CN105324717A - Colored photosensitive resin composition, cured film, color filter, method for producing color filter, solid state imaging element, and image display device - Google Patents

Colored photosensitive resin composition, cured film, color filter, method for producing color filter, solid state imaging element, and image display device Download PDF

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Publication number
CN105324717A
CN105324717A CN201480031561.6A CN201480031561A CN105324717A CN 105324717 A CN105324717 A CN 105324717A CN 201480031561 A CN201480031561 A CN 201480031561A CN 105324717 A CN105324717 A CN 105324717A
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carbon number
group
general formula
represent
pigment
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CN105324717B (en
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稲部阳树
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Fujifilm Corp
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Fujifilm Corp
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/02—Monoazo dyes prepared by diazotising and coupling from diazotised o-amino-hydroxy compounds
    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/32—Monoazo dyes prepared by diazotising and coupling from coupling components containing a reactive methylene group
    • C09B29/33—Aceto- or benzoylacetylarylides
    • C09B29/335—Aceto- or benzoylacetylarylides free of acid groups
    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
    • C09B29/3647—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms
    • C09B29/3652—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms containing a 1,2-diazoles or hydrogenated 1,2-diazoles
    • 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
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
    • C09B47/061—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide having halogen atoms linked directly to the Pc skeleton
    • 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
    • C09B57/00—Other synthetic dyes of known constitution
    • 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
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/004—Diketopyrrolopyrrole dyes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Engineering & Computer Science (AREA)
  • Materials For Photolithography (AREA)
  • Nonlinear Science (AREA)
  • Optical Filters (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)

Abstract

A colored photosensitive resin composition contains: (A) a pigment; (B) a basic dye derivative; (C-1) a phosphoric acid-based dispersing agent represented by general formula (II) or (C-2) a carboxylic acid-based dispersing agent resulting from reacting a polymer (POH) having a hydroxyl group at least at one terminus or a polymer (PNH2) having a primary amino group at least at one terminus, and a tricarboxylic acid anhydride or tetracarboxylic acid dianhydride; (D) a resin binder; (E) a photoinitiator; and (F) a polymerizable compound.

Description

The manufacture method of photosensitive composition, cured film, colored filter, colored filter, solid-state imager and image display device
Technical field
The present invention relates to one to be suitable for making liquid crystal display cells (liquid crystal display (LiquidCrystalDisplay, ) or solid-state imager (charge coupled cell (Charge-coupledDevice LCD), CCD), CMOS (Complementary Metal Oxide Semiconductor) (ComplementaryMetal-Oxide-Semiconductor, the photosensitive composition of colored filter used CMOS) etc.) etc., there is the colored filter of the painted areas made by described composition, and possess the solid-state imager of described colored filter, Organic Light Emitting Diode (LightEmittingDiode, LED) liquid crystal indicator is used.
Background technology
In recent years, along with the development of personal computer (personalcomputer), particularly large picture LCD TV, there is the tendency that the needs of liquid crystal display (LCD), particularly colour liquid crystal display device increase.Due to the requirement of further higher image quality, also expect to have the universal of organic electro luminescent (Electroluminescence, EL) display.On the other hand, due to digital camera (digitalcamera), mobile phone universal with camera, the needs of the solid-state imagers such as ccd image sensor also constantly increase.
As the key element (keydevice) of these displays or optical element, use colored filter, the requirement of further higher image quality improves constantly with requirement cost being reduced to (costdown).This kind of colored filter possesses redness (R), green (G) and blue (B) trichromatic colored pattern usually, in display element or imaging apparatus, plays and passed through light is divided into trichromatic effect.
For the colorant used in colored filter, the following characteristic of common prescription.
That is, following characteristic is needed: there is preferred dichroism in color reprodubility; There is not the optical perturbations such as the unevenness of the optical concentration of the light scattering causing the contrast of liquid crystal display to reduce or the irregular colour color spot sense causing solid-state imager; Fastness under used environmental baseline, such as thermotolerance, photostability, moisture-proof etc. are good; Molar absorptivity is large and can realize filming etc.
Therefore, colorant typically uses pigment.
When forming colored filter used in liquid crystal display cells (LCD) or solid-state imager (CCD, CMOS etc.) and organic LED liquid crystal indicator, usually, after the step being coated with photosensitive composition on substrate, implementation is carried out the step of pattern exposure and is utilized alkaline-based developer to carry out the step of developing.Now, sometimes coating photosensitive composition step after, carry out exposure imaging step before during place several days.Usually (PostCoatingDelay, PCD) is postponed after the placement after this kind of coating being called coating.Its reason is: sometimes in colored filter manufacture process, stores the substrate being coated with photosensitive composition in advance, vacates exposure imaging device, when then carrying out follow-up exposure imaging step in the lump, can effectively process.
Due to background as above, require in the formation of colored pattern, also not cause problem after PCD to photosensitive composition.Specifically, the schematic diagram of Fig. 1 for observing the colored pattern 1 formed when carrying out the situation of exposure imaging immediately after be coated with photosensitive composition on substrate from surface.Herein, colored pattern is formed as rectangle.For photosensitive composition, require the formation also keeping this kind of rectangular patterns after PCD.
But the kind depending on photosensitive composition is different, and as shown in Figure 2, the colored pattern 1 sometimes after PCD collapses significantly.
Such as, disclose and have a kind of color compositions in patent documentation 1 and patent documentation 2, it contains the alkali compounds containing triazine ring of ad hoc structure and specific acrylic resin.
In addition, disclosing in patent documentation 3 has a kind of color compositions and containing its colored filter, described color compositions contain ad hoc structure containing the alkali compounds of triazine ring and the carboxylic serials spreading agent of ad hoc structure.In addition, disclose in patent documentation 4 and patent documentation 5 and have a kind of color compositions, its contain ad hoc structure containing the alkali compounds of triazine ring and the phosphoric acid system spreading agent of ad hoc structure.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open 2006-291194 publication
[patent documentation 2] Japanese Patent Laid-Open 2007-156395 publication
[patent documentation 3] Japanese Patent Laid-Open 2007-131832 publication
[patent documentation 4] Japanese Patent Laid-Open 2007-231106 publication
[patent documentation 5] Japanese Patent Laid-Open 2007-231107 publication
Summary of the invention
[invention institute for solution problem]
Record in patent documentation 1 and patent documentation 2, by the alkali compounds containing triazine ring and specific acrylic resin also with ad hoc structure, the coloured composition that dispersion stabilization etc. is excellent can be obtained, but the ageing stability of irregular colour (color spot) when making colored filter or color spot in have the leeway of improvement further.Can think that its reason is: for the photosensitive composition as recording in patent documentation 1 or patent documentation 2, dispersion resin is unstable to the absorption of pigment particles, make composition for a long time through time process in, the dispersion resin being adsorbed in pigment particles surface departs from from pigment particles surface.Therefore infer, make composition for a long time through time process in, pigment particles causes secondary aggregation and pigment particle size becomes thick, cause through time after colored filter color spot deterioration.
Recording in patent documentation 3, by using the alkaline pigment derivative of ad hoc structure and the carboxylic serials spreading agent of ad hoc structure, the color compositions of viscosity stability excellence can be obtained.But, when the color compositions recorded in patent documentation 3 is directly used in the situation of photosensitive composition, in the patternability after the irregular colour (color spot) still when making colored filter or the ageing stability of color spot and then PCD, there is the leeway of improvement further.Can think that its reason is: if the color compositions recorded in patent documentation 3 is used as photosensitive composition, then form the poor compatibility of each composition of described photosensitive composition, in placement (PCD) process after coating, the a part of composition forming film is separated, and is collapsed significantly by the colored pattern of exposure imaging gained thereafter.
In addition, disclose in patent documentation 4 and patent documentation 5, by use ad hoc structure containing the alkali compounds of triazine ring and the phosphoric acid system spreading agent of ad hoc structure, the color compositions that dispersion stabilization etc. is excellent can be obtained.But, when the color compositions recorded in patent documentation 4 and patent documentation 5 is directly used in the situation of photosensitive composition, in the patternability after the irregular colour (color spot) still when making colored filter or the ageing stability of color spot and then PCD, also has the leeway of improvement further.Can think that its reason is: if the color compositions recorded in patent documentation 4 and patent documentation 5 is used as photosensitive composition, then form the poor compatibility of each composition of described photosensitive composition, in placement (PCD) process after coating, the a part of composition forming film is separated, and is collapsed significantly by the colored pattern of exposure imaging gained thereafter.
The present invention solves described problem, and it relates to the photosensitive composition of the patternability excellence after the ageing stability of a kind of irregular colour (color spot) or color spot and then PCD, utilizes the manufacture method of the cured film of described photosensitive composition, colored filter, colored filter, solid-state imager and image display device.
[solving the means of problem]
The people such as the present inventor study in detail, and found that, by using alkaline pigment derivative and set spreading agent, can solve described problem.
Specifically, described problem is solved by following means < 1 >, preferably means < 2 > ~ means < 15 >.
< 1 > photosensitive composition, contain: (A) pigment, (B) alkaline pigment derivative, phosphoric acid system spreading agent represented by (C-1) following general formula (II) or (C-2) carboxylic serials spreading agent, (D) resin binder, (E) Photoepolymerizationinitiater initiater and (F) polymerizable compound, wherein said (C-2) carboxylic serials spreading agent makes to have the polymkeric substance (POH) of hydroxyl at least one end or have the polymkeric substance (PNH of one-level amino at least one end 2) to react with tricarboxylic acid anhydride or tetracarboxylic dianhydride and form,
[changing 1]
In general formula (II), R 3represent that number average molecular weight is the polyester construction of 400 ~ 30000, y represents the integer of 1 or 2; When y is 2, multiple R 3can identical also can be different.
The photosensitive composition of < 2 > described in < 1 >, wherein (A) pigment is for being selected from least one in the cohort that is made up of red pigment, viridine green and yellow uitramarine.
The photosensitive composition of < 3 > described in < 1 > or < 2 >, in its formula of (II), R 3the number average molecular weight of represented polyester construction is 1900 ~ 10000.
The photosensitive composition that < 4 > is described any one of < 1 > to < 3 >, in its formula of (II), R 3represented polyester construction is by the polyester construction of two or more different internal ester monomer ring-opening polymerization gained.
The photosensitive composition that < 5 > is described any one of < 1 > to < 4 >, wherein (C-2) carboxylic serials spreading agent has the polymkeric substance (POH) of hydroxyl at least one end or has the polymkeric substance (PNH of one-level amino at least one end 2) be represented by following general formula (II'),
[changing 2]
In general formula (II'), Y 1represent the monovalence terminal groups with carbon number 1 ~ 20, oxygen number 0 ~ 12 and nitrogen number 0 ~ 3, X 2represent-O-,-S-or-N (R b)-, R brepresent hydrogen atom or the straight-chain of carbon number 1 ~ 18 or the alkyl of branch-like; G 1expression-R 11repetitive represented by O-, G 2represent-C (=O) R 12repetitive represented by O-, G 3represent-C (=O) R 13c (=O)-OR 14repetitive represented by O-, R 11represent the cycloalkylidene of the straight-chain of carbon number 2 ~ 8 or the alkylidene of branch-like or carbon number 3 ~ 8, R 12represent the cycloalkylidene of the straight-chain of carbon number 1 ~ 8 or the alkylidene of branch-like or carbon number 4 ~ 8, R 13represent the arlydene of the straight-chain of carbon number 2 ~ 6 or the alkylidene of branch-like, the straight-chain of carbon number 2 ~ 6 or the alkenylene of branch-like, the cycloalkylidene of carbon number 3 ~ 20 or carbon number 6 ~ 20, R 14represent-CH (R 15)-CH (R 16)-, R 15and R 16any one be hydrogen atom, another represents that the alkyl of carbon number 1 ~ 20, the thiazolinyl of carbon number 2 ~ 20, the aryl of carbon number 6 ~ 20, the carbon number of moieties are the alkoxymethylene of 1 ~ 20, the carbon number of alkenyl part is the alkene oxygen methylene of 2 ~ 20, the carbon number of aryl moiety is 6 ~ 20 and the aryloxy group methylene that aryl moiety can replace through halogen atom or N-methylene-phthalimide-based; Z 1represent-OH or-NH 2, R 17represent straight-chain or the alkylidene of branch-like, the cycloalkylidene of carbon number 3 ~ 8 of carbon number 2 ~ 8 ,-C (=O) R 12-or-C (=O) R 13c (=O)-OR 14-; M1 represents the integer of 0 ~ 100, and m2 represents the integer of 0 ~ 60, and m3 represents the integer of 0 ~ 30; Wherein, m1+m2+m3 is more than 1, less than 100; Described repetitive G in general formula (II') 1~ G 3configuration do not limit its order, represent in the polymkeric substance represented by general formula (II'), in radicals X 2with radicals R 17between contain repetitive G with random order 1~ repetitive G 3, and then, these repetitives G 1~ repetitive G 3can be any one of random or block type respectively.
The photosensitive composition that < 6 > is described any one of < 1 > to < 4 >, wherein in (C-2) carboxylic serials spreading agent, at least one end, there is the polymkeric substance (POH) of hydroxyl or there is at least one end the polymkeric substance (PNH of one-level amino 2) be represented by following general formula (III),
[changing 3]
In general formula (III), Y 1represent the monovalence terminal groups of carbon number 1 ~ 20, oxygen number 0 ~ 12 and nitrogen number 0 ~ 3, X 2represent-O-,-S-or-N (R b)-, R brepresent hydrogen atom or the straight-chain of carbon number 1 ~ 18 or the alkyl of branch-like; Z 1represent-OH or-NH 2;
G 4and G 5represent-C (=O) R respectively 12repetitive represented by O-, R 12represent the cycloalkylidene of the straight-chain of carbon number 1 ~ 8 or the alkylidene of branch-like or carbon number 4 ~ 8; Wherein, G 4in R 12and G 5in R 12for mutually different group; R 20represent-C (=O) R 12-;
M4 represents the integer of 5 ~ 60, and m5 represents the integer of 5 ~ 60;
Described repetitive G in general formula (III) 4, repetitive G 5configuration do not limit its order, represent in the polymkeric substance represented by general formula (III), in radicals X 2with group Z 1between contain repetitive G with random order 4, repetitive G 5, and then, these repetitives G 4, repetitive G 5can be any one of random or block type respectively.
The photosensitive composition that < 7 > is described any one of < 1 > to < 6 >, the wherein resin of (D) resin binder for making the compound (x) represented by following general formula (IV) and other have compound (y) copolymerization of ethene unsaturated double-bond
[changing 4]
In general formula (IV), R 4represent hydrogen atom or methyl, R 5represent the alkylidene of carbon number 2 or 3, R 6represent that hydrogen atom maybe can contain the alkyl of the carbon number 1 ~ 20 of phenyl ring, n represents the integer of 1 ~ 15.When n is the situation of more than 2, multiple R 5can identical also can be different.
The photosensitive composition that < 8 > is described any one of < 1 > to < 7 >, also has the resin of polymerism double bond at side chain containing (G).
The photosensitive composition of < 9 > described in < 8 >, the resin that the resin that wherein (G) has polymerism double bond at side chain reacts for making compound (b) and multipolymer (a), described compound (b) having can with the functional group of hydroxyl reaction and ethene unsaturated double-bond, described multipolymer (a) is for having more than 2 and the polymerizable monomer (p) of hydroxyl of less than 6 and the multipolymer of other polymerizable monomers (q).
The photosensitive composition that < 10 > is described any one of < 1 > to < 9 >, it is the painted areas for the formation of colored filter.
< 11 > cured film, it is that photosensitive composition sclerosis described any one of < 1 > to < 9 > is formed.
The manufacture method of a < 12 > colored filter, comprises the following steps: photosensitive composition described any one of < 1 > to < 10 > is applied to step support being formed coloring photosensitive combination layer; Coloring photosensitive combination layer is exposed into the step of pattern-like; And the development of unexposed portion is removed and forms the step of colored pattern.
The manufacture method of a < 13 > colored filter, comprises the following steps:
Photosensitive composition described any one of < 1 > to < 10 > is applied on support and forms coloring photosensitive combination layer, make it harden and form the step of dyed layer;
Dyed layer is formed the step of photoresist oxidant layer;
By carrying out exposing and developing by photoresist pattern layers, obtain the step of Resist patterns; And
Resist patterns is carried out the step of dry-etching to dyed layer as etching mask.
< 14 > colored filter, it is for having the colored filter of the cured film described in < 11 >
< 15 > colored filter, it is with the colored filter manufactured by the manufacture method of the colored filter described in < 12 > or < 13 >.
< 16 > solid-state imager, has the colored filter described in < 14 > or < 15 >.
< 17 > image display device, has the colored filter described in < 14 > or < 15 >.
[effect of invention]
According to the present invention, the photosensitive composition of the patternability excellence after the ageing stability of a kind of irregular colour (color spot) or color spot and then PCD can be provided, utilize the manufacture method of the cured film of described photosensitive composition, colored filter, colored filter, solid-state imager and image display device.
Accompanying drawing explanation
The schematic diagram of Fig. 1 for observing the colored pattern formed when carrying out the situation of exposure imaging immediately after be coated with photosensitive composition on substrate from surface.
The schematic diagram of Fig. 2 for observing the colored pattern formed when being coated with photosensitive composition and carrying out the situation of exposure imaging on substrate after PCD from surface.
Embodiment
Below, content of the present invention is described in detail.In addition, in present specification, so-called " ~ " comprises numerical value described before and after it to use as the implication of lower limit and higher limit.In addition, so-called organic EL of the present invention, refers to organic electroluminescent device.
In this manual, so-called total solid composition, refers to the gross mass removing the composition of solvent gained in total composition of photosensitive composition.
In the statement of group (atomic group) in this manual, do not record the statement being substituted and being unsubstituted and comprise not there is substituent group, and comprise yet there is substituent group.Such as, so-called " alkyl ", not only comprises and does not have substituent alkyl (alkyl be unsubstituted), and comprises and have substituent alkyl (alkyl be substituted).
In addition, in this instructions so-called " radioactive ray ", such as, the far ultraviolet representated by the bright-line spectrum of mercury vapor lamp, excimer laser, extreme ultraviolet line (EUV light (ExtremeUltraviolet)), X ray, electron beam etc. are referred to.In addition, so-called light in the present invention, refers to actinic ray or radioactive ray.In this instructions so-called " exposure ", as long as no special instructions, then not only refer to the exposure of the far ultraviolet, X ray, EUV light etc. utilized representated by mercury vapor lamp, excimer laser, utilize drawing of the particle beams such as electron beam, ion beam to be also included within exposure.
In addition; in this instructions; " (methyl) acrylate " represent acrylate and methacrylate two kinds or any one; " (methyl) acrylic acid " represent acrylic acid and methacrylic acid two kinds or any one, " (methyl) acryloyl group " represent acryloyl group and methacryl two kinds or any one.
In addition, in this manual, " monomer " and " monomer (monomer) " are identical meanings.Monomer in this instructions refer to distinguish mutually with oligomer and polymkeric substance, weight average molecular weight be 2, less than 000 compound.In this manual, so-called polymerizable compound, refers to the compound with polymerizable functional groups, can be monomer and also can be polymkeric substance.So-called polymerizable functional groups, refers to the group participating in polyreaction.
Weight average molecular weight and number average molecular weight can utilize gel permeation chromatography (GelPermeationChromatography, GPC) to obtain.
In this manual, the Me in chemical formula represents methyl, and Et represents ethyl, and Pr represents propyl group, and Bu represents butyl, and Ph represents phenyl.
In this instructions, " step " word, not only refers to independently step, when the situation clearly cannot distinguished with other steps, as long as can reach the predictive role of described step, is then also included within described term.
The present invention is in view of described situation forms, and its object is to the coloured composition providing a kind of color characteristics excellence.
In this manual, weight average molecular weight and number average molecular weight define with the polystyrene conversion value being measured gained by GPC.In this instructions, weight average molecular weight (Mw) and number average molecular weight (Mn) are such as by obtaining with under type: use HLC-8220 (eastern Cao (stock) manufacture), (eastern Cao (stock) manufactures to use tsk gel super (TSKgelSuper) AWM-H, 6.0mmID × 15.0cm is as tubing string, use lithium bromide 1-METHYLPYRROLIDONE (N-methylpyrrolidinone, the NMP) solution of 10mmol/L as eluent.
< photosensitive composition >
The feature of photosensitive composition of the present invention (hereinafter sometimes referred to " composition of the present invention ", " coloured composition ") is to contain: (A) pigment, (B) alkaline pigment derivative, phosphoric acid system spreading agent represented by (C-1) following general formula (II) or (C-2) make to be had the polymkeric substance (POH) of hydroxyl at least one end or have the polymkeric substance (PNH of one-level amino at least one end 2) react with tricarboxylic acid anhydride or tetracarboxylic dianhydride carboxylic serials spreading agent (below sometimes referred to as " (C-2) carboxylic serials spreading agent "), (D) resin binder, (E) Photoepolymerizationinitiater initiater and (F) polymerizable compound.
[changing 5]
In general formula (II), R 3represent that number average molecular weight is the polyester construction of 400 ~ 30000, y represents the integer of 1 or 2; When y is 2, multiple R 3can identical also can be different.
[changing 6]
In general formula (II), R 3represent that number average molecular weight is the polyester construction of 400 ~ 30000, y represents the integer of 1 or 2.When y is 2, multiple R 3can identical also can be different.
The composition of the application of the invention, the patternability after the ageing stability of irregular colour (color spot) or color spot and then PCD becomes excellent.Though the reason that can obtain this kind of effect of the present invention is uncertain, reason can be presumed as follows.
Can infer, if by alkaline to (B) pigment derivative (particularly, pigment derivative represented by aftermentioned general formula (I)) use with the spreading agent of (C-1) or (C-2), then the spreading agent of (C-1) or (C-2) can obtain following effect: spreading agent is strongly adsorbed in pigment particles, suppress along with composition through time color spot deterioration.Can infer that its reason is in addition: (B) alkaline pigment derivative plays function as a kind of bulking agent (compatibilizer), suppress to form situation about being separated in each composition placement after coating (PCD) process of composition of the present invention.Can think, the patternability thus after the ageing stability of irregular colour of the present invention (color spot) or color spot and then PCD becomes excellent.
Below, composition of the present invention is described in detail.
< < (A) pigment > >
Composition of the present invention contains (A) pigment.The pigment used in the present invention is preferably selected from the cohort be made up of red pigment, viridine green and yellow uitramarine, known various inorganic pigment or organic pigment before can using.Described pigment is preferably high-transmission rate.
Inorganic pigment can enumerate the represented metallic compound such as metal oxide, metallic complex salt, specifically can enumerate: the black pigments such as carbon black, titanium are black, the metal oxide of iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony etc., and the composite oxides of described metal.
Organic pigment include, for example:
Color index (ColorIndex, C.I.) pigment yellow 11, C.I. pigment yellow 24, C.I. pigment yellow 31, C.I. pigment yellow 53, C.I. pigment yellow 83, C.I. pigment yellow 93, C.I. pigment yellow 99, C.I. pigment yellow 108, C.I. pigment yellow 109, C.I. pigment yellow 110, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 147, C.I. pigment yellow 150, C.I. pigment yellow 151, C.I. pigment yellow 154, C.I. pigment yellow 155, C.I. pigment yellow 167, C.I. pigment yellow 180, C.I. pigment yellow 185, C.I. pigment yellow 199;
C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 43, C.I. pigment orange 71;
C.I. pigment red 81, C.I. paratonere 105, C.I. pigment red 122, C.I. pigment red 149, C.I. paratonere 150, C.I. paratonere 155, C.I. paratonere 171, C.I. paratonere 175, C.I. paratonere 176, C.I. paratonere 177, C.I. paratonere 209, C.I. paratonere 220, C.I. paratonere 224, C.I. paratonere 242, C.I. paratonere 254, C.I. paratonere 255, C.I. paratonere 264, C.I. paratonere 270;
C.I. pigment violet 19, C.I. pigment Violet 23, C.I. pigment violet 32, C.I. pigment violet 39;
C.I. pigment blue 1, C.I. alizarol saphirol 2, C.I. pigment blue 15, C.I. pigment blue 15: 1, C.I. pigment blue 15: 3, C.I. pigment blue 15: 6, C.I. pigment blue 16, C.I. alizarol saphirol 22, C.I. pigment blue 60, C.I. alizarol saphirol 66;
C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 37, C.I. naphthol green 58;
C.I. pigment brown 25, C.I. pigment brown 28;
C.I. pigment black 1 etc.
The pigment that can preferably use in the present invention can be enumerated following.But the present invention is not limited to these pigment.
C.I. pigment yellow 11, C.I. pigment yellow 24, C.I. pigment yellow 108, C.I. pigment yellow 109, C.I. pigment yellow 110, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 151, C.I. pigment yellow 154, C.I. pigment yellow 167, C.I. pigment yellow 180, C.I. pigment yellow 185
C.I. pigment orange 36, C.I. pigment orange 71,
C.I. pigment red 122, C.I. paratonere 150, C.I. paratonere 171, C.I. paratonere 175, C.I. paratonere 177, C.I. paratonere 209, C.I. paratonere 224, C.I. paratonere 242, C.I. paratonere 254, C.I. paratonere 255, C.I. paratonere 264
C.I. pigment violet 19, C.I. pigment Violet 23, C.I. pigment violet 32,
C.I. pigment blue 15: 1, C.I. pigment blue 15: 3, C.I. pigment blue 15: 6, C.I. pigment blue 16, C.I. alizarol saphirol 22, C.I. pigment blue 60, C.I. alizarol saphirol 66,
C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 37, C.I. naphthol green 58,
C.I. pigment black 1.
These organic pigments can be used alone or in order to adjust light splitting or improve colour purity and being used by multiple combination.The concrete example of described combination is below shown.Such as can use: a kind of separately as the anthraquione pigmentss, perylene pigment of red pigment, diketopyrrolopyrrolecocrystals series pigments, or at least one of these pigment and bisdiazo system yellow uitramarine, isoindoline system yellow uitramarine, the mixing of quinophthalone system yellow uitramarine Huo perylene system's red pigment.Such as anthraquione pigmentss can enumerate C.I. paratonere 177 perylene pigment can enumerate C.I. paratonere 155, C.I. paratonere 224, diketopyrrolopyrrolecocrystals series pigments can enumerate C.I. paratonere 254, with regard to the aspect of color decomposition, is preferably and the mixing of C.I. pigment yellow 13 9.In addition, the mass ratio of red pigment and yellow uitramarine is preferably 100:5 ~ 100:50.Described mass ratio is difficult to the light transmission suppressing 400nm ~ 500nm when being below 100:4, in addition, when described mass ratio is more than 100:51, predominant wavelength offsets to short wavelength, sometimes cannot improve color decomposition ability.The scope of what especially described mass ratio was the suitableeest is 100:10 ~ 100:30.In addition, when red pigment combination each other, may correspond to and adjust in required light splitting.
In addition, viridine green can be used alone halogenated phthalocyanines series pigments, or uses mixing of described halogenated phthalocyanines series pigments and bisdiazo system yellow uitramarine, quinophthalone system yellow uitramarine, azomethine system yellow uitramarine or isoindoline system yellow uitramarine.Such as, this kind of example is preferably C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 37, C.I. naphthol green 58 mix with C.I. pigment yellow 83, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 180 or C.I. pigment yellow 185.The mass ratio of viridine green and yellow uitramarine is preferably 100:5 ~ 100:150.Described mass ratio is especially preferably the scope of 100:30 ~ 100:120.
Blue pigment can be used alone phthualocyanine pigment, or uses mixing of described phthualocyanine pigment Yu dioxazine system violet pigment.Such as be preferably C.I. pigment blue 15: 6 with the mixing of C.I. pigment Violet 23.The mass ratio of blue pigment and violet pigment is preferably 100:0 ~ 100:100, is more preferably below 100:10.
In addition, black pigment can be used alone or as a mixture that carbon, titanium are black, iron oxide, titanium dioxide.When the situation these mixing used, be preferably carbon and the black combination of titanium, the carbon of described situation and the black mass ratio of titanium are preferably the scope of 100:0 ~ 100:60.
In addition, pigment of the present invention also can use AZO pigments represented by following general formula (A2), its dynamic isomer, these salt or hydrate.
General formula (A2)
[changing 7]
In general formula (A2), G represents hydrogen atom, fatty group, aryl or heterocyclic radical, R 1expression can have substituent amino, aliphatics oxygen base, fatty group, aryl or heterocyclic radical, R 2represent substituting group.
A represents the heterocycle with at least more than one the atom be selected from nitrogen-atoms, oxygen atom and sulphur atom.
M represents the integer of 0 ~ 5, and n represents the integer of 1 ~ 4.
The situation of n=2 represents and is situated between every R 1, R 2, A or G dipolymer.
The situation of n=3 represents and is situated between every R 1, R 2, A or G trimer.
The situation of n=4 represents and is situated between every R 1, R 2, A or G tetramer.
General formula (A2) does not have ionic water wettability base.
In general formula (A2), A preferably represents any one of following general formula (A-1) ~ general formula (A-32).In general formula (A-1) ~ general formula (A-32), R 51~ R 59represent hydrogen atom, substituting group respectively, adjacent substituting group also can bond and form 5 ring ~ 6 rings mutually.* the binding site with the azo group of general formula (A2) is represented.
[changing 8]
AZO pigments has the ad hoc structure represented by general formula (A2), can demonstrate the characteristic of colouring power, look equal color excellent thus, and also demonstrate the characteristic of the excellent in te pins of durability such as photostability, ozone resistance.Such as, the red pattern of the colored filter using the coloured composition of the present invention containing the AZO pigments represented by general formula (A2) to be formed demonstrates as red and better dichroism.Herein, so-called " dichroism as red and good ", such as, refer at least one of following character.The dichroism all meeting following 3 character is excellent especially.
The transmissivity of the wavelength coverage of 650nm ~ 750nm is high.
In the wavelength coverage of more than 540nm, transmittance graph sharply rises (sharp).
The transmissivity being less than the wavelength coverage (particularly 350nm ~ 400nm) of 540nm is low.
