lattice (Eiger Japan) company, Japan manufactures 250MKII ") after dispersion 3 hours, being filtered using 5.0 μm of the filter in aperture and make nonvolatile component is 20 mass % Colorant (P-1) green coloring composition (GP-1).
Colorant (P-1): 12.0 parts
Adhesive resin (F-4) solution: 25.0 parts
Propylene glycol methyl ether acetate (PGMAc): 60.0 parts
Resin type dispersing agent (" PB821 " of the manufacture of aginomoto microtechnic (Ajinomoto Fine-Techno) company)
: 3.0 parts
(green coloring composition (GP-2): colorant (P-2))
Colorant (P-1) is changed to colorant (P-2), in addition to this, using with green coloring composition (GP-1) phase With facture make the green coloring composition (GP-2) of colorant (P-2).
(green coloring composition (GP-3): colorant (P-3))
Colorant (P-1) is changed to colorant (P-3), in addition to this, using with green coloring composition (GP-1) phase With facture make the green coloring composition (GP-3) of colorant (P-3).
(green coloring composition (GP-4): colorant (P-4))
Colorant (P-1) is changed to colorant (P-4), in addition to this, using with green coloring composition (GP-1) phase With facture make the green coloring composition (GP-4) of colorant (P-4).
(green coloring composition (GP-5): PG58)
By colorant (P-1) be changed to C.I. naphthol green 58 (DIC (DIC) company manufacture " Fa Sigen is green (FASTGEN GREEN) A110 "), in addition to this, made using facture identical with green coloring composition (GP-1) The green coloring composition (GP-5) of PG58.
The production > of < red colored composition
(red colored composition (RP-1): PR254)
By colorant (P-1) be changed to C.I. paratonere 254 (BASF (BASF) company manufacture " Yi Lufoer is red (IRGAPHOR RED) B-CF "), in addition to this, made using facture identical with green coloring composition (GP-1) The red colored composition (RP-1) of PR254.
(red colored composition (RP-2): PR177)
Colorant (P-1) is changed to C.I. paratonere 177, and (that believes cruel (Cynic) company manufacture " believes that Electrolux is red (Cinilex RED) SR3C "), in addition to this, made using facture identical with green coloring composition (GP-1) The red colored composition (RP-2) of PR177.
(red colored composition (RP-3): colorant (P-5))
Colorant (P-1) is changed to colorant (P-5), in addition to this, using with green coloring composition (GP-1) phase With facture make the red colored composition (RP-3) of colorant (P-5).
(red colored composition (RP-4): PR269)
Colorant (P-1) is changed to commercially available C.I. paratonere 269, in addition to this, utilization and green coloring composition (GP-1) identical facture makes the red colored composition (RP-4) of PR269.
The production > of < yellow coloring composition
(yellow coloring composition (YP-41): PY138)
Colorant (Y-1) is changed to (" the Parriott Shandong Huang of BASF (BASF) company manufacture of C.I. pigment yellow 13 8 (Paliotol Yellow) K0960-HD "), in addition to this, using facture identical with yellow coloring composition (YP-1) come Make the yellow coloring composition (YP-41) of PY138.
(yellow coloring composition (YP-42): PY185)
Colorant (Y-1) is changed to (" the Pa Liao root Huang of BASF (BASF) company manufacture of C.I. pigment yellow 185 (Paliogen Yellow) D1155 "), in addition to this, made using facture identical with yellow coloring composition (YP-1) Make the yellow coloring composition (YP-42) of PY185.
(yellow coloring composition (YP-43): PY139)
Colorant (Y-1) is changed to (" the Yi Lufoer Huang of BASF (BASF) company manufacture of C.I. pigment yellow 13 9 (IRGAPHOR Yellow) 2R-CF "), in addition to this, made using facture identical with yellow coloring composition (YP-1) Make the yellow coloring composition (YP-43) of PY139.
The production > of < photosensitive coloring composition
Whenever manufacturing photosensitive composite, following preparations are carried out.
Binder resin solution A: adhesive resin (F-1)~adhesive resin (F-4) is mixed with 1:1:1:1 Made of mixed solution.
Polymerizable compound A: Aronix (Aronix) M402 that East Asia Synesis Company is manufactured, Aronix (Aronix) M520, Japanese chemical drug corporation are made Ka Yala get (KAYARAD) DPCA-30, the manufacture of chemical company, common prosperity society Mixture made of UA-510H is mixed with 1:1:1:1.
Photoepolymerizationinitiater initiater A: make 907 1 parts of gorgeous good solid (IRGACURE), 369 1 parts of gorgeous good solid (IRGACURE), gorgeous Good solid 1 part of (IRGACURE) OXE02 is dissolved in mixed solution made of in 100 parts of propylene glycol methyl ether acetate (PGMEA).
Sensitizer A: 1 part of " card sub- solid (KAYACURE) DETX-S ", 1 part of " EAB-F " is made to be dissolved in propylene glycol monomethyl ether Mixed solution made of in 100 parts of acetic acid esters (PGMEA).
Epoxide A: it is mixed made of jER E157S75, EHPE-3150, TEPIC-S are mixed with 1:1:1 It is fit.
Oxetane compound A: the OXT-221 of East Asia Synesis Company manufacture
Ultraviolet absorbing agent A: make BASF (BASF) company manufacture 1 part of " refined (TINUVIN) P of Supreme Being slave ", " Supreme Being slave is refined (TINUVIN) 405 " 1 parts, Kai meter Bu Luo (Chemipro) chemical conversion company manufacture 1 part of " Kai meter Suo Bu (KEMISORB) 10 " it is molten Solution in 100 parts of propylene glycol methyl ether acetate (PGMEA) made of mixed solution.
Polymerization inhibitor A: make 1 part of " 3- methyl catechol ", 1 part of " methyl hydroquinone ", " tert-butyl hydroquinone " 1 Part is dissolved in mixed solution made of in 100 parts of propylene glycol methyl ether acetate (PGMEA).
Antioxidant A: 1 part of " easy Lu Nuosi (IRGANOX) 1010 ", the Ai Dike for manufacturing BASF (BASF) company (ADEKA) " the Chinese mugwort that 1 part of " Ai Di Coase tower wave (Adekastab) LA-52 " of company's manufacture, Ai Dike (ADEKA) company manufacture " the Ai Di Coase tower wave that 1 part of enlightening Coase tower wave (Adekastab) PEP-36 ", Ai Dike (ADEKA) company manufacture (Adekastab) it is dissolved in mixed solution made of in 100 parts of propylene glycol methyl ether acetate (PGMEA) for 1 part of AO-412S ".
Mercaptan tethers transfer agent A: pentaerythrite tetrathio propionic ester
Silane coupling agent A: by silicone company, SHIN-ETSU HANTOTAI manufacture KBM-403, KBM-5103, KBM-1003, KBM-573, Mixture made of KBM-803 is mixed with 1:1:1:1:1.
Levelling agent A: make 1 part of " BYK-330 ", DIC (DIC) stock of chemical (BYK-Chemie) the company manufacture of Bi Ke What 1 part of " Mei Jiafa (Megafac) F-551 " of the manufacture of part Co., Ltd, Kao Corporation manufactured " admires fondly root (Emulgen) it is dissolved in mixed solution made of in 100 parts of propylene glycol methyl ether acetate (PGMEA) for 103 " 1 parts.
Solvent A: by propylene glycol methyl ether acetate, cyclohexanone, 3- ethoxyl ethyl propionate, 1,3 butylene glycol oxalic acid Mixed solution made of ester is mixed with 3:1:1:1.
[embodiment 101A]
(production of photosensitive coloring composition (GR-1))
To become to utilize the filter in 1 μm of aperture to carry out after following mixtures formed are stirred by uniform mode It filters and makes photosensitive coloring composition (GR-1).
Yellow coloring composition (YP-1): 16.0 parts
Green coloring composition (GP-1): 24.0 parts
A: 6.0 parts of binder resin solution
A: 1.0 parts of polymerizable compound
A: 8.0 parts of Photoepolymerizationinitiater initiater
A: 1.0 parts of sensitizer
A: 1.0 parts of epoxide
A: 1.0 parts of oxetane compound
A: 1.0 parts of ultraviolet absorbing agent
A: 1.0 parts of polymerization inhibitor
A: 1.0 parts of antioxidant
A: 1.0 parts of mercaptan tethers transfer agent
A: 1.0 parts of silane coupling agent
A: 1.0 parts of levelling agent
Solvent A: 36.0 parts
[embodiment 102A~embodiment 151A, comparative example 101A~comparative example 108A]
(production of photosensitive coloring composition (GR-2~GR-59))
Using yellow coloring composition and green coloring composition shown in table 5, and to meet when evaluating film in C light Mode under source for the coloration of x=0.240, y=0.660 changes the ratio of yellow coloring composition and green coloring composition (changing ratio in such a way that the total amount of coloured composition becomes 40 parts), in addition to this, with photosensitive coloring composition (GR-1) Similarly make photosensitive coloring composition (GR-2~GR-59).
The film of < photosensitive coloring composition evaluates >
Using following methods come to the film for using photosensitive coloring composition obtained (GR-1~GR-59) and making Lightness, tinting strength, tinting power, contrast ratio (CR), heat resistance and solvent resistance evaluated.
