CN102385246A - Colored photosensitive composition, color filter manufacture method, color filter and liquid crystal display device - Google Patents

Colored photosensitive composition, color filter manufacture method, color filter and liquid crystal display device Download PDF

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Publication number
CN102385246A
CN102385246A CN2011102379644A CN201110237964A CN102385246A CN 102385246 A CN102385246 A CN 102385246A CN 2011102379644 A CN2011102379644 A CN 2011102379644A CN 201110237964 A CN201110237964 A CN 201110237964A CN 102385246 A CN102385246 A CN 102385246A
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acid
methyl
coloring photosensitive
compound
photosensitive combination
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佐竹亮
冈部孝太郎
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Fujifilm Corp
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Fujifilm Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Liquid Crystal (AREA)

Abstract

The invention provides a colored photosensitive composition which, under the solution state, with excellent ageing stability and wide development latitude, causes no odor and allows formation of colored cured films with good solvent resistance, and also provides a color filter with good color characteristics of high color purity and high contrast ratio, a color filter manufacture method, and a liquid crystal display deice having such a color filter. The colored photosensitive composition comprises a halogenated zinc phthalocyanine pigment (A), a polymeric monomer (B) having an acid group, an adhesive resin (C), a photoplymerization initiator (D), a chain transfer agent (E) selected from secondary or tertiary aliphatic thiol compounds, and a solvent (F).

Description

Coloring photosensitive combination, manufacturing method of color filter, color filter and liquid crystal indicator
Technical field
The present invention relates to coloring photosensitive combination, used manufacturing method of color filter, color filter and the liquid crystal indicator of this coloring photosensitive combination.
Background technology
In the past; In small-sized liquid crystal indicator such as mobile phone, mobile game machine, PDA, must use secondary cell or dry cell etc. to have the back light of capacitance limits; Therefore; As the colorant of the color filter that in these display device, uses, advantageously use the transmission and carry out the colorant that color shows well of the high and bright line that can make backlight of the transparency always.
In recent years, the maximization of liquid crystal indicator is constantly development in purposes such as the LCD monitor of personal computer, LCD TV, in these liquid crystal indicators, no longer include the restriction of power supply backlight, and the RGB color reproduction of display device comes into one's own.Therefore, for the colorant of color filter, except the transparency that in the past required, also requiring the better pictures quality is the raising of contrast and colour purity.
To above-mentioned requirements; Developed the color filter that obtains as follows; And in the input practical application: more further add alkali soluble resins, optical polymerism compound, Photoepolymerizationinitiater initiater and other composition in the color compositions of miniaturization and process the coloring composition at the particle diameter of pigment, and use said composition on transparency carriers such as glass, to form patterns red, green, blue these 3 kinds of colors through photoetching process etc.
In the green coloring pattern wherein,, use chlorinated copper phthalocyanine pigment (C.I. pigment Green 7), chlorination bromination copper phthalocyanine viridine greens such as (C.I. pigment green 36s) usually from the viewpoint of tone and fastness.
As viridine green, in recent years, from the purpose of the chroma (colour purity and color depth) that improves pigment, studied central metal and be not copper but the metal halide phthalocyanine color of aluminium, titanium, cobalt, nickel, zinc, tin, lead etc. (for example with reference to patent documentation 1.), particularly about the high zinc halide phthalocyanine color of chroma (C.I. naphthol green 58), various pigment (for example with reference to patent documentation 2～4) have been proposed.For example; To the degree of substitution of Br, Cl, used the pigment facture of betaine type amphoteric surfactant, various crystal formations etc. to carry out detailed research; And reported in X-ray diffraction spectrum to be that 26.4 ° or the 25.5 ° copper halide phthalocyanines of locating to have the maximum diffraction peak are high chroma (colour purity and color depths) with respect to the Alpha-ray Bragg angle of Cu-K (2 θ ± 0.2 °); And ageing stability is excellent, is useful (for example with reference to patent documentation 5).In addition, proposed to use these pigment can obtain transparency height, color filter that colour purity is high.
Yet the metal halide phthalocyanine color of the high chroma high-contrast of high lightness produces following problem sometimes: particle size is little and the development tolerance is narrower than in the past, and time dependent can become unstable when preserving with the form of coloring photosensitive combination.In order to improve this ageing stability, proposed to use the mercaptan compound (for example with reference to patent documentation 6) of branched structure, but required the improvement of the operating environment that higher ageing stability and foul smell etc. are brought, the solvent resistance of curing caudacoria.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2003-161823 communique
Patent documentation 2: TOHKEMY 2007-284592 communique
Patent documentation 3: TOHKEMY 2004-70342 communique
Patent documentation 4: TOHKEMY 2008-24743 communique
Patent documentation 5: TOHKEMY 2009-223288 communique
Patent documentation 6: TOHKEMY 2004-264435 communique
Summary of the invention
The problem that the present invention will solve
The present invention is in view of the above problems and accomplishes, and problem of the present invention provides that a kind of ageing stability excellence, development tolerance under solution state is wide, the problem that does not have foul smell, the coloring photosensitive combination that can form the good color solidification film of solvent resistance.In addition, another problem of the present invention provides colour purity color characteristics high, that contrast is high that a kind of coloring photosensitive combination that uses the invention described above forms good color filter, manufacturing method of color filter and the liquid crystal indicator that possesses this color filter.
Be used to solve the means of problem
Present inventors further investigate in order to solve above-mentioned problem, and the result finds, can reach problem of the present invention through following means, thereby accomplish the present invention.
< 1>a kind of coloring photosensitive combination, it comprises chain-transferring agent and (F) solvent in the analiphatic sulphur alcoholic compound that polymerizable monomer, (C) adhesive resin, (D) Photoepolymerizationinitiater initiater, (E) that (A) zinc halide phthalocyanine color, (B) have acidic group be selected from secondary or three grades.
< 2>according to < 1>described coloring photosensitive combination, wherein, the analiphatic sulphur alcoholic compound of above-mentioned secondary or three grades is the analiphatic sulphur alcoholic compound of simple function or two senses.
< 3>according to < 1>or < 2>described coloring photosensitive combination, wherein, above-mentioned (D) Photoepolymerizationinitiater initiater is the hexa-aryl bi-imidazole compound.
< 4>according to each described coloring photosensitive combination in < 1 >～< 3 >, wherein, above-mentioned (C) adhesive resin is the resin with acidic group.
< 5>according to each described coloring photosensitive combination in < 1 >～< 4 >, it also comprises (G) light sensitizer.
< 6>a kind of pattern formation method, it comprises following operation: each described coloring photosensitive combination in < 1 >～< 5>is imparted on the substrate forms operation with the dyed layer that forms dyed layer; The exposure that formed dyed layer is carried out pattern appearance is so that the exposure process that solidify the exposure area; With the exposure after dyed layer in unexposed development, remove with formation pattern developing procedure.
< 7>a kind of color filter, it is made through < 6>described manufacturing approach.
< 8>a kind of liquid crystal indicator, it possesses < 7>described color filter.
The invention effect
According to the present invention, can provide that a kind of ageing stability under solution state is excellent, the development tolerance is wide, the problem that does not have foul smell, the coloring photosensitive combination that can form the good color solidification film of solvent resistance.Color filter, manufacturing method of color filter that the colour purity that in addition, can provide a kind of coloring photosensitive combination that uses the invention described above to form color characteristics high, that contrast is high is good and the liquid crystal indicator that possesses this color filter.
Embodiment
Below, to coloring photosensitive combination of the present invention, used the color filter of this coloring photosensitive combination and used the liquid crystal indicator of this color filter to be elaborated.
< coloring photosensitive combination >
Coloring photosensitive combination of the present invention is characterised in that, it comprises chain-transferring agent and (F) solvent in the analiphatic sulphur alcoholic compound that polymerizable monomer, (C) adhesive resin, (D) Photoepolymerizationinitiater initiater, (E) that (A) zinc halide phthalocyanine color, (B) have acidic group be selected from secondary or three grades.
Below each composition that constitutes coloring photosensitive combination of the present invention is described.
< (A) zinc halide phthalocyanine color >
The pigment that uses in the coloring photosensitive combination of the present invention is the zinc halide phthalocyanine.
Phthalocyanine is owing to having 16 hydrogen atoms, so can use maximum 16 bromine atoms and/or chlorine atom to replace these hydrogen atoms in the phthalocyanine ring.
These halogen atoms can be all identical, also can differ from one another.
Replacement number as halogen atom is preferably 8～16, more preferably 10～16 scope.
Substituted halogen atom is hydrogen atom, chlorine atom or bromine atoms respectively independently, and at least 1 in them is preferably chlorine atom or bromine atoms.
The zinc halide phthalocyanine color has the yellow high green of lightness through being replaced by the bromine atoms more than 8 thereby demonstrate, and is suitable in the green pixel portion pattern of color filter.