So-called substituting group of the present invention, as long as carrying out the group replaced, include, for example: fatty group, aryl, heterocyclic radical, acyl group, acyloxy, acyl amino, aliphatics oxygen base, aryloxy group, heterocyclic oxy group, aliphatics oxygen base carbonyl, aryloxycarbonyl, heterocyclyloxycarbonyl, carbamyl, aliphaticsulfonyl, aryl sulfonyl, heterocyclicsulfonyl, aliphaticsulfonyl oxygen base, aryl sulfonyl oxygen base, heterocyclicsulfonyl oxygen base, sulfamoyl, aliphatics sulfoamido, aryl-sulfonyl amino, heterocyclic sulfonamide base, amino, aliphatic amines, arylamino, heterocyclic amino group, aliphatics oxygen base carbonylamino, aryloxycarbonylamino, heterocyclyloxycarbonyl is amino, aliphatic sulfonamido base, aryl sulfonyl kia, aliphatics sulfenyl, arylthio, hydroxyl, cyano group, sulfo group, carboxyl, aliphatics oxygen base is amino, aryloxyamino, carbamyl is amino, sulphamoylamino, halogen atom, sulfamoyl carbamyl, carbamyl sulfamoyl, two aliphatics oxygen base phosphinyls, two aryloxy group phosphinyls etc.Below, so-called " group described in substituent item ", refers to described substituting group.
Fatty group represented by G also can have substituting group, can be saturated also can be unsaturated.
The preferred substituents that fatty group represented by G can have is hydroxyl, aliphatics oxygen base, carbamyl, aliphatics oxygen base carbonyl, aliphatics sulfenyl, amino, aliphatic amines, acyl amino, carbamyl amino.
Fatty group represented by G is preferably the fatty group of total carbon atom number 1 ~ 8, is more preferably the alkyl of total carbon atom number 1 ~ 6, include, for example methyl, ethyl, cyclohexyl etc.
In general formula (A2); aryl represented by G also can contracting ring; also substituting group can be had; as long as commutable group is for carrying out the group that replaces described in substituent item mentioned above; then can be any group, preferred substituting group is nitro, halogen atom, aliphatics oxygen base, carbamyl, aliphatics oxygen base carbonyl, aliphatics sulfenyl, amino, aliphatic amines, acyl amino, carbamyl amino.Aryl represented by G is preferably the aryl of carbon number 6 ~ 12, is more preferably the aryl of total carbon atom number 6 ~ 10, include, for example phenyl, 4-nitrobenzophenone, 4-acetvlaminophenvl, 4-methanesulfonylphenYl etc.
In general formula (A2), the heterocyclic radical represented by G also can have substituting group, can be saturated also can be unsaturated, also can contracting ring.As long as commutable group is for carrying out the group that replaces described in substituent item mentioned above; then can be any group, preferred substituting group is halogen atom, hydroxyl, aliphatics oxygen base, carbamyl, aliphatics oxygen base carbonyl, aliphatics sulfenyl, amino, aliphatic amines, acyl amino, carbamyl amino.Heterocyclic radical represented by G be preferably total carbon atom number 2 ~ 12 with the heterocyclic radical of carbon atom bond, be more preferably with the heterocyclic radical of 5 yuan of the total carbon atom number 2 ~ 10 of carbon atom bond ~ 6 yuan, include, for example 2-tetrahydrofuran base, 2-pyrimidine radicals (2-pyrimidyl) etc.
G is preferably hydrogen atom.Its reason is easily to be formed intersection hydrogen bond in intramolecular hydrogen bond or molecule.
R 1represented amino also can have substituting group, as long as commutable group is for carrying out the group that replaces described in substituent item mentioned above, then can be any group, substituting group preferably can enumerate fatty group, aryl, heterocyclic radical etc.
These substituting groups still can have substituting group, described substituting group is preferably fatty group, hydroxyl, has the substituting group of amido link, ehter bond, oxygen base ketonic link, thioether bond etc., with regard to easily forming the viewpoint of intermolecular ydrogen bonding equimolecular interphase interaction, be more preferably the substituting group of the key with heteroatoms and hydrogen atom.
R 1the amino that represented amino is preferably unsubstituted, the alkyl amino of total carbon atom number 1 ~ 10, the dialkyl amido of total carbon atom number 2 ~ 10 (dialkyl group also can mutually bond and form 5 ring ~ 6 rings), the arylamino of total carbon atom number 6 ~ 12, can be of total carbon atom number 2 ~ 12 saturatedly also can be undersaturated heterocyclic amino group, be more preferably the amino be unsubstituted, the alkyl amino of total carbon atom number 1 ~ 8, the dialkyl amido of total carbon atom number 2 ~ 8, the arylamino of total carbon atom number 6 ~ 10, can be of total carbon atom number 2 ~ 12 saturatedly also can be undersaturated heterocyclic amino group, include, for example methylamino, N, N-dimethylamino, N-phenyl amino, N-(2-pyrimidine radicals) is amino.
And then be preferably can be of the arylamino of total carbon atom number 6 ~ 13 and total carbon atom number 2 ~ 12 and saturatedly also can be undersaturated heterocyclic amino group.
At R 1during situation for arylamino, the substituting group on aryl preferably has substituent situation relative to the binding site with amino in contraposition, most preferably is and only in contraposition, has substituent situation.As long as described substituting group for carrying out the group that replaces described in substituent item mentioned above, then can be any group, preferably can enumerate: total carbon atom number 1 ~ 7, be more preferably fatty group (the such as methyl of total carbon atom number 1 ~ 4, ethyl, allyl, (different) propyl group, (uncle) butyl etc.), aliphatics oxygen base (the such as methoxyl of total carbon atom number 1 ~ 7, ethoxy, (different) propoxyl group, allyloxy etc.), halogen atom (such as fluorine, chlorine, bromine etc.), carbamyl (the such as carbamyl of total carbon atom number 1 ~ 7, N-phenylcarbamoyl, N-methylcarbamoyl etc.), total carbon atom number 1 ~ 7, be more preferably uride base (the such as uride base of total carbon atom number 1 ~ 4, N-methyl uride base, N, N-dimethyl uride base, N-4-pyridine radicals uride base, N-phenyl uride base etc.), nitro, total carbon atom number 1 ~ 7 with the heterocyclic radical (such as imidazoles ketone group) of aryl contracting ring, hydroxyl, total carbon atom number 1 ~ 7, be more preferably aliphatics sulfenyl (the such as methyl mercapto of total carbon atom number 1 ~ 4, ethylmercapto group, (different) rosickyite base, allyl sulfenyl, (uncle) butylthio etc.), total carbon atom number 2 ~ 7, be more preferably acyl amino (such as acetyl ammonia (acetoamino) base of total carbon atom number 2 ~ 4, propanoylamino, pivaloyl group is amino, benzoyl-amido etc.), total carbon atom number 2 ~ 7, be more preferably aliphatics oxygen base carbonylamino (the such as methyloxycarbonylamino of total carbon atom number 2 ~ 4, propoxy carbonylamino etc.), total carbon atom number 2 ~ 7, be more preferably aliphatics oxygen base carbonyl (the such as methoxycarbonyl of total carbon atom number 2 ~ 4, ethoxy carbonyl etc.), total carbon atom number 2 ~ 7, the acyl group being more preferably total carbon atom number 2 ~ 4 (can be aliphatic Oxo, also can be aryl carbonyl, also can be heterocyclecarbonyl, also can have substituting group, as long as commutable group for carrying out the group that replaces described in substituent item mentioned above, then can be any group.Be preferably the acyl group of total carbon atom number 2 ~ 7, be more preferably the acyl group of total carbon atom number 2 ~ 4, include, for example acetyl group, propiono, benzoyl, 3-pyridine carbonyl etc.) etc.
Substituting group on the aryl of arylamino is replaced in the situation in contraposition during relative to the binding site with amino, because substituting group is positioned at the end of molecule, therefore easily form the interphase interaction of intermolecular ydrogen bonding equimolecular, therefore form and aspect smarten (sharp).When substituting group on aryl also has substituent situation, be preferably fatty group, hydroxyl, there is the substituting group of amido link, ehter bond, oxygen base ketonic link, thioether bond etc., with regard to easily forming the viewpoint of intermolecular ydrogen bonding equimolecular interphase interaction, be more preferably the substituting group of the key with heteroatoms and hydrogen atom.
At R 1during situation for heterocyclic amino group, as long as its substituting group is for carrying out the group that replaces described in substituent item mentioned above, then can be any group, preferably be advisable with the substituting group identical with the situation of described arylamino, when substituting group on heterocyclic radical also has substituent situation, be preferably fatty group, hydroxyl, there is the substituting group of amido link, ehter bond, oxygen base ketonic link, thioether bond etc., with regard to easily forming the viewpoint of intermolecular ydrogen bonding equimolecular interphase interaction, be more preferably the substituting group of the key with heteroatoms and hydrogen atom.
R 1more preferably substituting group for the situation of arylamino, heterocyclic amino group be fatty group, aliphatics oxygen base, halogen atom, carbamyl, with heterocyclic radical, the aliphatics oxygen base carbonyl of aryl contracting ring.Fatty group, the aliphatics oxygen base of total carbon atom number 1 ~ 4, halogen atom, nitro, the carbamyl of total carbon atom number 1 ~ 4, the aliphatics oxygen base carbonyl of total carbon atom number 2 ~ 4 of substituting group and then preferably total carbon atom number 1 ~ 4.
R 1represented aliphatics oxygen base also can have substituting group; as long as substituting group is for carrying out the group that replaces described in substituent item mentioned above; then can be any group, preferred substituting group is hydroxyl, aliphatics oxygen base, carbamyl, aliphatics oxygen base carbonyl, aliphatics sulfenyl, amino, aliphatic amines, acyl amino, carbamyl amino.R 1aliphatics oxygen base be preferably the alkoxy of total carbon atom number 1 ~ 8, be more preferably the alkoxy of total carbon atom number 1 ~ 4, include, for example methoxyl, ethoxy, (uncle) butoxy, methoxy ethoxy, carbamyl methoxyl etc.
R 1represented fatty group also can have substituting group; as long as substituting group is for carrying out the group that replaces described in substituent item mentioned above; then can be any group, preferred substituting group is hydroxyl, aliphatics oxygen base, carbamyl, aliphatics oxygen base carbonyl, aliphatics sulfenyl, amino, aliphatic amines, acyl amino, carbamyl amino.R 1fatty group be preferably the alkyl of total carbon atom number 1 ~ 8, be more preferably the alkyl of total carbon number 1 ~ 4.
R 1represented aryl also can have substituting group; as long as substituting group is for carrying out the group that replaces described in substituent item mentioned above; then can be any group, preferred substituting group be fatty group, aliphatics oxygen base, halogen atom, carbamyl, with heterocyclic radical, the aliphatics oxygen base carbonyl of aryl contracting ring.R 1aryl be preferably the aryl of total carbon atom number 6 ~ 12, be more preferably the aryl of total carbon atom number 6 ~ 10, include, for example phenyl, 4-aminomethyl phenyl, 3-chlorphenyl etc.
R 1represented heterocyclic radical can be saturated heterocyclyl; also can be unsaturated heterocycle base; also substituting group can be had; as long as substituting group is for carrying out the group that replaces described in substituent item mentioned above; then can be any group, preferred substituting group be fatty group, aliphatics oxygen base, carbamyl, with heterocyclic radical, the aliphatics oxygen base carbonyl of assorted base contracting ring.R 1heterocyclic radical be preferably the heterocyclic radical of total carbon atom number 2 ~ 10, be more preferably total carbon atom number 2 ~ 8 with the non aromatic heterocyclyl of 5 ring ~ 6 rings of nitrogen-atoms bond, include, for example 1-piperidyl, 4-morpholinyl, 1-quinolyl (1-quinoyl), 2-pyrimidine radicals, 4-pyridine radicals etc.
R 1be preferably amino, aliphatics oxygen base, with the situation of the non aromatic heterocyclyl of 5 ring ~ 6 rings of nitrogen-atoms bond, be more preferably amino, aliphatics oxygen base, and then be preferably amino.
R 1be preferably amino situation.
R 2as long as represented substituting group is for carrying out the group that replaces described in substituent item mentioned above; then can be any group; be preferably fatty group, aryl, heterocyclic radical, aliphatics oxygen base carbonyl, carboxyl, carbamyl, acyl amino, sulfoamido, carbamyl amino, sulfamoyl, aliphatics oxygen base, aliphatics sulfenyl, cyano group, halogen atom; be more preferably aliphatics oxygen base carbonyl, carbamyl, acyl amino, carbamyl amino, aliphatics oxygen base, halogen atom, be especially preferably aliphatics oxygen base.
When these substituting groups also have substituent situation, be preferably fatty group, hydroxyl, there is the substituting group of amido link, ehter bond, oxygen base ketonic link, thioether bond etc., with regard to easily forming the viewpoint of intermolecular ydrogen bonding equimolecular interphase interaction, be more preferably the substituting group of the key with heteroatoms and hydrogen atom.
M is preferably the situation of 0 ~ 3, is more preferably the situation of 0 ~ 1, and then is preferably the situation of 0.
N is preferably the situation of 1 or 2.
R 2represented fatty group also can have substituting group, can be saturatedly also to can be unsaturated, as long as commutable group is for carrying out the group that replaces described in substituent item mentioned above, then can be any group.R 2fatty group be preferably the alkyl of total carbon atom number 1 ~ 8, be more preferably the alkyl of total carbon atom number 1 ~ 6, include, for example methyl, ethyl, isopropyl, cyclohexyl, the tert-butyl group etc.
R 2represented aryl also can have substituting group, as long as commutable group is for carrying out the group that replaces described in substituent item mentioned above, then can be any group.R 2aryl be preferably the aryl of total carbon atom number 6 ~ 12, be more preferably the aryl of total carbon atom number 6 ~ 10, include, for example phenyl, 3-methoxyphenyl, 4-Carbamoylphenyl etc.
R 2represented heterocyclic radical also can have substituting group, can be saturated also can be unsaturated, also can contracting ring, as long as commutable group is for carrying out the group that replaces described in substituent item mentioned above, then can be any group.R 2heterocyclic radical be preferably the heterocyclic radical of total carbon atom number 2 ~ 16, be more preferably the heterocyclic radical of 5 ring ~ 6 rings of total carbon atom number 2 ~ 12, include, for example 1-Pyrrolizidine base, 4-morpholinyl, 2-pyridine radicals, 1-pyrrole radicals, 1-imidazole radicals, 1-benzimidazolyl etc.
R 2represented aliphatics oxygen base carbonyl also can have substituting group, can be saturatedly also to can be unsaturated, as long as commutable group is for carrying out the group that replaces described in substituent item mentioned above, then can be any group.R 2aliphatics oxygen base carbonyl be preferably the alkoxy carbonyl of total carbon atom number 1 ~ 8, be more preferably the alkoxy carbonyl of total carbon atom number 1 ~ 6, include, for example methoxycarbonyl, isopropoxy carbonyl, carbamyl methoxycarbonyl etc.
R 2represented carbamyl also can have substituting group, as long as commutable group is for carrying out the group that replaces described in substituent item mentioned above, then can be any group, preferably fatty group, aryl, heterocyclic radical etc.R 2carbamyl be preferably carbamyl, the alkylcarbamoyl group of total carbon atom number 2 ~ 9, the dialkyl carbamyl of total carbon atom number 3 ~ 10, the aromatic yl ammonia methanoyl of total carbon atom number 7 ~ 13, the heterocycle carbamyl of total carbon atom number 3 ~ 12, be more preferably carbamyl, the alkylcarbamoyl group of total carbon atom number 2 ~ 7, the dialkyl carbamyl of total carbon atom number 3 ~ 6, the aromatic yl ammonia methanoyl of total carbon atom number 7 ~ 11, the heterocycle carbamyl of total carbon atom number 3 ~ 10, include, for example carbamyl, methylcarbamoyl, dimethylcarbamoyl, phenylcarbamoyl, 4-pyridine carbamyl etc.
R 2represented acyl amino also can have substituting group, can be aliphatics, also can be aromatic series, also can be heterocycle, as long as commutable group is for carrying out the group that replaces described in substituent item mentioned above, then can be any group.R 2acyl amino be preferably the acyl amino of total carbon atom number 2 ~ 12; be more preferably the acyl amino of total carbon atom number 1 ~ 8; and then be preferably the alkyl-carbonyl-amino of total carbon atom number 1 ~ 8, include, for example acetyl-amino, benzoyl-amido, 2-pyridine carbonylamino, propanoylamino etc.
R 2represented sulfoamido also can have substituting group, can be aliphatics, also can be aromatic series, also can be heterocycle.As long as commutable group for carrying out the group that replaces described in substituent item mentioned above, then can be any group.R 2sulfoamido be preferably the sulfoamido of total carbon atom number 1 ~ 12, be more preferably the sulfoamido of total carbon atom number 1 ~ 8, and then be preferably the alkylsulfonamido of total carbon atom number 1 ~ 8, include, for example methylsulfonyl amido, benzene sulfonamido, 2-pyridine sulfonyl sulfonyl amido etc.
R 2represented carbamyl amino also can have substituting group, as long as commutable group is for carrying out the group that replaces described in substituent item mentioned above, then can be any group, preferably fatty group, aryl, heterocyclic radical etc.R 2carbamyl amino to be preferably carbamyl amino, the alkylcarbamoyl group of total carbon atom number 2 ~ 9 is amino, the dialkyl carbamyl of total carbon atom number 3 ~ 10 is amino, the aromatic yl ammonia methanoyl of total carbon atom number 7 ~ 13 is amino, the heterocycle carbamyl of total carbon atom number 3 ~ 12 is amino, be more preferably carbamyl amino, the alkylcarbamoyl group of total carbon atom number 2 ~ 7 is amino, the dialkyl carbamyl of total carbon atom number 3 ~ 6 is amino, the aromatic yl ammonia methanoyl of total carbon atom number 7 ~ 11 is amino, the heterocycle carbamyl of total carbon atom number 3 ~ 10 is amino, include, for example: carbamyl is amino, methylcarbamoyl is amino, N, N-dimethylcarbamoyl is amino, phenylcarbamoyl is amino, 4-pyridine carbamyl is amino.
R 2represented sulfamoyl also can have substituting group, as long as commutable group is for carrying out the group that replaces described in substituent item mentioned above, then can be any group, preferably fatty group, aryl, heterocyclic radical etc.R 2sulfamoyl be preferably sulfamoyl, the alkylsulfamoyl group of total carbon atom number 1 ~ 9, the dialkyl sulfamine of total carbon atom number 2 ~ 10, the ammonia aryl sulfonyl of total carbon atom number 7 ~ 13, the heterocyclic sulfonamides base of total carbon atom number 2 ~ 12, be more preferably sulfamoyl, the alkylsulfamoyl group of total carbon atom number 1 ~ 7, the dialkyl sulfamine of total carbon atom number 3 ~ 6, the ammonia aryl sulfonyl of total carbon atom number 6 ~ 11, the heterocyclic sulfonamides base of total carbon atom number 2 ~ 10, include, for example: sulfamoyl, Methylsulfamoyl, N, N-DimethylsuIfamoyl, phenyl sulfamoyl base, 4-pyridine sulfamoyl etc.
R 2represented aliphatics oxygen base also can have substituting group, can be saturatedly also to can be unsaturated, as long as commutable group is for carrying out the group that replaces described in substituent item mentioned above, then can be any group.R 2aliphatics oxygen base be preferably the alkoxy of total carbon atom number 1 ~ 8, be more preferably the alkoxy of total carbon atom number 1 ~ 6, include, for example: methoxyl, ethoxy, isopropoxy, cyclohexyloxy, methoxy ethoxy etc.
R 2represented aliphatics sulfenyl also can have substituting group, can be saturatedly also to can be unsaturated, as long as commutable group is for carrying out the group that replaces described in substituent item mentioned above, then can be any group.R 2aliphatics sulfenyl be preferably the alkyl sulfenyl of total carbon atom number 1 ~ 8, be more preferably the alkyl sulfenyl of total carbon atom number 1 ~ 6, include, for example: methyl mercapto, ethylmercapto group, carbamyl methyl mercapto, tertiary butylthio etc.
R 2represented halogen atom is preferably fluorine atom, chlorine atom, bromine atoms, more preferably can enumerate chlorine atom.With regard to the aspect of effect of the present invention, R 2be preferably the situation of aliphatics oxygen base carbonyl, carbamyl.With regard to the aspect of effect of the present invention, m is preferably the situation of 0 or 1, is more preferably the situation of 0.
General formula (A-1) represented by A ~ general formula (A-32) is illustrated.Position represented by general formula (A-1) ~ general formula (A-32) is preferably total carbon atom number 2 ~ 15, is more preferably total carbon atom number 2 ~ 12.
R 51~ R 54as long as represented substituting group for carrying out the group that replaces described in substituent item mentioned above, then can be any group.R 51~ R 54substituting group be preferably fatty group, aryl, heterocyclic radical, aliphatics oxygen base carbonyl, carbamyl, acyl amino, sulfoamido, aliphatics oxygen base, aliphatics sulfenyl, cyano group etc., be more preferably fatty group, aliphatics oxygen base carbonyl, carbamyl, aliphatics oxygen base, cyano group etc.
With regard to the aspect of effect of the present invention, R 51~ R 54be preferably the situation of hydrogen atom, fatty group, aryl, heterocyclic radical, aliphatics oxygen base carbonyl, carbamyl, acyl amino, sulfoamido, aliphatics oxygen base, aliphatics sulfenyl, cyano group etc., be more preferably the situation of hydrogen atom, fatty group, aliphatics oxygen base carbonyl, carbamyl, aliphatics oxygen base, cyano group.
R 55as long as represented substituting group for carrying out the group that replaces described in substituent item mentioned above, then can be any group.R 55substituting group be preferably fatty group, aryl, heterocyclic radical etc., be more preferably fatty group, aryl, in the contiguous bits at the bond position with nitrogen-atoms containing aromatic series 5 yuan ~ 6 yuan heterocyclic radicals of nitrogen-atoms.
With regard to the aspect of effect of the present invention, R 55be preferably the situation of fatty group, aryl, heterocyclic radical, be more preferably fatty group, aryl, the situation of aromatic series 5 yuan ~ 6 yuan of heterocyclic radicals containing nitrogen-atoms in the contiguous bits at the bond position with nitrogen-atoms, and then be preferably the situation of the aromatic series 5 yuan ~ 6 yuan of heterocyclic radicals containing nitrogen-atoms in the contiguous bits at the bond position with nitrogen-atoms.By making R 55for aromatic series 5 yuan ~ 6 yuan heterocyclic radicals containing nitrogen-atoms in the contiguous bits at the bond position with nitrogen-atoms, not only easily form the intermolecular interaction of pigment molecular securely, and easily form intramolecular interaction securely.Easily form the stable pigment of molecules align thus, demonstrate good form and aspect, high fastness (fast light gas hot water etc.) in preferably.
With regard to the aspect of effect of the present invention, as R 55and preferred aromatic series 5 yuan ~ 6 yuan heterocyclic radicals containing nitrogen-atoms in the contiguous bits at the bond position with nitrogen-atoms also can have substituting group, as long as commutable group for carrying out the group that replaces described in substituent item mentioned above, then can be any group.Preferred substituting group is hydroxyl, aliphatics oxygen base, carbamyl, aliphatics oxygen base carbonyl, aliphatics sulfenyl, amino, aliphatic amines, acyl amino, carbamyl amino; can be saturated heterocyclyl and also can be unsaturated heterocycle base; also can be contracting ring heterocyclic radical; be preferably aromatic series 5 yuan ~ 6 yuan heterocyclic radicals containing nitrogen-atoms in the contiguous bits at the bond position with nitrogen-atoms of total carbon atom number 2 ~ 12, be more preferably aromatic series 5 yuan ~ 6 yuan heterocyclic radicals containing nitrogen-atoms in the contiguous bits at the bond position with nitrogen-atoms of total carbon atom number 2 ~ 10.Include, for example: 2-thiazolyl, 2-[4-morpholinodithio base, 2-oxazolyl, 2-benzoxazolyl, 2-pyridine radicals, 2-pyrazinyl, 3-pyridazinyl, 2-pyrimidine radicals (2-pyrimidinyl), 4-pyrimidine radicals, 2-imidazole radicals, 2-benzimidazolyl, 2-triazinyl etc., these heterocyclic radicals can be also tautomerism body structure together with substituting group.
With regard to the aspect of effect of the present invention, as R 55and preferred aryl also can have substituting group; as long as commutable group is for carrying out the group that replaces described in substituent item mentioned above; then can be any group, preferred substituting group is hydroxyl, nitro, fatty group, aliphatics oxygen base, carbamyl, aliphatics oxygen base carbonyl, aliphatics sulfenyl, amino, aliphatic amines, acyl amino, carbamyl amino.R 55aryl be preferably the aryl of total carbon atom number 6 ~ 12, be more preferably the aryl of total carbon atom number 6 ~ 10, include, for example phenyl, 3-methoxyphenyl, 4-Carbamoylphenyl etc., be preferably phenyl.
With regard to the aspect of effect of the present invention, as R 55and preferred fatty group also can have substituting group; as long as commutable group is for carrying out the group that replaces described in substituent item mentioned above; then can be any group, preferred substituting group is hydroxyl, nitro, aliphatics oxygen base, carbamyl, aliphatics oxygen base carbonyl, aliphatics sulfenyl, amino, aliphatic amines, acyl amino, carbamyl amino.R 55fatty group be preferably the alkyl of total carbon atom number 1 ~ 6, be more preferably the fatty group of total carbon atom number 1 ~ 4, include, for example methyl, ethyl, methoxy ethyl, carbamoyhnethyl etc., be preferably methyl.
In general formula (A2), R 55the preferably situation of any one of following (Y-1) ~ (Y-13), in order to easily obtain intramolecular hydrogen bond structure, be more preferably the situation of any one of following (Y-1) ~ (Y-6) of 6 rings, and then the situation of any one of preferably following (Y-1), (Y-3), (Y-4), (Y-6), the especially preferably situation of following (Y-1) or (Y-4).* in general formula (Y-1) ~ general formula (Y-13) represents the bond position with the atom N of pyrazole ring.Y 1~ Y 11represent hydrogen atom or substituting group.(Y-13) G in 11expression can form the non-metallic atom cohort of 5 yuan ~ 6 yuan of heterocycles, G 11represented heterocycle can be unsubstituted, and also can have substituting group, heterocycle can be monocycle and also can be contracting ring.Formula (Y-1) ~ formula (Y-13) can be also tautomerism body structure together with substituting group.
[changing 9]
Y 1~ Y 11as long as represented substituting group for carrying out the group that replaces described in substituent item mentioned above, then can be any group.Y 1~ Y 11substituting group be preferably fatty group, aryl, heterocyclic radical, aliphatics oxygen base carbonyl, carbamyl, acyl amino, sulfoamido, aliphatics oxygen base, aliphatics sulfenyl, cyano group etc., be more preferably fatty group, aliphatics oxygen base, aliphatics sulfenyl, cyano group etc.Y 1~ Y 11in, 2 adjacent substituting groups also can form 5 ring ~ 6 rings.
With regard to the aspect of effect of the present invention, Y 1~ Y 11be preferably the situation of hydrogen atom, fatty group, aryl, heterocyclic radical, aliphatics oxygen base carbonyl, carbamyl, acyl amino, sulfoamido, aliphatics oxygen base, aliphatics sulfenyl, cyano group etc., be more preferably the situation of hydrogen atom, fatty group, aliphatics oxygen base carbonyl, carbamyl, aliphatics oxygen base, cyano group.
With regard to the aspect of effect of the present invention, A in general formula (A2) is preferably the situation of 5 membered ring heterocyclic with regard to the aspect of form and aspect, be more preferably nitrogenous or the situation of sulfur-bearing 5 yuan of heterocycles, and then be preferably the situation of the heteroatomic 5 yuan of heterocycles containing more than 2.
R 56~ R 57, R 59as long as represented substituting group for carrying out the group that replaces described in substituent item mentioned above, then can be any group.R 56~ R 57, R 59substituting group be preferably fatty group, aryl, heterocyclic radical, aliphatics oxygen base carbonyl, carbamyl, acyl amino, sulfoamido, aliphatics oxygen base, aliphatics sulfenyl, cyano group etc., be more preferably fatty group, aliphatics oxygen base, aliphatics sulfenyl, cyano group etc.
With regard to the aspect of effect of the present invention, R 56~ R 57, R 59be preferably the situation of fatty group, aryl, heterocyclic radical, aliphatics oxygen base carbonyl, carbamyl, acyl amino, sulfoamido, aliphatics oxygen base, aliphatics sulfenyl, cyano group etc., be more preferably the situation of fatty group, aliphatics oxygen base, aliphatics sulfenyl, cyano group.
R 58as long as represented substituting group for carrying out the group that replaces described in substituent item mentioned above, then can be any group.With regard to the aspect of effect of the present invention, R 58be preferably heterocyclic radical, Hammett (Hammett) substituent constant σ p value be more than 0.2 draw electro base, be more preferably σ p value be more than 0.3 draw electro base.The upper limit be less than 1.0 draw electro base.
As the R drawing electro base that σ p value is more than 0.2 58concrete example can enumerate: acyl group, acyloxy, carbamyl, alkoxy carbonyl, aryloxycarbonyl, cyano group, nitro, dialkylphosphono, diaryl phosphono, diaryl phosphinyl, alkyl sulphinyl, aryl sulfonyl kia, alkyl sulphonyl, aryl sulfonyl, sulfonyl oxygen base, acyl mercapto, sulfamoyl, thiocyanate groups, thiocarbonyl, halogenated alkyl, halogenated alkoxy, halogen aryloxy, halogenated alkyl is amino, halogenated alkyl sulfenyl, through other aryl drawing electro base to replace that σ p value is more than 0.20, heterocyclic radical, halogen atom, azo group, or selenium is cyanate ester based.
In addition, with regard to the aspect of effect of the present invention, R 58be preferably the situation of described (Y-1) ~ (Y-13), in order to easily obtain intramolecular hydrogen bond structure, be more preferably the situation of any one of following (Y-1) ~ (Y-6) of 6 rings, and then be preferably the situation of any one of described (Y-1), (Y-3), (Y-4), (Y-6), be especially preferably the situation of described (Y-1) or (Y-4).
Enumerate in the heterocycle of (A-1) ~ (A-32) as the A in general formula (A2), as long as the atom adjacent with the carbon atom being binding on azo group is heteroatoms, then have light fastness, tendency that hot fastness uprises, by the pigment with this kind of architectural feature is used for colored filter, the colored filter demonstrating high-contrast can be obtained, therefore preferably.
With regard to the aspect of effect of the present invention, it is hydrogen atom that the AZO pigments represented by general formula (A2) is preferably following situation: G, R 1for amino or with the saturated heterocyclyl of nitrogen-atoms bond, m is 0 or 1, when m is the situation of 1, R 2for aliphatics oxygen base carbonyl, carbamyl or aliphatics oxygen base; A be (A-1), (A-10) ~ (A-17), (A-20) ~ (A-23), (A-27), (A-28), (A-30) ~ (A-32) any one, and n is 1 or 2.