(lightness evaluation)
Using spin coater, photosensitive coloring composition is coated on to the glass substrate of 100mm × 100mm, 1.1mm thickness On, it is then, 20 minutes dry at 70 DEG C, using extra-high-pressure mercury vapour lamp, with 300mJ/cm2Ultraviolet exposure is carried out, and is utilized 23 DEG C of alkaline-based developer develops.As alkaline-based developer, using including 1.5 mass % of sodium carbonate, 0.5 matter of sodium bicarbonate Measure %, anionic surfactant (KAO. Corp. SA manufactures " sending Simon Rex (Pelex) NBL ") 90 matter of 8.0 mass % and water Measure % person.In turn, it is heated 30 minutes at 230 DEG C, thus to obtain film.Use microspectrophotometer (Olympus (Olympus) " OSP-SP100 " of Optical Co., Ltd's manufacture) lightness (Y) of film obtained is measured, and according to following benchmark To determine.Furthermore made film is set as after 230 DEG C of heat treatment, become x (C)=0.240, y (C)=0.660.
◎: 44.0 or more (very good)
Zero: 43.0 or more, less than 44.0 (good)
△: 42.0 or more, less than 43.0 (implementable)
×: less than 42.0 (bad)
(evaluation of tinting strength, tinting power)
Using film identical with lightness estimator is carried out, film thickness when to the coloration for showing y (C)=0.660 is surveyed It is fixed, and determine according to following four stages benchmark.The film thickness for providing the coloration of x (C)=0.240, y (C)=0.660 is smaller, table Show that tinting strength, tinting power is bigger, can be described as excellent.
◎: less than 2.7 μm of film thickness (very good)
Zero: 2.7 μm of film thickness or more, less than 3.0 μm (good)
△: 3.0 μm of film thickness or more, less than 3.3 μm (implementable)
×: 3.3 μm of film thickness or more (bad)
(evaluation of contrast ratio)
Using lightness evaluate used in substrate come implement contrast than measurement.The evaluation of contrast ratio is with following four Stage is evaluated.
◎: 6000 or more (very good)
Zero: 5000 or more, less than 6000 (good)
△: 4000 or more, less than 5000 (implementable)
×: less than 4000 (bad)
(evaluation is precipitated in crystallization)
To film used in lightness evaluation, additional heating is used as heat-resistance test in 60 minutes at 250 DEG C.Thereafter, sharp It is observed and confirming has nodeless mesh precipitation with optical microscopy to ilm substrate is applied.Evaluation was evaluated with following three stages.
It is reheated after zero ... heats 30 minutes at 230 DEG C and at 250 DEG C and handles also nodeless mesh precipitation in 60 minutes (good)
Nodeless mesh is precipitated after heating 30 minutes at 230 DEG C though △ ..., and 60 points of processing is reheated at 250 DEG C Clock has crystallization that (can be practical) be precipitated
× ... there is crystallization that (bad) is precipitated after heating 30 minutes at 230 DEG C
(evaluation of heat resistance)
It is measured using microspectrophotometer (" OSP-SP100 " of the manufacture of Olympus (Olympus) Optical Co., Ltd) Coloration ([L* (1), a* (1), b* (1)]) of the substrate used in Evaluation of Heat Tolerance under illuminant-C, and find out at 230 DEG C The color difference Δ E*ab of the coloration ([L* (2), a* (2), b* (2)]) under illuminant-C at lower heat treatment 30 minutes.Heat resistance is commented Valence is determined according to following benchmark.
Δ E*ab=[[L* (2)-L* (1)]2+[a*(2)-a*(1)]2+[b*(2)-b*(1)]2]1/2
◎: Δ E*ab=less than 1: extremely good
Zero: Δ E*ab=1 or more, less than 3: good
△: Δ E*ab=3 or more, less than 5: can be practical
×: Δ E*ab=5 or more: bad
(evaluation of solvent resistance)
Using slit die coating machine, after colored filter is coated on glass substrate with photosensitive coloring composition, benefit 2 minutes prebake conditions are carried out with 90 DEG C of hot plates and form 2.4 μm of film thickness of film.Then, the substrate for being formed with film is cooling To room temperature, using high-pressure mercury-vapor lamp, it is situated between every striated photomask to film with 1,000J/m2Light exposure exposure include The radioactive ray of each wavelength of 365nm, 405nm and 436nm.After carrying out alkali development, cleaned using ultrapure water, in turn, at 230 DEG C Lower progress is toasted after 30 minutes, and the striated pixel of green is thus formed on substrate.Then, using microspectrophotometer " OSP-SP100 " of manufacture (Olympus (Olympus) Optical Co., Ltd) measures the striated pixel of green under illuminant-C Coloration ([L* (1), a* (1), b* (1)]).In turn, thereafter, the leaching in n-methyl-2-pyrrolidone (NMP) or methanol (MeOH) Stain 15 minutes, the coloration ([L* (2), a* (2), b* (2)]) under the illuminant-C after dipping is measured, is asked according to following formula Color difference Δ E*ab out.The evaluation of solvent resistance is determined according to following benchmark.
Δ E*ab=[[L* (2)-L* (1)]2+[a*(2)-a*(1)]2+[b*(2)-b*(1)]2]1/2
◎: Δ E*ab=less than 1: extremely good
Zero: Δ E*ab=1 or more, less than 3: good
△: Δ E*ab=3 or more, less than 5: can be practical
×: Δ E*ab=5 or more: bad
By photosensitive coloring composition made in Examples and Comparative Examples evaluation result is shown in table in 5, table 6.
[table 5]
[table 6]
As shown in table 5, table 6, combined by the way that quinophthalone system pigment (A1) is used as yellow coloring with block copolymer combinations Object, embodiment 101A~embodiment 151A lightness, tinting strength, tinting power, contrast be precipitated than, crystallization, heat resistance and solvent resistance are appointed Nothing × the evaluation of one project, and be particularly good result.On the other hand, about yellow coloring composition, compound (11) or It is the result of lightness and contrast than being substantially worse than the embodiment of the present invention in PY138, PY185.
Red sensitive coloured composition
[embodiment 201A~embodiment 221A, comparative example 201A~comparative example 205A]
(production of photosensitive coloring composition (RR-1~RR-26))
Using yellow coloring composition and red colored composition shown in table 7, table 8, and to meet when evaluating film Mode under illuminant-C for the coloration of x=0.640, y=0.330 changes yellow coloring composition and red colored composition Ratio (changes ratio in such a way that the total amount of coloured composition becomes 40 parts), in addition to this, with photosensitive coloring composition (GR-1) similarly photosensitive coloring composition (RR-1~RR-26) is made.
The film of < photosensitive coloring composition evaluates >
To use photosensitive coloring composition obtained (RR-1~RR-26) and the lightness of the film that makes, tinting strength, tinting power, Contrast ratio (CR), crystallization are precipitated, heat resistance and solvent resistance are evaluated.The evaluation of lightness and tinting strength, tinting power is to utilize following sides Method carries out.When the evaluation of solvent resistance is to utilize and photosensitive coloring composition (GR- for crystallization precipitation, heat resistance, contrast 1~GR-59) identical method implemented.
(lightness evaluation)
It is same as photosensitive coloring composition (GR-1~GR-59) for photosensitive coloring composition (RR-1~RR-26) Ground makes on the glass substrate of 100mm × 100mm, 1.1mm thickness applies ilm substrate.
It is measured using microspectrophotometer (" OSP-SP100 " of the manufacture of Olympus (Olympus) Optical Co., Ltd) The lightness (Y) of film obtained, and determine according to following benchmark.Furthermore made film is set as at 230 DEG C of heat After reason, become x=0.640, y=0.330.
◎: 21.0 or more (very good)
Zero: 20.5 or more, less than 21.0 (good)
△: 20.0 or more, less than 20.5 (implementable)
×: less than 20.0 (bad)
(evaluation of tinting strength, tinting power)
Using film identical with lightness estimator is carried out, film thickness when to the coloration for showing x=0.640 is measured, And determine according to following four stages benchmark.The film thickness for providing the coloration of x=0.640, y=0.330 is smaller, indicates that tinting strength, tinting power is got over Greatly, it can be described as excellent.
◎: less than 2.2 μm of film thickness (very good)
Zero: 2.2 μm of film thickness or more, less than 2.5 μm (good)
△: 2.5 μm of film thickness or more, less than 2.8 μm (implementable)
×: 2.8 μm of film thickness or more (bad)
[table 7]
[table 8]
As shown in table 7, table 8, combined by the way that quinophthalone system pigment (A1) is used as yellow coloring with block copolymer combinations Object, embodiment 201A~embodiment 221A lightness, tinting strength, tinting power, contrast be precipitated than, crystallization, heat resistance and solvent resistance are appointed Nothing × the evaluation of one project, and be particularly good result.On the other hand, about yellow coloring composition, compound (11) or It is the result of lightness and contrast than being substantially worse than the embodiment of the present invention in PY139.
The production > of < colored filter
Firstly, blue-sensitive coloured composition used in production to colored filter makes.