Particularly the replacement number of bromine atoms is that 10～16 zinc halide phthalocyanine color is because lightness is higher, so preferably use in the present invention.
The zinc halide phthalocyanine color that uses among the present invention can be made through for example various known manufacturing approaches such as chlorosulfonic acid method, halogenation phthalonitrile method, fusion method.
About manufacturing approach more specifically, the manufacturing approach of disclosed zinc halide phthalocyanine color is preferred from the viewpoint of cost in TOHKEMY 2004-70342 communique.
In addition, from the angle of stability, though also depend on the array mode of other adjuvant and subsequent handling, the disclosed zinc halide phthalocyanine color that has carried out crystal transfer in the preferred TOHKEMY 2008-19383 communique.
In addition, particularly in order to improve dispersiveness, disclosed in the TOHKEMY 2007-320986 communique is preferred mode through resin-coated zinc halide phthalocyanine color.
The average primary particle diameter of zinc halide phthalocyanine color of the present invention is preferably the scope of 10nm～100nm, more preferably the scope of 10nm～40nm.
The phthualocyanine pigment of the average primary particle diameter through using this scope can obtain the excellent and color filter that brightness is high, contrast is high of dispersion stabilization and colouring power and use coloring photosensitive combination.
In addition; Average primary particle diameter among the present invention is meant; With transmission electron microscope the particle in the visual field is taken; For 100 on the two dimensional image primary particles that constitute the phthalocyanine color of condensed matters, obtain the diameter (major diameter) of its length direction and the mean value of the diameter (minor axis) of short direction respectively, with its value that on average obtains.
If the length breadth ratio in length and breadth of the primary particle of zinc halide phthalocyanine color of the present invention further is 1～3 scope, then improve in each purposes field medium viscosity characteristic, it is higher that flowability becomes.
In order to obtain length breadth ratio, with the situation of the mean grain size of obtaining primary particle of above-mentioned that kind likewise, with transmission electron microscope or scanning electron microscope the particle in the visual field is taken.
Then,, obtain the diameter (major diameter) of length direction and the mean value of the diameter (minor axis) of lacking direction, be worth with these and calculate for 100 on the two dimensional image primary particles that constitute condensed matters.
In order to obtain the zinc halide phthalocyanine color that average primary particle diameter is the scope of 10nm～100nm; Can carry out micronize with arbitrary method; But, preferably adopt the lyonium salt mill to handle from easily suppressing crystalline growth and obtaining the angle of the smaller pigment particles of average primary particle diameter.
This lyonium salt mill is meant and grinds zinc halide phthalocyanine color, inorganic salts and organic solvent are mixing.
The zinc halide phthalocyanine color that particle diameter is big can carry out the lyonium salt mill after dry type grinds.
Particularly, zinc halide phthalocyanine color, inorganic salts and the organic solvent that do not dissolve them are put in the mixing roll, carried out mixing grinding therein.
Mixing roll as this moment can use for example kneader or mixer-mill (mix muller) etc.
As above-mentioned inorganic salts, can suitably use water-soluble inorganic salt, preferably use for example inorganic salts such as sodium chloride, potassium chloride, sodium sulphate.
In addition, more preferably using mean grain size is the inorganic salts of 0.5～50 μ m.
Such inorganic salts can be through easily obtaining common inorganic salts micro mist is broken.
In order to obtain the zinc halide phthalocyanine color that average primary particle diameter is the scope of 10nm～100nm, preferably improve inorganic salts consumption in the lyonium salt mill with respect to the ratio of the consumption of zinc halide phthalocyanine color.
That is, the consumption of these inorganic salts is preferably 5～20 parts in mass conversion with respect to 1 part of zinc halide phthalocyanine color, more preferably 7～15 parts.
As organic solvent; Preferred use can suppress the organic solvent of crystalline growth; As such organic solvent; Water-miscible organic solvent can be suitably used, for example diethylene glycol, glycerine, monoethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2-(methoxymethoxy) ethanol, butoxy ethanol, 2-(isoamoxy) ethanol, 2-(own oxygen base) ethanol, diethylene glycol monomethyl ether, TC, diethylene glycol single-butyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxyl-2-propyl alcohol, 1-ethoxy-2-propyl alcohol, DPG, DPGME, DPGME, DPG etc. can be used.
The consumption of the water-miscible organic solvent of this moment is not special to be limited, but is preferably 0.01～5 part in mass conversion with respect to 1 part of zinc halide phthalocyanine color, more preferably 0.8～2 part.
Temperature during the lyonium salt mill is preferably 30～150 ℃, more preferably 80～100 ℃.The time of lyonium salt mill is preferably 5～20 hours, more preferably 8～18 hours.
Thus; Can obtain containing zinc halide phthalocyanine color, inorganic salts and organic solvent potpourri as major component; Through from this potpourri, removing organic solvent and inorganic salts; And as required will with the zinc halide phthalocyanine color as the solid content of main body wash, filter, drying, pulverizing etc., thereby can obtain the powder of fine zinc halide phthalocyanine color.
As washing, can adopt in washing, the hot water wash any.Washing times can carry out with 1～5 time scope repeatedly.
Under the situation of the said mixture that has used water-soluble inorganic salt and water-miscible organic solvent, can easily remove organic solvent and inorganic salts through washing.
As the drying after above-mentioned filtration, the washing; Can enumerate out the heating source that for example is arranged on the dryer through utilization heats under 80～120 ℃ etc.; Pigment is dewatered and/or the batch (-type) of desolventizing or the drying of continous way etc.; As dryer, box dryer, band drier, spray dryer etc. are arranged usually.
In addition; Dried pulverizing is not in order to increase specific surface area or to reduce the mean grain size of primary particle and the operation carried out; But for as using for example box dryer, band drier to carry out the dry situation when pigment becomes bulk etc. pigment loosened and powderization and the operation carried out, can enumerate out and for example utilize pulverizing that mortar, beating crusher, disc mill, nail grinding machine, airflow milling etc. carry out etc.
(A) of the present invention zinc halide phthalocyanine color can obtain through for example above-mentioned method, also can use the zinc halide phthalocyanine color of common circulation or the goods of dispersible pigment dispersion.
(A) zinc halide phthalocyanine color that obtains like this so covering power becomes greatly, is made the painted epithelium of high-contrast owing to a little less than the cohesiveness of primary particle, have the character of loosening more easily easily.
Among the present invention, these zinc halide phthalocyanine colors can use separately, and other zinc halide phthalocyanine colors that also can be different with bromination rate or chlorination rate or central metal are used by mixing such as the bromination phthalocyanines of other metal replacements.
, thereby change the variation increase of the form and aspect that can expect to reproduce through changing bromination rate and chlorination rate or change central metal as the tone of pigment.
In the coloring photosensitive combination of the present invention, the form and aspect through other colorants of combination in (A) zinc halide phthalocyanine color are regulated coloring photosensitive combination can increase transmissivity.
For example, in order to form green pixel, can be to the zinc halide phthalocyanine color and with yellow uitramarine or orange pigment.
Example as yellow uitramarine; Except bisdiazo is that yellow uitramarine, isoindoline are that yellow uitramarine, quinophthalone are that yellow uitramarine, benzimidazolone are that yellow uitramarine, nickel azo are yellow uitramarine etc. the yellow uitramarine, also can use diketopyrrolo-pyrrole as required is that orange pigment, purple cyclic ketones are orange pigments such as orange pigment.
If enumerate out object lesson, C.I. pigment yellow 1,1:1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214 and C.I. pigment orange 2,5,13,16,17:1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73 etc. are arranged.
Wherein, Be preferably C.I. pigment yellow 20,24,31,53,83,86,93,94,109,110,117,125,137,138,139,147,148,150,153,154,166,173,180,185 etc., further be preferably C.I. pigment yellow 150, C.I. pigment yellow 185, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9.
When particularly using C.I. pigment yellow 150, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, because transmissivity is high, contrast is high, so preferred.
In addition, in order to form blue pixel, can and use violet pigment to the zinc halide phthalocyanine color.As the example of violet pigment, it is that violet pigment 、 oxazine is that violet pigment, anthraquinone are that violet pigment, indigoid (indigoid) are that violet pigment, xanthene are violet pigment etc. that quinoline a word used for translation ketone is arranged.
As object lesson, C.I. pigment violet 1,19,23,29,32,36,38 is arranged, particularly the C.I. pigment Violet 23 is because transmissivity is high, contrast is high, so preferred.
When the average primary particle diameter of these pigment is the scope of 10nm～40nm, because transmissivity is high, contrast is high, so preferred.The scope of 10nm～30nm more preferably.
The miniaturization in order to reduce average primary particle diameter, with the zinc halide phthalocyanine color likewise salt mill method be effectively, can carry out the salt mill with the zinc halide phthalocyanine color, also can carry out the salt mill respectively.