Be more preferably following situation: G is hydrogen atom, R 1for amino or with the saturated heterocyclyl of nitrogen-atoms bond, m is 0 or 1, when m is the situation of 1, R 2for aliphatics oxygen base carbonyl, carbamyl or aliphatics oxygen base; A be (A-1), (A-10), (A-11), (A-13) ~ (A-17), (A-20), (A-22) ~ (A-23), (A-27), (A-28), (A-30) ~ (A-32) any one, and n is 1 or 2.
And then preferably following situation: G is hydrogen atom, R 1for amino or with the saturated heterocyclyl of nitrogen-atoms bond, m is 0, A be (A-10), (A-11), (A-13) ~ (A-17), (A-20), (A-22) ~ (A-23), (A-27), (A-28), (A-30) ~ (A-32) any one, and n is 1 or 2.
Especially being preferably following situation: G is hydrogen atom, R 1for amino, m to be 0, A be (A-16) ~ (A-17), (A-20), (A-28), (A-32) any one, n is 1 or 2; Especially being preferably G is hydrogen atom, R 1for amino, m be 0, A is (A-16) and n is the situation of 1 or 2.
With regard to the aspect of effect of the present invention, the AZO pigments represented by general formula (A2) is more preferably the AZO pigments represented by following general formula (A3).
For the AZO pigments represented by general formula (A3), azo group is utilized to make Z or R 55formed with the hydroxyl of naphthalene nucleus and intersect hydrogen bond, improve the planarity of pigment structure, in molecule, intermolecular interaction grow, result light fastness, hot fastness, solvent resistance etc. improve significantly, therefore preferably.
Below, the AZO pigments represented by mutual-through type (A3), its dynamic isomer, these salt or hydrate are described in detail.
General formula (A3)
[changing 10]
In general formula (A3), R 21, R 22, R 55, R 59, m and n respectively with the R that defines in general formula (A2) 1, R 2, R 55, R 59, m and n be identical meanings.Z represent the σ p value of Hammett be more than 0.2 draw electro base.The situation of n=2 represents and is situated between every R 21, R 22, R 55, R 59or the dipolymer of Z.The situation of n=3 represents and is situated between every R 21, R 22, R 55, R 59or the trimer of Z.The situation of n=4 represents and is situated between every R 21, R 22, R 55, R 59or the tetramer of Z.General formula (A3) does not have ionic water wettability base.
The σ p value of the Hammett represented by Z be more than 0.2 substituting group can enumerate the R of general formula (A2) mentioned above 58the group described in explanation.
The R of the AZO pigments represented by general formula (A3) 21, R 22, R 55, R 59, the preferred substituting group of m, n, scope and general formula (A2) R 1, R 2, R 55, R 59, m and n be identical.
With regard to the aspect of effect of the present invention, Z is preferably acyl group, carbamyl, alkoxy carbonyl, cyano group, alkyl sulphonyl, sulfamoyl, is more preferably carbamyl, alkoxy carbonyl, cyano group, is especially preferably the situation of cyano group.
With regard to the aspect of effect of the present invention, the AZO pigments represented by general formula (A3) is preferably following situation: R 21for having substituent amino, m is 0 or 1, when m is the situation of 1, and R 22for aliphatics oxygen base carbonyl, carbamyl or aliphatics oxygen base, R 55for aromatic series 5 yuan ~ 6 yuan heterocyclic radicals containing nitrogen-atoms in the contiguous bits at bond position, R 59for hydrogen atom or fatty group, Z is acyl group, carbamyl, alkoxy carbonyl, cyano group, alkyl sulphonyl or sulfamoyl, and n is 1 or 2.
Be more preferably following situation: R 21for having substituent amino, m is 0, R 55for any one of (Y-1) ~ (Y-13), R 59for hydrogen atom or fatty group, Z is carbamyl, alkoxy carbonyl or cyano group, and n is 1 or 2.
And then be preferably following situation: R 21for having substituent amino, m is 0, R 55for any one of (Y-1) ~ (Y-6), R 59for hydrogen atom or fatty group, Z is carbamyl, alkoxy carbonyl or cyano group, and n is 1 or 2.
Especially following situation: R is preferably 21for having substituent amino, m is 0, R 55for (Y-1), (Y-4) or (Y-6), R 59for hydrogen atom, Z is cyano group, and n is 1 or 2.
With regard to the aspect of effect of the present invention, it is less than 40 that general formula (A2) or the AZO pigments represented by general formula (A3) are preferably " number of total carbon number/azo group ", is more preferably less than 30.With regard to the aspect of effect of the present invention, it is less than 700 that general formula (A2) or the AZO pigments represented by general formula (A3) are preferably " number of molecular weight/azo group ".With regard to the aspect of effect of the present invention, general formula (A2) or the AZO pigments represented by general formula (A3) are preferably the situation replaced without sulfo group, carboxyl isoiony substituting group.
Azo-compound represented by described general formula (A2) is in other forms, being preferably A is (A-1) ~ (A-9), (A-11) ~ (A-13), (A-17), (A-20) ~ (A-23), (A-27), (A-28), (A-30) ~ (A-32), be more preferably (A-11) ~ (A-13), (A-17), (A-20) ~ (A-23), (A-27), (A-28), (A-30) ~ (A-32), and then be preferably (A-17), (A-20), (A-22) ~ (A-23), (A-27), (A-28), (A-31), (A-32), and then be more preferably (A-20), (A-28), (A-32), especially be preferably (A-20).In addition, and then be preferably the R of (A-20) 56for R 59.
In the present invention, the dynamic isomer of general formula (A2) or the AZO pigments represented by general formula (A3) is also included within the scope of it.General formula (A2) or general formula (A3) represent with the form of canonical structure in multiple dynamic isomer desirable in chemical constitution, also can be the dynamic isomer beyond described structure, can also use with the form of the potpourri containing multiple dynamic isomer.
Such as, about the AZO pigments represented by general formula (A2), the dynamic isomer of the azo-hydrazone represented by following general formula (A1') can be expected.
In the present invention, as the dynamic isomer of the AZO pigments represented by general formula (A2) following general formula (A1') represented by pigment be also included within the scope of it.
General formula (A1')
[changing 11]
In general formula (A1'), G, R 1, R 2, m, n and A respectively with G, the R in general formula (A2) 1, R 2, m, n be identical meanings.
In AZO pigments represented by general formula (A2), the general formula example of especially preferred AZO pigments as described above can enumerate the AZO pigments represented by following general formula (A4-1) ~ general formula (A4-4).AZO pigments represented by described general formula (A2) is preferably the AZO pigments represented by following general formula (A4-1) ~ general formula (A4-4).
Below, the AZO pigments represented by mutual-through type (A4-1) ~ general formula (A4-4), its dynamic isomer, these salt or hydrate are described in detail.
[changing 12]
In general formula (A4-1) ~ general formula (A4-4), R 1, R 2, m and n respectively with the R in general formula (A2) 1, R 2, m and n be identical meanings.X represents carbon atom or nitrogen-atoms, Ax and X and adjacent carbon atom form aromatic series 5 yuan ~ 6 yuan heterocyclic radicals together, Bx forms aromatic series 5 yuan ~ 6 yuan heterocyclic radicals together with adjacent carbon atom, specifically, the corresponding group in (A-1) ~ (A-32) defined by the A of general formula (A2) is represented.Yx forms heterocyclic radical together with nitrogen-atoms and adjacent carbon atom, represents by the R of general formula (A2) 55corresponding group in the heterocyclic radical defined.R 23represent the R of general formula (A2) defined 51, R 54, R 57, R 58deng in substituting group, be equivalent to the substituting group of the group removing carbonyl gained in corresponding substituting group.R' 1represent the R of self-drifting (A2) defined 1amino in remove the corresponding substituting group of-NH-)
About the AZO pigments represented by described general formula (A2), general formula (A3), general formula (A4-1) ~ general formula (A4-4), multiple dynamic isomer can be expected.
In addition, in the present invention, the AZO pigments represented by general formula (A2) preferably has the substituting group forming intersection hydrogen bond in intramolecular hydrogen bond or molecule.Be more preferably the substituting group of the formation intramolecular hydrogen bond with at least more than one, especially preferably there is the substituting group of at least more than one formation molecule interior intersection hydrogen bond.
The factor being preferably described structure can be enumerated: the nitrogen-atoms forming the heterocyclic radical contained by AZO pigments structure as Suo Shi general formula (A4-1) ~ general formula (A4-4), the hydrogen atom of the substituent hydroxyl of naphthalene and oxygen atom, and the nitrogen-atoms of azo group or the hydrazone group as its dynamic isomer, or the carbonyl that azo composition contained by AZO pigments structure replaces, the hydrogen atom of the substituent hydroxyl of naphthalene and oxygen atom, and azo group or easily form intramolecular intersection hydrogen bond as the nitrogen-atoms of the hydrazone group of its dynamic isomer.
Result, the planarity of molecule improves, Intramolecular interphase interaction improves further, the crystallinity of the AZO pigments represented by general formula (A4-1) ~ general formula (A4-4) uprises (easily forming higher order structure), improve significantly as the requirement performance of pigment and light fastness, thermal stability, hydrothermal stability, water tolerance, gas resistance and/or solvent resistance, therefore become preferred example.
With regard to described viewpoint, also the AZO pigments represented by general formula (A2) is preferably general formula (A3), pigment represented by general formula (A4-1) ~ general formula (A4-4), be more preferably general formula (A3), general formula (A4-1) or the pigment represented by general formula (A4-2), be especially preferably the AZO pigments represented by general formula (A3).
Its content such as with reference to the compound recorded in the paragraph 0094 ~ paragraph 0116 of Japanese Patent Laid-Open 2011-162760 publication, can be incorporated in this instructions by the concrete example of AZO pigments used in the present invention.
In addition, pigment of the present invention also can use more than one the pigment be selected from following general formula (1A), general formula (1B) and the quinophthalone compound represented by general formula (1C) (hereinafter sometimes referred to " specific quinophthalone compound ").By using quinophthalone compound, have following effect: brightness is high and contrast is high, and colouring power is excellent, the lowering viscousity of colored filter coloured composition is excellent.
General formula (1A)
[changing 13]
General formula (1B)
[changing 14]
General formula (1C)
[changing 15]
In general formula (1A) ~ general formula (1C), R 14~ R 28, R 29~ R 43, R 44~ R 60separately represent hydrogen atom, halogen atom, substituent alkyl can be had, substituent alkoxy can be had, substituent aryl ,-SO can be had 3h;-COOH; And the slaine of 1 valency ~ 3 valency of these acidic groups; Alkylammonium salt, substituent phthalimide methyl can be had, maybe can have substituent sulfamoyl.
Herein, halogen atom can enumerate fluorine, chlorine, bromine, iodine.
In addition, substituent alkyl can be had except the straight chains such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group, neopentyl, n-hexyl, n-octyl, stearyl, 2-ethylhexyl or branched alkyl groups, can enumerate: trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-bis-bromoethyl, 2,2,3,3-tetra-fluoropropyl, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl, benzyl, 4-methyl-benzyl, 4-t-butylbenzyl, 4-methoxy-benzyl, 4-nitrobenzyl, 2,4-dichloro benzyls etc. have substituent alkyl.
In addition, substituent alkoxy can be had except methoxyl, ethoxy, propoxyl group, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, neopentyl oxygen, 2, 3-dimethyl-3-amoxy, just own oxygen base, n-octyloxy, stearic oxygen base, beyond the straight chains such as 2-ethyl hexyl oxy or branch's alkoxy, can enumerate: trichloromethoxy, trifluoromethoxy, 2, 2, 2-trifluoro ethoxy, 2, 2, 3, 3-tetrafluoro propoxyl group, 2, 2-di-trifluoromethyl propoxyl group, 2-ethoxy ethoxy, 2-Butoxyethoxy, 2-nitro propoxyl group, benzyloxies etc. have substituent alkoxy.
In addition, substituent aryl can be had except the aryl such as phenyl, naphthyl, anthryl, can enumerate: p-methylphenyl, to bromophenyl, p-nitrophenyl, p-methoxyphenyl, 2,4-dichlorophenyl, pentafluorophenyl group, 2-aminophenyl, 2-methyl-4-chlorphenyl, 4-hydroxyl-1-naphthyl, 6-methyl-2-naphthyl, 4, the chloro-2-naphthyl of 5,8-tri-, anthraquinonyl (anthraquinonyl), 2-amino anthracene quinonyl etc. have substituent aryl.
In addition, acidic groups can enumerate-SO 3h ,-COOH, the slaine of 1 valency ~ 3 valency of these acidic groups can be enumerated: sodium salt, sylvite, magnesium salts, calcium salt, molysite, aluminium salt etc.In addition, the alkylammonium salt of acidic groups can be enumerated: the ammonium salt of the long-chain monoalkylamine such as octyl amine, lauryl amine, stearic amine, the quaternary alkyl ammonium salt such as palmityl trimethyl ammonium, dilauryl dimethyl, distearyl dimethyl ammonium.
Substituent phthalimide methyl (C can be had 6h 4(CO) 2n-CH 2-) and substituent sulfamoyl (H can be had 2nSO 2-) in " substituting group " can enumerate: described halogen atom, substituent alkyl can be had, substituent alkoxy can be had, can substituent aryl etc. be had.
And then with regard to the viewpoint of the lowering viscousity of dispersion, quinophthalone compound is more preferably the R of general formula (1A) ~ general formula (1C) 14~ R 28, R 29~ R 43, R 44~ R 60for hydrogen atom or halogen atom.
The concrete example of quinophthalone compound can enumerate following shown quinophthalone compound (a) ~ quinophthalone compound (r) etc., but the present invention is not limited to these compounds.
[changing 16]
[changing 17]
[changing 18]
In addition, pigment of the present invention also can use the phthalocyanine dye (hereinafter sometimes referred to " specific phthalocyanine pigment ") represented by following general formula (1).
General formula (1)
[changing 19]
In general formula (1), A 1~ A 16separately represent hydrogen atom, halogen atom, nitro, substituent alkyl can be had maybe can have substituent aryl.R 1and R 2separately represent hydrogen atom, hydroxyl, substituent alkyl can be had, substituent aryl or-OR can be had 3, R 1with R 2also can bond and form ring mutually.R 3maybe substituent aryl can be had for substituent alkyl can be had.
Below enumerate the concrete example of spendable specific phthalocyanine pigment in the present invention, but be not limited to these concrete examples.
[changing 20]
[changing 21]
Pigment of the present invention also can use the diketopyrrolopyrrolecocrystals series pigments represented by following formula (2).
[changing 22]
(in formula (2), A and B separately for hydrogen atom, fluorine atom, atomic iodine, cyano group, carbon number 1 ~ 12 alkyl, substituent phenyl ,-CF can be had 3,-OR 1,-SR 2,-N (R 3) R 4,-COOR 5,-CONH 2,-CONHR 6,-CON (R 7) R 8,-SO 2nH 2,-SO 2nHR 9or-SO 2n (R 10) R 11, R 1~ R 11separately for carbon number 1 ~ 12 alkyl, substituent phenyl can be had maybe can have substituent aralkyl.Wherein, be hydrogen atom when A and B is different)
In the specific assorted diketo-pyrrolo pyrrole pigments represented by formula (2) used in pigment of the present invention, with regard to brightness, contrast and suppress crystallization effect aspect with regard to, be also preferably formula (2-1), formula (2-2), formula (2-3), formula (2-4).In addition, with regard to contrast and suppress crystallization effect aspect with regard to, the R of formula (2-3), formula (2-4) 6~ R 8the alkyl being preferably carbon number more than 4 maybe can have substituent phenyl.Can think these high-contrast and suppress crystallization in play the reason of effect and be: owing to having the steric effects of the bulky substituent such as carbonamido (carboamidegroup), phenyl, the tert-butyl group of the alkyl of carbon number more than 4, the cohesion of pigment is inhibited.In addition, have carbonamido, phenyl, the tert-butyl group specific assorted diketo-pyrrolo pyrrole pigments due to color characteristics also excellent, therefore the excellent brightness of bromination diketo-pyrrolo pyrrole pigments can not be undermined.
[changing 23]
(in formula (2-3) and formula (2-4), R 6~ R 8separately for the alkyl of carbon number 1 ~ 12 maybe can have substituent phenyl)
Below enumerate the concrete example of the specific assorted diketo-pyrrolo pyrrole pigments of spendable formula (2) in the present invention, but be not limited to these concrete examples.
[changing 24]
[changing 25]
[changing 26]
[changing 27]
About the primary particle size of pigment, when being used as the situation of colored filter, with regard to the viewpoint of irregular colour or contrast, being preferably below 100nm, in addition, with regard to the viewpoint of dispersion stabilization, being preferably more than 5nm.The primary particle size of pigment is more preferably 5nm ~ 75nm, and then is preferably 5nm ~ 55nm, is especially preferably 5nm ~ 35nm.Specific dispersion resin of the present invention can playing effect good especially with when having the pigment combinations of primary particle size of scope of 5nm ~ 35nm.
The primary particle size of pigment can utilize the known methods such as electron microscope to measure.
Pigment is preferably selected from anthraquinone pigment, diketo-pyrrolo pyrrole pigments, phthalocyanine color, quinophthalone pigments, isoindoline pigment, azomethine pigment Ji pigment in triazine dioxin pigment.Especially C.I. pigment red 122 most preferably is, C.I. paratonere 177 (anthraquinone pigment), C.I. paratonere 254 (diketo-pyrrolo pyrrole pigments), C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 58, C.I. pigment blue 15: 6 (phthalocyanine colors), C.I. pigment yellow 13 8 (quinophthalone pigments), C.I. pigment yellow 13 9, C.I. pigment yellow 185 (isoindoline pigment), C.I. pigment yellow 150 (azomethine pigment), C.I. pigment Violet 23 (triazine dioxin pigment).
In addition, composition of the present invention also can containing the known dyestuff beyond (A) pigment.Such as can use Japanese Patent Laid-Open No. Sho 64-90403 publication, Japanese Patent Laid-Open No. Sho 64-91102 publication, Japanese Patent Laid-Open 1-94301 publication, Japanese Patent Laid-Open 6-11614 publication, Jap.P. spy steps on No. 2592207, United States Patent (USP) No. 4808501 instructionss, United States Patent (USP) No. 5667920 instructionss, United States Patent (USP) No. 505950 instructionss, United States Patent (USP) No. 5667920 instructionss, Japanese Patent Laid-Open 5-333207 publication, Japanese Patent Laid-Open 6-35183 publication, Japanese Patent Laid-Open 6-51115 publication, the pigment disclosed in Japanese Patent Laid-Open 6-194828 publication etc.Chemical constitution can use: the dyestuff of pyrazoles azo system, pyrroles's methylene base system, anilino-azo system, triphenyl methane system, anthraquinone system, benzal base system, oxonols system, Pyrazolotriazole azo system, pyridone azo system, cyanine system, phenothiazine system, pyrrolo-pyrazole azomethine system etc.
In addition, dyestuff also can use pigment polymer.Pigment polymer can enumerate the compound recorded in Japanese Patent Laid-Open 2011-213925 publication, Japanese Patent Laid-Open 2013-041097 publication.
Relative to the total composition (solid constituent) except solvent contained by photosensitive composition, the content of the pigment in composition of the present invention is preferably 10 quality % ~ 70 quality %, be more preferably 20 quality % ~ 60 quality %, and then be preferably 30 quality % ~ 60 quality %.
Pigment can, only containing a kind of, also can contain two or more in the present compositions.When containing two or more situations, being preferably its total amount becomes described scope.
< < (B) alkaline pigment derivative > >
Composition of the present invention has alkaline pigment derivative.In addition, alkaline pigment derivative preferably has amino compound.
As an embodiment of (B) alkaline pigment derivative, the pigment derivative represented by general formula (P1) can be enumerated.
[changing 28]
A-N＝N-X-Y(P1)
In general formula (P1), A represents the composition that can form AZO pigments together with X-Y.As long as described A can form the compound of AZO pigments with diazo-compounds (diazoniumcompound) coupling, then can select arbitrarily.Below represent the concrete example of described A, but the present invention is not limited to these concrete examples.
[changing 29]
[changing 30]
In described general formula (P1), X represents singly-bound (mean Y and be directly binding on-N=N-) or is selected from the base of concatenating group of the divalence represented by following structural formula.
[changing 31]
In described general formula (P1), Y represents the base represented by following general formula (P2).
[changing 32]
In general formula (P2), Z represents low-grade alkylidene.Z represents-(CH 2) b-, described b represents the integer of 1 ~ 5, is preferably b and represents 2 or 3.In general formula (P2) ,-NR 2represent low-grade alkyl amino or 5 yuan of nitrogen atom or the saturated heterocyclic of 6 yuan.At described-NR 2when representing low-grade alkyl amino, described-NR 2represent-N (C nh 2n+1) 2, n represents the integer of 1 ~ 4, is preferably n and represents 1 or 2.On the other hand, at described-NR 2when representing the saturated heterocyclic of 5 yuan of nitrogen atom or 6 yuan, described-NR 2the heterocycle preferably represented by following structural formula.
[changing 33]
In described general formula (P2), Z and-NR 2low alkyl group, alkoxy alternatively base can be had respectively.In described general formula (P2), a represents 1 or 2, is preferably a and represents 2.
Below represent the concrete example (concrete example 1 ~ concrete example 22) of the compound represented by described general formula (P1), but the present invention is not limited to these concrete examples.
[changing 34]
[changing 35]
[changing 36]
[changing 37]
[changing 38]
In addition, (B) alkaline pigment derivative is also preferably the pigment derivative represented by general formula (I).This kind of pigment derivative plays function as a kind of bulking agent.Though its reason is indefinite, mechanism can be presumed as follows.Namely, (C-1) composition of the present invention or (C-2) composition have following tendency: its steric repulsion base (polyester construction etc.) easily condenses crystallization each other, cause with form other compositions (such as (E) polymerization initiator or (F) polymerizable compound etc.) of composition be separated and only (C-1) composition or (C-2) composition condense, crystallization.Can infer, if add the pigment derivative represented by (B) general formula (I) wherein, then play following effect: aromatic rings position that the three-dimensional upper volume of (B) composition is large (has substituent quinophthalone residue moiety or X represented by the Dye of general formula (I) 2represented part) enter in the steric repulsion base section of (C-1) composition or (C-2) composition and prevent the cohesion crystallization each other of steric repulsion base, the situation that result suppresses (C-1) composition or (C-2) composition to be separated.
General formula (I)
[changing 39]
(in general formula (I), Dye represents can have substituent quinophthalone residue, X 1expression-NR'SO 2-,-SO 2nR'-,-CONR'-,-CH 2nR'COCH 2nR'-or-NR'CO-, X 2expression can have substituent carbon number be 6 ~ 20 arlydene maybe can have the assorted fragrant cyclic group that substituent carbon number is 1 ~ 20, these groups also can through being selected from-NR'-,-O-,-SO 2-or-CO-in the mutual bond of bivalence linking base.X 3represent-NR'-or-O-.R' represents hydrogen atom, can have substituent carbon number be 1 ~ 20 alkyl, can have substituent carbon number be 2 ~ 20 thiazolinyl maybe can have the aryl that substituent carbon number is 6 ~ 20.A and B represents respectively and is selected from following general formula (1) or the group represented by following general formula (2) ,-O-(CH 2) n-R 8,-OR 9,-NR 10r 11,-Cl ,-F or-X 3-X 2-X 1group in-Dye, R 8the nitrogen heterocyclic ring residue that expression can be substituted, R 9, R 10, R 11represent hydrogen atom respectively, can have substituent carbon number be 1 ~ 20 alkyl, can have substituent carbon number be 2 ~ 20 thiazolinyl maybe can have the aryl that substituent carbon number is 6 ~ 20, n represents the integer of 0 ~ 20.Any one of A and B group ,-O-(CH represented by following general formula (1) or general formula (2) 2) n-R 8,-OR 9or-NR 10r 11, t represents the integer of 1 ~ 3.When t is the situation of more than 2, multiple X 1, X 2, X 3, A and B can identical also can be different)
[changing 40]
In general formula (1), Y 1represent-NR'-or-O-, Y 2expression can have substituent carbon number be 2 ~ 20 alkylidene, can have substituent carbon number be 2 ~ 20 alkenylene maybe can have the arlydene that substituent carbon number is 6 ~ 20, these groups also can through being selected from-NR'-,-O-,-SO 2-, the mutual bond of bivalence linking base in-CO-.R' represents hydrogen atom, can have substituent carbon number be 1 ~ 20 alkyl, can have substituent carbon number be 2 ~ 20 thiazolinyl maybe can have the aryl that substituent carbon number is 6 ~ 20.R 1, R 2respectively represent can have substituent carbon number be 1 ~ 20 alkyl maybe can have the thiazolinyl (R that substituent carbon number is 2 ~ 20 1with R 2also can be integral and form heterocycle structure, described heterocycle structure still can contain nitrogen-atoms, oxygen atom or sulphur atom, also can have substituting group).
In general formula (2), Z 1represent link triazine ring and nitrogen-atoms singly-bound ,-NR'-,-NR'-G-CO-, NR'-G-CONR "-,-NR'-G-SO 2-,-NR'-G-SO 2nR "-,-O-G-CO-,-O-G-CONR'-,-O-G-SO 2-or-O-G-SO 2nR'-, G represent can have substituent carbon number be 1 ~ 20 alkylidene, can have substituent carbon number be 2 ~ 20 alkenylene maybe can have the arlydene that substituent carbon number is 6 ~ 20, R' and R " represent hydrogen atom respectively, can have substituent carbon number be 1 ~ 20 alkyl, can have substituent carbon number be 2 ~ 20 thiazolinyl maybe can have the aryl that substituent carbon number is 6 ~ 20.R 3, R 4, R 5and R 6represent hydrogen atom respectively, can have substituent carbon number be 1 ~ 20 alkyl, can have substituent carbon number be 2 ~ 20 thiazolinyl maybe can have the aryl that substituent carbon number is 6 ~ 20, R 7expression can have substituent carbon number be 1 ~ 20 alkyl maybe can have the thiazolinyl that substituent carbon number is 2 ~ 20.
In general formula (I), Dye represents to have substituent quinophthalone residue.Quinophthalone residue is specifically represented by following general formula (II).
General formula (II)
[changing 41]
In general formula (II), D and E represent respectively be selected from hydrogen atom, halogen atom, carbon number 1 ~ 20 alkyl, formed together with the phenyl ring of D and E institute bond and substituent fragrant cyclic group or heterocyclic radical, hydroxyl, the alkoxy of carbon number 1 ~ 3, the acid amides of the ester of carboxyl or its salt or carbon number 1 ~ 20 or carbon number 1 ~ 20, sulfuryl or its salt, sulfamoyl ,-NR'R can be had "-, any one group in nitro.In formula, R' and R " represent hydrogen atom respectively, the alkyl of substituent carbon number 1 ~ 20 can be had, the aryl that the thiazolinyl of substituent carbon number 2 ~ 20 maybe can have substituent carbon number 6 ~ 20 can be had.P represents the integer of 0 ~ 4, and q represents the integer calculated by 4-p.* represent and the X in general formula (I) 1bond position.
D and E represent respectively be selected from hydrogen atom, halogen atom, carbon number 1 ~ 20 alkyl, formed together with the phenyl ring of D and E institute bond and substituent fragrant cyclic group or heterocyclic radical, hydroxyl, the alkoxy (such as methoxyl, ethoxy, propoxyl group) of carbon number 1 ~ 3, the acid amides of the ester of carboxyl or its salt or carbon number 1 ~ 20 or carbon number 1 ~ 20, sulfuryl or its salt, sulfamoyl ,-NR'R can be had "-, any one group in nitro.R' and R " represent hydrogen atom respectively, the alkyl of substituent carbon number 1 ~ 20 can be had, the aryl that the thiazolinyl of substituent carbon number 2 ~ 20 maybe can have substituent carbon number 6 ~ 20 can be had.
The alkyl of carbon number 1 ~ 20 is preferably the alkyl of carbon number 1 ~ 10, is more preferably the alkyl of carbon number 1 ~ 8.Specifically can enumerate: methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group, neopentyl, n-hexyl, n-octyl etc.
Fragrance cyclic group or heterocyclic radical include, for example: phenyl, naphthyl, thiophene cyclic group, pyridine cyclic group, pyrroles's cyclic group etc.
Fragrant cyclic group represented by D and E or heterocyclic radical, R' and R " represented by the aryl of the alkyl of carbon number 1 ~ 20, the thiazolinyl of carbon number 2 ~ 20 and carbon number 6 ~ 20 also can have substituting group, substituting group can enumerate the group described in described substituent item.
In these groups, D and E is preferably hydrogen atom, halogen atom.
P represents the integer of 0 ~ 4, is more preferably the integer of 1 ~ 4, and then is preferably 4.Q represents the integer calculated by 4-p, specifically, is preferably the integer of 0 ~ 3, is more preferably 2 ~ 3, and then be preferably 4.
With the X in general formula (I) 1there is no particular restriction at bond position, 5 or 8 that are preferably the chinoline backbone in quinophthalone residue be bond position, and being more preferably 8 is bond position.
In general formula (I), X 1expression-NR'SO 2-,-SO 2nR'-,-CONR'-,-CH 2nR'COCH 2nR'-or-NR'CO-, is preferably-NR'SO 2-.Moreover, when t is the situation of more than 2, multiple X 1can identical also can be different.
Described X 1in R' represent hydrogen atom, can have substituent carbon number be 1 ~ 20 alkyl, can have substituent carbon number be 2 ~ 20 thiazolinyl maybe can have the aryl that substituent carbon number is 6 ~ 20, be preferably hydrogen atom.
Described carbon number be 1 ~ 20 alkyl be preferably the alkyl of carbon number 1 ~ 10, be more preferably the alkyl of carbon number 1 ~ 6.Specifically can enumerate: methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group, neopentyl, n-hexyl, n-octyl etc.
The thiazolinyl of described carbon number 2 ~ 20 is preferably the thiazolinyl of carbon number 2 ~ 10, is more preferably the thiazolinyl of carbon number 2 ~ 6.Specifically can enumerate: vinyl, propenyl, butenyl group, pentenyl, hexenyl etc.
The aryl of described carbon number 6 ~ 20 is preferably the aryl of carbon number 6 ~ 10, specifically can enumerate phenyl, naphthyl, anthryl etc.
These groups also can have substituting group, and substituting group can enumerate the group described in described substituent item.
In general formula (I), X 2expression can have substituent carbon number be 6 ~ 20 arlydene maybe can have the assorted fragrant cyclic group that substituent carbon number is 4 ~ 20, these groups also can through being selected from-NR'-,-O-,-SO 2-or-CO-in the mutual bond of bivalence linking base (R' and described X 1in R' be identical meanings, preferable range is also identical).Moreover, when t is the situation of more than 2, multiple X 2can identical also can be different.