(preparation of blue-sensitive coloured composition (BR-1))
After following mixtures being stirred in a manner of becoming uniform, use the zirconium oxide bead and benefit of diameter 0.5mm With Chinese mugwort lattice grinding machine (eiger mill) (" mini (mini model) M- that Chinese mugwort lattice (Eiger Japan) company, Japan manufactures 250MKII ") after dispersion 5 hours, it is filtered using 5.0 μm of the filter in aperture and makes blue colored composition (BP-1).
Blue pigment (C.I. pigment blue 15: 6) 7.2 parts
4.8 parts of violet pigment (C.I. pigment Violet 23)
1.0 parts of resin type dispersing agent (" Ai Fuka (EFKA) 4300 " of Japanese BASF (BASF Japan) company manufacture)
35.0 parts of solution of adhesive resin (F-4)
52.0 parts of propylene glycol methyl ether acetate
Then, to become to utilize 1 μm of the filter in aperture after following mixtures formed are stirred by uniform mode It is filtered and makes blue-sensitive coloured composition (BR-1).
Blue colored composition (BP-1): 40.0 parts
A: 6.0 parts of binder resin solution
A: 1.0 parts of polymerizable compound
A: 8.0 parts of Photoepolymerizationinitiater initiater
A: 1.0 parts of sensitizer
A: 1.0 parts of epoxide
A: 1.0 parts of oxetane compound
A: 1.0 parts of ultraviolet absorbing agent
A: 1.0 parts of polymerization inhibitor
A: 1.0 parts of antioxidant
A: 1.0 parts of mercaptan tethers transfer agent
A: 1.0 parts of silane coupling agent
A: 1.0 parts of levelling agent
Solvent A: 36.0 parts
(production of colored filter)
Pattern processes black matrix" on the glass substrate, and is coloured red sensitive of the invention using spin coater Composition (RR-12) is with the film thickness as x=0.640, y=0.330 is coated on the substrate and forms coloring envelope.For The envelope is situated between every photomask and irradiates 200mJ/cm using extra-high-pressure mercury vapour lamp2Ultraviolet light.Then, using including 0.2 matter The alkaline-based developer for measuring the aqueous sodium carbonate of % carries out spray development after removing unexposed portion, utilizes ion exchange water It is cleaned, the substrate is heated 30 minutes at 230 DEG C, form red filter section.In addition, being made using identical method It is carried out in a manner of the coloration for meeting x=0.240, y=0.660 with green photosensitive coloured composition (GR-33) of the invention It is coated with and forms green filter section, using blue-sensitive coloured composition (BR-1) to become x=0.150, y=0.060 Film thickness is coated and forms blue filter section, to obtain colored filter.
By using red sensitive coloured composition (RR-12) of the invention and green photosensitive coloured composition (GR- 33) tinting strength, tinting power, lightness and contrast ratio, can be reached with high level, in turn, in terms of other physical property also no problem and can be suitable for making With.
[the 2nd embodiment group]
(weight-average molecular weight (Mw) of resin)
The weight-average molecular weight (Mw) of resin is using TSKgel tubing string (manufacture of Tosoh (Tosoh) company) and to utilize dress The GPC (manufacture of Tosoh (Tosoh) company, HLC-8120GPC) of RI detector is had, and THF is used to survey as expansion solvent The weight-average molecular weight (Mn) of fixed polystyrene conversion.
Then, spread out to binder resin solution used in Examples and Comparative Examples, resin type dispersant solution, pigment Biological, colorant manufacturing method is illustrated.
The manufacturing method > of < binder resin solution
(preparation of adhesive resin (F-5) solution)
In being equipped with thermometer, cooling tube, nitrogen ingress pipe, drop tube and agitating device in detachable four-hole boiling flask Reaction vessel in be packed into 196 parts of cyclohexanone, be warming up to 80 DEG C, in reaction vessel carry out nitrogen displacement after, spend 2 hours from drip Add pipe that 37.2 parts of n-BMA, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, right is added dropwise (East Asia synthesizes the " Aronix (Aronix) of limited liability company's manufacture to the ethylene-oxide-modified acrylate of cumyl phenol M110 ") 20.7 parts, 1.1 parts of 2,2'- azobis isobutyronitrile of mixture.After completion of dropwise addition, and then continue to react for 3 hours, To obtain the solution of acrylic resin.After being cooled to room temperature, about 2 parts of resin solution are sampled, heat drying 20 divides at 180 DEG C Clock, and measure nonvolatile component, in the resin solution synthesized before add acetic acid methoxyl group propyl ester so that nonvolatile component at For 20 mass %, to prepare adhesive resin (F-5) solution.Weight-average molecular weight (Mw) is 26000.
(preparation of adhesive resin (F-6))
In being equipped with thermometer, cooling tube, nitrogen ingress pipe, drop tube and agitating device in detachable four-hole boiling flask Reaction vessel in be packed into 207 parts of cyclohexanone, be warming up to 80 DEG C, in reaction vessel carry out nitrogen displacement after, spend 2 hours from drip Add pipe that 20 parts of methacrylic acid, the ethylene-oxide-modified acrylate of p -cumylphenol (sub- sieve of East Asia Synesis Company manufacture is added dropwise Nice (Aronix) M110) 20 parts, 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate and 2,2'- azo The mixture of 1.33 parts of double isobutyronitriles.After completion of dropwise addition, and then continue to react for 3 hours, to obtain copolymer resin liposoluble Liquid.Then, relative to copolymer solution total amount obtained, stop nitrogen and inject 1 hour dry gas, be stirred simultaneously Afterwards, after being cooled to room temperature, 3 hours dropwise addition 2- methacryloxyethyl isocyanates (Showa electrician companies are spent at 70 DEG C Ka Lunzi (Karenz) MOI of manufacture) 6.5 parts, the mixture of 0.08 part of dibutyl tin laurate, 26 parts of cyclohexanone.Knot is added dropwise Shu Hou, and then continue to react for 1 hour, to obtain the solution of acrylic resin.After being cooled to room temperature, resin solution is sampled About 2 parts, heat drying 20 minutes at 180 DEG C, and nonvolatile component is measured, hexamethylene is added in the resin solution synthesized before Ketone is so that nonvolatile component becomes 20 mass %, to prepare adhesive resin (F-6) solution.Weight-average molecular weight (Mw) is 18000。
The manufacturing method > of < resin type dispersant solution
(preparation of resin type dispersant solution 1)
2,2'- azobis isobutyronitrile (2,2'- is packed into the flask for having cooling tube, blender Azobisisobutyronitrile, AIBN) 186 mass parts of 1.0 mass parts and propylene glycol methyl ether acetate, then, loading 27 mass parts of methyl methacrylate, 27 mass parts of butyl methacrylate, 21 mass parts of 2-Ethylhexyl Methacrylate, first 3.6 mass parts of 18 mass parts of base benzyl acrylate and dithiobenzoic acid cumyl ester, and carry out nitrogen displacement in 30 minutes.Thereafter, It slowly stirs, and the temperature of reaction solution is risen to 60 DEG C, the temperature is kept for 24 hours and carries out living radical Polymerization.Then, addition makes 35 matter of 1.0 mass parts of AIBN and dimethylaminoethyl methacrylate in the reaction solution The solution that amount part is dissolved in 70 mass parts of propylene glycol methyl ether acetate and replaces through 30 minutes nitrogen, carries out 24 at 60 DEG C Hour active free radical polymerization, thus to obtain the solution of block copolymer.Chlorine is added in block copolymer solution obtained Change 25 mass parts of benzyl and 50 mass parts of propylene glycol monomethyl ether, carries out reacting and adjusting solid component concentration for 2 hours at 80 DEG C It is 40%, thus to obtain resin type dispersant solution 1.Resin type dispersing agent 1 is the block copolymer comprising A block and B block, The A block, which has, is originated from methacryloxyethyl benzyl chloride and dimethylaminoethyl acrylate methyl base aminoethyl Repetitive unit, the B block have be originated from methyl methacrylate, butyl methacrylate, methacrylic acid 2- ethyl hexyl The repetitive unit of ester and benzyl methacrylate.Proton NMR measurement as a result, the copolymerization ratio of each repetitive unit be methacryl Oxygroup Ethylbenzyl alkyl dimethyl ammonium chloride/dimethylaminoethyl acrylate methyl base aminoethyl/methyl methacrylate/methacrylic acid fourth Ester/2-Ethylhexyl Methacrylate/benzyl methacrylate=34/4/18/18/14/12 (mass ratio).
The manufacturing method > of < colorant
(manufacture of colorant (P-1))
Using with the identical system of blue colorant (PB-1) recorded in the embodiment of No. 4893859 bulletins of Japanese Patent No. It makes method and obtains the colorant (P-1) as aluminium phthalocyanine color.