About average primary particle diameter, observe with SEM or TEM, in the size of 100 particles of the uncongealed part measurement of particle, calculate mean value, thereby obtain average primary particle diameter.
In the coloring photosensitive combination of the present invention; About the total amount of the pigment that comprises the zinc halide phthalocyanine color, the total solid composition of having removed solvent with respect in the coloring photosensitive combination of the present invention is preferably 5～60% in mass conversion; More preferably 10～50%, the best is 15～45%.
Through adopting the addition of this scope, can obtain color characteristics excellence, high, the high color filter of brightness of contrast.
In addition, " solid constituent " of the photosensitive composition among the present invention comprises whole compositions of the coloring photosensitive combination of having removed solvent.
< pigment dispensing composition >
In preparation during coloring photosensitive combination of the present invention and under the situation with multiple pigment, in advance together or to disperse and process pigment dispensing composition respectively be preferred mode with (A) zinc halide phthalocyanine color and other pigment.
Pigment dispensing composition is that above-mentioned pigment and solvent are disperseed the composition that forms, and can add back uses such as spreading agent, resin this moment as required.
Can further use pigment derivative etc., as required and other one-tenth that use assign to constitute.
The preparation of-pigment dispensing composition-
The not special restriction of the preparation method of pigment dispensing composition of the present invention; For example can be through using vertical or desk-top sand mill, nail grinding machine, slit comminutor (slit mill), ultrasonic dispersing machine etc.; The use particle diameter is that the bead of being processed by glass, zirconia etc. of 0.01～1mm carries out the diffusing processing of differential to pigment, pigment dispersing agent and solvent, thereby obtains.
Before carrying out the bead dispersion; Also can use two roller mills, triple-roller mill, bowl mill, drum sieve (trommel), dispersion machine, kneader, two-way kneader, refiner, mixer, single screw rod or double screw extrusion machine etc., carry out mixing dispersion treatment while apply strong shearing force.
In addition, relevant mixing, the detailed content of disperseing, on the books in " the Paint Flow and Pigment Dispersion " of T.C.Patton work (John Wiley and Sons society periodical in 1964) etc.
-pigment concentration-
As the content of pigment in pigment dispensing composition, with respect to removing of said composition the total solid composition of solvent, be preferably 10～60 quality % in mass conversion, more preferably 15～50 quality %.
The content of pigment is in above-mentioned scope the time, for guaranteeing that abundant, the excellent color characteristics of color depth is effective.
-spreading agent-
Pigment dispensing composition contains at least a kind of spreading agent.
Through containing this spreading agent, can improve dispersing of pigments property.
As spreading agent, can suitably select to use for example known pigment dispersing agent or surfactant.
Particularly; Can use multiple compound, for example can enumerating out, organic siloxane polymer KP341 (Shin-Etsu Chemial Co., Ltd's system), (methyl) acrylic acid series (being total to) polymer P OLYFLOW No.75, No.90, No.95 (above by chemical industry Co., Ltd. of common prosperity society system), W001 kations such as (Yu Business Co., Ltd's systems) are surfactant; Nonionics such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether, NONIN HS 240, polyoxyethylene nonylplenyl ether, polyethylene glycol dilaurate, polyglycol distearate, sorbitan fatty acid ester are surfactant; W004, W005, W017 negative ion such as (above by Yu Business Co., Ltd's system) are surfactant; Amphoteric surfactant with carboxybetaine structure, amide betaine structure, sulfobetaines structure, hydroxyl betaine structure etc.; MEGAFAC F171, F172, F173 fluorine such as (above by Dainippon Ink Chemicals's system) are surfactant; EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (above), Disperse AID 6, Disperse AID 8, Disperse AID 15, Disperse AID 9100 macromolecule dispersing agents such as (above) by SAN NOPCO corporate system by Ciba Specialty Chemicals system; Various SOLSPERSE spreading agents such as SOLSPERSE 3000,5000,9000,12000,13240,13940,17000,24000,26000,28000 (above) by Japanese Lubrizol Co., Ltd. system; ADEKA PLURONIC L31; F38; L42; L44; L61; L64; F68; L72; P95; F77; P84; F87; P94; L101; P103; F108; L121; P-123 (above) and ISONET S-20 (Sanyo Chemical Industries Co., Ltd.'s system) by rising sun electrification Co., Ltd. system; Disperbyk 101; 103; 106; 108; 109; 111; 112; 116; 130; 140; 142; 162; 163; 164; 166; 167; 170; 171; 174; 176; 180; 182; 2000; 2001; 2050; 2150 (above) by BYK-Chemie Co., Ltd. system.
In addition; Can enumerate out acrylic acid series copolymer, have N, the oligomer of N-disubstituted amido or acidic-group isopolarity group or polymkeric substance, the AB type of in the urethane resin of tertiary amine modification, TOHKEMY 2009-52010 communique, putting down in writing, ABA block polymer etc. in molecular end or side chain.
As the content of spreading agent in pigment dispensing composition, be preferably 1～100 quality % with respect to the gross mass of pigment, more preferably 3～70 quality %.
-pigment derivative-
Can add pigment derivative as required in the pigment dispensing composition.
Has the part of compatibility with spreading agent or the pigment derivative of polar group is adsorbed in surface of pigments through making to have introduced; Utilize its adsorption site as spreading agent; Thereby pigment is scattered in the coloring photosensitive combination with fine particulate forms; Can prevent that it from reassociating, be effective for constituting contrast color filter high, that the transparency is excellent.
Particularly, pigment derivative is as precursor skeleton, introduced acidic-group or basic group, aromatic group as substituent compound at side chain with organic pigment.
Particularly, the organic pigment that becomes precursor skeleton can be enumerated out quinoline a word used for translation ketone series pigments, phthualocyanine pigment, azo pigment, quinophthalone series pigments, isoindoline series pigments, isoindoline ketone series pigments, quinoline pigment, diketopyrrolo-pyrrole pigment, benzimidazolone pigment etc.Usually, also comprise flaxen aromatic series polycyclic compunds such as the naphthalene system that is not called as pigment, anthraquinone system, triazine system, quinoline system.
As pigment derivative, can use the pigment derivative of record in japanese kokai publication hei 11-49974 communique, japanese kokai publication hei 11-189732 communique, japanese kokai publication hei 10-245501 communique, TOHKEMY 2006-265528 communique, japanese kokai publication hei 8-295810 communique, japanese kokai publication hei 11-199796 communique, TOHKEMY 2005-234478 communique, TOHKEMY 2003-240938 communique, the TOHKEMY 2001-356210 communique etc.
As the content of pigment derivative in pigment dispensing composition, be preferably 1～30 quality % with respect to the gross mass of pigment, more preferably 3～20 quality %.
When the content of pigment derivative is in this scope, can the viscosity of pigment dispensing composition be suppressed lower, and can disperse well, improve the dispersion stabilization after disperseing simultaneously.
Thus; Can obtain to have the transmissivity height, the coloring photosensitive combination of excellent color characteristics; So, when in the making purposes that this coloring photosensitive combination is applicable to color filter for example, the color filter that can obtain to have good color characteristics, contrast is high.
In addition, macromolecular compounds such as alkali soluble resins of stating after can also in pigment dispensing composition, further adding etc.
To be considered to for dispersing of pigments also be effectively to contained acidic group isopolarity group in the alkali soluble resins, and the dispersion stabilization for dispersible pigment dispersion under a lot of situation is effective.
-solvent-
As the solvent in the pigment dispensing composition, so long as used organic solvent in the general pigment-dispersing composition, then not special the qualification.
For example can enumerate out 1-methoxyl-2-propyl-acetic acid ester, 1-methoxyl-2-propyl alcohol, glycol monomethyl methyl ether, diethylene glycol monomethyl ether, ethyl acetate, butyl acetate, ethyl lactate, acetone, MEK, methyl isobutyl ketone, cyclohexanone, n-propanol, 2-propyl alcohol, normal butyl alcohol, cyclohexanol, monoethylene glycol, diethylene glycol, toluene, xylene equal solvent; In order to regulate fusing point, viscosity, dispersing of pigments property, also can and use their central multiple solvents.
In addition, (F) solvent that is used to prepare coloring photosensitive combination of stating after also can using.
The content of the solvent in the pigment dispensing composition can wait according to the purposes of pigment dispensing composition suitably and select.
Under the situation of the coloring photosensitive combination of after pigment dispensing composition is used to prepare, stating; From the viewpoint of operability, can according to the summation that makes pigment and pigment dispersing agent with respect to removing of pigment dispensing composition the gross mass of the solvent mode that reaches 5～50 quality % contain solvent.