The arlydene of carbon number 6 ~ 20 is preferably the arlydene of carbon number 6 ~ 10, specifically can enumerate phenylene, naphthylene, anthrylene etc.
The assorted fragrant cyclic group of carbon number 4 ~ 20 is preferably the assorted fragrant cyclic group of carbon number 4 ~ 10, specifically can enumerate thiophene cyclic group, pyridine cyclic group, pyrroles's cyclic group etc.
These groups also can have substituting group, and substituting group can enumerate the group described in described substituent item.
X 3represent-NR'-or-O-, be preferably-NR'-.Moreover, when t is the situation of more than 2, multiple X 3can identical also can be different.R' and described R' is identical meanings, and preferable range is also identical.
A and B represents respectively and is selected from following general formula (1) or the group represented by following general formula (2) ,-O-(CH 2) n-R 8,-OR 9,-NR 10r 11,-Cl ,-F or-X 3-X 2-X 1group in-Dye, any one of A and B group ,-O-(CH represented by following general formula (1) or general formula (2) 2) n-R 8,-OR 9or-NR 10r 11.Wherein, A and B is all preferably following general formula (1) or the group represented by following general formula (2).
R 8the nitrogen heterocyclic ring residue that expression can be substituted, specifically can enumerate pyrrole ring residue, pyridine ring residue etc.
R 9, R 10, R 11represent hydrogen atom respectively, can have substituent carbon number be 1 ~ 20 alkyl, can have substituent carbon number be 2 ~ 20 thiazolinyl maybe can have the aryl that substituent carbon number is 6 ~ 20.R 9, R 10, R 11be identical meanings with described R', preferable range is also identical.
General formula (1)
[changing 42]
In general formula (1), Y 1represent-NR'-or-O-, Y 2expression can have substituent carbon number be 2 ~ 20 alkylidene, can have substituent carbon number be 2 ~ 20 alkenylene maybe can have the arlydene that substituent carbon number is 6 ~ 20, these groups also can through being selected from-NR'-,-O-,-SO 2-, the mutual bond of bivalence linking base in-CO-.R' represents hydrogen atom, can have substituent carbon number be 1 ~ 20 alkyl, can have substituent carbon number be 2 ~ 20 thiazolinyl maybe can have the aryl that substituent carbon number is 6 ~ 20.R 1, R 2respectively represent can have substituent carbon number be 1 ~ 20 alkyl maybe can have the thiazolinyl (R that substituent carbon number is 2 ~ 20 1with R 2also can be integral and form heterocycle structure, described heterocycle structure still can contain nitrogen-atoms, oxygen atom or sulphur atom, also can have substituting group).
Y 1represent-NR'-or-O-, be preferably-NR'-.R' and described R' is identical meanings, and preferable range is also identical.
Y 2expression can have substituent carbon number be 1 ~ 20 alkylidene, can have substituent carbon number be 2 ~ 20 alkenylene maybe can have the arlydene that substituent carbon number is 6 ~ 20, these groups also can through being selected from-NR'-,-O-,-SO 2-, the mutual bond of bivalence linking base (R' and described R' is identical meanings, and preferable range is also identical) in-CO-.
Described carbon number be 1 ~ 20 alkylidene be preferably the alkylidene of carbon number 1 ~ 10, be more preferably the alkylidene of carbon number 1 ~ 6, and then be preferably the alkylidene of carbon number 1 ~ 3.Specifically can enumerate: methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene etc.Alkylidene also can have substituting group, and substituting group can enumerate the group described in described substituent item.
Described carbon number be 2 ~ 20 alkenylene be preferably the alkenylene of carbon number 2 ~ 10, be more preferably the alkenylene of carbon number 2 ~ 6, and then be preferably the alkenylene of carbon number 2 ~ 3.Specifically can enumerate: ethenylidene, allylidene, butenylidene, inferior pentenyl, sub-hexenyl etc.Alkenylene also can have substituting group, and substituting group can enumerate the group described in described substituent item.
Described carbon number be 6 ~ 20 arlydene be preferably the arlydene of carbon number 6 ~ 20, be more preferably the arlydene of carbon number 6 ~ 10.Specifically can enumerate phenylene, naphthylene, anthrylene etc.Arlydene also can have substituting group, and substituting group can enumerate the group described in described substituent item.
R 1, R 2respectively represent can have substituent carbon number be 1 ~ 20 alkyl maybe can have the thiazolinyl (R that substituent carbon number is 2 ~ 20 1with R 2also can be integral and form heterocycle structure, described heterocycle structure still can contain nitrogen-atoms, oxygen atom or sulphur atom, also can have substituting group).
Described carbon number be 1 ~ 20 alkyl be preferably the alkyl of carbon number 1 ~ 10, be more preferably the alkyl of carbon number 1 ~ 6.Specifically can enumerate: methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group, neopentyl, n-hexyl, n-octyl etc.
The thiazolinyl of described carbon number 2 ~ 20 is preferably the thiazolinyl of carbon number 2 ~ 10, is more preferably the thiazolinyl of carbon number 2 ~ 6.Specifically can enumerate: vinyl, propenyl, butenyl group, pentenyl, hexenyl etc.
These groups also can have substituting group, and substituting group can enumerate the group described in described substituent item.R 1, R 2preferably represent identical group.
General formula (2)
[changing 43]
In general formula (2), Z 1represent link triazine ring and nitrogen-atoms singly-bound ,-NR'-,-NR'-G-CO-, NR'-G-CONR "-,-NR'-G-SO 2-,-NR'-G-SO 2nR "-,-O-G-CO-,-O-G-CONR'-,-O-G-SO 2-or-O-G-SO 2nR'-, G represent can have substituent carbon number be 1 ~ 20 alkylidene, can have substituent carbon number be 2 ~ 20 alkenylene maybe can have the arlydene that substituent carbon number is 6 ~ 20, R' and R " represent hydrogen atom respectively, can have substituent carbon number be 1 ~ 20 alkyl, can have substituent carbon number be 2 ~ 20 thiazolinyl maybe can have the aryl that substituent carbon number is 6 ~ 20.R 3, R 4, R 5and R 6represent hydrogen atom respectively, can have substituent carbon number be 1 ~ 20 alkyl, can have substituent carbon number be 2 ~ 20 thiazolinyl maybe can have the aryl that substituent carbon number is 6 ~ 20, R 7expression can have substituent carbon number be 1 ~ 20 alkyl maybe can have the thiazolinyl that substituent carbon number is 2 ~ 20.
Z 1represent link triazine ring and nitrogen-atoms singly-bound ,-NR'-,-NR'-G-CO-, NR'-G-CONR "-,-NR'-G-SO 2-,-NR'-G-SO 2nR "-,-O-G-CO-,-O-G-CONR'-,-O-G-SO 2-or-O-G-SO 2nR'-, is preferably singly-bound.
R' and R " represent hydrogen atom respectively, can have substituent carbon number be 1 ~ 20 alkyl, can have substituent carbon number be 2 ~ 20 thiazolinyl maybe can have the aryl that substituent carbon number is 6 ~ 20.R' and R " with general formula (1) in R' be identical meanings, preferable range is also identical.
G represent can have substituent carbon number be 1 ~ 20 alkylidene, can have substituent carbon number be 2 ~ 20 alkenylene maybe can have the arlydene that substituent carbon number is 6 ~ 20.Y in G and general formula (1) 2for identical meanings, preferable range is also identical.
R 3, R 4, R 5and R 6represent hydrogen atom respectively, can have substituent carbon number be 1 ~ 20 alkyl, can have substituent carbon number be 2 ~ 20 thiazolinyl maybe can have the aryl that substituent carbon number is 6 ~ 20.R 3, R 4, R 5and R 6be identical meanings with the R' in general formula (1), preferable range is also identical.
R 7expression can have substituent carbon number be 1 ~ 20 alkyl maybe can have the thiazolinyl that substituent carbon number is 2 ~ 20.R 7with the R in general formula (1) 1for identical meanings, preferable range is also identical.
T in general formula (I) represents the integer of 1 ~ 3, is preferably 1 or 2, is more preferably 1.
The concrete example of pigment derivative used in the present invention is below shown, but the present invention is not limited to these concrete examples.
[changing 44]
[changing 45]
[changing 46]
[changing 47]
[changing 48]
About the content of (B) pigment derivative in the present invention, be preferably more than 0.5 quality %, below 40 quality % with solid component meter, be more preferably more than 1 quality %, below 15 quality %.
In addition, relative to (A) pigment 100 mass parts, the content of (B) pigment derivative is preferably below more than 0.5 mass parts, 50 mass parts, is more preferably below more than 1 mass parts, 25 mass parts.
Pigment derivative can, only containing a kind of, also can contain two or more in the present compositions.When containing two or more situations, being preferably its total amount becomes described scope.
< < (C) spreading agent > >
Composition of the present invention contains phosphoric acid system spreading agent represented by (C-1) general formula (II) or aftermentioned (C-2) to be made to have the polymkeric substance (POH) of hydroxyl at least one end or have the polymkeric substance (PNH of one-level amino at least one end 2) the carboxylic serials spreading agent that reacts with tricarboxylic acid anhydride or tetracarboxylic dianhydride.By containing described spreading agent, spreading agent is strongly adsorbed in pigment particles, can suppress along with composition through time color spot deterioration.Spreading agent used in the present invention has the tendency with the poor compatibility of other compositions, through time color spot large, the non-constant of patternability after PCD, but in the present invention by with (B) alkaline pigment derivative (pigment derivative particularly, represented by general formula (I)) and with and eliminate described problem.
-the phosphoric acid system spreading agent represented by (C-1) general formula (II)-
Composition of the present invention contains the phosphoric acid system spreading agent represented by (C-1) general formula (II).By containing described spreading agent, spreading agent is strongly adsorbed in pigment particles, can suppress along with composition through time color spot deterioration.
General formula (II)
[changing 49]
In general formula (II), R 3represent that number average molecular weight is the polyester construction of 400 ~ 30000, y represents 1 or 2.When y is the situation of 2, multiple R 3can identical also can be different.
R 3represent that number average molecular weight is the polyester construction of 400 ~ 30000, when y is the situation of 2, multiple R 3can identical also can be different.The number average molecular weight of described polyester construction is more preferably 1900 ~ 10000, and then is preferably 400 ~ 3000, is especially preferably 2000 ~ 3000.Lack pigment-dispersing ability when being less than the situation of 400, therefore cannot use.
Polyester construction can be enumerated: by the polyester-based of internal ester monomer ring-opening polymerization gained, has the polyester construction of styryl, acryloyl group, cyanoacrylate acyl group, methacryl, vinyl ether etc., is preferably the polyester-based of internal ester monomer ring-opening polymerization gained.
Phosphoric acid system spreading agent represented by general formula (II) can be R 3for the phosphate of single kind, also can use and multiplely comprise different R 3phosphate.In addition, the phosphoric acid system spreading agent that can be y=1 is a kind of separately, also can be the potpourri of the phosphoric acid system spreading agent of y=1 and the phosphoric acid system spreading agent of y=2.
About the phosphate represented by general formula (II), if the phosphoric acid system spreading agent of y=1 is 100:0 ~ 100:30 with the existence ratio of the phosphoric acid system spreading agent of y=2, then pigment-dispersing becomes well and preferably.
In addition, if the R of the phosphoric acid system spreading agent represented by general formula (II) 3for number average molecular weight is the polyester construction of 400 ~ 10000, then pigment-dispersing becomes well and preferably.Be more preferably 400 ~ 3000.
And then, if the R of the phosphoric acid system spreading agent represented by general formula (II) 3for the polyester construction by two or more different internal ester monomer ring-opening polymerization gained, then effect of the present invention becomes excellent, very preferably.
And then, the R of the phosphoric acid system spreading agent represented by general formula (II) 3be preferably represented by following general formula (11).
General formula (11)
R 12-O-R 13-(O-R 14) S
(in formula, R 12represent alkylidene, R 13represent the polyol structure of more than ternary, R 14represent acryloyl group, cyanoacrylate acyl group, methacryl, s represents more than 2)
R 12be preferably the alkylidene of carbon number less than 8.In addition, with regard to the viewpoint of pigment-dispersing, s is preferably more than 2.When described situation, R 14also mutually different group can be used.S is more preferably 2 ~ 5, is especially preferably 2.
R 13polyvalent alcohol more than ternary used can be enumerated: glycerine, propyl alcohol, pentaerythrite, dipentaerythritol etc.Especially ternary ~ hexahydroxylic alcohols is preferably.
The acid number of phosphoric acid system spreading agent is preferably 10mgKOH/g ~ 300mgKOH/g, is more preferably 30mgKOH/g ~ 200mgKOH/g, and then is preferably 40mgKOH/g ~ 150mgKOH/g.
The manufacture of phosphoric acid system spreading agent can utilize known method to manufacture, such as, with reference to the record of the paragraph 0037 ~ paragraph 0051 of Japanese Patent Laid-Open 2007-231107 publication, its content can be incorporated in this instructions.
Phosphoric acid system spreading agent used in the present invention is preferably the phosphoric acid system spreading agent of the open loop addition gained used by 6-caprolactone and δ-valerolactone.
-(C-2) makes to be had the polymkeric substance (POH) of hydroxyl at least one end or has the polymkeric substance (PNH of one-level amino at least one end 2), the carboxylic serials spreading agent that reacts with tricarboxylic acid anhydride or tetracarboxylic dianhydride-
Composition of the present invention contains (C-2) to be made to have the polymkeric substance (POH) of hydroxyl at least one end or have the polymkeric substance (PNH of one-level amino at least one end 2), the carboxylic serials spreading agent that reacts with tricarboxylic acid anhydride or tetracarboxylic dianhydride.By containing described spreading agent, spreading agent is strongly adsorbed in pigment particles, can suppress along with composition through time color spot deterioration.
Carboxylic serials spreading agent can make to be had the polymkeric substance (POH) of hydroxyl at least one end or has the polymkeric substance (PNH of one-level amino at least one end 2), react with tricarboxylic acid anhydride or tetracarboxylic dianhydride and obtain.
(there is the polymkeric substance (POH) of hydroxyl at least one end, there is at least one end the polymkeric substance (PNH of one-level amino 2))
At at least one end, there is the polymkeric substance (POH) of hydroxyl or there is at least one end the polymkeric substance (PNH of one-level amino 2) preferred configuration be such as preferably represented by the general formula (II').
[changing 50]
In general formula (II'), Y 1represent the monovalence terminal groups with carbon number 1 ~ 20, oxygen number 0 ~ 12 and nitrogen number 0 ~ 3, X 2represent-O-,-S-or-N (R b)-, R brepresent hydrogen atom or the straight-chain of carbon number 1 ~ 18 or the alkyl of branch-like.G 1expression-R 11repetitive represented by O-, G 2represent-C (=O) R 12repetitive represented by O-, G 3represent-C (=O) R 13c (=O)-OR 14repetitive represented by O-, R 11represent the cycloalkylidene of the straight-chain of carbon number 2 ~ 8 or the alkylidene of branch-like or carbon number 3 ~ 8, R 12represent the cycloalkylidene of the straight-chain of carbon number 1 ~ 8 or the alkylidene of branch-like or carbon number 4 ~ 8, R 13represent the arlydene of the straight-chain of carbon number 2 ~ 6 or the alkylidene of branch-like, the straight-chain of carbon number 2 ~ 6 or the alkenylene of branch-like, the cycloalkylidene of carbon number 3 ~ 20 or carbon number 6 ~ 20, R 14represent-CH (R 15)-CH (R 16)-, R 15and R 16any one be hydrogen atom, another represents that the alkyl of carbon number 1 ~ 20, the thiazolinyl of carbon number 2 ~ 20, the aryl of carbon number 6 ~ 20, the carbon number of moieties are the alkoxymethylene of 1 ~ 20, the carbon number of alkenyl part is the alkene oxygen methylene of 2 ~ 20, the carbon number of aryl moiety is 6 ~ 20 and the aryloxy group methylene that aryl moiety can replace through halogen atom or N-methylene-phthalimide-based.Z 1represent-OH or-NH 2, R 17represent the straight-chain of carbon number 2 ~ 8 or alkylidene, the cycloalkylidene of carbon number 3 ~ the 8 ,-C (=O) R of branch-like 12-or-C (=O) R 13c (=O)-OR 14-.M1 represents the integer of 0 ~ 100, and m2 represents the integer of 0 ~ 60, and m3 represents the integer of 0 ~ 30.Wherein, m1+m2+m3 is more than 1, less than 100.Described repetitive G in general formula (II') 1~ repetitive G 3configuration do not limit its order, represent in the polymkeric substance represented by general formula (II'), in radicals X 2with radicals R 17between contain repetitive G with random order 1~ repetitive G 3, and then, these repetitives G 1~ repetitive G 3can be any one of random or block type respectively.
Y 1represent that there is the monovalence terminal groups of carbon number 1 ~ 20, oxygen number 0 ~ 12 and nitrogen number 0 ~ 3, with regard to the lowering viscousity of pigment dispersion and the viewpoint of storage stability, be preferably oxygen number and nitrogen number be 0, carbon number is the straight-chain of 1 ~ 18 or the alkyl of branch-like.
In addition, other forms are preferably Y 1there is ethene unsaturated double-bond.When described situation, active energy ray hardening can be given to (C-2) spreading agent.In addition, when the situation of m2=0, m3=0, Y 1be preferably the straight-chain of carbon number 1 ~ 7 or the alkyl of branch-like, or there is ethene unsaturated double-bond.
When there is ethene unsaturated double-bond, the group containing ethene unsaturated double-bond must be had.This kind of group include, for example vinyl or (methyl) acryloyl group etc., is preferably (methyl) acryloyl group.These kinds with the group of double bond can be one and also can be multiple.
X 2represent-O-,-S-or-N (R b)-, is preferably-O-or-N (R b)-.
R brepresent hydrogen atom or the straight-chain of carbon number 1 ~ 18 or the alkyl of branch-like.The straight-chain of carbon number 1 ~ 18 or the alkyl of branch-like are preferably the alkyl of carbon number 1 ~ 6.Specifically can enumerate: methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group, neopentyl, n-hexyl, cyclohexyl etc.
Z 1represent-OH or-NH 2, be preferably-OH.
G 1expression-R 11repetitive represented by O-, R 11represent the cycloalkylidene of the straight-chain of carbon number 2 ~ 8 or the alkylidene of branch-like or carbon number 3 ~ 8.R 11represented concrete alkylidene or cycloalkylidene can be enumerated: ethylidene, propylidene, butylidene, pentylidene, hexylidene, cyclopentylene, cyclohexylidene etc.
G 2represent-C (=O) R 12repetitive represented by O-, R 12represent the cycloalkylidene of the straight-chain of carbon number 1 ~ 8 or the alkylidene of branch-like or carbon number 4 ~ 8.R 12represented concrete alkylidene or cycloalkylidene can be enumerated: methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, cyclopentylene, cyclohexylidene etc.
G 3represent-C (=O) R 13c (=O)-OR 14repetitive represented by O-, R 13represent the arlydene of the straight-chain of carbon number 2 ~ 6 or the alkylidene of branch-like, the straight-chain of carbon number 2 ~ 6 or the alkenylene of branch-like, the cycloalkylidene of carbon number 3 ~ 20 or carbon number 6 ~ 20.R 13represented concrete alkylidene or cycloalkylidene can be enumerated: methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, cyclopentylene, cyclohexylidene etc.R 13represented concrete alkenylene can be enumerated: ethenylidene, allylidene, butenylidene, inferior pentenyl, sub-hexenyl etc.R 13represented concrete arlydene can be enumerated: phenylene, naphthylene, anthrylene etc.
R 14represent-CH (R 15)-CH (R 16)-.R 15and R 16one be hydrogen atom, another represents that the alkyl of carbon number 1 ~ 20, the thiazolinyl of carbon number 2 ~ 20, the aryl of carbon number 6 ~ 20, the carbon number of moieties are the alkoxymethylene of 1 ~ 20, the carbon number of alkenyl part is the alkene oxygen methylene of 2 ~ 20, the carbon number of aryl moiety is 6 ~ 20 and the aryloxy group methylene that aryl moiety can replace through halogen atom or N-methylene-phthalimide-based.
The alkyl of carbon number 1 ~ 20 is preferably the alkyl of carbon number 1 ~ 10, is more preferably the alkyl of carbon number 1 ~ 6.Specifically can enumerate: methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group, neopentyl, n-hexyl, n-octyl etc.
The thiazolinyl of described carbon number 2 ~ 20 is preferably the thiazolinyl of carbon number 2 ~ 10, is more preferably the thiazolinyl of carbon number 2 ~ 6.Specifically can enumerate: ethinyl, propenyl, butenyl group, pentenyl, hexenyl etc.
The aryl of described carbon number 6 ~ 20 is preferably the aryl of carbon number 6 ~ 10, specifically can enumerate: phenyl, naphthyl, anthryl etc.
The carbon number of described moieties be 1 ~ 20 alkoxymethylene be that oxygen methylene is binding on R 14the form of the alkyl of represented carbon number 1 ~ 20, the alkyl of described carbon number 1 ~ 20 and R 14the alkyl of represented carbon number 1 ~ 20 is identical meanings, and preferable range is also identical.
The carbon number of described alkenyl part be 2 ~ 20 alkene oxygen methylene be that oxygen methylene is binding on R 14the form of the thiazolinyl of represented carbon number 2 ~ 20, the thiazolinyl of described carbon number 2 ~ 20 and R 14the thiazolinyl of represented carbon number 2 ~ 20 is identical meanings, and preferable range is also identical.
The carbon number of described aryl moiety be 6 ~ 20 aryloxy group methylene be that oxygen methylene is binding on R 14the form of the aryl of represented carbon number 6 ~ 20, the aryl of described carbon number 6 ~ 20 and R 14the aryl of represented carbon number 6 ~ 20 is identical meanings, and preferable range is also identical.
R 17represent the straight-chain of carbon number 2 ~ 8 or alkylidene, the cycloalkylidene of carbon number 3 ~ the 8 ,-C (=O) R of branch-like 12-or-C (=O) R 13c (=O)-OR 14-.R 17represented concrete alkylidene or cycloalkylidene can be enumerated: ethylidene, propylidene, butylidene, pentylidene, hexylidene, cyclopentylene, cyclohexylidene etc.R 12and R 13with R mentioned above 12and R 13for identical meanings, preferable range is also identical.
M1 represents the integer of 0 ~ 100, is preferably the integer of 0 ~ 60, is more preferably the integer of 0 ~ 40.
M2 represents the integer of 0 ~ 60, is preferably the integer of 2 ~ 50, is more preferably the integer of 3 ~ 40.With regard to the lowering viscousity of pigment dispersion and the viewpoint of storage stability, being preferably m2 is the integer of 3 ~ 15.
M3 represents the integer of 0 ~ 30, is preferably the integer of 0 ~ 25, is more preferably the integer of 0 ~ 20.
Moreover m1+m2+m3 is preferably more than 1, less than 100, is more preferably 2 ~ 60, and then be preferably the integer of 3 ~ 40.
About the synthetic method of the compound represented by general formula (II'), known method can be utilized synthesize, such as with reference to the record of the paragraph 0047 ~ paragraph 0082 of Japanese Patent Laid-Open 2007-131832 publication, its content can be incorporated in this instructions.
Carboxylic serials spreading agent used in the present invention is preferably the carboxylic serials spreading agent of the open loop addition gained used by 6-caprolactone based compound and δ-valerolactone based compound.
In addition, at least one end, there is the polymkeric substance (POH) of hydroxyl or there is at least one end the polymkeric substance (PNH of one-level amino 2) preferred configuration be such as more preferably represented by general formula (III).
[changing 51]
In general formula (III), Y 1represent the monovalence terminal groups of carbon number 1 ~ 20, oxygen number 0 ~ 12 and nitrogen number 0 ~ 3, X 2represent-O-,-S-or-N (R b)-, R brepresent hydrogen atom or the straight-chain of carbon number 1 ~ 18 or the alkyl of branch-like.Z 1represent-OH or-NH 2.
G 4and G 5represent C (=O) R respectively 12repetitive represented by O-, R 12represent the cycloalkylidene of the straight-chain of carbon number 1 ~ 8 or the alkylidene of branch-like or carbon number 4 ~ 8.Wherein, G 4in R 12and G 5in R 12for mutually different group.R 20represent-C (=O) R 12.M4 represents the integer of 5 ~ 60, and m5 represents the integer of 5 ~ 60.Described repetitive G in general formula (III) 4, repetitive G 5configuration do not limit its order, represent in the polymkeric substance represented by general formula (III), in radicals X 2with group Z 1between contain repetitive G with random order 4, repetitive G 5, and then, these repetitives G 4, repetitive G 5can be any one of random or block type respectively.
In general formula (III), Y 1with the Y in general formula (II') 1for identical meanings, preferable range is also identical.When the situation of m5=0, Y 1be preferably the straight-chain of carbon number 1 ~ 7 or the alkyl of branch-like, or there is ethene unsaturated double-bond.
In general formula (III), X 2with the X in general formula (II') 2for identical meanings, preferable range is also identical.
In general formula (III), Z 1with the Z in general formula (II') 1for identical meanings, preferable range is also identical.
G 4and G 5represent C (=O) R respectively 12repetitive represented by O-, R 12represent the cycloalkylidene of the straight-chain of carbon number 1 ~ 8 or the alkylidene of branch-like or carbon number 4 ~ 8.Wherein, G 4in R 12and G 5in R 12for mutually different group.G 4and G 5with the G in general formula (II') 2for identical meanings, preferable range is also identical.R in general formula (III) 12with the R in general formula (II') 12for identical meanings, preferable range is also identical.
R 20represent-C (=O) R 12.Described R 12with the R in general formula (II') 12for identical meanings, preferable range is also identical.
M4 represents the integer of 5 ~ 60, is preferably the integer of 5 ~ 50, is more preferably the integer of 10 ~ 40.
M5 represents the integer of 5 ~ 60, is preferably the integer of 5 ~ 50, is more preferably the integer of 10 ~ 40.With regard to the lowering viscousity of pigment dispersion and the viewpoint of storage stability, being preferably m5 is the integer of 10 ~ 20.
About the synthetic method of the compound represented by general formula (III), known method can be utilized synthesize, such as with reference to the record of the paragraph 0047 ~ paragraph 0082 of Japanese Patent Laid-Open 2007-131832 publication, its content can be incorporated in this instructions.
Carboxylic serials spreading agent used in the present invention is preferably the carboxylic serials spreading agent of the open loop addition gained used by 6-caprolactone based compound and δ-valerolactone based compound.
In addition, the present invention also can use the polymkeric substance represented by following general formula (6) to be used as having the polymkeric substance (POH) of hydroxyl at single end or have the polymkeric substance (PNH of one-level amino at single end 2).
General formula (6)
[changing 52]
In general formula (6), Y 2represent that the polymerization of ethylene-based polymer stops base, Z 2represent-OH or-NH 2, R 21and R 22separately represent hydrogen atom or methyl, R 23and R 24any one represent hydrogen atom, another represents aromatic series base or-C (=O)-X 6-R 25(wherein, X 6represent-O-or-N (R 26)-, R 25, R 26the alkyl of the had aromatic series base representing the straight-chain of hydrogen atom or carbon number 1 ~ 18 or branch-like alternatively base), X 4expression-O-R 27-or-S-R 27-, R 27represent the straight-chain of carbon number 1 ~ 18 or the alkylidene of branch-like, n represents the integer of 2 ~ 50.
Y 2representing that the polymerization of ethylene-based polymer stops base, is the arbitrary known polymerization stopping base importing when utilizing usual way to implement the situation of the polymerization of common ethylene unsaturated monomer.Such as can be the group deriving from polymerization initiator, the group deriving from chain-transferring agent, derive from the group of solvent or derive from the group of ethylene unsaturated monomer.Even if Y 2have these arbitrary chemical constitution, spreading agent of the present invention does not also stop base Y by polymerization 2impact and its effect can be played.Polymerization stops base can enumerating carboxylic acid residues, alcohol residue etc., is preferably carboxylic acid residues.
Z 2represent-OH or-NH 2.
R 21and R 22represent hydrogen atom or methyl respectively, be preferably hydrogen atom.
R 23and R 24any one represent hydrogen atom, another represents aromatic series base or-C (=O)-X 6-R 25(wherein, X 6for-O-or-N (R 26)-).
Aromatic series base is preferably the aromatic series base of carbon number 6 ~ 20, is more preferably the aromatic series base of carbon number 6 ~ 14, and then is preferably the aromatic series base of carbon number 6 ~ 10.Specifically can enumerate phenyl, naphthyl, anthryl etc.
X 6represent-O-or-N (R 26)-, R 25and R 26represent the straight-chain of hydrogen atom or carbon number 1 ~ 18 or branch-like respectively and the alkyl of aromatic series base alternatively base can be had.The straight-chain of carbon number 1 ~ 18 or branch-like alkyl are preferably the alkyl of carbon number 1 ~ 10, are more preferably the alkyl of carbon number 1 ~ 6.Specifically can enumerate: methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group, neopentyl, n-hexyl, n-octyl etc.The aromatic series base of the alternatively base that described alkyl has is preferably the aromatic series base of carbon number 6 ~ 20, is more preferably the aromatic series base of carbon number 6 ~ 14, and then is preferably the aromatic series base of carbon number 6 ~ 10.Specifically can enumerate phenyl, naphthyl, anthryl etc.
X 4represent singly-bound ,-O-R 27-or S-R 27-.
R 27represent the straight-chain of carbon number 1 ~ 18 or the alkylidene of branch-like.The alkylidene of carbon number 1 ~ 18 is preferably the alkylidene of carbon number 1 ~ 10, is more preferably the alkylidene of carbon number 1 ~ 6.Specifically can enumerate: methylene, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene, hexylidene etc.
N represents the integer of 2 ~ 50, is preferably the integer of 2 ~ 40, is more preferably the integer of 2 ~ 30.
(tricarboxylic acid anhydride or tetracarboxylic dianhydride)
First tricarboxylic acid anhydride can enumerate aliphatic tricarboxylic acids acid anhydride or aromatic tricarboxylic acids acid anhydride.
Aliphatic tricarboxylic acids acid anhydride include, for example: 3-carboxymethyl group glutaric anhydride, 1,2,4-butane tricarboxylic acid-1,2-acid anhydride, cis-propylene-1,2,3-tricarboxylic acids-1,2-acid anhydride, 1,3,4-cyclopentane tricarboxylic acid anhydride etc.