(manufacture of colorant (P-2))
109 parts of sulfonic acid chloride, 131 parts of aluminium chloride, 18 parts of sodium chloride, 30 parts of ZnPc, bromine 52 are packed into 300mL flask Part.It spends 40 hours and is warming up to 130 DEG C, after taking out into water, green thick pigment is obtained and being filtered.It will be obtained green 20 parts of the thick pigment of color, 1.8 parts of 32 parts of 140 parts of sodium chloride, diethylene glycol, the dimethylbenzene loadings through crushing to 1L dual-arm kneader In, it is kneaded 6 hours at 100 DEG C.After mixing take out into 80 DEG C of water 2kg, stirring 1 hour after, be filtered, hot water wash, Dry, crushing, thus to obtain colorant (P-2).Colorant (P-2) obtained is following zinc halide phthalocyanine color, the halogen It is 12.69 average that change ZnPc pigment, which be the halogen atom number in a molecule according to x-ray fluorescence analysis, wherein bromine is former Subnumber is averagely 8.54, amount of chlorine atom is 4.16 average.
(manufacture of colorant (P-3))
Using identical as phthalocyanine color (P-10) recorded in the embodiment of Japanese Patent Laid-Open 2017-197685 bulletin Manufacturing method and obtain the colorant (P-3) as aluminium phthalocyanine color.
(manufacture of colorant (P-4))
Using with phthalocyanine color (PCY-9) phase for being recorded in the embodiment of Japanese Patent Laid-Open 2016-153481 bulletin With manufacturing method and obtain the colorant (P-4) as aluminium phthalocyanine color.
(manufacture of colorant (P-5))
Utilize manufacturing method identical with the azopigment 1 recorded in the embodiment of No. 5187326 bulletins of Japanese Patent No. And obtain colorant (P-5).
The manufacturing method > of < pigment derivative
Using with the quinophthalone compound (QL-c- that is recorded in the embodiment of Japanese Patent Laid-Open 2015-172732 bulletin 1) identical manufacturing method and obtain quinophthalone compound (B-1).
It obtains according to the synthetic method recorded in No. 4585781 bulletins of Japanese Patent No. as quinophthalone compound (B- 2) quinophthalone compound (B-15) of Al salt.
Using identical with the quinophthalone compound (B-3) recorded in the embodiment of No. 6160061 bulletins of Japanese Patent No. Manufacturing method and obtain the quinophthalone compound (B-16) as the lauryl trimethyl ammonium salt of quinophthalone compound (B-3).
Using with the quinophthalone compound (QL-f- that is recorded in the embodiment of Japanese Patent Laid-Open 2015-172732 bulletin 1) identical manufacturing method and obtain quinophthalone compound (B-4).
(identification method of quinophthalone compound)
(identification method of quinophthalone compound (A))
MALDI TOF-MS spectrum is used in the identification of quinophthalone compound used in the present invention.MALDI TOF-MS Spectrum is the MALDI quality analysis apparatus manufactured using Brooker dalton (Bruker-daltonics) company AutoflexIII, it is consistent and right with the mass number by calculating acquisition based on mass spectrographic molecular ion wave crest obtained Compound obtained is identified.
The average value of the substitution number of halogen atom is to obtain in the following way: firing pigment using oxygen burning flask method It burns, by ion chromatograph (the ICS-2000 chromatography of ions, Dai An (DIONEX) company manufacture) come to inhaling the comburant Liquid made of closing in water is analyzed and is quantified to halogen quantity, and the substitution number for being scaled halogen atom is averaged Value.
(the halogen distribution of quinophthalone compound (A1))
It is calculated and each ingredient about halogen distribution using MALDI TOF-MS spectrum and in mass spectrum obtained The signal strength (each peak value) of comparable molecular ion wave crest and by each peak value it is accumulative obtained by value (total peak value), to each peak value The quantity for the wave crest that ratio relative to total peak value is 1% or more is counted, and is set as halogen distribution.
(synthesis of quinophthalone compound (A1-1))
150 parts of 2,3- naphthalene dicarboxylic acids acid anhydride and 230 parts of trichloroisocyanuric acid are added in 1200 parts of 98% sulfuric acid, at 80 DEG C Reaction 4 hours.Reaction solution is injected into 9000 parts of agitated ice water, to precipitate generated to filter, wash, 1% Sodium hydrate aqueous solution cleaning, the sequence washed are handled, and are dried and obtain 220 parts of intermediate (a1-1).For Intermediate (a1-1), calculates chlorine substituent number, and result is 3.5 average.By 190 parts of intermediate obtained (a1-1), 8- ammonia 45 parts of base quinaldine, 60 parts of benzoic acid make an addition in 280 parts of methyl benzoate, heating stirring 6 hours at 180 DEG C.It is cooled to After room temperature, reaction mixture is put into 3000 parts of acetone, is stirred at room temperature 1 hour.Separation is filtered to product, benefit It is cleaned and is dried with methanol, to obtain 203 parts of quinophthalone compound (A1-1).Quality is carried out using TOF-MS Analysis, is as a result accredited as quinophthalone compound (A1-1).In addition, halogen distribution is 5.
[changing 58]
Quinophthalone compound (A1-1)
(synthesis of quinophthalone compound (A1-2))
Compound (12) are obtained according to the synthetic method recorded in Japanese Patent Laid-Open 2012-226110 bulletin.? (12) 105 parts of compound, 150 parts of intermediate (a1-1), 100 parts of benzoic acid are added in 500 parts of methyl benzoate, are heated to 180 DEG C and carry out 4 hours stir.In turn, after being cooled to room temperature, reaction mixture is put into 5000 parts of acetone, is stirred at room temperature It mixes 1 hour.Separation is filtered to product, carries out methanol cleaning and drying, to obtain 183 parts of quinophthalone compound (A1- 2).Quality analysis is carried out using TOF-MS, is as a result accredited as quinophthalone compound (A1-2).In addition, halogen distribution is 3.
[changing 59]
Quinophthalone compound (A1-2)
(synthesis of quinophthalone compound (A1-3))
150 parts of 2,3- naphthalene dicarboxylic acids acid anhydride and 220 parts of N- chlorosuccinimide are added in 1200 parts of 98% sulfuric acid, 50 It is reacted 4 hours at DEG C.Reaction solution is injected into 9000 parts of agitated ice water, precipitate is filtered and separates and is subject to water Wash and be washed to filtrate ratio conductivity become 50 μ S/cm or less until, thus to obtain water paste.Water obtained is pasted at 80 DEG C Lower drying 24 hours and obtain 220 parts of intermediate (a1-3).For intermediate (a1-3), chlorine substituent number is calculated, result is flat Equal 2.220 parts of intermediate obtained (a1-3), 45 parts of 8- amidoquinaldine, 60 parts of benzoic acid are made an addition into methyl benzoate In 300 parts, heating stirring 6 hours at 180 DEG C.After being cooled to room temperature, reaction mixture is put into 3000 parts of acetone, It stirs 1 hour at room temperature.Separation is filtered to product, is cleaned and is dried using methanol, to obtain 170 parts Quinophthalone compound (A1-3).Quality analysis is carried out using TOF-MS, is as a result accredited as quinophthalone compound (A1-3).In addition, Halogen distribution is 3.
[changing 60]
Quinophthalone compound (A1-3)
(synthesis of quinophthalone compound (A1-4))
In the synthesis of intermediate (a1-1), N- bromo-succinimide 244 is changed to by 230 parts of trichloroisocyanuric acid Part, in addition to this, is synthesized using identical method and obtain intermediate (a1-4).For intermediate (a1-4), calculates bromine and take For radix, result is 1.5 average.By 225 parts of intermediate obtained (a1-4), 45 parts of 8- amidoquinaldine, benzoic acid 60 Part makes an addition in 300 parts of methyl benzoate, heating stirring 6 hours at 180 DEG C.After being cooled to room temperature, reaction mixture is thrown Enter into 3000 parts of acetone, is stirred at room temperature 1 hour.Separation is filtered to product, cleaned using methanol and is carried out It is dry, to obtain 204 parts of quinophthalone compound (A1-4).Quality analysis is carried out using TOF-MS, is as a result accredited as quinoline phthalein Ketone compound (A1-4).In addition, halogen distribution is 3.
[changing 61]
Quinophthalone compound (A1-4)
(synthesis of quinophthalone compound (A1-5))
150 parts of 2,3- naphthalene dicarboxylic acids and 600 parts of sodium dichloroisocyanurate are added in 1200 parts of 98% sulfuric acid, at 80 DEG C Reaction 4 hours.Reaction solution is injected into 9000 parts of agitated ice water, to precipitate generated to filter, wash, 1% Sodium hydrate aqueous solution cleaning, the sequence washed are handled, and are dried and obtain 255 parts of intermediate (a1-5).For Intermediate (a1-5), calculates chlorine substituent number, and result is 4 average.Then, in the synthesis of quinophthalone compound (A1-2), It is changed to 165 parts of intermediate (a1-5) by 150 parts of intermediate (a1-1), in addition to this, is synthesized and is obtained using identical method Obtain 187 parts of quinophthalone compound (A1-5).Quality analysis is carried out using TOF-MS, is as a result accredited as quinophthalone compound (A1- 5).In addition, halogen distribution is 2.