Content as the pigment dispensing composition in the coloring photosensitive combination of the present invention; With respect to removing of coloring photosensitive combination the quality of total solid composition of solvent; The content that is preferably pigment reaches the amount of the scope of 5～70 quality %, more preferably reaches the amount of the scope of 15～60 quality %.
When the content of pigment dispensing composition is in above-mentioned scope, for guaranteeing that abundant, the excellent color characteristics of color depth is effective.
As (A) zinc halide phthalocyanine color of coloring photosensitive combination of the present invention, except that above-mentioned pigment, also can and use dyestuff.Through also using dyestuff, can expect that the contrast of color filter rises.
As the dyestuff that uses in the coloring photosensitive combination of the present invention; So long as dissolve in the dyestuff in the organic solvent; Then not special the qualification; If distinguish, can enumerate out azo based dye, anthraquinone based dye, phthalocyanine based dye, quinone imines based dye, quinoline based dye, nitro based dye, carbonyl based dye, methine based dye and their derivant etc. with chemical constitution.
As the azo based dye, for example can enumerate out that C.I. acid yellow 11, C.I. acid orange 7, C.I. acid red 37, C.I. acid red 18 0, C.I. acid blue 29, C.I. are directly red 28, C.I. is directly red 83, C.I. is directly yellow 12, C.I. Direct Yellow 26, C.I. direct green 28, C.I. direct green 59, C.I. reactive yellow 2, C.I. reactive red 17, C.I. reactive red 120, C.I. disperse orange 5, C.I. disperse red 58, C.I. disperse blue 165, C.I. alkali blue 41, C.I. Basic Red 18, C.I. medium red 7, C.I. media yellow 5 etc.
As the anthraquinone based dye, can enumerate out for example C.I. Vat blue 4, C.I. Acid Blue 40, C.I. ACID GREEN 25, C.I. active blue 19, C.I. reactive blue 49, C.I. disperse red 60, C.I. Disperse Blue-56, C.I. disperse blue 60 etc.
In addition, as the phthalocyanine based dye, can enumerate out for example C.I. vat blue 5 etc.; As the quinone imines based dye; For example C.I. alkali blue 3, C.I. alkali blue 9 etc. can be enumerated out,, for example C.I. solvent yellow 33, C.I. quinoline yellow, C.I. dispersion yellow 64 etc. can be enumerated out as the quinoline based dye; As the nitro based dye, can enumerate out for example C.I. Indian yellow 1, C.I. acid orange 3, C.I. Disperse Yellow 42 etc.
The polymerizable monomer of acidic group < (B) have >
In the coloring photosensitive combination of the present invention,, contain the polymerizable monomer that (B) more than at least a kind has acidic group as the curable composition.
Through using the polymerizable monomer that in structure, has acidic group, unexposed development obtains promoting, so the development tolerance is by improvement significantly.Wherein, the polymerizable monomer with acidic groups such as carboxyl, phenol property hydroxyl, sulfonic group, phosphates is owing to the raising of alkali dissolution property, so development property raising and big, preferred especially to the contribution of inhibition residue.Except after the alkali solubility of (C) adhesive resin of stating bestow the effect; The effect that has the polymerizable monomer of acidic group through use; Even in the colored resin composition that has increased pigment concentration in order to improve brightness, the development tolerance is also wide, can make stable color filter.
As the polymerizable monomer that contains carboxyl,, can enumerate out through carboxy-modified polyfunctional acrylic ester compound except acrylic acid, methacrylic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, cinnamic acid etc. the unsaturated fatty acid.As through carboxy-modified polyfunctional acrylic ester compound; Succinic acid modification pentaerythritol triacrylate, succinic acid modification trimethylolpropane triacrylate, succinic acid modification tetramethylol methane tetraacrylate, succinic acid modification dipentaerythritol five acrylic ester, succinic acid modification dipentaerythritol acrylate, hexane diacid modification pentaerythritol triacrylate, hexane diacid modification trimethylolpropane triacrylate, hexane diacid modification tetramethylol methane tetraacrylate, hexane diacid modification dipentaerythritol five acrylic ester, hexane diacid modification dipentaerythritol tetraacrylate etc. can be enumerated out, ARONIX M-510, ARONIX M-520, ARONIX TO-2349, ARONIX TO-2359 commercially available compounds such as (above) can be suitably used by Toagosei Co., Ltd's system.
As the polymerizable monomer that contains phenol property hydroxyl; Can enumerate out para hydroxybenzene ethene, 3; 4-dihydroxy benzenes ethene, 3; 5-dihydroxy benzenes ethene, 2; 4,6-trihydroxy benzene ethene, (to hydroxyl) benzyl acrylic ester, salicylic acid modification pentaerythritol triacrylate, salicylic acid modification trimethylolpropane triacrylate, salicylic acid modification tetramethylol methane tetraacrylate, salicylic acid modification dipentaerythritol five acrylic ester, salicylic acid modification dipentaerythritol acrylate etc. are preferably salicylic acid modification dipentaerythritol acrylate, salicylic acid modification dipentaerythritol five acrylic ester.
As containing sulfonic polymerizable monomer, vinyl sulfonic acid, allyl sulphonic acid, styrene sulfonic acid, butyl sulfonic acid modified propylene acid amides etc. are arranged.As the polymerizable monomer that contains phosphate, can enumerate out vinyl phosphoric acid, styrene phosphoric acid, butyl phosphoric acid modified propylene acid amides etc.In the middle of these, be preferably butyl sulfonic acid modified propylene acid amides,, ATBS (Toagosei Co., Ltd's system) arranged as commercially available compound.
These have in the polymerizable monomer of acidic group, from making the viewpoint of adaptability and cost, are preferably the polymerizable monomer with carboxyl, the polymerizable monomer with phenol property hydroxyl, more preferably have the polymerizable monomer of carboxyl.
In the coloring photosensitive combination of the present invention, can use single polymerizable monomer as polymerizable monomer with acidic group, also can be also with multiple polymerizable monomer with acidic group.In addition, also can be respectively and with the polymerizable monomer that contains acidic group more than a kind with do not have the polymerizable monomer of acidic group.In order to take into account solvent resistance, ITO sputter adaptability and development tolerance, preferably except polymerizable monomer, and and with the polymerizable monomer that does not have acidic group with acidic group.
(polymerizable monomer that does not have acidic group)
As long as among the present invention can with the polymerizable monomer that does not have acidic group of polymerizable monomer with acidic group and usefulness can polymerization; The compound that low molecular compound with the two keys of at least 1 ethylenic, dipolymer, trimer, oligomer etc. can addition polymerization can be suitably used in then not special restriction.
As ethylenic compound, the ethylenic compound that the hydroxyl compound reaction that can enumerate out the ester of for example ester, aromatic polyhydroxy compounds and the unsaturated carboxylic acid of ester, aliphatic polyhydroxy compound and the unsaturated carboxylic acid of unsaturated carboxylic acid and monohydroxy compound, ester, polyisocyanate compounds that the esterification through polyols such as unsaturated carboxylic acid and polybasic carboxylic acid and above-mentioned fatty acid polyol, aromatic polyhydroxy compounds obtains and contain (methyl) acryloyl group obtains etc. with carbamate skeleton.
Concrete polymerizable monomer can be described below to classify according to the number of the polymerizable group in 1 molecule and enumerate, but is not limited thereto.
The compound that has 1 polymerizable group in (1) 1 molecule
As the example that has the compound of 1 polymerizable group in 1 molecule; Can enumerate out for example (methyl) Hexyl 2-propenoate, (methyl) 2-EHA, (methyl) stearyl acrylate base ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 4-normal-butyl cyclohexyl, (methyl) acrylic acid norbornene ester, (methyl) IBOA, (methyl) benzyl acrylate, (methyl) acrylic acid 2-ethohexadiol ester, (methyl) acrylic acid butoxy ethyl ester, (methyl) acrylic acid 2-chloroethene ester, (methyl) acrylic acid cyanic acid ethyl ester, (methyl) acrylic acid 3-methoxyl butyl ester, (methyl) acrylic acid 2-(2-methoxy ethoxy) ethyl ester, (methyl) acrylic acid 2; 2; 2-tetrafluoro ethyl ester, (methyl) acrylic acid 1H; 1H; 2H; 2H perfluor ester in the last of the ten Heavenly stems, (methyl) phenyl acrylate, (methyl) acrylic acid 2; 4,5-tetramethyl phenyl ester, (methyl) acrylic acid 4-chlorobenzene ester, (methyl) acrylic acid phenoxy group methyl esters, (methyl) glycidyl acrylate, (methyl) acrylic acid glycidoxypropyl butyl ester, (methyl) acrylic acid glycidoxypropyl ethyl ester, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxyl butyl ester, (methyl) acrylic acid 4-hydroxyl butyl ester, (methyl) acrylic acid 3-hydroxy propyl ester, polyoxyethylene monomethyl ether (methyl) acrylic ester, few ethylene oxide monomethyl ether (methyl) acrylic ester, polyoxyethylene (methyl) acrylic ester, few ethylene oxide (methyl) acrylic ester, (methyl) acrylic acid 2-hydroxyl-3-phenoxy group propyl ester, EO modified phenol (methyl) acrylic ester, EO modification cresols (methyl) acrylic ester, EO modification nonyl phenol (methyl) acrylic ester, PO modification nonyl phenol (methyl) acrylic ester, EO modification-(methyl) 2-EHA etc.