Aromatic tricarboxylic acids acid anhydride include, for example: benzene tricarbonic acid's acid anhydride (1,2,3-benzene tricarbonic acid acid anhydride, trimellitic anhydride (1,2,4-benzene tricarbonic acid acid anhydride) etc.), naphthalene tricarboxylic acid anhydride (1,2,4-naphthalene tricarboxylic acid anhydride, Isosorbide-5-Nitrae, 5-naphthalene tricarboxylic acid anhydride, 2,3,6-naphthalene tricarboxylic acid anhydride, 1,2,8-naphthalene tricarboxylic acid anhydride etc.), 3,4,4'-benzophenone tricarboxylic acid anhydrides, 3,4,4'-Biphenyl Ether tricarboxylic acid anhydride, 3,4,4'-biphenyl tricarboxylic acid anhydrides, 2,3,2'-biphenyl tricarboxylic acid anhydride, 3,4,4'-biphenyl methane tricarboxylic acid anhydrides, 3,4,4'-biphenyl sulfone tricarboxylic acid anhydride etc.
When using the situation of tricarboxylic acid anhydride, in described, be preferably aromatic tricarboxylic acids acid anhydride.
Tetracarboxylic dianhydride include, for example: aliphatics tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride or polycycle tetracarboxylic dianhydride.
Aliphatics tetracarboxylic dianhydride include, for example: 1, 2, 3, 4-butane tetracarboxylic acid dianhydride, 1, 2, 3, 4-cyclo-butane tetracarboxylic dianhydride, 1, 3-dimethyl-1, 2, 3, 4-cyclo-butane tetracarboxylic dianhydride, 1, 2, 3, 4-cyclopentane tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 2, 3, 5, 6-tetracarboxylic cyclohexane dianhydride, 2, 3, 5, 6-tetracarboxylic norbornane dianhydride, 3, 5, 6-tri-carboxyl norbornane-2-acetic acid dianhydride, 2, 3, 4, 5-tetrahydrofuran tetracarboxylic dianhydride, 5-(2, 5-dioxotetrahydro fural)-3-methyl-3-cyclohexene-1, 2-dicarboxylic acid dianhydride, dicyclo [2, 2, 2]-Xin-7-alkene-2, 3, 5, 6-tetracarboxylic dianhydride etc.
Aromatic tetracarboxylic acid's dianhydride include, for example: pyromellitic acid anhydride, ethylene glycol bisthioglycolate trimellitic anhydride ester, propylene glycol two trimellitic anhydride ester, butylene glycol two trimellitic anhydride ester, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyl sulfone tetracarboxylic dianhydride, 2,2', 3,3'-biphenyl sulfone tetracarboxylic dianhydride, Isosorbide-5-Nitrae, 5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3', 4,4'-Biphenyl Ether tetracarboxylic dianhydride, 3,3', 4,4'-dimethyl diphenyl silane tetracarboxylic dianhydride, 3,3', 4,4'-tetraphenyl silane tetracarboxylic dianhydride, 1,2,3,4-furans tetracarboxylic dianhydride, two (3,4-di carboxyl phenyloxy) the diphenylsulfide dianhydride of 4,4'-, two (3,4-di carboxyl phenyloxy) the diphenyl sulfone dianhydride of 4,4'-, two (3,4-di carboxyl phenyloxy) the diphenyl propane dianhydride of 4,4'-, 3,3', 4,4'-perfluoroiso-propylidene two O-phthalic acid dianhydride, 3,3', 4,4'-biphenyl tetracarboxylic dianhydride, two (phthalic acid) phenylphosphine oxide dianhydride, to phenylene-bis-(triphenyl phthalic acid) dianhydride, metaphenylene-bis-(triphenyl phthalic acid) dianhydride, two (triphenyl phthalic acid)-4,4'-diphenyl ether dianhydride, two (triphenyl phthalic acid)-4,4'-diphenyl methane dianhydride, two (3,4-dicarboxyphenyi) the fluorenes dianhydride of 9,9-, two [4-(3,4-di carboxyl phenyloxy) phenyl] fluorenes dianhydrides of 9,9-etc.
Polycycle tetracarboxylic dianhydride include, for example: 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-6-methyl isophthalic acid-naphthalene succinic dianhydrides etc.
When using the situation of tetracarboxylic dianhydride, in described, be preferably aromatic tetracarboxylic acid's dianhydride.
The tricarboxylic acid anhydride used in the present invention or tetracarboxylic dianhydride are not limited to described illustrative compound, can adopt arbitrary structures.These can be used alone, also can and use.With regard to the viewpoint of the lowering viscousity of pigment dispersion or various ink, in the present invention, preferably can use aromatic tricarboxylic acids acid anhydride or aromatic tetracarboxylic acid's dianhydride.And then be preferably pyromellitic acid anhydride, 3,3', 4,4'-biphenyl tetracarboxylic dianhydrides, 9,9-two (3,4-dicarboxyphenyi) fluorenes dicarboxylic anhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydrides, ethylene glycol bisthioglycolate trimellitic anhydride ester, trimellitic anhydride.
(at least one end, there is the polymkeric substance (POH) of hydroxyl or there is at least one end the polymkeric substance (PNH of one-level amino 2), with the reaction of tricarboxylic acid anhydride or tetracarboxylic dianhydride)
Carboxylic serials spreading agent of the present invention is by making the hydroxyl of " having the polymkeric substance (POH) of hydroxyl at least one end " or describedly " having the polymkeric substance (PNH of one-level amino at least one end 2) " one-level amino, react with the anhydride group of tricarboxylic acid anhydride or tetracarboxylic dianhydride and obtain.
By the hydroxyl of polymkeric substance (POH) or polymkeric substance (PNH 2) the molal quantity of one-level amino be set as < H >, when the molal quantity of the acid anhydride of tricarboxylic acid anhydride or tetracarboxylic dianhydride is set as < N >, reactive ratio is preferably 0.5 < < H >/< N > < 1.2, and then be preferably 0.7 < < H >/< N > < 1.1, most preferably be the situation of < H >/< N >=1.When carrying out the situation of reacting with < H >/< N > < 1, the water of necessary amount also can be utilized to use after remaining anhydride hydrolyzes.
Polymkeric substance (POH) or polymkeric substance (PNH 2) with the reaction of tricarboxylic acid anhydride or tetracarboxylic dianhydride in also can use catalyzer.Catalyzer such as can use tertiary amine based compound, include, for example: triethylamine, triethylenediamine, N, N-dimethyl benzyl amine, N-methylmorpholine, 1,8-diazabicyclo-[5.4.0]-7-hendecene, 1,5-diazabicyclo-[4.3.0]-5-nonene etc.
Polymkeric substance (POH) or polymkeric substance (PNH 2) can carry out under condition of no solvent with the reaction of tricarboxylic acid anhydride or tetracarboxylic dianhydride, also can use suitable dehydrated organic solvent.The solvent used in reaction can be removed by operations such as distillations after the completion of reaction, or directly as the product of spreading agent a part and use.
About polymkeric substance (POH) or polymkeric substance (PNH 2) with the temperature of reaction of tricarboxylic acid anhydride or tetracarboxylic dianhydride, when using the situation of " there is at least one end the polymkeric substance (POH) of hydroxyl ", being preferably 80 DEG C ~ 180 DEG C, being more preferably in the scope of 90 DEG C ~ 160 DEG C and reacting.If temperature of reaction is less than 80 DEG C, reaction velocity is slow, if more than 180 DEG C, sometimes reacts and the acid anhydrides of open loop generates cyclic anhydride again, and reaction is difficult to terminate.In addition, " there is at least one end the polymkeric substance (PNH of one-level amino in use 2) " situation time, being preferably 0 DEG C ~ 150 DEG C, reacting in the scope that is more preferably 10 DEG C ~ 100 DEG C.If be less than 0 DEG C, sometimes react, if more than 150 DEG C, sometimes carry out imidizate and not good enough.
Relative to total solid composition, the content of the spreading agent in composition of the present invention is preferably 1 quality % ~ 30 quality %, is more preferably 2 quality % ~ 20 quality %, and then is preferably 4 quality % ~ 15 quality %.
In addition, relative to (A) pigment 100 mass parts, the content of spreading agent is preferably 5 mass parts ~ 60 mass parts, is more preferably 9 mass parts ~ 40 mass parts.
Spreading agent can, only containing a kind of, also can contain two or more in the present compositions.When containing two or more situations, being preferably its total amount becomes described scope.
Except described, also can contain other spreading agents, also can contain the spreading agent recorded in 0338 ~ 0333 of Japanese Patent Laid-Open 2013-073104 publication, these contents are incorporated in present specification.
< < (D) resin binder > >
Composition of the present invention contains (D) resin binder.By adding (D) resin binder, suitable dispersion stabilization or alkali-developable can be given to photosensitive composition of the present invention.
There is no particular restriction for the kind of (D) resin binder used in composition of the present invention, such as, preferably make the compound (x) represented by following general formula (IV), have the resin of compound (y) copolymerization of ethene unsaturated double-bond with other.
General formula (IV)
[changing 53]
In general formula (IV), R 4represent hydrogen atom or methyl, R 5represent the alkylidene of carbon number 2 or 3, R 6represent that hydrogen atom maybe can contain the alkyl of the carbon number 1 ~ 20 of phenyl ring, n represents the integer of 1 ~ 15.When n is the situation of more than 2, multiple R 5can identical also can be different.When n is the situation of more than 2, multiple R 5can identical also can be different.
R 5represent the alkylidene of carbon number 2 or 3, when n is the situation of more than 2, multiple R 5can identical also can be different.
R 6represent that hydrogen atom maybe can contain the alkyl of the carbon number 1 ~ 20 of phenyl ring.R 6represented alkyl to be carbon number be 1 ~ 20 alkyl, be preferably the alkyl of carbon number 1 ~ 10.At R 6when the carbon number of represented alkyl is 1 ~ 10, alkyl becomes obstacle and suppresses resin each other close, promotes the absorption/orientation to pigment, if but carbon number more than 10, then the steric effects of alkyl uprises, and demonstrates and also hinders phenyl ring to the tendency of the absorption/orientation of pigment.Described tendency is along with R 6the carbon chain length of alkyl elongated and become significantly, if carbon number is more than 20, then absorption/orientation of phenyl ring extremely reduces.
R 6represented alkyl can be enumerated: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl etc.
R 6the represented alkyl containing phenyl ring can be enumerated: 1-phenylethyl, 1-phenyl propyl, 1-phenyl butyl, 1-phenylpentyl, 1-Phenylhexyl, 1-phenylheptyl, 1-phenyl octyl group, 1-phenyl nonyl, 1-phenyl decyl, benzyl, 2-phenyl (different) propyl group etc.
In these, be preferably benzyl, 2-phenyl (different) propyl group.
Compound (x) can be enumerated: the oxirane (EthyleneOxide of phenol, the EO of EO) modification (methyl) acrylate, p-cumylphenol or epoxypropane (PropyleneOxide, PO) modification (methyl) acrylate, EO modification (methyl) acrylate of nonyl phenol, PO modification (methyl) acrylate etc. of nonyl phenol.In these compounds, EO or PO modification (methyl) acrylate of p-cumylphenol not only has the effect of the pi-electron of described phenyl ring, and except its stereoeffect, also can form the absorption/oriented surface better to pigment, therefore effect is higher.
The compound (y) with ethene unsaturated double-bond can be enumerated: (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid (different) propyl ester, (methyl) acrylic acid (different) butyl ester, (methyl) acrylic acid (different) pentyl ester, (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, (methyl) glycidyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid phosphorus acyloxy ethyl ester, (methyl) acrylic acid phosphorus acyloxy propyl ester, (methyl) acrylic acid-3-chloro-2-acid phosphorus acyloxy ethyl ester, acid phosphorus acyloxy polyethyleneglycol (methyl) acrylate etc.
The ratio of the compound (x) in (D) of the present invention resin is 0.1 quality % ~ 50 quality %, is more preferably 10 quality % ~ 35 quality %.If the ratio of compound (x) is less than 10 quality %, then pigment dispersion effect reduce, and if then be less than 0.1 quality %, then cannot obtain sufficient dispersion effect.In addition, if more than 35 quality %, hydrophobicity becomes large, sometimes the developability of photosensitive composition reduces, or cause residue, if and then more than 50 quality %, obviously reduce with the compatibility of other constituents in photosensitive composition, sometimes also cause the precipitation of monomer or Photoepolymerizationinitiater initiater.
The weight average molecular weight (Mw) of (D) of the present invention resin (multipolymer) is preferably 5000 ~ 100000, is more preferably 10000 ~ 50000.
When the situation of (methyl) acrylate using (methyl) acrylic acid phosphorus acyloxy ethyl ester, (methyl) acrylic acid phosphorus acyloxy propyl ester, (methyl) acrylic acid-3-chloro-2-acid phosphorus acyloxy ethyl ester, acid phosphorus acyloxy polyethyleneglycol (methyl) acrylate etc. containing phosphate as compound (y), higher pigment dispersion effect sometimes can be obtained.
The ratio of (methyl) acrylate of described phosphorous acidic group is 0.05 quality % ~ 10 quality %, is more preferably 0.1 quality % ~ 5 quality %.If the ratio of (methyl) acrylate of phosphorous acidic group is less than 0.05 quality %, then cannot obtain sufficient dispersion effect.In addition, if more than 10 quality %, the polarity of resin increases, and developing powder obviously accelerates, or reduces with the compatibility of other hydrophobic combination and resin is separated out.
In addition, improving the sensitivity of photosensitive composition to make monomer or resin react each other, ethene double bond can be imported on the side chain of (D) of the present invention resin (multipolymer).Specifically, when resin has the situation of hydroxyl isoreactivity functional group, by making (methyl) glycidyl acrylate, 2-(methyl) acryloxy isocyanate etc. has and reacts with the functional group of described reactive functional radical reaction and the compound of ethene unsaturated group, and on side chain, import ethene double bond.
(D) manufacture of resin can utilize known method to manufacture, such as, with reference to the record of the paragraph 0041 ~ paragraph 0045 of Japanese Patent Laid-Open 2004-101728 publication, its content can be incorporated in this instructions.
Relative to total solid composition, the content of (D) resin of composition of the present invention is preferably 1 quality % ~ 50 quality %, is more preferably 3 quality % ~ 40 quality %, and then is preferably 5 quality % ~ 30 quality %.
(D) resin can, only containing a kind of, also can contain two or more in the present compositions.When containing two or more situations, being preferably its total amount becomes described scope.
< (E) Photoepolymerizationinitiater initiater >
With regard to improving the viewpoint of sensitivity further, composition of the present invention contains Photoepolymerizationinitiater initiater.
As long as described Photoepolymerizationinitiater initiater has the ability of the polymerization causing aftermentioned polymerizable compound, then there is no particular restriction, suitably can select in known Photoepolymerizationinitiater initiater.Such as preferably have photosensitive to ultraviolet ray range to luminous ray.In addition, also can be and some occurs through light activated sensitizer act on and the activating agent generating living radical, also can be the kind according to monomer and the initiating agent caused as cationic polymerization.
In addition, described Photoepolymerizationinitiater initiater is preferably and in the scope of about 300nm ~ 800nm (being more preferably 330nm ~ 500nm), has the compound of molecule absorptivity at least about 50 containing at least one.
Described Photoepolymerizationinitiater initiater include, for example: halogenated hydrocarbon derivant (such as have triazine skeleton, Ju You oxadiazole skeleton etc.), oxime compound, organic peroxide, sulphur compound, ketonic compound, aromatic series salt, ketoxime ether, aminoacetophenone compounds, the hydroxy acetophenones etc. such as acylphosphine compounds, six aryl bisglyoxalines, 9 oxime derivate such as acylphosphine oxide.
In addition, with regard to exposing the viewpoint of sensitivity, preferably be selected from by trihalomethyl group triaizine compounds, benzil dimethyl ketal compound, alpha-hydroxyacetone compounds, alpha-amido ketonic compound, acylphosphine compounds, phosphine oxide compound, metallocene compound, oxime compound, triarylimidazoles dipolymer, compound, benzothiazole compound, benzophenone cpd, acetophenone compound and derivant thereof, cyclopentadiene-benzene-iron complex and salt thereof, Lu is for Jia oxadiazole compound, compound in the cohort that 3-aryl substituted cumarin compound forms.
Trihalomethyl group triaizine compounds also can use commercially available product, such as, also can use TAZ-107 (manufacture of green (midori) chemical company).
Especially when composition of the present invention is used for the situation making the colored filter that solid-state imager possesses, fine pattern must be formed with the shape of sharp-pointed (sharp), therefore importantly hardening with develop without residue in unexposed portion.Plant viewpoint, Photoepolymerizationinitiater initiater especially preferably uses oxime compound at this point.When especially forming the situation of fine pattern in solid-state imager, step printing is used when sclerosis exposes, but described exposure machine sustains damage because of halogen sometimes, also must the addition of Photoepolymerizationinitiater initiater be suppressed low, if therefore consider these aspects, then especially being preferably when forming the fine pattern as solid-state imager, using oxime compound as (E) Photoepolymerizationinitiater initiater.
Described have the halogenated hydrocarbon derivant of triazine skeleton, described ketonic compound and described beyond Photoepolymerizationinitiater initiater can refer in the paragraph 0074 ~ paragraph 0077 of Japanese Patent Laid-Open 2013-077009 publication record compound, its content is incorporated in this instructions.
Photoepolymerizationinitiater initiater also can preferably use hydroxy acetophenone compound, aminoacetophenone compounds and acylphosphine compounds.More specifically, the aminoacetophenone series initiators recorded in Japanese Patent Laid-Open 10-291969 publication, the acylphosphine oxide series initiators recorded in Jap.P. No. 4225898 publication can such as also be used.
Hydroxy acetophenone series initiators can use: gorgeous good solid (IRGACURE)-184, Da Luoka (DAROCUR)-1173, gorgeous good solid (IRGACURE)-500, gorgeous good solid (IRGACURE)-2959, gorgeous good solid (IRGACURE)-127 (trade name: be BASF (BASF) company and manufacture).Aminoacetophenone series initiators can use: as gorgeous good solid (IRGACURE)-907 of commercially available product, gorgeous good solid (IRGACURE)-369 and gorgeous good solid (IRGACURE)-379, gorgeous good solid (IRGACURE)-OXE379 (trade name: be BASF (BASF) company and manufacture).Aminoacetophenone series initiators also can use the isometric wave source of absorbing wavelength and 365nm or 405nm to mate the compound recorded in the Japanese Patent Laid-Open 2009-191179 publication of (matching).In addition, acylphosphanes series initiators also can be used as gorgeous good solid (IRGACURE)-819 or Da Luoka (the DAROCUR)-TPO of commercially available product (trade name: be BASF (BASF) company and manufacture).
Photoepolymerizationinitiater initiater more preferably can enumerate oxime compound.The concrete example of oxime compound can use the compound recorded in the compound recorded in Japanese Patent Laid-Open 2001-233842 publication, the compound recorded in Japanese Patent Laid-Open 2000-80068 publication, Japanese Patent Laid-Open 2006-342166 publication.In addition, oxime compound can be enumerated: " Englishize association will (JournaloftheChemicalSociety, J.C.S.) pul gold proceedings (Perkin) II " (1979) pp.1653-1660, " Englishize association will (JournaloftheChemicalSociety, J.C.S.) pul gold proceedings (Perkin) II " (1979) pp.156-162, " photopolymer science and technology periodical (JournalofPhotopolymerScienceandTechnology) " (nineteen ninety-five) pp.202-232, the compound recorded in Japanese Patent Laid-Open 2000-66385 publication, Japanese Patent Laid-Open 2000-80068 publication, Jap.P. spy table 2004-534797 publication, the compound etc. recorded in each publication of Japanese Patent Laid-Open 2006-342166 publication.
Commercially available product also preferably can use gorgeous good solid (IRGACURE)-OXE01 (manufacture of BASF (BASF) company), gorgeous good solid (IRGACURE)-OXE02 (manufacture of BASF (BASF) company), TR-PBG-304 (Changzhou Tronly New Electronic Materials Co., Ltd.'s manufacture).
Preferably can be used as the oxime compounds such as the 9 oxime derivate of Photoepolymerizationinitiater initiater of the present invention and can refer to the compound recorded in the paragraph 0080 ~ paragraph 0116 of Japanese Patent Laid-Open 2013-077009 publication, its content is incorporated in this instructions.
Oxime compound has maximum absorption wavelength in the wavelength coverage of 350nm ~ 500nm, preferably in the wavelength coverage of 360nm ~ 480nm, has absorbing wavelength, and the absorbance being especially preferably 365nm and 455nm is high.
With regard to the viewpoint of sensitivity, the molar absorptivity under 365nm or 405nm of oxime compound is preferably 1, and 000 ~ 300,000, be more preferably 2,000 ~ 300,000, be especially preferably 5,000 ~ 200,000.
The molar absorptivity of compound can use known method to measure, specifically, such as preferably use ultraviolet-visible pectrophotometer (in the card that Varian (Varian) company manufactures-5 (Carry-5) spectrophotometer (spectrophotometer)), use ethyl acetate solvent to measure with the concentration of 0.01g/L.
Optionally also use capable of being combined is two or more for Photoepolymerizationinitiater initiater used in the present invention.
When containing the situation of (E) Photoepolymerizationinitiater initiater in the present compositions, relative to the total solid composition of composition, (E) content of Photoepolymerizationinitiater initiater is preferably more than 0.1 quality %, below 50 quality %, be more preferably more than 0.5 quality %, below 30 quality %, and then be preferably more than 1 quality %, below 20 quality %.Better sensitivity and patternability can be obtained in described scope.
< < (F) polymerizable compound > >
Composition of the present invention contains (F) polymerizable compound.In the present invention, the known polymerizable compound be cross-linked by free radical, acid, heat and can carrying out can be used, include, for example the polymerizable compound containing ethene unsaturated link, cyclic ether (epoxy, oxetanes), methylol etc.With regard to the viewpoint of sensitivity, (F) polymerizable compound be preferably be selected from have at least one, be preferably plural terminal ethylene unsaturated link compound in.Wherein, being preferably 4 officials can above multifunctional polymerizable compound, so be preferably 5 officials can above multifunctional polymerizable compound.
This kind of compound cohort is widely known by the people in this industrial field, can use these compounds without particular limitation in the present invention.These compounds such as can be any one of following chemical form: monomer, prepolymer and dipolymer, trimer and oligomer or these potpourri and these oligomer etc.Polymerizable compound of the present invention can be used alone one, also can and with two or more.
More specifically, the example of monomer and prepolymer thereof can be enumerated: unsaturated carboxylic acid (such as acrylic acid, methacrylic acid, itaconic acid, butenoic acid, methacrylate, maleic acid etc.) or its ester class, amide-type and these polymer, is preferably unsaturated carboxylic acid and the ester of aliphatic polybasic alcoholic compound and the amide-type of unsaturated carboxylic acid and aliphatic polybasic amines and these polymer.In addition, also can preferably use following reactant: there is the esters of unsaturated carboxylic acids of hydroxyl or the nucleophilic substitution such as amino, sulfydryl base or the addition reaction of amide-type and simple function or polyfunctional isocyanate's class or epoxies, or with the dehydration condensation thing etc. of simple function or polyfunctional carboxylic acid.In addition, following reactant is also preferred: the addition reaction with the substituent esters of unsaturated carboxylic acids of the electrophilicity such as isocyanate group or epoxy radicals or amide-type and simple function or polyfunctional alcohols, amine, thio-alcohol, and then has the substituted reactant of the substituent esters of unsaturated carboxylic acids of the detachment such as halogen radical or tosyloxy or amide-type and simple function or polyfunctional alcohols, amine, thio-alcohol.In addition, as other examples, also can use and replace described unsaturated carboxylic acid and replace to the compound cohort of vinyl benzene derivant, vinethene, the allyl ethers etc. such as unsaturated phosphonic acids, styrene.
As these particular compound, also the compound recorded in the numbered paragraphs of Japanese Patent Laid-Open 2009-288705 publication [0095] ~ numbered paragraphs [0108] can be preferably used in the present invention.
In addition, described polymerizable compound also preferably has at least one vinyl that can carry out addition polymerization and has the compound with ethene unsaturated group of the boiling point of more than 100 DEG C at ambient pressure.Its content with reference to the compound recorded in the paragraph 0124 of Japanese Patent Laid-Open 2013-077009 publication, can be incorporated in this instructions by its example.
In addition, there is the boiling point of more than 100 DEG C at ambient pressure and there is the compound that at least one compound that can carry out the ethene unsaturated group of addition polymerization is also preferably record in numbered paragraphs [the 0254] ~ numbered paragraphs [0257] of Japanese Patent Laid-Open 2008-292970 publication.
Except described, with reference to the free radical polymerization monomer represented by general formula (the MO-1) ~ general formula (MO-5) recorded in the paragraph 0126 ~ paragraph 0129 of Japanese Patent Laid-Open 2013-077009 publication, its content can be incorporated in this instructions.
In addition, following compound also can be used as described polymerizable compound: the compound of (methyl) acroleic acid esterification in addition after the addition of ethylene oxide on described polyfunctional alcohol recorded in the lump with its concrete example as general formula (1) and general formula (2) in Japanese Patent Laid-Open 10-62986 publication or epoxypropane.
Wherein, described polymerizable compound is preferably dipentaerythritol triacrylate (commercially available product is Ka Yala get (KAYARAD) D-330; Japan chemical drug incorporated company manufacture), (commercially available product is Ka Yala get (KAYARAD) D-320 to dipentaerythritol tetraacrylate; Japan chemical drug incorporated company manufacture), (commercially available product is Ka Yala get (KAYARAD) D-310 to dipentaerythritol five (methyl) acrylate; Japan chemical drug incorporated company manufacture), (commercially available product is Ka Yala get (KAYARAD) DPHA to dipentaerythritol six (methyl) acrylate; Chemical drug incorporated company of Japan manufactures, A-DPH-12E; Chemical company of Xin Zhong village manufactures) and these (methyl) acryloyl group be situated between every the structure of glycol residue, diol residues.Also can use these oligomer type.The form of preferred described polymerizable compound is below shown.
Described polymerizable compound also can be polyfunctional monomer, and also can have the acidic groups such as carboxyl, sulfonic group, phosphate.As long as ethene compound has unreacted carboxyl as described above as the situation of potpourri, then directly can utilize, optionally also can make the hydroxyl reaction of non-aromatic carboxylic acid anhydrides and described ethene compound and import acidic group.When described situation, the concrete example of the non-aromatic carboxylic acid anhydrides used can be enumerated: tetrabydrophthalic anhydride, alkylation tetrabydrophthalic anhydride, hexahydrophthalic anhydride, alkylation hexahydrophthalic anhydride, succinic anhydride, maleic anhydride.
In the present invention, the monomer with acidic group is the ester of aliphatic polyhydroxy compound and unsaturated carboxylic acid, preferably makes the unreacted hydroxyl reaction of non-aromatic carboxylic acid anhydrides and aliphatic polyhydroxy compound and has the polyfunctional monomer of acidic group,
Especially being preferably in its ester aliphatic polyhydroxy compound is pentaerythrite and/or dipentaerythritol.Commercially available product include, for example M-510, M-520 etc. as modified by polyacid acrylate oligomers that East Asia synthesis incorporated company manufactures.
These monomers can be used alone one, but with regard to manufacture view, are difficult to use single compound, therefore also can be used in combination two or more.In addition, optionally also can also with not there is the polyfunctional monomer of acidic group and there is the polyfunctional monomer of acidic group as monomer.
The preferred acid number with the polyfunctional monomer of acidic group is 0.1mgKOH/g ~ 40mgKOH/g, is especially preferably 5mgKOH/g ~ 30mgKOH/g.If the acid number of polyfunctional monomer is too low, then developer dissolves characteristic reduction, if too high, manufacture or operation become difficult and the reduction of photopolymerization performance, the hardening variation such as the surface smoothness of pixel.Therefore, and by the situation of the different polyfunctional monomer of two or more acidic groups or and with when not there is the situation of polyfunctional monomer of acidic group, preferably adjust in the mode of the acidic group of overall polyfunctional monomer in described scope.
In addition, be also preferred configuration containing the multi-functional monomer with caprolactone structure as polymerizable monomer.
As long as the multi-functional monomer with caprolactone structure has caprolactone structure in its molecule, then be not particularly limited, include, for example 6-caprolactone modification multifunctional (methyl) acrylate, described 6-caprolactone modification multifunctional (methyl) acrylate is by by trimethylolethane, two-trimethylolethane, trimethylolpropane, two-trimethylolpropane, pentaerythrite, dipentaerythritol, tripentaerythritol, glycerine, two glycerine, the in addition esterification and obtaining of the polyvalent alcohols such as trimethylol melamine and (methyl) acrylic acid and 6-caprolactone.Wherein, with reference to the compound recorded in the paragraph 0135 ~ paragraph 0153 of Japanese Patent Laid-Open 2013-077009 publication, its content can be incorporated in this instructions.
The commercially available product of this kind of described polymerizable compound include, for example: the four functional acrylate SR-494 with 4 inferior ethoxyl chains that Sartomer (Sartomer) company manufactures, and what Japanese chemical drug incorporated company manufactured has six functional acrylate DPCA-60 of 6 sub-amoxy chains, has the trifunctional acrylate TPA-330 etc. of 3 sub-isobutoxy chains.
In addition, described polymerizable compound be also preferably Jap.P. examined patent publication 48-41708 publication, Japanese Patent Laid-Open No. Sho 51-37193 publication, Japanese Patent Laid-fair 2-32293 publication, record in Japanese Patent Laid-fair 2-16765 publication as propenoic methyl carbamate class, or the carbamate compounds class with oxirane pastern bone frame that Jap.P. examined patent publication 58-49860 publication, Jap.P. examined patent publication 56-17654 publication, Jap.P. examined patent publication 62-39417 publication, Jap.P. examined patent publication 62-39418 publication are recorded.And then, there is the addition polymerization compounds of amino structure or sulfide based structural as described polymerizable compound by using in the molecule recorded in Japanese Patent Laid-Open No. Sho 63-277653 publication, Japanese Patent Laid-Open No. Sho 63-260909 publication, Japanese Patent Laid-Open 1-105238 publication, the curable adhensive compositions that film speed is very excellent can be obtained.
The commercially available product of described polymerizable compound can be enumerated: urethane oligomer UAS-10, urethane oligomer UAB-140 (manufacture of adret state basic policy paper pulp company), " UA-7200 " (manufacture of chemical company of Xin Zhong village), DPHA-40H (Japanese chemical drug Inc. makes), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufacture of common prosperity society), (commercially available product is A-TMPT to trimethylolpropane triacrylate; Chemical company of Xin Zhong village manufactures) etc.