[changing 62]
Quinophthalone compound (A1-5)
(synthesis of quinophthalone compound (A1-6))
In the synthesis of intermediate (a1-1), bromo- 5, the 5- dimethyl second of 1,3- bis- is changed to by 230 parts of trichloroisocyanuric acid 100 parts of interior uride is synthesized using identical method in addition to this and obtains intermediate (a1-6).For intermediate (a1-6), Bromine substituent number is calculated, result is 3.8 average.By 225 parts of intermediate obtained (a1-6), 45 parts of 8- amidoquinaldine, 60 parts of benzoic acid make an addition in 300 parts of methyl benzoate, heating stirring 6 hours at 180 DEG C.After being cooled to room temperature, it will react Mixture is put into 3000 parts of acetone, is stirred at room temperature 1 hour.Separation is filtered to product, is carried out using methanol clear It washes and is dried, to obtain 204 parts of quinophthalone compound (A1-6).Quality analysis is carried out using TOF-MS, is as a result reflected It is set to quinophthalone compound (A1-6).In addition, halogen distribution is 6.
[changing 63]
Quinophthalone compound (A1-6)
(synthesis of quinophthalone compound (A1-8))
In the synthesis of quinophthalone compound (A1-2), intermediate (a1-6) 250 is changed to by 150 parts of intermediate (a1-1) Part, in addition to this, 208 parts of quinophthalone compound (A1-8) is synthesized and obtained using identical method.Using TOF-MS into As a result row quality analysis is accredited as quinophthalone compound (A1-8).In addition, halogen distribution is 3.
[changing 64]
Quinophthalone compound (A1-8)
(synthesis of quinophthalone compound (A1-9))
50 parts of 8- amidoquinaldine, 115 parts of intermediate (a1-1), benzoic acid 140 are added in 200 parts of methyl benzoate Part, it is stirred 4 hours at 120 DEG C.Then, 143 parts of intermediate (a1-4) is added in turn in the reactive mixture, is heated to 180 DEG C, water is distilled remove on one side, carries out stirring for 4 hours on one side.After being cooled to room temperature, reaction mixture is put into acetone 2000 In part, it is stirred at room temperature 1 hour.Separation is filtered to product, is cleaned and is dried using methanol, to obtain 167 parts of quinophthalone compound (A1-9).Quality analysis is carried out using TOF-MS, is as a result accredited as quinophthalone compound (A1- 9).In addition, halogen distribution is 4.
[changing 65]
Quinophthalone compound (A1-9)
(synthesis of quinophthalone compound (A1-10))
(12) 100 parts and 54 parts of N- bromo-succinimide of compound are added in 700 parts of n,N-Dimethylformamide, It is reacted 3 hours at 85 DEG C.Reaction solution is injected into 6000 parts of agitated methanol, is stirred at room temperature 1 hour.To product into Row is separated by filtration, and is cleaned and is dried using methanol, to obtain (18) 105 parts of compound.In methyl benzoate 400 (18) 100 parts of compound, 115 parts of intermediate (a1-1), 30 parts of benzoic acid are added in part, are heated to 180 DEG C, are on one side distilled water Removal, carries out stirring for 4 hours on one side.After being cooled to room temperature, reaction mixture is put into 4000 parts of acetone, is stirred at room temperature It mixes 1 hour.Separation is filtered to product, is cleaned and is dried using methanol, to obtain 159 parts of quinophthalone It closes object (A1-10).Quality analysis is carried out using TOF-MS, is as a result accredited as quinophthalone compound (A1-10).In addition, halogen point Cloth range is 3.
[changing 66]
Compound (18)
[changing 67]
Quinophthalone compound (A1-10)
The manufacturing method > of < quinophthalone compound (A2)
As quinophthalone compound (A2-1), (" in the pa of BASF (BASF) company manufacture of C.I. pigment yellow 13 8 is used Ao Telu Huang (Paliotol Yellow) K0960-HD ").
Quinophthalone compound is obtained according to the synthetic method recorded in Japanese Patent Laid-Open 2012-226110 bulletin (A2-3)。
Using identical as the quinophthalone compound (r) recorded in the embodiment of Japanese Patent Laid-Open 2012-47306 bulletin Manufacturing method and obtain quinophthalone compound (A2-4).
[changing 68]
Quinophthalone compound (A2-4)
(synthesis of quinophthalone compound (A2-7))
190 parts of intermediate (a1-1), 48 parts of 6- methyl -8- amidoquinaldine, 60 parts of benzoic acid are made an addition into benzoic acid first In 280 parts of ester, heating stirring 6 hours at 180 DEG C.After being cooled to room temperature, reaction mixture is put into 3000 parts of acetone, It is stirred at room temperature 1 hour.Separation is filtered to product, is cleaned and is dried using methanol, to obtain 148 parts Intermediate (a2-7).Then, changed according to the synthetic method recorded in Japanese Patent Laid-Open 2008-81566 bulletin Close (19) 82 parts of object.(19) 80 parts of compound obtained, 55 parts of tetrachlorophthalic tetrachlorophthalic anhydrid, 50 parts of benzoic acid are made an addition into benzene In 400 parts of methyl formate, heating stirring 5 hours at 160 DEG C.After being cooled to room temperature, reaction mixture is put into acetone In 4000 parts, it is stirred at room temperature 1 hour.Separation is filtered to product, is cleaned and is dried using methanol, thus Obtain 115 parts of quinophthalone compound (A2-7).Quality analysis is carried out using TOF-MS, is as a result accredited as quinophthalone compound (A2-7)。
[changing 69]
Compound (19)
[changing 70]
Quinophthalone compound (A2-7)
(synthesis of quinophthalone compound (A2-13))
(12) 40 parts, 22 parts of N- bromo-succinimide of compound are made an addition in 300 parts of n,N-Dimethylformamide, It is stirred 4 hours at 80 DEG C.Reaction solution is injected into the mixed solvent of 700 parts agitated of 300 parts/water of methanol, at room temperature Stirring 1 hour.To precipitate generated to filter, wash, methanol cleaning, washing sequence handle, and be dried And obtain 48 parts of intermediate (a2-13).By 45 parts of intermediate obtained (a2-13), 37 parts of tetrachlorophthalic tetrachlorophthalic anhydrid, benzene first 35 parts of acid makes an addition in 100 parts of methyl benzoate, heating stirring 4 hours at 160 DEG C.After being cooled to room temperature, reaction is mixed Object is put into 1000 parts of acetone, is stirred at room temperature 1 hour.Separation is filtered to product, is cleaned simultaneously using methanol It is dried, to obtain 65 parts of quinophthalone compound (A2-13).Quality analysis is carried out using TOF-MS, is as a result accredited as Quinophthalone compound (A2-13).
[changing 71]
Compound (12)
[changing 72]
Quinophthalone compound (A2-13)
(manufactures of yellow colorants (Y-1))
100 parts of quinophthalone compound (A1-1), 1200 parts of sodium chloride and 120 parts of diethylene glycol are packed into stainless steel 1 In gallon kneader (manufacture of Jing Shang manufacturing company), it is kneaded 8 hours at 60 DEG C.Then, the mixture is put into temperature In water, 1 hour being stirred while being heated to about 70 DEG C and pulp-like is made, repeated filtration is washed to remove sodium chloride and two After ethylene glycol, a drying for one day night at 80 DEG C, to obtain 97 parts of yellow colorants (Y-1).
(manufactures of yellow colorants (Y-2~Y-21))
Hereinafter, as shown in table 9, change composition, blending amount obtain yellow in the same manner as yellow colorants (Y-1) in addition to this Chromatic colorant agent (Y-2~Y-21).
(manufactures of yellow colorants (Y-22))
(11) 100 parts of compound, 1200 parts of sodium chloride and 120 parts of diethylene glycol are packed into 1 gallon of stainless steel and are mediated In machine (manufacture of Jing Shang manufacturing company), it is kneaded 8 hours at 60 DEG C.Then, the mixture is put into warm water, on one side 70 DEG C are heated to about to stir 1 hour on one side and pulp-like is made, repeated filtration is washed come after removing sodium chloride and diethylene glycol, A drying for one day night at 80 DEG C, to obtain 95 parts of yellow colorants (Y-22).
[changing 73]
Compound (11)
[table 9]
The manufacturing method > of < colored filter coloured composition
[embodiment 1-1B]
(manufacture of coloured composition (YP-1))
To become to use the zirconium oxide bead of diameter 0.5mm after following mixtures formed are stirred by uniform mode Grain simultaneously utilizes Chinese mugwort lattice grinding machine (eiger mill) (" mini (mini of Chinese mugwort lattice (Eiger Japan) company, Japan manufacture Model) M-250 MKII ") after dispersion 5 hours, it is filtered using 5.0 μm of the filter in aperture and makes coloured composition (YP-1)。
[embodiment 1-2B~embodiment 1-33B, comparative example 1-1B~comparative example 1-4B]
(manufacture of coloured composition (YP-2~YP-37))
Total content of colorant and pigment derivative is fixed as 11.0 parts, and coloring is changed as recorded in table 10 The type and quality ratio of agent and pigment derivative obtain coloured composition (YP-2~YP-37) in the same manner as embodiment 1-1B.
[table 10]
The evaluation > of < yellow coloring composition
About the evaluation of yellow coloring composition, film is made using yellow coloring composition, and to its lightness, film thickness And contrast ratio is measured, and is thus evaluated.In addition, also evaluating heat resistance.Evaluation method described below.