(2) in 1 molecule, has the compound of 2 polymerizable groups
As the example that in 1 molecule, has the compound of 2 polymerizable groups; Can enumerate out and in a part, have the compound of 2 (methyl) acryloyl groups as polymerizable group; Can enumerate out for example ethylene glycol bisthioglycolate (methyl) acrylic ester, diethylene glycol two (methyl) acrylic ester, triethylene glycol two (methyl) acrylic ester, polyglycol two (methyl) acrylic ester, 1; 3-butylene glycol two (methyl) acrylic ester, 1; 4-butylene glycol two (methyl) acrylic ester, 1; 6-hexanediol two (methyl) acrylic ester, neopentyl glycol two (methyl) acrylic ester, propylene glycol two (methyl) acrylic ester, DPG two (methyl) acrylic ester, tripropylene glycol two (methyl) acrylic ester, polypropylene glycol two (methyl) acrylic ester, 2-hydroxyl-1; 3-two propylene acyloxy propane, 2; Two [4-(acryloyl-oxy base oxethyl) phenyl] propane, 2 of 2-; Two (acryloxy ethyl) ethers of two [4-(acryloxy diethoxy) phenyl] propane of 2-, bisphenol-A, (methyl) acrylic acid modified thing of bisphenol A type epoxy resin, 3-methyl pentanediol two (methyl) acrylic ester, 2-hydroxyl-3-acryloxy propyl methyl acid esters, dihydroxymethyl-tristane two (methyl) acrylic ester etc. preferably can be enumerated out (methyl) acrylic acid modified thing of dihydroxymethyl-tristane two (methyl) acrylic ester, neopentyl glycol two (methyl) acrylic ester, ethoxylation bisphenol-A two (methyl) acrylic ester, bisphenol A type epoxy resin etc.
(3) in 1 molecule, has the compound of 3 polymerizable groups
As the example of the compound that in a part, has three polymerizable groups, can enumerate out alkylene oxide modification three (methyl) acrylic ester, pentaerythrite three (methyl) acrylic ester, dipentaerythritol three (methyl) acrylic ester, trimethylolpropane tris ((methyl) acryloxy propyl group) ether, isocyanuric acid alkylene oxide modification three (methyl) acrylic ester, propionic acid dipentaerythritol three (methyl) acrylic ester, three ((methyl) acryloxy ethyl) isocyanuric acid ester, hydroxy pivalin aldehyde modification dihydroxy methylpropane three (methyl) acrylic ester, D-sorbite three (methyl) acrylic ester, propoxylation trimethylolpropane tris (methyl) acrylic ester, ethoxylated glycerol triacrylate of for example trimethylolpropane tris (methyl) acrylic ester, trimethylolethane trimethacrylate (methyl) acrylic ester, trimethylolpropane etc.
(4) in 1 molecule, has the compound of 4 above polymerizable groups
As the compound that in 1 molecule, has 4 above polymerizable groups, can enumerate out the urethane acrylate such as UA-306H, UA-306T, UA-306I of alkylene oxide modification six (methyl) acrylic ester, caprolactone modification dipentaerythritol six (methyl) acrylic ester, Kyoeisha Chemical Co., Ltd.'s system of for example pentaerythrite four (methyl) acrylic ester, D-sorbite four (methyl) acrylic ester, two (trihydroxy methyl) propane four (methyl) acrylic ester, propionic acid dipentaerythritol four (methyl) acrylic ester, ethoxylation pentaerythrite four (methyl) acrylic ester, dipentaerythritol five (methyl) acrylic ester, dipentaerythritol six (methyl) acrylic ester, D-sorbite five (methyl) acrylic ester, D-sorbite six (methyl) acrylic ester, phosphonitrile.
In the middle of these; From suitably keeping solvent patience, the adaptive viewpoint of ITO sputter; Be preferably (methyl) acrylate monomer of (methyl) acryloyl group that in a part, has more than 2, more preferably have (methyl) acrylate monomer of (methyl) acryloyl group more than 3.
(methyl) acrylate monomer that particularly has (methyl) acryloyl group more than 4 is favourable; For example from solvent patience, the adaptive viewpoint of ITO sputter; Preferred dipentaerythritol five acrylic ester, dipentaerythritol acrylate, (mixture ratio of mass conversion is dipentaerythritol five acrylic ester: dipentaerythritol acrylate=2～4: potpourri 8～6) can suitably to use their potpourri.
Under the situation of the polymerizable monomer that will have acidic group and the polymerizable monomer and the usefulness that do not have acidic group; To have the polymerizable monomer of acidic group when being designated as 100 mass parts with the total that does not have a polymerizable monomer of acidic group; Preferably in the scope of 1～50 mass parts and with polymerizable monomer with acidic group; The scope of 1～40 mass parts more preferably further is preferably the scope of 5～20 mass parts.
In the coloring photosensitive combination of the present invention; Amount to the preferred content of the polymerizable monomer that obtains about polymerizable monomer that will have acidic group and the polymerizable monomer that does not have acidic group; With respect to removing of coloring photosensitive combination the total solid composition of solvent; Be preferably 5～80 quality %, 10～60 quality % more preferably further are preferably the scope of 15～50 quality %.
(C) adhesive resin
As (C) applicatory among the present invention adhesive resin,, then all can use so long as dissolve in the macromolecular compound of solvent.Adhesive resin can use single compound respectively, also can and use multiple compound.As the preferred adhesive resin,, then preferably have resin (following suitably be called " alkali soluble resins " of acidic group if consider to utilize photolithographic alkali-developable.)。
Alkali soluble resins can contain in the stage of the above-mentioned pigment dispensing composition of preparation, also can contain at preparation pigment dispensing composition and these two the stage gradation of preparation coloring photosensitive combination.
Alkali soluble resins is the wire organic high molecular polymer; Wherein, The alkali solubility macromolecule that preferably has at least 1 alkali solubility group (for example carboxyl, phosphate, sulfonic group etc.), the alkali soluble resins that more preferably dissolves in organic solvent and can utilize weak base aqueous solution to develop.
The manufacturing of alkali soluble resins can application examples like method based on known radical polymerization.
The polymerizing conditions such as kind of the kind of the temperature when making alkali soluble resins through radical polymerization, pressure, radical initiator and amount thereof, solvent, those skilled in the art can easily set, and also can confirm condition through experiment.
As the wire organic high molecular polymer that is used as alkali soluble resins, preferably has the polymkeric substance of carboxyl at side chain.
Can enumerate out the methacrylic acid copolymer put down in writing in each communique of for example japanese kokai publication sho 59-44615 number, special public clear 54-34327 number of Japan, special public clear 58-12577 number of Japan, special public clear 54-25957 number of Japan, japanese kokai publication sho 59-53836 number, japanese kokai publication sho 59-71048 number, acrylic copolymer, itaconic acid copolymer, crotonic acid multipolymer, maleic acid, partial esterification maleic acid etc. and side chain have carboxylic acid the acid cellulose derivant, have addition acid anhydrides on the polymkeric substance of hydroxyl and the polymkeric substance that obtains etc., also can enumerate out have (methyl) acryloyl group at side chain high molecular polymer as preferred polymkeric substance.
Wherein, especially preferably by multiple copolymer that (methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) benzyl acrylate/(methyl) acrylic acid/other monomer constitutes.
In addition, also can enumerate out multipolymer that the 2-hydroxyethyl methacrylate copolymerization is obtained etc. as useful adhesive resin.
This polymkeric substance can use with amount mixing arbitrarily.
Except that above-mentioned, can enumerate out (methyl) acrylic acid 2-hydroxy propyl ester/polystyrene macromolecular monomer/benzyl methacrylate/methacrylic acid copolymer of putting down in writing in the japanese kokai publication hei 7-140654 communique, acrylic acid 2-hydroxyl-3-phenoxy group propyl ester/polymethylmethacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromolecular monomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromolecular monomer/benzyl methacrylate/methacrylic acid copolymer etc.
As other alkali soluble resins, can use the known macromolecular compound of record in japanese kokai publication hei 7-207211 communique, japanese kokai publication hei 8-259876 communique, japanese kokai publication hei 10-300922 communique, japanese kokai publication hei 11-140144 communique, japanese kokai publication hei 11-174224 communique, TOHKEMY 2000-56118 number, TOHKEMY 2003-233179 number, TOHKEMY 2009-52020 communique etc.