About cyclic ether (epoxy, oxetanes), such as having epoxy radicals, bisphenol A type epoxy resin is JER-827, JER-828, JER-834, JER-1001, JER-1002, JER-1003, JER-1055, JER-1007, JER-1009, JER-1010 (being japan epoxy resin (stock) manufacture above), Chinese mugwort is than clone (EPICLON) 860, Chinese mugwort is than clone (EPICLON) 1050, Chinese mugwort is than clone (EPICLON) 1051, Chinese mugwort is than clone (EPICLON) 1055 (being that Di Aisheng (DIC) (stock) manufactures above) etc., bisphenol f type epoxy resin is JER-806, JER-807, JER-4004, JER-4005, JER-4007, JER-4010 (above for japan epoxy resin (stock) manufactures), Chinese mugwort is than cloning (EPICLON) 830, Chinese mugwort than clone (EPICLON) 835 (being that Di Aisheng (DIC) (stock) manufactures above), LCE-21, RE-602S (above is Japanese chemical drug (stock) manufacture) etc., phenol novolak type epoxy resin is JER-152, JER-154, JER-157S70, JER-157S65 (above for japan epoxy resin (stock) manufactures), and Chinese mugwort is than cloning (EPICLON) N-740, Chinese mugwort than clone (EPICLON) N-770, Chinese mugwort ratio clone (EPICLON) N-775 (being that Di Aisheng (DIC) (stock) manufactures above) etc., cresol novolak type epoxy resin being Chinese mugwort ratio clone (EPICLON) N-660, ending than clone (EPICLON) N-665, ending than cloning (EPICLON) N-670, Chinese mugwort than cloning (EPICLON) N-673, Chinese mugwort ratio clone (EPICLON) N-680, Chinese mugwort ratio clone (EPICLON) N-690, ending than clone (EPICLON) N-695 (being Di Aisheng (DIC) (stock) manufacture above), EOCN-1020 (being Japanese chemical drug (stock) manufacture above), aliphatic epoxy resin can be enumerated: Ai Dike resin (ADEKARESIN) EP-4080S, Ai Dike resin (ADEKARESIN) EP-4085S, Ai Dike resin (ADEKARESIN) EP-4088S (being that Ai Dike (ADEKA) (stock) manufactures above), Sai Luo West Germany (Celloxide) 2021P, Sai Luo West Germany (Celloxide) 2081, Sai Luo West Germany (Celloxide) 2083, Sai Luo West Germany (Celloxide) 2085, EHPE-3150 (1,2-epoxy-4-(2-oxiranyl) the cyclohexane addition product of two (the hydroxymethyl)-n-butyl alcohol of 2,2-), Ai Boli obtains (EPOLEAD) PB3600, Ai Boli obtains (EPOLEAD) PB4700 (above for Daicel (Daicel) chemical industry (stock) manufactures), for that Cauer (Denacol) EX-211L, for that Cauer (Denacol) EX-212L, for that Cauer (Denacol) EX-214L, for that Cauer (Denacol) EX-216L, for that Cauer (Denacol) EX-321L, for that Cauer (Denacol) EX-850L (changing into (NagaseChemtex) (stock) manufacture for length is rapids above), Ai Dike resin (ADEKARESIN) EP-4000S, Ai Dike resin (ADEKARESIN) EP-4003S, Ai Dike resin (ADEKARESIN) EP-4010S, Ai Dike resin (ADEKARESIN) EP-4011S (being that Ai Dike (ADEKA) (stock) manufactures above), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (being that Ai Dike (ADEKA) (stock) manufactures above), JER-1031S (japan epoxy resin (stock) manufacture) etc.This kind of polymerizable compound is suitable for utilizing dry etching method to form the situation of pattern.
About these polymerizable compounds, its structure, be used alone or and the details of the using method such as use, addition can set arbitrarily according to the final performance design of photosensitive composition.Such as with regard to the viewpoint of sensitivity, be preferably the structure that the unsaturated group content of every a part is many, when many, be preferably more than two senses.In addition, with regard to improving the viewpoint of the sclerosis film strength formed by photosensitive composition, with more than trifunctional being advisable, and then, by also regulating the method for sensitivity and intensity also effective with (such as acrylate, methacrylate, styrenic, vinethene based compound) that the different polymerism base of official's energy radix is different.And then, and with more than trifunctional and the different polymerizable compound of oxirane chain length with regard to following aspect preferably: the developability of adjustable photosensitive composition, can obtain excellent pattern Forming ability.
In addition, for compatibility, dispersiveness with other compositions (such as Photoepolymerizationinitiater initiater, by dispersion, alkali soluble resin etc.) contained by photosensitive composition, the choice for use method of polymerizable compound is also important factor, such as, sometimes by using low-purity compound or and improving compatibility with two or more.In addition, with regard to the viewpoint of the adhesion of the hard surface of raising and support etc., also specific structure can be selected.
Relative to the total solid composition in photosensitive composition, the content of (F) polymerizable compound in composition of the present invention is preferably 0.1 quality % ~ 90 quality %, and then be preferably 1.0 quality % ~ 50 quality %, be especially preferably 2.0 quality % ~ 30 quality %.
Other compositions of < < > >
Composition of the present invention, except described each composition, also in the scope not undermining effect of the present invention, also can have other compositions such as resin, organic solvent, crosslinking chemical of polymerism double bond at side chain containing (G).
-(G) side chain have the resin of polymerism double bond-
In the present invention, and then optionally also can have the resin (hereinafter also referred to " (G) resin ") of polymerism double bond at side chain containing (G).By also having the resin of polymerism double bond at side chain containing (G), composition of the present invention can be made more effectively to harden.Polymerism double bond is preferably (methyl) acrylate.
(G) as long as the resin having a polymerism double bond at side chain has polymerism double bond on side chain, then there is no particular restriction, preferably makes to have the resin that can react with the multipolymer (a) of the compound (b) of the functional group of hydroxyl reaction and ethene unsaturated double-bond and the polymerizable monomer (p) and other polymerizable monomers (q) with 2 ~ 6 hydroxyls.
Form (G) and there is the polymerizable monomer (p) with 2 ~ 6 hydroxyls of the resin of polymerism double bond for there are more than 2 and the compound of the hydroxyl of less than 6 and ethene unsaturated double-bond at side chain, such as, can use the monomer represented by following general formula (1).
General formula (1)
[changing 54]
(in formula, R 1and R 4represent the alkyl be substituted of hydrogen atom, carbon number 1 ~ 5 respectively, R 2represent the alkylidene of carbon number 1 ~ 4, R 3represent alkylidene or the singly-bound of carbon number 1 ~ 4, n represents the integer of more than 2, less than 6)
Monomer represented by described general formula (1) can enumerate the monoesters etc. of the polyvalent alcohol with ethene unsaturated double-bond, is preferably glycerine list (methyl) acrylate.
Other polymerizable monomers (q) are can with the polymerizable monomer of polymerizable monomer (p) copolymerization with 2 ~ 6 hydroxyls, include, for example: (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) benzyl acrylate, (methyl) phenyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) isobornyl acrylate, (methyl) 2-Hydroxy ethyl acrylate, (methyl) esters of acrylic acids such as (methyl) tetrahydrofurfuryl acrylate, NVP, the phenylethylene such as Styrene and its derivatives, α-methyl styrene, the acrylic amides such as (methyl) acrylamide, methylol (methyl) acrylamide, alkoxy methylol (methyl) acrylamide, two acetone (methyl) acrylamide, other vinyl compounds such as (methyl) vinyl cyanide, ethene, propylene, butylene, vinyl chloride, vinyl acetate, and the macromonomer class etc. such as polymethylmethacrylate macromonomer, Group-capped Polystyrene Macromer.These monomers can be used alone one, or used in combination two or more.
In addition, the copolymerization ratio of the polymerizable monomer (p) and other polymerizable monomers (q) with 2 ~ 6 hydroxyls is preferably 5 quality %:95 quality % ~ 5, quality % ~ 95 quality %, is more preferably 30 quality %:70 quality % ~ 30, quality % ~ 70 quality %.In the copolymerization of polymerizable monomer (p) than when being less than the situation of 5 quality %, the ethene unsaturated double-bond number that can import is few, and the numerical value of double bond equivalent (the double bond equivalent that following formula defines) becomes large, cannot obtain sufficient sensitivity.When the situation more than 95 quality % is compared in the copolymerization of polymerizable monomer (p), a large amount of ethene unsaturated double-bonds can be imported, but the ratio step-down of polymerizable monomer (q), therefore be difficult to maintain the physical property such as dispersion stabilization, dissolubility, chemical-resistant.
There is the 2 ~ polymerizable monomer (p) of 6 hydroxyls can utilize known method to manufacture with the manufacture of the multipolymer (a) of other polymerizable monomers (q), such as with reference to the record of the paragraph 0013 of Japanese Patent Laid-Open 2005-156930 publication, its content can be incorporated in this instructions.
(G) resin having a polymerism double bond at side chain can react with described multipolymer (a) with the compound (b) of the functional group of hydroxyl reaction and ethene unsaturated double-bond by making to have and obtain.Have can with the compound (b) of the functional group of hydroxyl reaction and ethene unsaturated double-bond as can with the functional group of hydroxyl reaction, can isocyanate group, carboxyl etc. be enumerated, especially with regard to reactive aspect, be preferably isocyanate group.
The compound with isocyanate group and ethene unsaturated double-bond specifically can enumerate 2-acryloyl ethyl isocyanates, 2-methacryl ethyl isocyanate etc.In addition, the compound with carboxyl and ethene unsaturated double-bond specifically can enumerate acrylic acid, methacrylic acid, maleic anhydride.
The amount being directed into the ethene unsaturated double-bond in multipolymer (a) by hydroxyl is represented by " the double bond equivalent " of the resin of gained.So-called double bond equivalent, become the standard of double bond amount contained in molecule, if the photoresist that molecular weight is identical, then the numerical value of double bond equivalent is less, and the import volume of double bond more becomes many.
[double bond equivalent]=[molecular weight of constitutional repeating unit]/[double key number in constitutional repeating unit]
The double bond equivalent of (G) of the present invention resin is preferably 200 ~ 2,000, is more preferably 300 ~ 900.When the double bond equivalent of (G) resin is less than the situation of 200, the ratio importing the polymerizable monomer (p) of ethene unsaturated double-bond uprises, and cannot make polymerizable monomer (q) copolymerization of the substantial amount of the various characteristic of maintenance.More than 2, during the situation of 000, ethene unsaturated double-bond number is few, therefore cannot obtain sufficient sensitivity.
In addition, with regard to the aspect of the favorable dispersibility of composition of the present invention, the weight average molecular weight (Mw) of described (G) resin is preferably 2000 ~ 200000, is more preferably 5000 ~ 50000.
Multipolymer (a), with have and can utilize known method to carry out with the reaction of the compound (b) of the functional group of hydroxyl reaction and ethene unsaturated double-bond, such as with reference to the record of the paragraph 0016 of Japanese Patent Laid-Open 2005-156930 publication, its content can be incorporated in this instructions.
Relative to total solid composition, (G) in composition of the present invention has the resin of polymerism double bond content at side chain is preferably 0.1 quality % ~ 50 quality %, be more preferably 0.3 quality % ~ 40 quality %, and then be preferably 0.5 quality % ~ 30 quality %.
(G) resin having a polymerism double bond at side chain in the present compositions can only containing a kind of, also can containing two or more.When containing two or more situations, being preferably its total amount becomes described scope.
-alkali soluble resin-
Composition of the present invention also can also contain alkali soluble resin as bonding agent.Moreover, in alkali soluble resin described herein, do not comprise and contain the composition in composition of the present invention as dispersion. formulation.
Alkali soluble resin suitably can be selected in following alkali soluble resin, described alkali soluble resin is linear organic high molecular polymer, and has the group that at least one promotes alkali-soluble in molecule (being preferably using acrylic acid series copolymer, styrene based copolymer as the molecule of main chain).With regard to the viewpoint of thermotolerance, be preferably polyhydroxy styrene system resin, polysiloxane series resin, acrylic resin, acrylamide resin, acrylic acid/acrylamide copolymer resin, with regard to controlling the viewpoint of developability, be preferably acrylic resin, acrylamide resin, acrylic acid/acrylamide copolymer resin.
Its content such as with reference to the alkali soluble resin recorded in the paragraph 0179 ~ paragraph 0208 of Japanese Patent Laid-Open 2013-077009 publication, can be incorporated in this instructions by alkali soluble resin.
In addition, these contents with reference to the later record of the paragraph 0558 ~ paragraph 0571 of Japanese Patent Laid-Open 2012-208494 publication ([0685] ~ [0700] of corresponding U.S. Patent Application Publication No. 2012/0235099 instructions), can be incorporated in present specification by alkali soluble resin.
And then be preferably alkali soluble resin used in the multipolymer (B) and embodiment recorded in numbered paragraphs 0029 ~ numbered paragraphs 0063 of using and recording in Japanese Patent Laid-Open 2012-32767 publication, adhesive resin used in the adhesive resin recorded in the numbered paragraphs 0088 ~ numbered paragraphs 0098 of Japanese Patent Laid-Open 2012-208474 publication and embodiment, adhesive resin used in the adhesive resin recorded in the numbered paragraphs 0022 ~ numbered paragraphs 0032 of Japanese Patent Laid-Open 2012-137531 publication and embodiment, adhesive resin used in the adhesive resin recorded in the numbered paragraphs 0132 ~ numbered paragraphs 0143 of Japanese Patent Laid-Open 2013-024934 publication and embodiment, adhesive resin used in the numbered paragraphs 0092 ~ numbered paragraphs 0098 of Japanese Patent Laid-Open 2011-242752 publication and embodiment, the adhesive resin recorded in the numbered paragraphs 0030 ~ numbered paragraphs 0072 of Japanese Patent Laid-Open 2012-032770 publication.These contents are incorporated in present specification.
The acid number of alkali soluble resin being preferably 30mgKOH/g ~ 200mgKOH/g, be more preferably 50mgKOH/g ~ 150mgKOH/g and be advisable, most preferably be 70mgKOH/g ~ 120mgKOH/g.
In addition, the weight average molecular weight (Mw) of alkali soluble resin is preferably 2,000 ~ 50,000, and then is preferably 5,000 ~ 30,000, most preferably is 7,000 ~ 20,000.
When containing the situation of alkali soluble resin in coloured composition, relative to the total solid composition of coloured composition, the content of alkali soluble resin in coloured composition is preferably 1 quality % ~ 15 quality %, is more preferably 2 quality % ~ 12 quality %, is especially preferably 3 quality % ~ 10 quality %.
Composition of the present invention only can contain a kind of alkali soluble resin, also can containing two or more.When containing two or more situations, being preferably its total amount becomes described scope.
-organic solvent-
Composition of the present invention also can contain organic solvent.
As long as organic solvent meets the dissolubility of each composition or the coating of photosensitive composition, then substantially be not particularly limited, especially preferably consider the dissolubility of ultraviolet light absorber, alkali soluble resin or spreading agent etc., coating, security and selecting.In addition, when preparing composition of the present invention, at least two kinds of organic solvents are preferably comprised.
Organic solvent can preferably be enumerated: as the such as ethyl acetate of ester class, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ethoxyacetic acid Arrcostab (such as ethoxyacetic acid methyl esters, ethoxyacetic acid ethyl ester, ethoxyacetic acid butyl ester (such as methoxy menthyl acetate, ethyl methoxyacetate, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate etc.)), 3-oxygen base alkyl propionates class (such as 3-oxygen base methyl propionate, (the such as 3-methoxy methyl propionates such as 3-oxygen base ethyl propionate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate etc.)), 2-oxygen base alkyl propionates class (such as 2-oxygen base methyl propionate, 2-oxygen base ethyl propionate, (the such as 2-methoxy methyl propionates such as 2-oxygen base propyl propionate, 2-methoxypropionate, 2-methoxy propyl propyl propionate, 2-ethoxypropanoate, 2-ethoxyl ethyl propionate)), 2-oxygen base-2 Methylpropionic acid methyl esters and 2-oxygen base-2 Methylpropionic acid ethyl ester (such as 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester etc.), methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-Oxobutyric acid methyl esters, 2-Oxobutyric acid ethyl ester etc., and as the such as diethylene glycol dimethyl ether, tetrahydrofuran, glycol monoethyl ether, ethylene glycol monoethyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters etc. of ethers, and as the such as methyl ethyl ketone, cyclohexanone, 2-HEPTANONE, 3-heptanone etc. of ketone, and as aromatic hydrocarbon based such as toluene, dimethylbenzene, cyclopentanone etc.
With regard to improveing the viewpoint of the dissolubility, coated surface state etc. of ultraviolet light absorber and alkali soluble resin, these organic solvents also preferably mix two or more.When described situation, be especially preferably by two or more the formed mixed solution be selected from following solvent: described 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxy methyl propionate, 2-HEPTANONE, cyclohexanone, ethylcarbitol acetate, acetate of butyl carbitol, propylene glycol monomethyl ether and propylene glycol methyl ether acetate.
With regard to the viewpoint of coating, organic solvent content in the composition is preferably set as that the total solid constituent concentration of composition becomes the amount of 5 quality % ~ 80 quality %, and then be preferably 5 quality % ~ 60 quality %, be especially preferably 10 quality % ~ 50 quality %.
-crosslinking chemical-
Also can supplement in the present compositions and use crosslinking chemical, improve the hardness of the cured film that composition is hardened further.
As long as crosslinking chemical carries out film sclerosis by cross-linking reaction, be then not particularly limited, include, for example: (a) epoxy resin; B melamine compound, guanidine amines, glycoluril compounds or carbamide compound that () at least one substituting group through being selected from methylol, alkoxy methyl and pivaloyloxymethyl replaces; C oxybenzene compound, naphthol compound or hydroxyl anthracene compound that () at least one substituting group through being selected from methylol, alkoxy methyl and pivaloyloxymethyl replaces.Wherein, polyfunctional epoxy resin is preferably.
About the details such as concrete example of crosslinking chemical, can refer to the record of the paragraph 0134 ~ paragraph 0147 of Japanese Patent Laid-Open 2004-295116 publication.
When containing the situation of crosslinking chemical in the present compositions, the allotment amount of crosslinking chemical is not particularly limited, and is preferably 2 quality % ~ 30 quality % of the total solid composition of composition, is more preferably 3 quality % ~ 20 quality %.
Composition of the present invention only can contain a kind of crosslinking chemical, also can containing two or more.When containing two or more situations, being preferably its total amount becomes described scope.
-polymerization inhibitor-
In the present compositions, in order to stop the unwanted thermal polymerization of polymerizable compound in the manufacture of described composition or in preserving, it is desirable to add a small amount of polymerization inhibitor.
In the present invention, spendable polymerization inhibitor can be enumerated: p-dihydroxy-benzene, p methoxy phenol, two-Butylated Hydroxytoluene, pyrogallol, tert-butyl catechol, benzoquinones, 4, the sub-cerium salt of 4'-thiobis (3 methy 6 tert butyl phenol), 2,2'-di-2-ethylhexylphosphine oxides (4-methyl-6-tert-butylphenol), N-nitroso-phenylhydroxylamine etc.
When containing the situation of polymerization inhibitor in the present compositions, relative to the quality of all compositions, the addition of polymerization inhibitor is preferably about 0.01 quality % ~ about 5 quality %.
Composition of the present invention only can contain a kind of polymerization inhibitor, also can containing two or more.When containing two or more situations, being preferably its total amount becomes described scope.
-surfactant-
In composition of the present invention, with regard to improving the viewpoint of coating further, also can add various surfactant.
Surfactant can use: the various surfactants such as fluorine system surfactant, nonionic system surfactant, kation system surfactant, negative ion system surfactant, silicone-based surfactant.
Especially composition of the present invention is by containing fluorine system surfactant, and the solution properties (particularly mobility) when being prepared into coating fluid improves further, therefore can improve the homogeneity of coating thickness further or economize fluidity.
That is, when using the coating fluid that applies composition containing fluorine system surfactant to carry out the situation of film formation, by making applied to reduce with the interfacial tension of coating fluid, the wetting quality of applied is improved, to the coating raising of applied.Therefore, even if when forming the situation of film of several microns (μm) left and right with a small amount of liquid measure, the film that also more preferably can carry out the little uniform thickness of uneven thickness is formed, with regard in this respect effectively.
Fluorine containing ratio in fluorine system surfactant is preferably 3 quality % ~ 40 quality %, is more preferably 5 quality % ~ 30 quality %, is especially preferably 7 quality % ~ 25 quality %.Fluorine containing ratio be the fluorine system surfactant in described scope the homogeneity of the thickness of coated film or economize fluidity in effectively, dissolubility is in the composition also good.
Fluorine system surfactant such as can be enumerated: Mei Jiafa (Megafac) F171, Mei Jiafa (Megafac) F172, Mei Jiafa (Megafac) F173, Mei Jiafa (Megafac) F176, Mei Jiafa (Megafac) F177, Mei Jiafa (Megafac) F141, Mei Jiafa (Megafac) F142, Mei Jiafa (Megafac) F143, Mei Jiafa (Megafac) F144, Mei Jiafa (Megafac) R30, Mei Jiafa (Megafac) F437, Mei Jiafa (Megafac) F475, Mei Jiafa (Megafac) F479, Mei Jiafa (Megafac) F482, Mei Jiafa (Megafac) F554, Mei Jiafa (Megafac) F780, Mei Jiafa (Megafac) F781 (being that Di Aisheng (DIC) (stock) manufactures above), Fu Lade (Fluorad) FC430, not rad (Fluorad) FC431, not rad (Fluorad) FC171 (being that Sumitomo 3M (stock) manufactures above), Sha Fulong (Surflon) S-382, Sha Fulong (Surflon) SC-101, Sha Fulong (Surflon) SC-103, Sha Fulong (Surflon) SC-104, Sha Fulong (Surflon) SC-105, Sha Fulong (Surflon) SC1068, Sha Fulong (Surflon) SC-381, Sha Fulong (Surflon) SC-383, Sha Fulong (Surflon) S393, Sha Fulong (Surflon) KH-40 (being Asahi Glass (stock) manufacture above) etc.
Nonionic system surfactant specifically can be enumerated: glycerine, trimethylolpropane, trimethylolethane and these ethoxylate and propoxylate (such as propoxylated glycerol, ethoxylated glycerol etc.), polyoxyethylenelauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylplenyl ether, polyethylene glycol dilaurate, polyglycol distearate, sorbitan carboxylic esters (Pu Luonike (Pluronic) L10 that BASF (BASF) company manufactures, Pu Luonike (Pluronic) L31, Pu Luonike (Pluronic) L61, Pu Luonike (Pluronic) L62, Pu Luonike (Pluronic) 10R5, Pu Luonike (Pluronic) 17R2, Pu Luonike (Pluronic) 25R2, Te Luonike (Tetronic) 304, Te Luonike (Tetronic) 701, Te Luonike (Tetronic) 704, Te Luonike (Tetronic) 901, Te Luonike (Tetronic) 904, Te Luonike (Tetronic) 150R1), Paasche (Solsperse) 20000 (Japanese Lu Borun (Lubrizol) (stock)) etc. exerted by rope.
Kation system surfactant specifically can be enumerated: phthalocyanine derivates (trade name: EFKA (EFKA)-745, gloomy lower industry (stock) manufactures), organic siloxane polymer KP341 (SHIN-ETSU HANTOTAI's chemical industry (stock) manufacture), (methyl) acrylic acid series (being total to) polymkeric substance Pohle is Lip river (Polyflow) No.75, Pohle not Lip river (Polyflow) No.90, Pohle not Lip river (Polyflow) No.95 (common prosperity society chemistry (stock) manufacture), W001 (abundant business (stock) manufacture) etc. not.
Negative ion system surfactant specifically can enumerate W004, W005, W017 (manufacture of abundant business (stock) company) etc.
Silicone-based surfactant such as can be enumerated: " eastern beautiful silicone (ToraySilicone) DC3PA " that eastern beautiful DOW CORNING (Toray-Dowcorning) (stock) manufactures, " eastern beautiful silicone (ToraySilicone) SH7PA ", " eastern beautiful silicone (ToraySilicone) DC11PA ", " eastern beautiful silicone (ToraySilicone) SH21PA ", " eastern beautiful silicone (ToraySilicone) SH28PA ", " eastern beautiful silicone (ToraySilicone) SH29PA ", " eastern beautiful silicone (ToraySilicone) SH30PA ", " eastern beautiful silicone (ToraySilicone) SH8400 ", steps " TSF-4440 " that figure new high-tech material (MomentivePerformanceMaterials) company manufactures, " TSF-4300 ", " TSF-4445 ", " TSF-4460 ", " TSF-4452 ", " KP341 " that silicone incorporated company of SHIN-ETSU HANTOTAI manufactures, " KF6001 ", " KF6002 ", Bi Ke chemistry (BYKChemie) company manufactures " Bi Ke (BYK) 307 ", " Bi Ke (BYK) 323 ", " Bi Ke (BYK) 330 " etc.
Surfactant only can use one, also capable of being combined two or more.
When containing the situation of surfactant in the present compositions, relative to the gross mass of composition, the addition of surfactant is preferably 0.001 quality % ~ 2.0 quality %, is more preferably 0.005 quality % ~ 1.0 quality %.
Composition of the present invention only can contain a kind of surfactant, also can containing two or more.When containing two or more situations, being preferably its total amount becomes described scope.
-other additives-
In composition of the present invention, optionally adjustable various additive, such as filling agent, contiguity promoter, antioxidant, ultraviolet light absorber, anticoalescent etc.These additives can enumerate in the paragraph 0155 ~ paragraph 0156 of Japanese Patent Laid-Open 2004-295116 publication record.
In the present compositions, can containing Japanese Patent Laid-Open 2004-295116 publication paragraph 0078 in record sensitizer or light stabilizer, described publication paragraph 0081 in record thermal polymerization inhibitor.
Ultraviolet light absorber specifically preferably uses following compound.
[changing 55]
--organic carboxyl acid, organic carboxyl acid acid anhydride--
Composition of the present invention also can be organic carboxyl acid and/or the organic carboxyl acid acid anhydride of less than 1000 containing molecular weight.
Organic carboxylic acid compounds specifically can enumerate aliphatic carboxylic acid or aromatic carboxylic acid.Aliphatic carboxylic acid include, for example: the monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylace tonitric, caproic acid, Glycolic acid, acrylic acid, methacrylic acid, the dicarboxylic acid such as oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, cyclohexane dicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, 1, the tricarboxylic acids etc. such as 2,3-propanetricarboxylic acid, aconitic acid.In addition, aromatic carboxylic acid include, for example: the carboxyl such as benzoic acid, phthalic acid is directly binding on the carboxylic acid of phenyl, and to be situated between every carbon bond the carboxylic acids of bond carboxyl from phenyl.In these, be especially preferably molecular weight less than 600, particularly molecular weight 50 ~ 500, specifically, such as, be preferably maleic acid, malonic acid, succinic acid, itaconic acid.
Organic carboxyl acid acid anhydride include, for example aliphatic carboxylic acid acid anhydride, aromatic carboxylic acid acid anhydride, specifically, include, for example: acetic anhydride, Trichloroacetic anhydride, trifluoroacetic anhydride, tetrabydrophthalic anhydride, succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1, the aliphatic carboxylic acid acid anhydrides such as 2-cyclohexene dicarboxylic anhydride, n-octadecane base succinic anhydride, 5-norborene-2,3-dicarboxylic anhydride.Aromatic carboxylic acid acid anhydride include, for example: phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, naphthalic anhydride etc.In these, be especially preferably molecular weight less than 600, particularly molecular weight 50 ~ 500, specifically, such as, be preferably maleic anhydride, succinic anhydride, citraconic anhydride, itaconic anhydride.
In the present compositions containing organic carboxyl acid, organic carboxyl acid acid anhydride situation time, the addition of these organic carboxyl acids and/or organic carboxyl acid acid anhydride is 0.01 quality % ~ 10 quality % usually in total solid composition, be preferably 0.03 quality % ~ 5 quality %, be more preferably the scope of 0.05 quality % ~ 3 quality %.
By adding organic carboxyl acid and/or the organic carboxyl acid acid anhydride that these molecular weight are less than 1000, high pattern adhesion can be kept, and reduce the remaining of the non-dissolved matter of composition further.
The preparation method > of < photosensitive composition
Composition of the present invention is by composition mentioned above mixing being prepared.
Moreover, when preparing composition, by forming the disposable allotment of each composition of composition, also each component dissolves can be scattered in after in solvent and successively allocate.In addition, during allotment, ordering in launching or operating condition are not particularly limited.Such as all the components can be dissolved to be scattered in solvent simultaneously and prepare composition, optionally also in advance each composition can suitably be made two or more Solution Dispersion liquid, and these mixing are prepared into composition by (during coating) in use.
The composition of preparation as mentioned above can use preferably 0.01 μm ~ 3.0 μm, aperture, be more preferably the filtrator etc. in 0.05 μm ~ about 0.5 μm, aperture carry out after isolated by filtration for.
Composition of the present invention can form the cured film of thermotolerance and color characteristics excellence, therefore can be preferably used for the colored pattern (dyed layer) forming colored filter.In addition, composition of the present invention preferably can be used as the colored pattern formation use of colored filter used in the image display device such as solid-state imager (such as CCD, CMOS etc.) or liquid crystal indicator (LCD) etc.And then, also can be preferably used for the making purposes of printing-ink, jetted ink and coating etc.Wherein, the making purposes of the colored filter of the solid-state imagers such as CCD and CMOS can be preferably used for.
The manufacture method > of < cured film, pattern formation method, colored filter and colored filter
Then, painted cured film of the present invention, pattern formation method and colored filter are described in detail by its manufacture method.
Pattern formation method of the present invention comprises the following steps: coloring photosensitive combination layer forming step, is imparted to by photosensitive composition of the present invention on support and forms coloring photosensitive combination layer (hereinafter also referred to " coloring compositions nitride layer "); Step of exposure, exposes into described coloring compositions nitride layer to pattern-like; And pattern forming step, the development of unexposed portion is removed and forms colored pattern.
Pattern formation method of the present invention preferably can be applied to the colored pattern (pixel) forming colored filter and have.
Utilize pattern formation method of the present invention to form the support of pattern except the plate objects such as substrate, as long as can be applicable to the support that pattern is formed, be then not particularly limited.
Below, by the manufacture method of solid-state imager colored filter, each step in pattern formation method of the present invention is described in detail, but the present invention is not limited to described method.
The manufacture method of colored filter of the present invention applies pattern formation method of the present invention, comprises the step using pattern formation method of the present invention to form colored pattern on support.