(lightness evaluation)
Yellow coloring composition is coated on the glass substrate of 100mm × 100mm, 1.1mm thickness using spin coater, It is heated 20 minutes at 230 DEG C, thus to obtain film.At this point, the film thickness about film, after 230 DEG C of heat treatment, with C light Mode under source as x=0.440 changes application conditions (revolving speed of spin coater, time) in due course to be coated.It uses Microspectrophotometer " OSP-SP100 " of manufacture (Olympus (Olympus) Optical Co., Ltd) measures film obtained Lightness (Y), and determine according to following benchmark.
◎: 90.0 or more (very good)
Zero: 89.0 or more~less than 90.0 (good)
△: 87.5 or more~less than 89.0 (implementable)
×: less than 87.5 (bad)
(tinting strength, tinting power evaluation)
Using film identical with lightness estimator is carried out, film thickness when to the coloration for showing x=0.440 is measured, And determine according to following benchmark.The film thickness for providing the coloration of x=0.440 is smaller, indicates that tinting strength, tinting power is bigger, can be described as excellent.
Zero: less than 1.0 [μm] (good)
△: 1.0 or more~less than 1.5 [μm] (implementable)
×: 1.5 or more [μm] (bad)
(contrast is than evaluation)
Come from the light of liquid crystal display back light unit by polarizer by polarisation, thus by being coated on glass substrate On coloured composition film, reach another polarizer.At this point, light is saturating if polarizer is parallel with the plane of polarisation of polarizer Polarizer is crossed, but in the case where plane of polarisation is orthogonal, light is interdicted by polarizer.But pass through by the light of polarizer polarisation When the film of color composition, if generating scattering etc. because of colorant particle, and offset is generated in a part of plane of polarisation, then inclined When tabula rasa is parallel, the light quantity of transmission is reduced, and when polarizer is orthogonal, a part of light is penetrated.The light that penetrates is measured as polarisation Brightness on plate, calculate polarizer it is parallel when brightness with it is orthogonal when brightness ratio as contrast ratio.
(contrast ratio)=(brightness when parallel)/(brightness when orthogonal)
Therefore, if generating scattering because of the colorant in film, brightness when parallel is reduced, and it is orthogonal when brightness increase Add, therefore contrast ratio is lower.
Furthermore as luminance meter, using color luminance meter (" BM-5A " that opens up the manufacture of Pu Kang (Topcon) company), as Polarizer uses polarizer (" NPF-G1220DUN " of the manufacture of Dong electrician company).When measurement, it is interposed between determination part and is separated by The black mask in the hole of 1cm square is measured.Using film identical with lightness estimator is carried out, and according to following benchmark To determine.
◎: 3000 or more (very good)
Zero: 2500 or more~less than 3000 (good)
△: 2000 or more~less than 2500 (implementable)
×: less than 2000 (bad)
(evaluation of heat resistance)
Using spin coater, to become the condition of x=0.440 under illuminant-C for coloured composition (YP-1~YP-37) It is coated on the glass substrate of 100mm × 100mm, 1.1mm thickness, it is then, 20 minutes dry at 70 DEG C, then at 230 DEG C It heats 60 minutes and carries out placement cooling, thus production applies ilm substrate.As heat-resistance test, heated 60 minutes at 250 DEG C. Thereafter, it is observed and confirming has nodeless mesh precipitation using optical microscopy to ilm substrate is applied.The evaluation of heat resistance is with following Three stages were evaluated.
Zero ... heat at 230 DEG C processing is reheated after sixty minutes and at 250 DEG C 60 minutes also nodeless mesh be precipitated
Heat nodeless mesh precipitation after sixty minutes at 230 DEG C though △ ..., 60 points of processing is reheated at 250 DEG C Clock has crystallization to be precipitated
× ... heating at 230 DEG C after sixty minutes has crystallization to be precipitated
[table 11]
It is defined according to table 11, and is used as the reality of colorant with quinophthalone compound (A1) and quinophthalone compound (A2) The lightness of a 1-1B~embodiment 1-33B yellow coloring composition, contrast are applied than excellent and show high tinting strength, tinting power.It is another Aspect, using be used alone quinophthalone compound (A1) yellow colorants comparative example 1-1B yellow coloring composition with and Quinophthalone compound (A2) compared when being used in mixed way and be lightness, tinting strength, tinting power, contrast than difference result.
In addition, clearly: the comparative example 1-2B of the yellow colorants of utilization exclusive use quinophthalone compound (A2)~compare The yellow coloring composition of example 1-4B is that lightness, contrast ratio, tinting strength, tinting power are poor, and heat resistance is also undesirable as a result, to can not Obtain simultaneously meet lightness, tinting strength, tinting power, contrast when heat resistance whole results.
The production > of < green coloring composition
(green coloring composition (GP-1): colorant (P-1))
By 11.0 parts of colorant (P-1), 31.2 parts of adhesive resin (F-5), 1 6.9 parts of resin type dispersant solution, third After 50.9 parts of glycol monomethylether acetate are equably stirred, ground using the zirconium oxide bead of diameter 0.5mm and using Chinese mugwort lattice Machine (eiger mill) (" mini (mini model) M-250MKII " of the manufacture of Chinese mugwort lattice (Eiger Japan) company, Japan) After dispersion 3 hours, the green coloring composition of colorant (P-1) is filtered and made using 5.0 μm of the filter in aperture (GP-1)。
(green coloring composition (GP-2): colorant (P-2))
Colorant (P-1) is changed to colorant (P-2), in addition to this, using with green coloring composition (GP-1) phase With facture make the green coloring composition (GP-2) of colorant (P-2).
(green coloring composition (GP-3): colorant (P-3))
Colorant (P-1) is changed to colorant (P-3), in addition to this, using with green coloring composition (GP-1) phase With facture make the green coloring composition (GP-3) of colorant (P-3).
(green coloring composition (GP-4): colorant (P-4))
Colorant (P-1) is changed to colorant (P-4), in addition to this, using with green coloring composition (GP-1) phase With facture make the green coloring composition (GP-4) of colorant (P-4).
(green coloring composition (GP-5): PG58)
By colorant (P-1) be changed to C.I. naphthol green 58 (DIC (DIC) company manufacture " Fa Sigen is green (FASTGEN GREEN) A110 "), in addition to this, made using facture identical with green coloring composition (GP-1) The green coloring composition (GP-5) of PG58.
The production > of < red colored composition
(red colored composition (RP-1): PR254)
By colorant (P-1) be changed to C.I. paratonere 254 (BASF (BASF) company manufacture " Yi Lufoer is red (IRGAPHOR RED) B-CF "), in addition to this, made using facture identical with green coloring composition (GP-1) The red colored composition (RP-1) of PR254.
(red colored composition (RP-2): PR177)
Colorant (P-1) is changed to C.I. paratonere 177 " A2B " of manufacture (BASF (BASF) company), except this with Outside, the red colored composition (RP-2) of PR177 is made using facture identical with green coloring composition (GP-1).
(red colored composition (RP-3): colorant (P-5))
Colorant (P-1) is changed to colorant (P-5), in addition to this, using with green coloring composition (GP-1) phase With facture make the red colored composition (RP-3) of colorant (P-5).
(red colored composition (RP-4): PR269)
Colorant (P-1) is changed to commercially available C.I. paratonere 269, in addition to this, utilization and green coloring composition (GP-1) identical facture makes the red colored composition (RP-4) of PR269.
The production > (yellow coloring composition (YP-38): PY185) of < yellow coloring composition
Colorant (P-1) is changed to (" the Pa Liao root Huang of BASF (BASF) company manufacture of C.I. pigment yellow 185 (Paliogen Yellow) D1155 "), in addition to this, made using facture identical with green coloring composition (GP-1) Make the yellow coloring composition (YP-38) of PY185.
(yellow coloring composition (YP-39): PY139)
Colorant (P-1) is changed to (" the Yi Lufoer Huang of BASF (BASF) company manufacture of C.I. pigment yellow 13 9 (IRGAPHOR Yellow) 2R-CF "), in addition to this, made using facture identical with green coloring composition (GP-1) Make the yellow coloring composition (YP-39) of PY139.
The production > of < photosensitive coloring composition
[embodiment 2-1B]
(production of photosensitive coloring composition (GR-1))
To become to utilize the filter in 1 μm of aperture to carry out after following mixtures formed are stirred by uniform mode It filters and makes photosensitive coloring composition (GR-1).
18.4 parts of yellow coloring composition (YP-1)
26.6 parts of green coloring composition (GP-1)
4.5 parts of solution of adhesive resin (F-6)
2.6 parts of optical polymerism list amount body (" Aronix (Aronix) M402 " of the manufacture of East Asia Synesis Company)
2.0 parts of optical polymerism list amount body (" Aronix (Aronix) M350 " of the manufacture of East Asia Synesis Company)
1.2 parts of Photoepolymerizationinitiater initiater (" gorgeous good solid (IRGACURE) OXE02 " of the manufacture of BASF (BASF) company)
0.2 part of sensitizer (" EAB-F " of the manufacture of hodogaya chemical industrial group)
45.4 parts of propylene glycol methyl ether acetate
[embodiment 2-2B~embodiment 2-47B, comparative example 2-1B~comparative example 2-7B]
(production of photosensitive coloring composition (GR-2~GR-54))
Using yellow coloring composition and green coloring composition shown in table 12, and to meet when evaluating film in C Mode under light source for the coloration of x=0.240, y=0.660 changes the ratio of yellow coloring composition and green coloring composition (changing ratio in such a way that the total amount of coloured composition becomes 45 parts), in addition to this, with photosensitive coloring composition (GR-1) Similarly make photosensitive coloring composition (GR-2~GR-54).