About the concrete structural unit of alkali soluble resins, particularly (methyl) acrylic acid and can be with the multipolymer of other monomer of its copolymerization owing to can obtain easily, and regulate alkali dissolution property etc. easily, so preferred the use.
As can with other monomer of above-mentioned (methyl) acrylic acid copolymer, can enumerate out (methyl) alkyl acrylate, (methyl) acrylic acid aryl ester, vinyl compound etc.
Here, the hydrogen atom of alkyl and aryl can be substituted the base replacement.
As the object lesson of above-mentioned (methyl) alkyl acrylate and (methyl) acrylic acid aryl ester, can enumerate out (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) phenyl acrylate, benzyl acrylate, CA, acrylic acid naphthalene ester, cyclohexyl acrylate etc.
As above-mentioned vinyl compound, can enumerate out for example styrene, AMS, vinyltoluene, (methyl) glycidyl acrylate, vinyl cyanide, vinyl acetate, N-vinyl pyrrolidone, (methyl) acrylic acid tetrahydro furfuryl ester, polystyrene macromolecular monomer, polymethylmethacrylate macromonomer, CH 2=CR 31R 32(R here, 31Expression hydrogen atom or carbon number are 1～5 alkyl, R 32The expression carbon number is 6～10 aromatic hydrocarbon ring.), CH 2=C (R 31) (COOR 33) (R here, 31Expression hydrogen atom or carbon number are 1～5 alkyl, R 33The expression carbon number is that 1～8 alkyl or carbon number are 6～12 aralkyl.) etc.
These can copolymerization other monomer can a kind use separately or make up more than 2 kinds and use.
Preferably other monomer of ability copolymerization is for being selected from CH 2=CR 31R 32, CH 2=C (R 31) (COOR 33), in (methyl) phenyl acrylate, (methyl) benzyl acrylate and the styrene at least a kind, be preferably CH especially 2=CR 31R 32And/or CH 2=C (R 31) (COOR 33).R in them 31, R 32And R 33Implication with above-mentioned group is identical respectively.
In addition; As the content of the adhesive resins such as alkali soluble resins in the coloring photosensitive combination,, be preferably 1～20 quality % with respect to the total solid composition of having removed the solvent that is contained in the coloring photosensitive combination; More preferably 2～15 quality % are preferably 3～12 quality % especially.
In addition; About the polymerizable monomer that will have acidic group and do not have a ratio of polymerizable monomer that the polymerizable monomer of acidic group amounts to and the content of adhesive resin; Be preferably 0.1～10 scope in mass ratio (quality of the gross mass/adhesive resin of polymerizable monomer); More preferably 0.4～8 scope further is preferably 0.5～5 scope.
(D) Photoepolymerizationinitiater initiater
(D) Photoepolymerizationinitiater initiater in the coloring photosensitive combination of the present invention is so long as the compound of initiated polymerization, then not qualification especially through exposure.
As (D) Photoepolymerizationinitiater initiater, can use for example camphorquinone, benzophenone, benzophenone derivates, oxime compound, acylphosphanes, acylphosphanes derivant, acetophenone, acetophenone derivs, hexa-aryl bi-imidazole compound, boronic acid compounds etc.
As concrete example, also can use Alpha-hydroxy naphthenic base phenyl ketone or 2-hydroxy-2-methyl-1-phenyl-acetone, dialkoxy acetophenone class, Alpha-hydroxy-or 4-aroyl-1,3-dioxa penta lopps, benzoin alkylether class and benzil ketals class for example benzyl dimethyl ketal, glyoxalic acid phenyl ester and derivant thereof, dipolymer glyoxalic acid phenyl ester, perester class for example benzophenone tetrabasic carboxylic acid perester class (for example the Europe patented claim discloses the 1st; The perester of putting down in writing in 126, No. 541 instructionss), halomethyl triazines 2-(2-(4-methoxyl-phenyl)-vinyl)-4 for example, 6-is two-trichloromethyl (1; 3,5) triazine, 2-(4-methoxyl-phenyl)-4,6-pair-trichloromethyl (1; 3,5) triazine, 2-(3,4-dimethoxy-phenyl)-4; 6-pair-trichloromethyl (1; 3,5) triazine, 2-methyl-4,6-pair-trichloromethyl (1; 3,5) adjacent chlorine hexaphenyl-two imidazoles of for example combining with 2-mercaptobenzothiazole of triazine, hexa-aryl bi-imidazole/common initiating agent system; Ferrocene-containing compound or two luxuriant titanium classes, for example dicyclopentadienyl-two (2,6-two fluoro-3-pyrroles-phenyl) titanium; For example with BrP the 2nd, 339, the potpourri of the O-acyl group oxime ester compound of putting down in writing in No. 571 instructionss.As and the Photoepolymerizationinitiater initiater of usefulness, also can use boronic acid compounds.
In the coloring photosensitive combination of the present invention, the preferred hexa-aryl bi-imidazole compound that uses in above-mentioned (D) Photoepolymerizationinitiater initiater.Coloring photosensitive combination layer through using the hexa-aryl bi-imidazole compound to form pattern can show good photostability.
(hexa-aryl bi-imidazole compound)
As the hexa-aryl bi-imidazole compound, so long as replaced 3 aryl imidazole ring dipolymer all can, be preferably the compound shown in the formula (1) especially, more preferably the compound shown in the general formula (2).
In the general formula (1), a plurality of X represent independently that respectively hydrogen atom, halogen atom, cyanic acid, carbon number are that 1～4 alkyl or carbon number are 6～9 aryl, a plurality of A represent independently respectively carbon number be 1～12 alkoxy or-COO-R 9(wherein, R 9The expression carbon number is that 1～4 alkyl or carbon number are 6～9 aryl.)。N is 1～3 integer, and m is 1～3 integer.
Figure BDA0000084314610000201
In the general formula (2), X 1, X 2And X 3Represent independently that respectively hydrogen atom, halogen atom, cyanic acid, carbon number are that 1～4 alkyl or carbon number are 6～9 aryl.Wherein, X 1, X 2And X 3In be not hydrogen atom simultaneously more than 2.
As the hexa-aryl bi-imidazole compound, can enumerate out for example 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2-chlorphenyls)-4; 4 ', 5,5 '-four (4-ethoxy carbonyl phenyl) two imidazoles, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) two imidazoles, 2; 2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl) two imidazoles, 2,2 '-two (2; The 4-dichlorophenyl)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) two imidazoles, 2,2 '-two (2,4; The 6-trichlorophenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl) two imidazoles, 2,2 '-two (2,4; The 6-trichlorophenyl)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) two imidazoles, 2,2 '-two (2-cyano-phenyl)-4,4 '; 5,5 '-four (4-ethoxy carbonyl phenyl) two imidazoles, 2,2 '-two (2-cyano-phenyl)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) two imidazoles, 2; 2 '-two (2-aminomethyl phenyl)-4,4 ', 5,5 '-four (4-methoxycarbonyl phenyl) two imidazoles, 2,2 '-two (2-aminomethyl phenyl)-4,4 '; 5,5 '-four (4-ethoxy carbonyl phenyl) two imidazoles, 2,2 '-two (2-aminomethyl phenyl)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) two imidazoles, 2; 2 '-two (2-ethylphenyl)-4,4 ', 5,5 '-four (4-methoxycarbonyl phenyl) two imidazoles, 2,2 '-two (2-ethylphenyl)-4,4 '; 5,5 '-four (4-ethoxy carbonyl phenyl) two imidazoles, 2,2 '-two (2-ethylphenyl)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) two imidazoles, 2; 2 '-two (2-phenyl)-4,4 ', 5,5 '-four (4-methoxycarbonyl phenyl) two imidazoles, 2,2 '-two (2-phenyl)-4,4 '; 5,5 '-four (4-ethoxy carbonyl phenyl) two imidazoles, 2, two imidazole compounds of the two imidazoles of 2 '-two (2-phenyl)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) etc.;
2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-four-(p-methoxyphenyl) two imidazoles, 2,2 '-two (Chloro-O-Phenyl)-4; 4 ', 5,5 '-four-(m-methoxyphenyl) two imidazoles, 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5; 5 '-four-(3, the 4-Dimethoxyphenyl) two imidazoles, 2,2 '-two (2-chlorphenyl)-4,4 ', 5; 5 '-four-(4-methoxyphenyl) two imidazoles, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four-(3-methoxyphenyl) two imidazoles, 2; 2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four-(3, the 4-Dimethoxyphenyl) two imidazoles;
2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2,4, the 6-trichlorophenyl)-4; 4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2; 4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2,4-dicyano phenyl)-4,4 ', 5; 5 '-tetraphenyl double imidazole, 2,2 '-two (2,4,6-tricyano phenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2; The 4-3,5-dimethylphenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2,4, the 6-trimethylphenyl)-4,4 '; 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2,4-diethyl phenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2; 4,6-triethyl phenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2,4-diphenyl phenyl)-4,4 '; 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2,4,6-triphenyl phenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2; 2 '-two (2-fluorophenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (adjacent fluorophenyl)-4,4 ', 5, two imidazole compounds such as 5 '-tetraphenyl double imidazole etc.