That is, the manufacture method of colored filter of the present invention applies pattern formation method of the present invention, and it is characterized in that comprising the following steps: coloring photosensitive combination of the present invention is applied to step support being formed coloring photosensitive combination layer; To the step that described coloring photosensitive combination layer exposes with pattern-like; And the development of unexposed portion is removed and forms the step of colored pattern.
And then, optionally also can arrange and carry out the step (pre-bake step) of toasting facing to colour cell compound layer and to the step of toasting through the colored pattern of development (after baking procedure).Below, sometimes these steps are referred to as pattern forming step.
Colored filter of the present invention can utilize described manufacture method and preferably obtain.
Below, sometimes by solid-state imager colored filter referred to as " colored filter ".
Below, each step of pattern formation method of the present invention is described in detail by the manufacture method of colored filter of the present invention.
< forms the step > of coloring photosensitive combination layer
In the step forming coloring photosensitive combination layer, support is applied composition of the present invention and forms coloring photosensitive combination layer.
In described step, spendable support such as can use: on substrate (such as silicon substrate), be provided with charge coupled cell (ChargeCoupledDevice, or the solid-state imager substrate of the imaging apparatus (photo detector) such as CMOS (Complementary Metal Oxide Semiconductor) (ComplementaryMetal-OxideSemiconductor, CMOS) CCD).
Colored pattern of the present invention can be formed at the imaging apparatus forming surface side (surface) of solid-state imager substrate, also can be formed at the side, face (back side) not forming imaging apparatus.
Also photomask can be provided with between the colored pattern of solid-state imager or on the back side of solid-state imager substrate.
In addition, on support, undercoat optionally also can be set to improve with the contiguity of the layer on top, prevent the diffusion of material or realize the planarization of substrate surface.
The method that support is applied composition of the present invention can apply the various coating processes such as slot coated, ink-jet method, rotary coating, cast coat, roller coat cloth, screen painting method.
The drying (prebake conditions) coating the coloring photosensitive combination layer on support can utilize hot plate (hotplate), baking oven (oven) etc. to carry out 10 seconds ~ 300 seconds at the temperature of 50 DEG C ~ 140 DEG C.
Step (utilizing photoetching process to carry out the situation of pattern formation) the > > that < < exposes with pattern-like coloring phototonus composition layer
-step of exposure-
In step of exposure, such as, use the exposure devices such as stepper, be situated between every the mask with set mask pattern, pattern exposure is carried out to the coloring photosensitive combination layer formed in coloring phototonus composition layer forming step.Cured film can be obtained thus.
During exposure, spendable radioactive ray (light) especially preferably can use the ultraviolet such as g ray, i ray (being especially preferably i ray).Exposure (exposure) is preferably 30mJ/cm 2~ 1500mJ/cm 2, be more preferably 50mJ/cm 2~ 1000mJ/cm 2, most preferably be 80mJ/cm 2~ 500mJ/cm 2.
The thickness of cured film is preferably less than 1.0 μm, is more preferably 0.1 μm ~ 0.9 μm, and then is preferably 0.2 μm ~ 0.8 μm.
By thickness is set as less than 1.0 μm, high analyticity, high density of access can be obtained, therefore preferably.
In addition, in described step, also the cured film of the thin thickness with less than 0.7 μm can preferably be formed, by utilizing aftermentioned pattern forming step to carry out development treatment to the cured film of gained, even if can obtain as the also excellent colored pattern of film developability, rough surface inhibition and pattern form.
< < < forms the step > > > of colored pattern
Then carry out alkali development treatment, the coloring photosensitive combination layer stripping without light-struck part thus in step of exposure is in alkaline aqueous solution, and the part only through photo-hardening remains.
Developer solution it is desirable to the organic base developer solution imaging apparatus or circuit etc. of bottom not being caused to damage (damage).Development temperature is generally 20 DEG C ~ 30 DEG C, is 20 seconds ~ 90 seconds before development time.In order to remove residue further, also there is the situation of enforcement 120 seconds ~ 180 seconds in recent years.And then, in order to improve the residue property removed further, sometimes also repeat following steps several times: got rid of developer solution every 60 seconds, again supply developer solution further.
Alkaline agent used in developer solution include, for example: ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium, hydroxide benzyltrimethylammon.um, choline, pyrroles, piperidines, 1, the organic basic compounds such as 8-diazabicyclo-[5.4.0]-7-hendecene, preferably can use and utilize pure water that these alkaline agents are become 0.001 quality % ~ 10 quality % using concentration, be preferably alkaline aqueous solution that the mode of 0.01 quality % ~ 1 quality % dilutes as developer solution.
Moreover also can use inorganic base in developer solution, inorganic basis is as being preferably NaOH, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate etc.
Moreover, when use comprises the situation of the developer solution of this kind of alkaline aqueous solution, usually utilize pure water to carry out cleaning (drip washing) after development.
Then, carry out after preferably implementing drying heating (toasting afterwards).If form the colored pattern of multiple color, then can often kind of color one by one sequentially repeating said steps manufacture sclerosis epithelium.Colored filter can be obtained thus.
Rear baking is the heating after sclerosis is developed completely, usually at 100 DEG C ~ 240 DEG C, preferably 200 DEG C ~ 240 DEG C, carries out thermmohardening process.
The heating arrangements such as hot plate or convection oven (hot air circulation type drying machine), high frequency heating machine can be used, with continous way or batch, described rear baking process is carried out to the coated film after development in the mode becoming described condition.
< < forms the step of photoresist oxidant layer, the step of acquisition Resist patterns and carries out step (utilizing dry etching method to carry out the situation of pattern formation) the > > of dry-etching
Patterned photoresist oxidant layer can use etching gas to carry out as mask by dry-etching.Specifically, the dyed layer making coloring photosensitive combination layer sclerosis gained is coated with the radiation sensitive compositions of eurymeric or minus, and makes it dry, form photoresist oxidant layer thus.When the formation of photoresist oxidant layer, be preferably and implement prebake conditions process further.The formation process of photoresist oxidant layer especially it is desirable to the form of the heating (toasting process afterwards) after the heating (postexposure bake (Post-ExposureBake, PEB)) after implementing exposure, development.
Photoresist such as can use the radiation sensitive compositions of eurymeric.The radiation sensitive compositions of described eurymeric use sense can answer the eurymeric anti-corrosion agent composition being suitable for positive light anti-etching agent of the radioactive ray such as ultraviolet (g ray, h ray, i ray), the far ultraviolet comprising excimer laser etc., electron beam, ion beam and X ray.In radioactive ray, be preferably g ray, h ray, i ray, be wherein preferably i ray.
Specifically, the radiation sensitive compositions of eurymeric is preferably the composition containing quinone di-azido compound and alkali soluble resin.The radiation sensitive compositions of the eurymeric containing quinone di-azido compound and alkali soluble resin utilizes following situation: the illumination because of the wavelength of below 500nm is penetrated and quinone diazido occurs to decompose and produces carboxyl, and result becomes alkali-soluble from the insoluble state of alkali.The parsing power of described positive light anti-etching agent is obviously excellent, therefore can be used for making the integrated circuit such as integrated circuit (IntegratedCircuit, IC) or large scale integrated circuit (LargeScaleIntegration, LSI).Quinone di-azido compound can enumerate naphthalene quinone di-azido compound.Commercially available product include, for example " FHi622BC " (manufacture of Fujiphoto electronic material (FujifilmElectronicMaterials) company).
The thickness of photoresist oxidant layer is preferably 0.1 μm ~ 3 μm, is preferably 0.2 μm ~ 2.5 μm, and then is preferably 0.3 μm ~ 2 μm.Moreover, utilize the formation being coated with the photoresist oxidant layer of carrying out that the coating process of already described dyed layer can be used above to carry out aptly.
Then, photoresist oxidant layer is exposed, developed, form the Resist patterns (patterned photoresist oxidant layer) being provided with resist through hole cohort thus.There is no particular restriction in the formation of Resist patterns, can by former known photoetching technique suitably optimization carry out.By exposure, develop and resist through hole cohort is set in photoresist oxidant layer, thus the Resist patterns of etching mask used in follow-up etching being arranged on dyed layer.
The exposure of photoresist oxidant layer is by carrying out with under type: be situated between every set mask pattern, and the radiation sensitive compositions of eurymeric or minus is utilized to g ray, h ray, i ray etc., is preferably i ray enforcement exposure.After exposure, by utilizing developer solution to carry out development treatment, and accordingly photoresist is removed with the region for forming colored pattern.
As long as described developer solution does not impact the dyed layer containing colorant, and the unhardened portion of the exposure portion of eurymeric resist and negative resist is dissolved, then all can use, such as, can use combination or the alkaline aqueous solution of various organic solvent.The alkaline aqueous solution that alkali compounds preferably dissolves in the mode that concentration becomes 0.001 quality % ~ 10 quality %, be preferably 0.01 quality % ~ 5 quality % and prepares by alkaline aqueous solution.Alkali compounds include, for example: NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrroles, piperidines, 1,8-diazabicyclo [5.4.0]-7-hendecene etc.In addition, when the situation using alkaline aqueous solution as developer solution, water is usually utilized to implement cleaning treatment after development.
Then, using Resist patterns as etching mask, carry out patterning in the mode forming through hole cohort in dyed layer by dry-etching.Form colored pattern thus.Through hole cohort is arranged in dyed layer with chessboard trellis.Therefore, the 1st colored pattern being provided with through hole cohort in dyed layer has the 1st colored pixels of multiple square shape with chessboard trellis.
Formed closer to the viewpoint of rectangle or with regard to reducing further to the damage of support viewpoint with regard to making pattern section, dry-etching is preferably undertaken by following form.
Preferably comprise the etching in the 1st stage, the etching in the 2nd stage and overetched form, the etching in described 1st stage uses fluorine system gas and oxygen (O 2) mixed gas, till carrying out etching the region (degree of depth) of not exposing until support, described 2nd stage be etched in the etching in described 1st stage after, use nitrogen (N 2) and oxygen (O 2) mixed gas, carry out etching till being preferably near the region (degree of depth) that support exposes, described to cross etching be carry out after support exposes.Below, to the concrete grammar of dry-etching and the etching in the 1st stage, the etching in the 2nd stage and cross etching and be illustrated.
Dry-etching utilizes following method to obtain etching condition in advance to carry out.
(1) etch-rate (nm/min) of the etching in the 1st stage and the etch-rate (nm/min) of the etching in the 2nd stage is calculated respectively.(2) calculate the time etching desired thickness in the etching in the 1st stage respectively and in the etching in the 2nd stage, etch time of desired thickness.(3) etching in the 1st stage is implemented according to the etching period calculated in described (2).(4) etching in the 2nd stage is implemented according to the etching period calculated in described (2).Or, detected by terminal (endpoint) and decide etching period, implement the etching in the 2nd stage according to determined etching period.(5) total ascent time for described (3), (4) calculated etching period, implemented etching.
With regard to using as be processed into the viewpoint of rectangle by the organic material of etching-film with regard to, mixed gas used in the etching step in described 1st stage is preferably containing fluorine system gas and oxygen (O 2).In addition, the etching step in the 1st stage, by being set as carrying out etching the form till the region of not exposing until support, can avoid the damage of support.In addition, with regard to avoiding the viewpoint of the damage of support, etching step and the described etching step of crossing in described 2nd stage preferably utilize the mixed gas of fluorine system gas and oxygen to implement to etch after till the region that support does not expose in the etching step in the 1st stage, use the mixed gas of nitrogen and oxygen to carry out etch processes.
Etch quantity in the etching step in the 1st stage, importantly to be decided by the mode of the rectangularity of the etch processes gained in the etching step in the 1st stage not undermine with the ratio of the etch quantity in the etching step in the 2nd stage.Moreover, the ratio of the latter in total etch quantity (summation of the etch quantity in the etching step in the etch quantity in the etching step in the 1st stage and the 2nd stage) be preferably greater than 0% and be less than 50% scope, be more preferably 10% ~ 20%.So-called etch quantity, refer to according to the amount that calculates by the difference of the thickness before the remaining thickness of etching-film and etching.
In addition, etching preferably comprised etch processes.Cross etch processes preferably to set etching ratio to carry out.In addition, cross etching ratio preferably to calculate according to the disposing time of carrying out at first.Cross etching ratio can set arbitrarily, with regard to maintain photoresist elching resistant and by with regard to the aspect of the rectangularity of etched pattern, be preferably less than 30% of the disposing time in etching step, be more preferably 5% ~ 25%, be especially preferably 10% ~ 15%.
Then, Resist patterns (i.e. etching mask) remaining after etching is removed.The removal of Resist patterns preferably comprises the following steps: on Resist patterns, give stripper or solvent and Resist patterns is adjusted to the step of removable state; And the step using rinse water to be removed by Resist patterns.
Resist patterns is given stripper or solvent and the step that Resist patterns is adjusted to removable state include, for example: on Resist patterns, at least give stripper or solvent, make it stagnate the set time and carry out soaking the step of putting development.The time that stripper or solvent are stagnated, there is no particular restriction, is preferably tens seconds to a few minutes.
In addition, use rinse water the step that Resist patterns is removed be include, for example: the injection nozzle of self-spray formula or fountain to Resist patterns jet cleaning water, by Resist patterns removal step.Rinse water preferably can use pure water.In addition, injection nozzle can be enumerated: in its spray regime, comprise the injection nozzle of whole support or comprise the injection nozzle of whole support for movable injection nozzle and its movable range.When injection nozzle is movable situation, in the step removing Resist patterns, the movement to support end of self-supporting body central part can carrys out jet cleaning water 2 times more than, more effectively remove Resist patterns thus.
Stripper containing organic solvent, still can contain inorganic solvent usually.Organic solvent include, for example: 1) hydrocarbon system compound, 2) halogenated hydrocarbon based compound, 3) alcohol based compound, 4) ether or acetal based compound, 5) ketone or aldehyde based compound, 6) ester based compound, 7) polyvalent alcohol based compound, 8) carboxylic acid or its acid anhydrides based compound, 9) phenol system compound, 10) nitrogen-containing compound, 11) sulfocompound, 12) fluorochemicals.Stripper is preferably containing nitrogen-containing compound, is more preferably containing non-annularity nitrogen-containing compound and cyclic nitrogen compound.
Non-annularity nitrogen-containing compound preferably has the non-annularity nitrogen-containing compound of hydroxyl.Specifically, include, for example: monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ehtylethanolamine, N, N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanolamine, triethanolamine etc., be preferably monoethanolamine, diethanolamine, triethanolamine, be more preferably monoethanolamine (H 2nCH 2cH 2oH).In addition, cyclic nitrogen compound can be enumerated: isoquinoline, imidazoles, N-ethylmorpholine, epsilon-caprolactams, quinoline, 1,3-dimethyl-2-imidazolidinone, α-methylpyridine, beta-picoline, γ-picoline, pipecoline, 3-methyl piperidine, 4-methyl piperidine, piperazine, piperidines, pyrazine, pyridine, Pyrrolizidine, METHYLPYRROLIDONE, N-phenyl-morpholine, 2,4-lutidines, 2,6-lutidines etc., be preferably METHYLPYRROLIDONE, N-ethylmorpholine, be more preferably METHYLPYRROLIDONE (NMP).
Stripper is preferably containing non-annularity nitrogen-containing compound and cyclic nitrogen compound, wherein, be more preferably containing being selected from least one in monoethanolamine, diethanolamine and triethanolamine and at least one be selected from METHYLPYRROLIDONE and N-ethylmorpholine as cyclic nitrogen compound as non-annularity nitrogen-containing compound, and then be preferably containing monoethanolamine and METHYLPYRROLIDONE.
When utilizing stripper to remove, as long as the Resist patterns be formed on the 1st colored pattern is removed, when being namely convenient to be attached with the situation as the deposit (precipitate) of etch products on the sidewall of the 1st colored pattern, described deposit also can not be removed completely.So-called deposit, refers to that etch products attachment is piled up on the sidewall of dyed layer.
Stripper it is desirable to relative to stripper 100 mass parts but not the content of cyclic nitrogen compound is below more than 9 mass parts, 11 mass parts, and the content of cyclic nitrogen compound is below more than 65 mass parts, 70 mass parts relative to stripper 100 mass parts.In addition, stripper preferably utilizes pure water by the mixture diluted of non-annularity nitrogen-containing compound and cyclic nitrogen compound.
Moreover, manufacture method of the present invention optionally also can comprise manufacture method as solid-state imager colored filter and known step be used as described beyond step.Such as after carrying out described coloring photosensitive combination layer forming step, step of exposure and pattern forming step, optionally also can comprise by heating and/or exposing the cure step making formed colored pattern sclerosis.
In addition, when using the situation of composition of the present invention, such as, sometimes produce the nozzle of apparatus for coating blowing unit or the blocking in pipe arrangement portion or because of the pollution etc. caused by the attachment sedimentation drying in coating machine of coloured composition or pigment.Therefore, in order to clean the pollution caused by composition of the present invention efficiently, being preferably and the solvent relevant with this composition mentioned above is used as cleaning fluid.In addition, the cleaning that the cleaning fluid recorded in Japanese Patent Laid-Open 7-128867 publication, Japanese Patent Laid-Open 7-146562 publication, Japanese Patent Laid-Open 8-278637 publication, Japanese Patent Laid-Open 2000-273370 publication, Japanese Patent Laid-Open 2006-85140 publication, Japanese Patent Laid-Open 2006-291191 publication, Japanese Patent Laid-Open 2007-2101 publication, Japanese Patent Laid-Open 2007-2102 publication, Japanese Patent Laid-Open 2007-281523 publication etc. also can be preferably used for composition of the present invention is removed.
In described, be preferably alkylene glycol monoalkyl ethers carboxylate and alkylene glycol monoalkyl ethers.
These solvents can be used alone also can be used in combination two or more.When mixing two or more situations, preferably the solvent with hydroxyl is mixed with the solvent without hydroxyl.The solvent with hydroxyl is 1/99 ~ 99/1 with the mass ratio of the solvent without hydroxyl, is preferably 10/90 ~ 90/10, is more preferably 20/80 ~ 80/20.Especially propylene glycol methyl ether acetate (Propyleneglycolmonomethyletheracetate is preferably, PGMEA) with the mixed solvent of propylene glycol monomethyl ether (Propyleneglycolmonomethylether, PGME) and its ratio is 60/40.Moreover, in order to improve the perviousness of cleaning fluid to pollutant, also the surfactant relevant with this composition mentioned above can be added in cleaning fluid.
Colored filter of the present invention is because using composition of the present invention, therefore can carry out exposing the excellent exposure of tolerance limit (margin), and the pattern form of the colored pattern formed (colored pixels) is excellent, the residue of the coarse or development section of patterned surfaces is inhibited, therefore color characteristics becomes excellent.
Colored filter of the present invention can be preferably used for the solid-state imagers such as CCD, CMOS, is particularly suitable for more than high-resolution CCD or CMOS etc. as 1,000,000 pixels.Solid-state imager colored filter of the present invention such as can be used as being configured at each pixel forming CCD or CMOS light accepting part, and in order to carry out optically focused lenticule (microlens) between colored filter.
Moreover the thickness of the colored pattern (colored pixels) of colored filter of the present invention is preferably less than 2.0 μm, is more preferably less than 1.0 μm, and then be preferably less than 0.7 μm.
In addition, the size (pattern width) of colored pattern (colored pixels) is preferably less than 2.5 μm, is more preferably less than 2.0 μm, is especially preferably less than 1.7 μm.
[solid-state imager]
Solid-state imager of the present invention possesses already described colored filter of the present invention above.The formation of solid-state imager of the present invention, for possessing the formation of colored filter of the present invention, as long as the formation for playing function as solid-state imager, is then not particularly limited, include, for example following formation.
So-called solid-state imager is following formation: on support, have formation solid-state imager (ccd image sensor, cmos image sensor etc.) light area multiple photodiodes (photodiode) and comprise the transmission electrode of polysilicon etc., described photodiode and described transmission electrode have the photomask comprising tungsten etc. of the light accepting part opening of only photodiode, the element protection film comprising silicon nitride etc. that the mode that photomask has to cover whole of photomask and photodiode light accepting part is formed, described element protection film has solid-state imager colored filter of the present invention.
And then, also can be (side near support) on described element protection layer and under colored filter and there are optically focused mechanism (such as lenticule etc.Identical below) formation or there is the formation etc. of optically focused mechanism on colored filter.
[image display device]
Colored filter of the present invention not only can be used for described solid-state imager, and can be used for the image display device such as liquid crystal indicator or organic EL display, is particularly suitable for the purposes of liquid crystal indicator.The liquid crystal indicator possessing colored filter of the present invention can show with hypograph: the good and high resolution image of display characteristic excellence of the tone of display image.
About the definition of display device or the details of each display device, such as be recorded in " electronic console element (the wooden clear husband's work of assistant assistant, census of manufacturing meeting (stock), nineteen ninety issue) ", " display device (and she blow along chapter work, industry books (stock), 1989 distribution) " etc. in.In addition, about liquid crystal indicator, such as, be recorded in " LCD Technology of future generation (Uchida Tatsuo edits, census of manufacturing meeting (stock), distribution in 1994) ".There is no particular restriction for the applicable liquid crystal indicator of the present invention, such as, can be applicable to the liquid crystal indicator of the various modes recorded in described " LCD Technology of future generation ".
Colored filter of the present invention also can be used for the liquid crystal indicator of colorful film transistor (ThinFilmTransistor, TFT) mode.About the liquid crystal indicator of colored TFT mode, such as, be recorded in " color TFT-LCD display (vertical publish (stock) is issued for 1996 altogether) ".And then, the present invention also can be applicable to the transverse electric field type of drive such as coplanar switching (IPS), vertical orientated (the Multi-domainVerticalAlignment of many quadrants, the liquid crystal indicator of the visual angles such as pixel partitioning scheme through expanding or the STN Super TN (SuperTwistedNematic such as MVA), STN), twisted nematic (TwistedNematic, TN), vertical orientated (VerticalAlignment, VA), optical compensation inclination (OpticallyCompensatedSplay, OCS), fringing field switches (FringeFieldSwitching, and reflective optic compensated bend (Reflective-OpticallyCompensatedBend FFS), R-OCB) etc.
In addition, colored filter of the present invention also can be used for becoming clear and colorful optical filter array (Color-filterOnArray, the COA) mode of fine.In the liquid crystal indicator of COA mode, require except characteristic to the requirement characteristic of color filter layers except common as mentioned above, sometimes also need the requirement characteristic of interlayer dielectric, i.e. low-k and resistance to stripping fluidity.In colored filter of the present invention, because using the dyestuff polymer of form and aspect excellence, therefore the good and excellent hue of colored pattern (pixel) such as colour purity, transmitance, therefore a kind of resolution can be provided high and the liquid crystal indicator of the COA mode of long durability excellence.Moreover, in order to meet the requirement characteristic of low-k, also resin coating can be set in color filter layers.
About these image display patterns, such as be recorded in " electroluminescence (Electroluminescence, EL), plasma display (PlasmaDisplayPanel, PDP), liquid crystal display (LiquidCrystalDisplay, LCD) new advancement-(eastern beautiful research centre (TorayResearchCenter) investigates department, calendar year 2001 issue) in display-technology and market " 43 pages etc. in.
The liquid crystal indicator possessing colored filter of the present invention, except colored filter of the present invention, is ensure that the various components such as film formed by electrode base board, light polarizing film, phase retardation film, backlight, distance piece (spacer), visual angle.Colored filter of the present invention can be applicable to by the liquid crystal indicator that these known components are formed.About these components, such as be recorded in " market (the island Itou Kentaro of ' 94 liquid crystal display periphery material-chemicals, CMC (stock), distribution in 1994) ", " present situation of 2003 liquid crystal relevant markets is with looking forward to (last volume) (shows good Ji in the future, Fuji Kai Meilai always grinds (stock), distribution in 2003) " in.
About backlight, be in 18 pages ~ 24 pages (island health is abundant) in the Dec, 2005 number being recorded in " Society for Information Display's minutes (SIDmeetingDigest) " 1380 (2005) people such as () A. modern wild (A.Konno) or monthly magazine " display " and described document 25 pages ~ 30 pages (Yagi spark gap is grand bright) etc.
If colored filter of the present invention is used for liquid crystal indicator, then when with before three wavelength tube of known cold-cathode tube combine time, high contrast can be realized, and then by red, green, blue LED light source (RGB-LED) are set as backlight, the liquid crystal indicator that color reprodubility that high, the other colour purity of brightness is high is good can be provided.
[embodiment]
Below enumerate embodiment and then the present invention is illustrated.Material shown in following embodiment, use amount, ratio, contents processing, processing sequence etc. only otherwise depart from purport of the present invention, then can suitably change.Therefore, scope of the present invention is not limited to concrete example shown below.Moreover as long as no special instructions, then " % " and " part " is quality criteria.
The synthesis > of < phosphoric acid system spreading agent (C-1)
Synthesis example 1
In being provided with in the reaction vessel of condenser pipe, nitrogen ingress pipe, stirring machine on three mouthfuls of round-bottomed flasks, add lauryl alcohol 18.6g (manufacture of Na Kalai science and technology (NacalaiTesque) incorporated company), 6-caprolactone monomer 57.1g (manufacturing with Guang Chun medicine incorporated company), butyl titanate 0.06g (Tokyo changes into incorporated company and manufactures), utilize nitrogen to after replacing in reaction vessel, at 120 DEG C, add thermal agitation 3 hours.Pass through 1h-nuclear magnetic resonance (NuclearMagneticResonance, NMR) confirms the disappearance of internal ester monomer.After till reaction solution is cooled to room temperature, the polyphosphoric acid 8.45g being 116% with orthophosphoric acid (orthophosphoricacid) conversion content mixes, and slowly heats up, and adds thermal agitation 6 hours at 80 DEG C, obtains the R in general formula (II) 3number average molecular weight be 760, the existence of y=1 and y=2 is than phosphoric acid system spreading agent (C-1) for 100:12.The acid number of the phosphoric acid system spreading agent of gained is 166.
Synthesis example 2 ~ synthesis example 4
The kind addition of the kind addition of monohydroxy alcohol used and the internal ester monomer used is changed as described in Table 1, in addition, the method identical with described synthesis example 1 is utilized to obtain phosphoric acid system spreading agent (C-2) ~ phosphoric acid system spreading agent (C-4).
[table 1]
The synthesis > of < resin binder 1
Synthesis example 5
In being provided with in the reaction vessel of thermometer, condenser pipe, nitrogen ingress pipe, stirring apparatus on detachable four-hole boiling flask, add propylene glycol methyl ether acetate, one side imports nitrogen one side and is heated to 100 DEG C in reaction vessel, within 1 hour, drip the potpourri of benzyl methacrylate 123.3g, methacrylic acid 25.8g, azobis isobutyronitrile 10.0g at the same temperature from dropping Guan Zhongyong, carry out polyreaction.
After till the resin solution of gained is cooled to room temperature, sample about 3g and heat drying measured nonvolatile component after 20 minutes at 180 DEG C, the mode becoming 40 quality % with nonvolatile component in the resin solution of in advance synthesis adds propylene glycol acetate, obtains the solution of resin binder 1.
The synthesis > of < (D) resin binder
Synthesis example 6
In being provided with thermometer on detachable four-hole boiling flask, condenser pipe, nitrogen ingress pipe, in the reaction vessel of stirring apparatus, add propylene glycol methyl ether acetate, one side imports nitrogen one side and is heated to 80 DEG C in reaction vessel, within 2 hours, benzyl methacrylate 123.3g is dripped at the same temperature from dripping Guan Zhongyong, methacrylic acid 17.2g, the ethylene-oxide-modified acrylate of p-cumylphenol (" sub-Luo Nisi (Aronix) M110 " that East Asia synthesis incorporated company manufactures) 31.0g, the potpourri of azobis isobutyronitrile 10.0g, carry out polyreaction.
After till the resin solution of gained is cooled to room temperature, sample about 3g and heat drying measured nonvolatile component after 20 minutes at 180 DEG C, the mode becoming 40 quality % with nonvolatile component in the resin solution of in advance synthesis adds propylene glycol acetate, obtains the solution of resin binder (D-1).
< (G) has the synthesis > of the resin of polymerism double bond at side chain
Synthesis example 7
In being provided with in the reaction vessel of thermometer, condenser pipe, nitrogen ingress pipe, stirring apparatus on detachable four-hole boiling flask, add propylene glycol methyl ether acetate, one side imports nitrogen one side and is heated to 80 DEG C in reaction vessel, within 2 hours, drip the potpourri of benzyl methacrylate 123.3g, methacrylic acid 17.2g, glycerin monomethyl acrylic ester 14.6g, azobis isobutyronitrile 10.0g at the same temperature from dropping Guan Zhongyong, carry out polyreaction.
The resin solution of gained was dripped at 70 DEG C to the potpourri of 2-methacryl ethyl isocyanate (" Ka Lanci (Karenz) MOI " that Showa electrician incorporated company manufactures) 23.3g, dibutyl tin laurate 0.3g, cyclohexanone 90g with 3 hours.
After till the resin solution of gained is cooled to room temperature, sample about 3g resin solution and heat drying measured nonvolatile component after 20 minutes at 180 DEG C, the mode becoming 40 quality % with nonvolatile component in the resin solution of in advance synthesis adds propylene glycol acetate, obtains the solution of resin binder (G-1).
The manufacture > of < Red Pigment Dispersion composition
After the potpourri of following composition is uniformly mixed equably, utilizes ball mill mixing dispersion 3 hours and prepare Red Pigment Dispersion composition (R-a).
[changing 56]
Composition is changed to the composition recorded in following table 2, in addition, the method identical with the preparation of described Red Pigment Dispersion composition (R-a) is utilized to prepare Red Pigment Dispersion composition (R-b) ~ Red Pigment Dispersion composition (R-q).
In described table 2, each mark refers to following compound.
PR254 diketopyrrolopyrrolecocrystals system red pigment (C.I. paratonere 254)
PY139 isoindoline system yellow uitramarine (C.I. pigment yellow 13 9)
PR177 anthraquinone system red pigment (C.I. paratonere 177)
PR122 quinacridone red pigment (C.I. pigment red 122)
PO71 diketopyrrolopyrrolecocrystals system orange pigment (C.I. pigment orange 71)
The azo system red pigment of Red-a following structural formula
[changing 57]
The compound of pigment derivative (B-2) following structural formula
[changing 58]
The compound of pigment derivative (B-3) following structural formula
[changing 59]
The compound of pigment derivative (B-4) following structural formula
[changing 60]
The preparation > of < viridine green dispersive composition
After the potpourri of following composition is uniformly mixed equably, utilizes ball mill mixing dispersion 3 hours and prepare viridine green dispersive composition (G-a).
Composition is changed to the composition recorded in following table 3, in addition, the method identical with the preparation of described viridine green dispersive composition (G-a) is utilized to adjust viridine green dispersive composition (G-b) ~ viridine green dispersive composition (G-p).