The film of < photosensitive coloring composition evaluates >
Using following methods come to the film for using photosensitive coloring composition obtained (GR-1~GR-54) and making Lightness, tinting strength, tinting power, contrast ratio (CR), heat resistance and electrical characteristics evaluated.
(lightness evaluation)
Using spin coater, photosensitive coloring composition is coated on to the glass substrate of 100mm × 100mm, 1.1mm thickness On, it is then, 20 minutes dry at 70 DEG C, using extra-high-pressure mercury vapour lamp, with 300mJ/cm2Ultraviolet exposure is carried out, and is utilized 23 DEG C of alkaline-based developer develops.As alkaline-based developer, using including 1.5 mass % of sodium carbonate, 0.5 matter of sodium bicarbonate Measure %, anionic surfactant (KAO. Corp. SA manufactures " sending Simon Rex (Pelex) NBL ") 90 matter of 8.0 mass % and water Measure % person.In turn, it is heated 30 minutes at 230 DEG C, thus to obtain film.Use microspectrophotometer (Olympus (Olympus) " OSP-SP100 " of Optical Co., Ltd's manufacture) lightness (Y) of film obtained is measured, and according to following benchmark To determine.Furthermore made film is set as after 230 DEG C of heat treatment, become x (C)=0.240, y (C)=0.660.
◎: 44.0 or more (very good)
Zero: 43.0 or more, less than 44.0 (good)
△: 42.0 or more, less than 43.0 (implementable)
×: less than 42.0 (bad)
(evaluation of tinting strength, tinting power)
Using film identical with lightness estimator is carried out, film thickness when to the coloration for showing y (C)=0.660 is surveyed It is fixed, and determine according to following four stages benchmark.The film thickness for providing the coloration of x (C)=0.240, y (C)=0.660 is smaller, table Show that tinting strength, tinting power is bigger, can be described as excellent.
◎: less than 2.7 μm of film thickness (very good)
Zero: 2.7 μm of film thickness or more, less than 3.0 μm (good)
△: 3.0 μm of film thickness or more, less than 3.3 μm (implementable)
×: 3.3 μm of film thickness or more (bad)
(evaluation of contrast)
Using lightness evaluate used in substrate implement contrast measurement.The evaluation of contrast is with following quadravalence sections It is evaluated.
◎: 6000 or more (very good)
Zero: 5000 or more, less than 6000 (good)
△: 4000 or more, less than 5000 (implementable)
×: less than 4000 (bad)
(evaluation of heat resistance)
To film used in lightness evaluation, additional heating is used as heat-resistance test in 60 minutes at 250 DEG C.Thereafter, sharp It is observed and confirming has nodeless mesh precipitation with optical microscopy to ilm substrate is applied.The evaluation of heat resistance be with following three stages into Row evaluation.
It is reheated after zero ... heats 30 minutes at 230 DEG C and at 250 DEG C and handles also nodeless mesh precipitation in 60 minutes
Nodeless mesh is precipitated after heating 30 minutes at 230 DEG C though △ ..., and 60 points of processing is reheated at 250 DEG C Clock has crystallization to be precipitated
× ... there is crystallization to be precipitated after heating 30 minutes at 230 DEG C
(evaluations of electrical characteristics)
Using spin coater, photosensitive coloring composition (GR-1~GR-54) is applied in such a way that film thickness becomes 2.5 μm It is distributed on the glass substrate of 100mm × 100mm, 1.1mm thickness, it is then, 20 minutes dry at 70 DEG C, use super-pressure mercury Lamp, to add up light quantity 200mJ/cm2Ultraviolet exposure is carried out, and is developed using 23 DEG C of alkaline-based developer, to obtain Apply ilm substrate.It is cut from painting ilm substrate obtained and takes film 0.05g, film is impregnated in liquid crystal 2.0g (Merck (Merck) (stock) Manufacture, MJ971189), it is etched 60 minutes using 90 DEG C of cleaning ovens, after 5000rpm progress centrifuge separation in 20 minutes, is taken Thus supernatant makes and cooks liquid for the pollution sources of liquid crystal.After pollution sources cook, takes out liquid crystal and enclose to having In the glass unit of ITO electrode, kept using liquid crystal evaluation of physical property machine (the 6254 of the manufacture of Dongyang technology company) to measure voltage Rate (applying conservation rate after 16.7 milliseconds under voltage 5V) (%), and evaluated with following benchmark.× it is unworkable water It is quasi-.
Zero: 95% or more (good)
△: 90% or more, less than 95% (usable)
×: less than 90% (being difficult with)
By photosensitive coloring composition made in Examples and Comparative Examples evaluation result is shown in table in 12.
[table 12]
As shown in table 12, about and be used as feature of the invention quinophthalone system pigment (A1) and quinophthalone system pigment (A2) as embodiment 2-1B~embodiment 2-47B of yellow coloring composition, lightness, tinting strength, tinting power, contrast, heat resistance and Equal nothing × evaluation in any project of electrical characteristics and be particularly good result.
On the other hand, be used alone quinophthalone system pigment (A1) as yellow coloring composition comparative example 2-1B, compare Example 2-6B, comparative example 2-7B are the result that lightness and tinting strength, tinting power are worse than the embodiment of the present invention.Quinophthalone system pigment is used alone It (A2) is the result of lightness, heat resistance and electrical characteristics difference as comparative example 2-2B~comparative example 2-4B of yellow coloring composition. In addition, the PY185 of comparative example 2-5B is the result that contrast is substantially worse than the embodiment of the present invention.
Red sensitive coloured composition
[embodiment 3-1B~embodiment 3-20B, comparative example 3-1B~comparative example 3-5B]
(production of photosensitive coloring composition (RR-1~RR-25))
Using yellow coloring composition and red colored composition shown in table 13, and to meet when evaluating film in C Mode under light source for the coloration of x=0.640, y=0.330 changes the ratio of yellow coloring composition and red colored composition (changing ratio in such a way that the total amount of coloured composition becomes 45 parts), in addition to this, with photosensitive coloring composition (GR-1) Similarly make photosensitive coloring composition (RR-1~RR-25).
The film of < photosensitive coloring composition evaluates >
To use photosensitive coloring composition obtained (RR-1~RR-25) and the lightness of the film that makes, tinting strength, tinting power, Contrast ratio (CR), heat resistance and electrical characteristics are evaluated.The evaluation of lightness and tinting strength, tinting power is carried out using following methods.It is resistance to The evaluation of hot, contrast when electrical characteristics be using method identical with photosensitive coloring composition (GR-1~GR-54) come Implement.
(lightness evaluation)
It is same as photosensitive coloring composition (GR-1~GR-54) for photosensitive coloring composition (RR-1~RR-25) Ground makes on the glass substrate of 100mm × 100mm, 1.1mm thickness applies ilm substrate.
It is measured using microspectrophotometer (" OSP-SP100 " of the manufacture of Olympus (Olympus) Optical Co., Ltd) The lightness (Y) of film obtained, and determine according to following benchmark.Furthermore made film is set as at 230 DEG C of heat After reason, become x=0.640, y=0.330.
◎: 21.0 or more (very good)
Zero: 20.5 or more, less than 21.0 (good)
△: 20.0 or more, less than 20.5 (implementable)
×: less than 20.0 (bad)
(evaluation of tinting strength, tinting power)
Using film identical with lightness estimator is carried out, film thickness when to the coloration for showing x=0.640 is measured, Determine according to following four stages benchmark.The film thickness for providing the coloration of x=0.640, y=0.330 is smaller, indicates that tinting strength, tinting power is got over Greatly, it can be described as excellent.
◎: less than 2.2 μm of film thickness
Zero: 2.2 μm of film thickness or more, 2.5 μm less than
△: 2.5 μm of film thickness or more, 2.8 μm less than
×: 2.8 μm of film thickness or more
[table 13]
As shown in table 13, about and be used as feature of the invention quinophthalone system pigment (A1) and quinophthalone system pigment (A2) as embodiment 3-1B~embodiment 3-20B of yellow coloring composition, lightness, tinting strength, tinting power, contrast, heat resistance and Equal nothing × evaluation in any project of electrical characteristics and be particularly good result.
On the other hand, be used alone quinophthalone system pigment (A1) as yellow coloring composition comparative example 3-1B, compare In example 3-4B, poor contrast is in the embodiment of the present invention, and lightness and tinting strength, tinting power also and are unsatisfactory for.In addition, comparative example 3-3B, ratio PY139 compared with example 3-5B is the result that contrast is substantially worse than the embodiment of the present invention.
The production > of < colored filter
Firstly, blue-sensitive coloured composition used in production to colored filter makes.