In above-mentioned,, can enumerate out 2,2 '-two (2-chlorphenyls)-4 as preferred especially compound; 4 ', 5,5 '-tetraphenyl double imidazole (B-CIM, HODOGAYA chemical industry Co., Ltd. system), 2,2 '-two (Chloro-O-Phenyl)-4; 4 ', 5,5 '-four-(3, the 4-Dimethoxyphenyl) two imidazoles (HABI1311, Japanese Shiiberuheguna Co., Ltd. system), 2; 2 '-two (2-aminomethyl phenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole (dark fund changes into Co., Ltd.'s system).
Content about the Photoepolymerizationinitiater initiater in the coloring photosensitive combination of the present invention; When the content of polymerizable monomer (will have the polymerizable monomer that the polymerizable monomer of acidic group and the polymerizable monomer that does not have acidic group amount to) is designated as 100 mass parts; Be preferably about 0.05～30 quality %; Further be preferably 0.1～20 quality %, more preferably 0.2～10 quality %.
In addition; About with hexa-aryl bi-imidazole compound and the Photoepolymerizationinitiater initiater of structure except that the hexa-aryl bi-imidazole compound and the ratio of the content of time spent; The content of hexa-aryl bi-imidazole compound is designated as at 1 o'clock; Content in the Photoepolymerizationinitiater initiater of the structure of quality criteria except that the hexa-aryl bi-imidazole compound is preferably 0.1～5.0, further is preferably 0.2～3.0, is preferably 0.3～2.0 especially.
Through being set at this scope, it is good especially that photostability becomes.
(E) chain-transferring agent
Coloring photosensitive combination of the present invention is characterised in that, it comprises the chain-transferring agent in the analiphatic sulphur alcoholic compound that (E) be selected from secondary or three grades.The analiphatic sulphur alcoholic compound of secondary or three grades has hydrogen as chain-transferring agent and supplies with property.Among the present invention, the carbon number that carbon atom combined of series expression and mercapto adjacency.
Usually, there is the tendency of stabilization through interacting easily each other in the compound that has a similar structures.Phthalocyanine compound is owing to have planar structure; And there be the deep or light of electron density between nitrogen-atoms that constitutes and the carbon atom; So have can along with the structure of parallel plane direction stack, and produce interaction with the deep or light compound that complementally has electron density easily.
(A) zinc halide phthalocyanine color among the present invention is the high chroma high-contrast of high lightness, and dispersiveness and dispersion stabilization are bad but then.When using the high polymerizable monomer of acid number in order to ensure the alkali-developable of coloring photosensitive combination, coloring photosensitive combination oxytropism lateral deviation is moved.Think and cause the soda acid interaction between zinc halide phthalocyanine color and the spreading agent to weaken the skew of stably dispersing zone thus.Can think that if existence this moment is easy and interactional compound takes place the zinc halide phthalocyanine color, then the interaction between zinc halide phthalocyanine color and the spreading agent can cause disperse state to become unstable, the possibility that pigment produces cohesion uprises.
From such viewpoint; Use the aromatic mercaptans compound as chain-transferring agent if consider to (A) zinc halide phthalocyanine color among the present invention; Then through the structure of mercaptan and the effect of aromatic ring structure, the interaction between zinc halide phthalocyanine color and the aromatic mercaptans compound makes mercaptan compound become and is adsorbed on the surface of zinc halide phthalocyanine color easily.Consequently, the cohesion of zinc halide phthalocyanine color causes the time dependent of coloring photosensitive combination (viscosity, contrast) to have problems.
Among the present invention; Can think, owing to use the analiphatic sulphur alcoholic compound, so be difficult for producing the effect of the above-mentioned aromatic rings that results from mercaptan compound; And owing to use the compound of mercapto with secondary or three grades; So a little less than the interaction of mercaptan compound and zinc halide phthalocyanine color, can not cause the cohesion of zinc halide phthalocyanine color, can bring into play function fully as chain-transferring agent.
Surface adsorption spreading agent through at the zinc halide phthalocyanine color is guaranteed dispersion stabilization; But, make the adsorption site inactivation on the surface of zinc halide phthalocyanine color so can't be adsorbed on whole adsorption sites on surface of zinc halide phthalocyanine color because spreading agent is generally macromolecule.That is, the adsorption site that is not adsorbed remains in the surface of zinc halide phthalocyanine color, might pass through long-time back pigment thus and condense.But,,, can not produce the cohesion of pigment because of aforesaid mercapto so this monomer with acidic group is adsorbed on the adsorption site of residual surface of pigments owing to use polymerizable monomer among the present invention as polymerizable monomer with acidic group.Promptly; In order to prevent the cohesion of zinc halide phthalocyanine color; Through the analiphatic sulphur alcoholic compound and synergy of the secondary selected among the present invention or three grades with polymerizable monomer of acidic group, the surface of zinc halide phthalocyanine color can prevent coloring photosensitive combination of the present invention time dependent can deterioration.Can realize the good color characteristics that the zinc halide phthalocyanine color is had thus.
In addition, the analiphatic sulphur alcoholic compound of secondary or three grades performance chain transfer among the present invention can provide that sensitivity is excellent, the good coloring photosensitive combination of development property.
In addition, the mercaptan compound that has sulphur atom sends distinctive foul smell.Known foul smell and volatility have much relations; Usually aliphatics one-level mercaptan compound is because volatility is high; So preferably in the purposes of preparation coloring photosensitive combination, do not use; Among opposite the present invention owing to use the analiphatic sulphur alcoholic compound of secondary or three grades, so the foul smell problem when not using coloring photosensitive combination, the coloring photosensitive combination that can obtain to be fit to.
Analiphatic sulphur alcoholic compound as secondary or three grades; Can enumerate out uncle's butane mercaptan, octyl group-2 mercaptopropionic acid ester, octyl group-3-sulfydryl butyric ester, stearyl-2 mercaptopropionic acid ester, stearyl-3-sulfydryl butyric ester, 2; 5-hexane two mercaptan, 2; 9-decane two mercaptan, 1; The 4-butylene glycol is two-2 mercaptopropionic acid ester, 1, and the 4-butylene glycol is two-3-sulfydryl butyric ester, ethylene glycol bis-2 mercaptopropionic acid ester, ethylene glycol bis-3-sulfydryl butyric ester, trimethylolpropane tris-2 mercaptopropionic acid ester, trimethylolpropane tris-3-sulfydryl butyric ester, pentaerythrite four-2 mercaptopropionic acid ester, pentaerythrite four-3-sulfydryl butyric ester, dipentaerythritol five-2 mercaptopropionic acid ester, dipentaerythritol five-3-sulfydryl butyric ester etc.
Wherein, The analiphatic sulphur alcoholic compound of simple function or two senses is because ageing stability becomes better and preferred; Special preferred tertiary butane mercaptan, octyl group-2 mercaptopropionic acid ester, octyl group-3-sulfydryl butyric ester, stearyl-2 mercaptopropionic acid ester, stearyl-3-sulfydryl butyric ester, 2; 5-hexane two mercaptan, 2; 9-decane two mercaptan, 1, the 4-butylene glycol is two-2 mercaptopropionic acid ester, 1, and the 4-butylene glycol is two-3-sulfydryl butyric ester, ethylene glycol bis-2 mercaptopropionic acid ester, ethylene glycol bis-3-sulfydryl butyric ester.
In the coloring photosensitive combination of the present invention,, the analiphatic sulphur alcoholic compound of a kind of secondary or three grades be can use separately, secondary or three grades analiphatic sulphur alcoholic compound more than 2 kinds also can be used as chain-transferring agent.
Content about the analiphatic sulphur alcoholic compound of the secondary in the coloring photosensitive combination of the present invention or three grades; With respect to the total solid composition of removing the solvent that is contained in the coloring photosensitive combination; Be preferably 0.2～10 quality %; More preferably 0.3～8 quality % is preferably 0.5～5 quality % especially.
In addition; The analiphatic sulphur alcoholic compound of the secondary in the coloring photosensitive combination or three grades is preferably 5～150 quality % with respect to the content of the total amount of (D) Photoepolymerizationinitiater initiater in quality criteria; More preferably 10～100 quality % are preferably 10～50 quality % especially.
Through in this scope, thereby the polymerization can promote to process the coloring photosensitive combination layer time forms the high and good pattern of sensitivity.