In described table 3, each mark refers to following compound.
PG7 chlorinated copper phthalocyanine system viridine green (C.I. pigment Green 7)
PG36 halogenated copper phthalocyanine system viridine green (C.I. pigment green 36)
PG58 zinc halide phthalocyanine system viridine green (C.I. naphthol green 58)
PY139 isoindoline system yellow uitramarine (C.I. pigment yellow 13 9)
PY150 nickel azo system yellow uitramarine (C.I. pigment yellow 150)
PY185 isoindoline system yellow uitramarine (C.I. pigment yellow 185)
Pigment derivative (B-2)
[changing 61]
The compound of pigment derivative (B-4) following structural formula
[changing 62]
The preparation > of < Yellow Pigment Dispersion composition
After the potpourri of following composition is uniformly mixed equably, utilizes ball mill mixing dispersion 3 hours and prepare Yellow Pigment Dispersion composition (Y-a).
The preparation > of < red sensitive resin combination
The potpourri of following composition is uniformly mixed equably, prepares red sensitive resin combination (RR-a).
Composition is changed to the composition recorded in following table, in addition, the method identical with the preparation of described red sensitive resin combination (RR-a) is utilized to prepare red sensitive resin combination (RR-b) ~ red sensitive resin combination (RR-w).
< evaluates >
(evaluation of the patternability after PCD)
(1) preparation (minus) of transparent Resist Solution A
By following compositions mixed dissolution, prepare transparent Resist Solution A.
(2) with the making of the glass substrate of undercoat
After utilizing 0.5%NaOH water to carry out Ultrasonic Cleaning to glass substrate (healthy and free from worry (Corning) 1737), carry out washing, dehydration bake (200 DEG C/20 minutes).Then, spin coater is used to coat on the glass substrate of cleaning by the mode that the transparent Resist Solution A of gained in described (1) becomes 2 μm with dried thickness, heat drying 1 hour at 220 DEG C and form undercoat, prepares the glass substrate with undercoat thus.
(3) exposure imaging (colored pattern formation) of photosensitive composition
Prepare 2 with infrabasal plate: use spin coater to be coated by red sensitive resin combination (the RR-a) ~ red sensitive resin combination (RR-w) by described main points gained on the undercoat of the glass substrate with undercoat of described (2) middle gained in the mode that dried thickness becomes 0.6 μm, the substrate in prebake conditions 120 second at 100 DEG C.
For a slice in described substrate, i ray step printing device FPA-i5+ (Canon (Canon) (stock) manufactures) is used immediately after coating red sensitive resin combination, by the mask of live width 1.1 μm, coated film is irradiated with the suitableeest exposure that the length formed is the block check master drawing case of 1.1 μm with the wavelength of 365nm.After exposure, use developer solution CD-2000 (Fujiphoto electronic material (FujifilmElectronicMaterials) (stock) manufactures) with 25 DEG C, the condition in 40 seconds develops.Thereafter, with after flowing water drip washing 30 second, carry out spraying dry, obtain colored pattern.
Then, for another sheet in described substrate, after coating red sensitive resin combination, place 72 hours (PCD) in the toilet (cleanroom) of room temperature after, utilize and obtain colored pattern with described identical method.
Utilize sweep electron microscope (ScanningElectronMicroscope, SEM) 2 kinds of colored patterns of gained as are so observed, the colored pattern that after coating, (without PCD) carries out exposure imaging gained is immediately compared with the shape of the colored pattern carrying out exposure imaging gained after PCD, evaluates by following benchmark.
A: compared with the shape of the colored pattern without PCD, the shape of the colored pattern after PCD does not change completely
The shape of the colored pattern after B:PCD changes as seen slightly, but no problem
The shape of the colored pattern after C:PCD is collapsed, and has problem
The shape of the colored pattern after D:PCD is collapsed significantly
Described PCD evaluation result is gathered and is shown in following table.
(4) evaluation of color spot (irregular colour)
Spin coater is used to coat on glass substrate by the mode that red sensitive resin combination (RR-a) ~ red sensitive resin combination (RR-w) becomes 0.6 μm with dried thickness by described main points gained, prebake conditions 120 second at 100 DEG C and obtain painted film 1.
In addition, make by described main points gained red sensitive resin combination (RR-a) ~ red sensitive resin combination (RR-w) at room temperature through time 6 months after, the spin coater mode that becomes 0.6 μm with dried thickness is used to coat on glass substrate, prebake conditions 120 second at 100 DEG C and obtain painted film 2.
Be arranged between the observation camera lens of optical microscope and light source by each painted film of gained, irradiate light towards observation camera lens, using and being provided with multiplying power is that the optical microscope of the digital camera of 1000 times is to observe its transmitted light state.Being arranged at the CCD carrying 1,280,000 pixels in the digital camera in optical microscope, utilize described digital camera to take the painted film coated surface being in transmitted light state.Shooting image preserves as carrying out the data (digital picture) of digital conversion with the bitmap of 8 (bit) (bitmap) form.
Moreover the shooting of painted film coated surface carries out optional 20 regions.In addition, about the data through digital conversion, to shooting image with 0 ~ 255 the CONCENTRATION DISTRIBUTION of 256 grades the respective brightness number of RGB three primary colors is preserved.
Then, for preserved digital picture, become clathrate with 0.5 μm of tetragonal model split that 1 grid size is equivalent in actual substrate, by the brightness equalization in a block.In the present embodiment, utilize the digital camera of 1,280,000 pixels to take the image of optics 1000 times, therefore 0.5 μm of 0.5mm become on shooting image in actual substrate, the picture size on display is 452mm × 352mm, therefore the total block counts in a region is 636416.
For all blocks in each region, measure the mean flow rate of any 1 block and all of its neighbor block adjacent with it.By the difference of the mean flow rate with adjacent block be more than 5 block regard as significant difference block, calculate the average total number of the significant difference block in whole region.Described numerical value is less, and less with the concentration difference of adjacent block, color spot is fewer, represents that the characteristic as colored filter is more excellent.
Using the value of the average total number of the color spot of painted film 1 as the color spot after just preparation, using the average total number of the color spot of painted film 2 as at room temperature through time 6 months after the value of color spot, and then by room temperature through time 6 months after be shown in following table 4 divided by the color spot Magnification of the value of the color spot after just preparation.
In described table 4, each mark refers to following compound.
Photoepolymerizationinitiater initiater (E-2) ethyl ketone; 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-; 1-(O-acetyl group oxime) (BASF (BASF) company manufactures, gorgeous good solid (IRGACURE) OXE02)
Photoepolymerizationinitiater initiater (E-3) 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone (BASF (BASF) company manufactures, gorgeous good solid (IRGACURE) 379)
The potpourri (Japanese chemical drug incorporated company manufactures, Ka Yala get (KAYARAD) DPHA) of ethene unsaturated compound (F-2) dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate
Ethene unsaturated compound (F-3) trimethylolpropane triacrylate (chemical industry incorporated company of Xin Zhong village manufactures, A-TMPT)
The compound of ultraviolet light absorber following structural formula
[changing 63]
Result according to described table 4, the red sensitive resin combination (RR-s) of comparative example 1 and comparative example 3 and red sensitive resin combination (RR-u) are though contain (C-1) phosphoric acid system spreading agent as required composition in composition of the present invention, but do not contain the pigment derivative as (B) ad hoc structure of required composition in composition of the present invention, therefore patternability after PCD is deteriorated significantly, color spot through time increase also slightly large.In addition, the red sensitive resin combination (RR-t) of comparative example 2 and comparative example 4 and red sensitive resin combination (RR-v) are though contain the pigment derivative as (B) ad hoc structure of required composition in composition of the present invention, but do not contain (C-1) phosphoric acid system spreading agent as required composition in composition of the present invention, therefore color spot through time increase very large, the patternability after PCD also has room for improvement.
Relative to these comparative examples, learn red sensitive resin combination (RR-a) of the present invention such as shown in embodiment 1 containing in composition of the present invention as the pigment derivative of (B) ad hoc structure of required composition and (C-1) phosphoric acid system spreading agent, therefore color spot through time increase be inhibited, the patternability after PCD is also significantly improved.
Also learn in addition, be used in resin (G-1) that side chain the has polymerism double bond embodiment 5 ~ embodiment 19 as (G) resin, the Magnification of color spot is inhibited further.
Compared with learning the embodiment 11 of use phosphoric acid system spreading agent (C-3), embodiment 18 and using the embodiment of other phosphoric acid system spreading agents, the patternability after PCD is more excellent.
The preparation > of < green photonasty resin composition
The potpourri of following composition is uniformly mixed equably, prepares green photonasty resin composition (GR-a).
Component content is changed to the composition of following table, in addition, the method identical with the preparation of described green photonasty resin composition (GR-a) is utilized to prepare green photonasty resin composition (GR-b) ~ green photonasty resin composition (GR-v).
About green photonasty resin composition (the GR-a) ~ green photonasty resin composition (GR-v) of gained, utilize the method identical with embodiment 1 to carry out just prepare afterwards and at room temperature through time 6 months after the value of color spot and the evaluation of patternability after PCD.Result is gathered and is shown in following table 5.
Result according to described table 5, the green photonasty resin composition (GR-s) of comparative example 5 and comparative example 7 and green photonasty resin composition (GR-u) are though contain (C-1) phosphoric acid system spreading agent as required composition in composition of the present invention, but do not contain the pigment derivative as (B) ad hoc structure of required composition in composition of the present invention, therefore patternability after PCD is deteriorated significantly, color spot through time increase also slightly large.In addition, the green photonasty resin composition (GR-t) of comparative example 6 and comparative example 8 and green photonasty resin composition (GR-v) are though contain the pigment derivative as (B) ad hoc structure of required composition in composition of the present invention, but do not contain (C-1) phosphoric acid system spreading agent as required composition in composition of the present invention, therefore color spot through time increase very large, the patternability after PCD also has room for improvement.
Relative to these comparative examples, learn green photonasty resin composition of the present invention (GR-a) such as shown in embodiment 20 containing in composition of the present invention as the pigment derivative of (B) ad hoc structure of required composition and (C-1) phosphoric acid system spreading agent, therefore at room temperature through time 6 months after color spot increase be inhibited, the patternability after PCD is significantly improved.
Also learn in addition, be used in resin (G-1) that side chain the has polymerism double bond embodiment 24 ~ embodiment 37 as (G) resin, the Magnification of color spot is inhibited further.
Compared with learning the embodiment 30 of use phosphoric acid system spreading agent (C-3), embodiment 37 and using the embodiment of other phosphoric acid system spreading agents, the patternability after PCD is more excellent.
The synthesis > of < (C-2) carboxylic serials spreading agent
Synthesis example 8
In being provided with in the reaction vessel of thermometer, condenser pipe, nitrogen ingress pipe and stirring machine on four mouthfuls of round-bottomed flasks, add DODECANOL, 1-6.26g, 6-caprolactone 28.74g, Mono-n-butyltin (IV) 0.01g as catalyzer, after carrying out nitrogen displacement in reaction vessel, at 120 DEG C, add thermal agitation 4 hours.Pass through 1h-NMR adds pyromellitic dianhydride 3.66g wherein after measuring and confirming the disappearance of caprolactone monomer, reacts 2 hours at 120 DEG C.By measure acid number confirm the acid anhydrides of more than 98% through half-esterification and terminate reaction, obtain spreading agent (C-11).The acid number of the spreading agent (C-11) of gained is 49mgKOH/g.
Synthesis example 9 ~ synthesis example 13
The kind addition of the monohydroxy alcohol that as shown in table 6, change uses, alkylene oxide, internal ester monomer, carboxylic acid anhydrides, in addition, utilize the method identical with described synthesis example 8 and obtain carboxylic serials spreading agent (C-12) ~ carboxylic serials spreading agent (C-16).
[table 6]
In described table 6, each mark refers to following compound.
Blanc is (Blemmer) PP500 polypropylene glycol monomethacrylate (Japanese grease incorporated company manufactures: trade name Blanc is (Blemmer) PP500 not, hydroxyl value: 95.1mgKOH/g) not
PMA pyromellitic acid anhydride
Two (3,4-dicarboxyphenyi) the fluorenes dicarboxylic anhydride of BPAF9,9-
NPDA2,3,6,7-naphthalene tetracarboxylic acid dianhydride
TMEG ethylene glycol bisthioglycolate trimellitic anhydride ester (new Japan Chemical incorporated company manufactures: trade name keep house moral (Rikacid) TMEG-100)
TMA trimellitic anhydride
DMBA dimethyl benzyl amine
Synthesis example 14
In the reaction vessel identical with synthesis example 5, (Mitsui Chemicals method grace (MitsuiChemicalsfine) incorporated company manufactures: single terminal methoxy group polyoxyethylene polyoxypropylene amine to add bright (Jeffamine) XTJ-506 that binds up one's hair, number average molecular weight is 1000, amine value is 56mgKOH/g) 35.0g and ethylene glycol bisthioglycolate trimellitic anhydride ester (new Japan Chemical incorporated company manufactures: trade name keep house moral (Rikacid) TMEG-100) 7.18g, reacts 3 hours at 50 DEG C.Confirming that the acid anhydrides of more than 97% terminates reaction through half amide by measuring acid number, obtaining carboxylic serials spreading agent (C-17).
Synthesis example 15
In the reaction vessel possessing gas introduction tube, thermometer, condenser and stirring machine, add DODECANOL, 1-6.26g, 6-caprolactone 28.74g and the Mono-n-butyltin (IV) 0.1 part as catalyzer, utilize nitrogen to after replacing in reaction vessel, at 120 DEG C, add thermal agitation 4 hours.Pass through 1after H-NMR measures and confirms the disappearance of caprolactone monomer, add succinic anhydride 3.36g, 2-hexyl glycidyl ether 6.25g and N wherein, N-dimethyl benzyl amine 0.2g, reacts 8 hours at 80 DEG C.
In the reaction solution of gained, add pyromellitic acid anhydride 2.88g and react 5 hours at 100 DEG C.Confirming that the acid anhydrides of more than 97% terminates reaction through half amide by measuring acid number, obtaining carboxylic serials spreading agent (C-18).
Synthesis example 16
In the reaction vessel possessing gas introduction tube, thermometer, condenser and stirring machine, add n-BMA 10.0g, benzyl methacrylate 10.0g and 2 mercapto ethanol 1.0g, utilize nitrogen to replace.80 DEG C will be heated in reaction vessel and react 12 hours.Pass through 1h-NMR measures the disappearance confirming monomer component.
In the reaction solution of gained, add pyromellitic acid anhydride 1.4g, cyclohexanone 9.59g and 1,8-diazabicyclo-[the 5.4.0]-7-hendecene 0.04g as catalyzer, react 7 hours at 130 DEG C.Confirming that the acid anhydrides of more than 98% is through half-esterification by measuring acid number, in reaction solution, adding cyclohexanone 12.8g and terminate reaction, obtaining carboxylic serials spreading agent (C-19).
The manufacture > of < Red Pigment Dispersion composition
After the potpourri of following composition is uniformly mixed equably, utilizes ball mill mixing dispersion 3 hours and prepare Red Pigment Dispersion composition (R-1a).
[changing 64]
Composition is changed to the composition recorded in following table, in addition, the method identical with the preparation of described Red Pigment Dispersion composition (R-1a) is utilized to prepare Red Pigment Dispersion composition (R-1b) ~ Red Pigment Dispersion composition (R-1v).
In described table 7, each mark refers to following compound.
PR254 diketopyrrolopyrrolecocrystals system red pigment (C.I. paratonere 254)
PY139 isoindoline system yellow uitramarine (C.I. pigment yellow 13 9)
PR177 anthraquinone system red pigment (C.I. paratonere 177)
PR122 quinacridone red pigment (C.I. pigment red 122)
PO71 diketopyrrolopyrrolecocrystals system orange pigment (C.I. pigment orange 71)
The azo system red pigment of Red-a following structural formula
[changing 65]
The compound of pigment derivative (B-2) following structural formula
[changing 66]
The compound of pigment derivative (B-3) following structural formula
[changing 67]
The compound of pigment derivative (B-4) following structural formula
[changing 68]
The preparation > of < viridine green dispersive composition
After the potpourri of following composition is uniformly mixed equably, utilizes ball mill mixing dispersion 3 hours and prepare viridine green dispersive composition (G-1a).
Composition is changed to the composition recorded in following table 8, in addition, the method identical with the preparation of described viridine green dispersive composition (G-1a) is utilized to prepare viridine green dispersive composition (G-1b) ~ viridine green dispersive composition (G-1u).
In described table 8, each mark refers to following compound.
PG7 chlorinated copper phthalocyanine system viridine green (C.I. pigment Green 7)
PG36 halogenated copper phthalocyanine system viridine green (C.I. pigment green 36)
PG58 zinc halide phthalocyanine system viridine green (C.I. naphthol green 58)
PY139 isoindoline system yellow uitramarine (C.I. pigment yellow 13 9)
PY150 nickel azo system yellow uitramarine (C.I. pigment yellow 150)
PY185 isoindoline system yellow uitramarine (C.I. pigment yellow 185)
The compound of pigment derivative (B-2) following structural formula
[changing 69]
The compound of pigment derivative (B-4) following structural formula
[changing 70]
The manufacture > of < Yellow Pigment Dispersion composition
After the potpourri of following composition is uniformly mixed equably, utilizes ball mill mixing dispersion 3 hours and prepare Yellow Pigment Dispersion composition (Y-a).
The preparation > of < red sensitive resin combination
The potpourri of following composition is uniformly mixed equably, prepares red sensitive resin combination (RR-1a).
Composition is changed to the composition recorded in following table, in addition, the method identical with the preparation of described red sensitive resin combination (RR-1a) is utilized to prepare red sensitive resin combination (RR-1b) ~ red sensitive resin combination (RR-1z), red sensitive resin combination (RR-1aa) ~ red sensitive resin combination (RR-1ab).
About red sensitive resin combination (the RR-1a) ~ red sensitive resin combination (RR-1ab) of gained, utilize the method identical with embodiment 1 to carry out just prepare afterwards and at room temperature through time 6 months after the value of color spot and the evaluation of patternability after PCD.Result is gathered and is shown in following table 9.
In described table 9, each mark refers to following compound.
Photoepolymerizationinitiater initiater (E-2) ethyl ketone; 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-; 1-(O-acetyl group oxime) (BASF (BASF) company manufactures, gorgeous good solid (IRGACURE) OXE02)
Photoepolymerizationinitiater initiater (E-3) 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone (BASF (BASF) company manufactures, gorgeous good solid (IRGACURE) 379)
The potpourri (Japanese chemical drug incorporated company manufactures, Ka Yala get (KAYARAD) DPHA) of ethene unsaturated compound (F-2) dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate
Ethene unsaturated compound (F-3) trimethylolpropane triacrylate (chemical industry incorporated company of Xin Zhong village manufactures, A-TMPT)
The compound of ultraviolet light absorber following structural formula
[changing 71]
Result according to described table, the red sensitive resin combination (RR-1x) of comparative example 101 and comparative example 103 and red sensitive resin combination (RR-1z) are though contain (C-2) carboxylic serials spreading agent as required composition in composition of the present invention, but do not contain the pigment derivative as (B) ad hoc structure of required composition in composition of the present invention, therefore patternability after PCD is deteriorated significantly, color spot through time increase also slightly large.In addition, the red sensitive resin combination (RR-1y) of comparative example 102 and comparative example 104 and red sensitive resin combination (RR-1aa) are though contain the pigment derivative as (B) ad hoc structure of required composition in composition of the present invention, but do not contain (C-2) carboxylic serials spreading agent as required composition in composition of the present invention, therefore color spot through time increase very large, the patternability after PCD also has room for improvement.
Relative to these comparative examples, learn red sensitive resin combination (RR-1a) of the present invention such as shown in embodiment 101 containing in composition of the present invention as the pigment derivative of (B) ad hoc structure of required composition and (C-2) carboxylic serials spreading agent, therefore color spot through time increase be inhibited, the patternability after PCD is also significantly improved.
Also learn in addition, be used in resin (G-1) that side chain the has polymerism double bond embodiment 104 ~ embodiment 124 as (G) resin, the Magnification of color spot is inhibited further.
Learn that the embodiment 105, embodiment 108 and the embodiment 123 that use carboxylic serials spreading agent (C-12) and carboxylic serials spreading agent (C-15) are compared with using the embodiment of other carboxylic serials spreading agents, the patternability after PCD is excellent.
The preparation > of < green photonasty resin composition
The potpourri of following composition is uniformly mixed equably, prepares green photonasty resin composition (GR-1a).
Composition is changed to the composition recorded in following table 10, in addition, the method identical with the preparation of described green photonasty resin composition (GR-1a) is utilized to prepare green photonasty resin composition (GR-1b) ~ green photonasty resin composition (GR-1z) and green photonasty resin composition (GR-1aa).
About green photonasty resin composition (the GR-1a) ~ green photonasty resin composition (GR-1aa) of gained, utilize the method identical with embodiment 1 to carry out just prepare afterwards and at room temperature through time 6 months after the value of color spot and the evaluation of patternability after PCD.Result is gathered and is shown in following table.
Result according to described table 10, the green photonasty resin composition (GR-1x) of comparative example 105 and comparative example 107 and green photonasty resin composition (GR-1z) are though contain (C-2) carboxylic serials spreading agent as required composition in composition of the present invention, but do not contain the pigment derivative as (B) ad hoc structure of required composition in composition of the present invention, therefore patternability after PCD is deteriorated significantly, color spot through time increase also slightly large.In addition, the green photonasty resin composition (GR-1y) of comparative example 106 and comparative example 108 and green photonasty resin composition (GR-1aa) are though contain the pigment derivative as (B) ad hoc structure of required composition in composition of the present invention, but do not contain (C-2) carboxylic serials spreading agent as required composition in composition of the present invention, therefore color spot through time increase very large, the patternability after PCD also has room for improvement.
Relative to these comparative examples, learn green photonasty resin composition of the present invention (GR-1a) such as shown in embodiment 125 containing in composition of the present invention as the pigment derivative of (B) ad hoc structure of required composition and (C-2) carboxylic serials spreading agent, therefore color spot through time increase be inhibited, the patternability after PCD is significantly improved.
Also learn in addition, be used in resin (G-1) that side chain the has polymerism double bond embodiment 128 ~ embodiment 147 as (G) resin, the Magnification of color spot is inhibited further.
Learn that the embodiment 129, embodiment 132 and the embodiment 147 that use carboxylic serials spreading agent (C-12) and carboxylic serials spreading agent (C-15) are compared with using the embodiment of other carboxylic serials spreading agents, the patternability after PCD is more excellent.
Except being changed into except the following compound of equivalent by (B) the alkaline pigment derivative in described each embodiment, prepare photosensitive composition in the same fashion.Evaluate the patternability of obtained photosensitive composition, results verification can form good pattern.
[changing 72]

Claims (17)

1. a photosensitive composition, contain: (A) pigment, (B) alkaline pigment derivative, phosphoric acid system spreading agent represented by (C-1) following general formula (II) or (C-2) carboxylic serials spreading agent, (D) resin binder, (E) Photoepolymerizationinitiater initiater and (F) polymerizable compound, wherein said (C-2) carboxylic serials spreading agent makes to have the polymkeric substance (POH) of hydroxyl at least one end or have the polymkeric substance (PNH of one-level amino at least one end 2) to react with tricarboxylic acid anhydride or tetracarboxylic dianhydride and form,
In general formula (II), R 3represent that number average molecular weight is the polyester construction of 400 ~ 30000, y represents the integer of 1 or 2;
When y is 2, multiple R 3can identical also can be different.
2. photosensitive composition according to claim 1, wherein said (A) pigment is for being selected from least one in the cohort that is made up of red pigment, viridine green and yellow uitramarine.
3. photosensitive composition according to claim 1 and 2, in wherein said general formula (II), described R 3the number average molecular weight of represented polyester construction is 1900 ~ 10000.
4. photosensitive composition according to any one of claim 1 to 3, in wherein said general formula (II), described R 3represented polyester construction is by the polyester construction of two or more different internal ester monomer ring-opening polymerization gained.
5. photosensitive composition according to any one of claim 1 to 4, described in wherein said (C-2) carboxylic serials spreading agent has the polymkeric substance (POH) of hydroxyl at least one end or has the polymkeric substance (PNH of one-level amino at least one end 2) be represented by following general formula (II'),
In general formula (II'), Y 1represent the monovalence terminal groups with carbon number 1 ~ 20, oxygen number 0 ~ 12 and nitrogen number 0 ~ 3, X 2represent-O-,-S-or-N (R b)-, R brepresent hydrogen atom or the straight-chain of carbon number 1 ~ 18 or the alkyl of branch-like;
G 1expression-R 11repetitive represented by O-, G 2represent-C (=O) R 12repetitive represented by O-, G 3represent-C (=O) R 13c (=O)-OR 14repetitive represented by O-, R 11represent the cycloalkylidene of the straight-chain of carbon number 2 ~ 8 or the alkylidene of branch-like or carbon number 3 ~ 8, R 12represent the cycloalkylidene of the straight-chain of carbon number 1 ~ 8 or the alkylidene of branch-like or carbon number 4 ~ 8, R 13represent the arlydene of the straight-chain of carbon number 2 ~ 6 or the alkylidene of branch-like, the straight-chain of carbon number 2 ~ 6 or the alkenylene of branch-like, the cycloalkylidene of carbon number 3 ~ 20 or carbon number 6 ~ 20, R 14represent-CH (R 15)-CH (R 16)-, R 15and R 16any one be hydrogen atom, another represents that the alkyl of carbon number 1 ~ 20, the thiazolinyl of carbon number 2 ~ 20, the aryl of carbon number 6 ~ 20, the carbon number of moieties are the alkoxymethylene of 1 ~ 20, the carbon number of alkenyl part is the alkene oxygen methylene of 2 ~ 20, the carbon number of aryl moiety is 6 ~ 20 and the aryloxy group methylene that aryl moiety can replace through halogen atom or N-methylene-phthalimide-based;
Z 1represent-OH or-NH 2, R 17represent the straight-chain of carbon number 2 ~ 8 or alkylidene, the cycloalkylidene of carbon number 3 ~ the 8 ,-C (=O) R of branch-like 12-or-C (=O) R 13c (=O)-OR 14-;
M1 represents the integer of 0 ~ 100, and m2 represents the integer of 0 ~ 60, and m3 represents the integer of 0 ~ 30;
Wherein, m1+m2+m3 is more than 1, less than 100;
Described repetitive G in general formula (II') 1~ repetitive G 3configuration do not limit its order, represent in the polymkeric substance represented by general formula (II'), in radicals X 2with radicals R 17between contain repetitive G with random order 1~ repetitive G 3, and then, these repetitives G 1~ repetitive G 3can be any one of random or block type respectively.
6. photosensitive composition according to any one of claim 1 to 4, wherein in described (C-2) carboxylic serials spreading agent, described have the polymer P OH of hydroxyl at least one end or have the polymer P NH of one-level amino at least one end 2represented by following general formula (III),
In general formula (III), Y 1represent the monovalence terminal groups of carbon number 1 ~ 20, oxygen number 0 ~ 12 and nitrogen number 0 ~ 3, X 2represent-O-,-S-or-N (R b)-, R brepresent hydrogen atom or the straight-chain of carbon number 1 ~ 18 or the alkyl of branch-like;
Z 1represent-OH or-NH 2;
G 4and G 5represent-C (=O) R respectively 12repetitive represented by O-, R 12represent the cycloalkylidene of the straight-chain of carbon number 1 ~ 8 or the alkylidene of branch-like or carbon number 4 ~ 8; Wherein, G 4in R 12and G 5in R 12for mutually different group;
R 20represent-C (=O) R 12-;
M4 represents the integer of 5 ~ 60, and m5 represents the integer of 5 ~ 60;
Described repetitive G in general formula (III) 4, repetitive G 5configuration do not limit its order, represent in the polymkeric substance represented by general formula (III), in radicals X 2with group Z 1between contain repetitive G with random order 4, repetitive G 5, and then, these repetitives G 4, repetitive G 5can be any one of random or block type respectively.
7. photosensitive composition according to any one of claim 1 to 6, wherein said (D) resin binder is for making the compound (x) represented by following general formula (IV), having the resin that the compound (y) of ethene unsaturated double-bond carries out copolymerization with other
In general formula (IV), R 4represent hydrogen atom or methyl, R 5represent the alkylidene of carbon number 2 or 3, R 6represent that hydrogen atom maybe can contain the alkyl of the carbon number 1 ~ 20 of phenyl ring, n represents the integer of 1 ~ 15;
When n is the situation of more than 2, multiple R 5can identical also can be different.
8. photosensitive composition according to any one of claim 1 to 7, also has the resin of polymerism double bond at side chain containing (G).
9. photosensitive composition according to claim 8, the resin that wherein said (G) has polymerism double bond resin at side chain reacts for making compound (b) and multipolymer (a), described compound (b) having can with the functional group of hydroxyl reaction and ethene unsaturated double-bond, described multipolymer (a) is for having more than 2 and the polymerizable monomer (p) of hydroxyl of less than 6 and the multipolymer of other polymerizable monomers (q).
10. photosensitive composition according to any one of claim 1 to 9, it is the painted areas for the formation of colored filter.
11. 1 kinds of cured films, it photosensitive composition according to any one of claim 1 to 9 is hardened form.
The manufacture method of 12. 1 kinds of colored filters, comprising: photosensitive composition according to any one of claim 1 to 10 is applied to step support being formed coloring photosensitive combination layer; Described coloring photosensitive combination layer is exposed into the step of pattern-like; And the development of unexposed portion is removed and forms the step of colored pattern.
The manufacture method of 13. 1 kinds of colored filters, comprising:
Photosensitive composition according to any one of claim 1 to 10 is applied on support and forms coloring photosensitive combination layer, and make it harden and form the step of dyed layer;
Described dyed layer is formed the step of photoresist oxidant layer;
By carrying out exposing and developing by described photoresist pattern layers, obtain the step of Resist patterns; And
Described Resist patterns is carried out the step of dry-etching to described dyed layer as etching mask.
14. 1 kinds of colored filters, have cured film according to claim 11.
15. 1 kinds of colored filters, it forms with the manufacture method manufacture of the colored filter according to claim 12 or 13.
16. 1 kinds of solid-state imagers, have the colored filter according to claims 14 or 15.
17. 1 kinds of image display devices, have the colored filter according to claims 14 or 15.
CN201480031561.6A 2013-08-05 2014-07-31 Colored photosensitive resin composition, cured film, color filter and method for producing same, solid-state imaging element, and image display device Active CN105324717B (en)

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