(preparation of blue-sensitive coloured composition (BR-1))
After following mixtures being stirred in a manner of becoming uniform, use the zirconium oxide bead and benefit of diameter 0.5mm With Chinese mugwort lattice grinding machine (eiger mill) (" mini (mini model) M- that Chinese mugwort lattice (Eiger Japan) company, Japan manufactures 250MKII ") after dispersion 5 hours, it is filtered using 5.0 μm of the filter in aperture and makes blue colored composition (BP-1).
Blue pigment (C.I. pigment blue 15: 6) 7.2 parts
4.8 parts of violet pigment (C.I. pigment Violet 23)
1.0 parts of resin type dispersing agent (" Ai Fuka (EFKA) 4300 " of Japanese BASF (BASF Japan) company manufacture)
35.0 parts of solution of adhesive resin (F-5)
52.0 parts of propylene glycol methyl ether acetate
Then, to become to utilize 1 μm of the filter in aperture after following mixtures formed are stirred by uniform mode It is filtered and makes blue-sensitive coloured composition (BR-1).
34.0 parts of blue colored composition (BP-1)
15.2 parts of solution of adhesive resin (F-6)
3.3 parts of optical polymerism list amount body (" Aronix (Aronix) M400 " of the manufacture of East Asia Synesis Company)
Photoepolymerizationinitiater initiater (" gorgeous good solid (IRGACURE) 907 " of Japanese BASF (BASF Japan) company manufacture)
2.0 part
0.4 part of sensitizer (" EAB-F " of the manufacture of hodogaya chemical company)
45.1 parts of propylene glycol methyl ether acetate
(production of colored filter)
Pattern processes black matrix" on the glass substrate, and is coloured red sensitive of the invention using spin coater Composition (RR-13) is with the film thickness as x=0.640, y=0.330 is coated on the substrate and forms coloring envelope.For The envelope is situated between every photomask and irradiates 200mJ/cm using extra-high-pressure mercury vapour lamp2Ultraviolet light.Then, using including 0.2 matter The alkaline-based developer for measuring the aqueous sodium carbonate of % carries out spray development after removing unexposed portion, utilizes ion exchange water It is cleaned, the substrate is heated 30 minutes at 230 DEG C, form red filter section.In addition, being made using identical method It is applied in a manner of the coloration for meeting x=0.240, y=0.660 with green photosensitive coloured composition (GR-2) of the invention Cloth and form green filter section, become the film of x=0.150, y=0.060 using blue-sensitive coloured composition (BR-1) Thickness is coated and forms blue filter section, to obtain colored filter.
By using red sensitive coloured composition (RR-13) of the invention and green photosensitive coloured composition (GR- 2) tinting strength, tinting power, lightness and contrast, can be reached with high level, in turn, in terms of other physical property also no problem and can be suitable for using.

Claims (9)

1. a kind of colored filter coloured composition, containing colorant, resin and solvent, and the colored filter is used Color composition is characterized in that:
The colorant includes quinophthalone compound (A1) represented by the following general formula (1),
The resin includes acrylic block copolymer as alkaline dispersing agent (C)；
General formula (1)
In general formula (1), X1、X2、Y1Separately indicate halogen atom；N, m indicate 0~6 integer, p indicate 0~5 it is whole Number；It (n+m) is 1 or more.
2. colored filter coloured composition according to claim 1, it is characterised in that: the acrylic block is total Polymers have comprising selected from by the repetitive unit represented by the following general formula (5), repetitive unit represented by the following general formula (6) and under State the block of the repetitive unit of one or more of group composed by repetitive unit represented by general formula (7)；
General formula (5)
In general formula (5), R1~R3It indicates hydrogen atom independently of each other or can have the chain or cricoid alkyl of substituent group, R1~R3In two or more can be bonded each other and form cyclic structure；R4Indicate that hydrogen atom or methyl, X indicate bivalence linking base, Y-Indicate counter anion,
General formula (6)
In general formula (6), R5And R6It indicates hydrogen atom independently of each other or can have the chain or cricoid alkyl of substituent group, R5And R6It can be bonded each other and form cyclic structure；R4Indicate that hydrogen atom or methyl, X indicate bivalence linking base,
General formula (7)
In general formula (7), R7Indicate the aralkyl of hydrogen atom, the alkyl of carbon number 1~18, the aryl of carbon number 6~20, carbon number 7~12 Base, acyl group, oxygen radical or OR12, R12Indicate hydrogen atom, the alkyl of carbon number 1~18, the aryl of carbon number 6~20, carbon number 7~12 Aralkyl or acyl group, R8、R9、R10、R11Separately indicate methyl, ethyl or phenyl；R4Indicate hydrogen atom or methyl, X Indicate bivalence linking base.
3. a kind of colored filter coloured composition, containing colorant, resin and solvent, and the colored filter is used Color composition is characterized in that:
The colorant includes quinophthalone compound (A1) represented by the following general formula (1) and is selected from by the following general formula (2), general formula (3) and the quinophthalone compound (A2) of one or more of group composed by general formula (4)；
General formula (1)
In general formula (1), X1、X2、Y1Separately indicate halogen atom；N, m indicate 0~6 integer, p indicate 0~5 it is whole Number；It (n+m) is 1 or more,
General formula (2)
General formula (3)
General formula (4)
In general formula (2)~general formula (4), R18~R30、R31~R45、R46~R60Separately indicate hydrogen atom, halogen atom, can Alkyl with substituent group, the alkoxy that can have substituent group, the aryl that can have substituent group, the adjacent benzene two that can have substituent group Carboximide methyl or the sulfamoyl that can have substituent group.
4. colored filter coloured composition according to claim 3, it is characterised in that: the quinophthalone compound (A1) content be relative to the total of the quinophthalone compound (A1) and the quinophthalone compound (A2) 3 mass %~ 90 mass %.
5. colored filter coloured composition according to claim 1 or 3, it is characterised in that: also derivative containing pigment Object, the pigment derivative include the pigment derivative with acidic substituent.
6. colored filter coloured composition according to claim 5, it is characterised in that: the pigment derivative includes Quinophthalone compound (B) with sulfo group, the metal salt of sulfo group or alkylammonium salt.
7. colored filter coloured composition according to claim 1 or 3, it is characterised in that: the colorant includes Selected from by phthalocyanine color, isoindoline system pigment, diketopyrrolo-pyrrole system pigment, anthraquione pigmentss, azo pigment, be One or more of group composed by pigment, quinacridone pigment, oxa- anthracene dye and cyanine based dye.
8. colored filter coloured composition according to claim 1 or 3, it is characterised in that: also containing poly- selected from light One or more of conjunction property list amount body (E) and Photoepolymerizationinitiater initiater (F).
9. a kind of colored filter, it is characterised in that: have on substrate by colored filter as claimed in claim 1 or 3 Optical filtering section is formed by with coloured composition.
CN201811569918.2A 2017-12-22 2018-12-21 Colored filter coloured composition and colored filter Pending CN109960108A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012068559A (en) * 2010-09-27 2012-04-05 Toyo Ink Sc Holdings Co Ltd Coloring composition for color filter and color filter
CN102981364A (en) * 2011-09-05 2013-03-20 Jsr株式会社 Coloring composition used for color filter, color filter and display element

Family Cites Families (11)

* Cited by examiner, † Cited by third party
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JP4821316B2 (en) 2005-03-30 2011-11-24 東レ株式会社 Red colorant composition and color filter
JP2007133131A (en) 2005-11-10 2007-05-31 Toyo Ink Mfg Co Ltd Red colored composition for color filter, color filter and liquid crystal display device
JP5540649B2 (en) 2009-10-29 2014-07-02 東レ株式会社 Red coloring composition for color filter, color filter substrate for liquid crystal display device, and liquid crystal display device
TWI443458B (en) * 2010-04-21 2014-07-01 Toyo Ink Sc Holdings Co Ltd Red-coloring composition for color filter and color filter
WO2012102395A1 (en) * 2011-01-28 2012-08-02 東洋インキＳｃホールディングス株式会社 Colored composition for color filters, and color filter
JP4993026B1 (en) 2011-04-19 2012-08-08 東洋インキＳｃホールディングス株式会社 Colorant for color filter, coloring composition, and color filter
KR101550427B1 (en) * 2011-03-18 2015-09-04 토요잉크Sc홀딩스주식회사 Colored composition for color filters, and color filters
JP5982657B2 (en) * 2011-07-15 2016-08-31 東洋インキＳｃホールディングス株式会社 Coloring composition for color filter, and color filter
TWI494378B (en) * 2011-03-29 2015-08-01 Toyo Ink Sc Holdings Co Ltd Red coloring composition for color filter, and color filter
JP6458522B2 (en) 2015-02-06 2019-01-30 東洋インキＳｃホールディングス株式会社 Pigment, coloring composition for color filter, and color filter
JP2017058652A (en) * 2015-09-15 2017-03-23 東洋インキＳｃホールディングス株式会社 Colored composition for color filter and color filter

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012068559A (en) * 2010-09-27 2012-04-05 Toyo Ink Sc Holdings Co Ltd Coloring composition for color filter and color filter
CN102981364A (en) * 2011-09-05 2013-03-20 Jsr株式会社 Coloring composition used for color filter, color filter and display element

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