In addition, the analiphatic sulphur alcoholic compound of the secondary in the coloring photosensitive combination or three grades is preferably 1～10 quality % with respect to the content of (A) zinc halide phthalocyanine color in quality criteria, and more preferably 2～8 quality % are preferably 3～5 quality % especially.
Through in this scope, the storage stability of coloring photosensitive combination is good.
(F) solvent
Coloring photosensitive combination of the present invention contains (F) solvent.
As employable among the present invention (F) solvent, can enumerate out being categorized as ester class, ethers, ketone, aromatic hydrocarbon based etc. solvent.
(F) solvent also can be used to prepare above-mentioned pigment dispensing composition.
Example as the ester class that is used as (F) solvent; For example except ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, hydroxy methyl acetate, hydroxyl ethyl acetate, glycolic acid butyl ester, methoxy menthyl acetate, methoxyacetic acid ethyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate etc., can enumerate out 3-hydracrylic acid alkyl esters such as 3-hydroxy methyl propionate and 3-hydracrylic acid ethyl ester; 2 hydroxy propanoic acid alkyl esters such as 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester, 2 hydroxy propanoic acid propyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate; 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, 2-ethoxyl ethyl propionate, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-alkoxypropan acid alkyl esters such as 2 Methylpropionic acid ethyl ester; Methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-ketobutyric acid methyl esters, 2-ketobutyric acid ethyl ester etc.
As the example of ethers, can enumerate out for example diethylene glycol dimethyl ether, tetrahydrofuran, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, acetic acid methyl cellosolve, acetate ethyl cellosolve, diethylene glycol monomethyl ether, TC, diethylene glycol single-butyl ether, methyl proxitol acetate, propylene glycol ethylether acetic acid esters, propylene glycol propyl ether acetic acid esters etc.
As the example of ketone, can enumerate out for example MEK, cyclohexanone, 2-heptanone, 3-heptanone etc.
As aromatic hydrocarbon based example, can enumerate out for example toluene, xylene etc.
In these solvents, preferred 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, acetate ethyl cellosolve, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid methyl esters, 2-heptanone, cyclohexanone, acetate ethyl card must esters, acetate butyl card must ester, methyl proxitol acetate etc.
Solvent can use separately, also can make up more than 2 kinds and use.
The content of (F) solvent in the coloring photosensitive combination of the present invention can be considered suitably decisions such as the coating of coloring photosensitive combination, and generally speaking, the content of (F) solvent in the coloring photosensitive combination is 76 quality %～88 quality %.
(G) light sensitizer
Coloring photosensitive combination of the present invention can also further contain (G) light sensitizer.
As (G) light sensitizer, can suitably use the compound that has maximum absorption wavelength at 350～450nm place.
For example except (squarium) type (for example in side's acid) in the polynuclear aromatic same clan (for example Bi 、 perylene, terphenyl), xanthene class (for example luciferin, eosin, erythrosine, rhodamine B, rose-red), cyanine class (for example sulphur carbon cyanines (thiacarbocyanine), oxygen carbon cyanines (oxacarbocyanine)), part cyanines class (for example part cyanines, carbon part cyanines), thiazide (for example thionine, methylene blue, toluidine blue), acridine (for example acridine orange, chloroflavin, acriflavine), anthraquinone class (for example anthraquinone), the side's acid, benzophenone (for example 4; 4 '-diethylamino benzophenone) etc. beyond the compound group, can enumerate out the compound of putting down in writing in TOHKEMY 2007-91806 communique, TOHKEMY 2008-9323 communique, the TOHKEMY 2010-49160 communique.
The analiphatic sulphur alcoholic compound of (D) Photoepolymerizationinitiater initiater among the present invention, (E) secondary or three grades and (G) ratio (mass ratio) that contains of light sensitizer be preferably Photoepolymerizationinitiater initiater/mercaptan compound/light sensitizer=20～50/30～70/10～30; More preferably Photoepolymerizationinitiater initiater/mercaptan compound/light sensitizer=30～40/40～60/10～20 further are preferably Photoepolymerizationinitiater initiater/mercaptan compound/light sensitizer=35～40/50～55/10～15.
Through using each composition, thereby improve, obtain colored pattern easily corresponding to the high live width of the precision of exposure area for the exposure sensitivity of g ray, h ray and i ray with these ratios.
In addition, coloring photosensitive combination of the present invention also preferably contains common sensitizer.Among the present invention, altogether sensitizer has further raising light sensitizer or Photoepolymerizationinitiater initiater to the sensitivity of active radioactive ray or suppress the effects such as polymerization inhibition of the optical polymerism compound that oxygen causes.
Example as so common sensitizer; Can enumerate out the for example compound etc. of work such as M.R.Sander " Journal of Polymer Society " the 10th volume 3173 pages of (1972), special public clear 44-20189 communiques of Japan, japanese kokai publication sho 51-82102 communique, japanese kokai publication sho 52-134692 communique, japanese kokai publication sho 59-138205 communique, japanese kokai publication sho 60-84305 communique, japanese kokai publication sho 62-18537 communique, japanese kokai publication sho 64-33104 communique, No. 33825 records of Research Disclosure of amine; Particularly, can enumerate out triethanolamine, ESCAROL 507 ethyl ester, to the formoxyl xylidin, to methyl sulfo-xylidin etc.
As other example of sensitizer altogether, the hydrogen that can enumerate out organometallics (for example tributyltin acetate etc.), the special public clear 55-34414 communique record of Japan of amino-acid compound (for example N-phenylglycine etc.), the special public clear 48-42965 communique record of Japan is supplied with the sulphur compound of body, the record of japanese kokai publication hei 6-308727 communique (for example trithiane etc.) etc.
About being total to the content of sensitizer; The viewpoint of the raising of the curing rate that brings from the balance of aggregation growth speed and chain transfer; Quality optimization with respect to all solids composition of photosensitive composite is the scope of 0.1～30 quality %; The scope of 1～25 quality % more preferably further is preferably the scope of 0.5～20 quality %.
< adjuvant >
In the coloring photosensitive combination of the present invention, can contain free radical scavenger, light stabilizer, auxiliary curing agent, thermal polymerization, surfactant, bonding auxiliary agent, development accelerant, hot polymerization inhibitor, spreading agent, other the various adjuvants of adjuvant (filling agent, ultraviolet light absorber, anticoalescent etc.) as required.
(free radical scavenger)
Among the present invention,, can add various free radical scavengers in order to improve photostability.The kind of free radical scavenger is not special to be limited, from thermotolerance, photostability viewpoint, and preferred azoxy based compound and various light stabilizer.As the object lesson of azoxy based compound, can enumerate out azoxybenzene, azoxydianisole, azoxy phenetol, 4,4 '-dioctyl azoxybenzene etc.
(light stabilizer)
For improving photostability, various light stabilizers are also brought into play effect.Do not limit about the kind of light stabilizer is special, consider that from the aspect of versatility can suitably use hindered amine is light stabilizer; For example two (2,2,6,6-tetramethyl-4-piperidyl) adipates, two (1,2,2,6; 6-pentamethyl-4-piperidyl) adipate, two (2,2,6,6-tetramethyl-4-piperidyl) sebacate, two (1,2,2,6; 6-pentamethyl-4-piperidyl) sebacate, four (2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-tetraacrylate, four (1; 2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-tetraacrylate, hindered phenol are light stabilizer; Pentaerythrite-four (3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester etc. for example.
About the content of the light stabilizer among the present invention, be preferably about 0.1～5.0 quality % with respect to all solids composition of coloring photosensitive combination, further be preferably 0.2～4.0 quality %, more preferably 0.5～2.0 quality %.If be below the 0.1 quality %, then can not get desired photostability, if be more than the 5.0 quality %, then sensitivity reduces, so not preferred.
(auxiliary curing agent)
As auxiliary curing agent,, can use compound with epoxide ring in order to improve formed coating film strength.Have the compound of epoxide ring through use, thermal polymerization is carried out, the raising of solvent patience, the raising of ITO sputter adaptability etc., so preferred.
As compound, be the compound that has 2 above epoxide rings in bisphenol A-type, cresols novolac type, biphenyl type, the alicyclic epoxy compound equimolecular with epoxide ring.
For example; As bisphenol A-type; Except (above), PLAXEL GL-61 such as Epo Tohto YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 etc. (above), Denacol EX-1101, EX-1102, EX-1103, GL-62, G101, the G102 (above), also can enumerate out their similar Bisphenol F types, bisphenol S type by Daicel chemistry system by Dongdu system of changing into by the Nagase system of changing into.In addition, also can use Ebecryl 3700,3701,600 epoxy acrylates such as (above) by Daicel (U.S.A.) system.
As cresols novolac type; Can enumerate out (above) such as Epo Tohto YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704 etc. (above), Denacol EM-125 by the Nagase system of changing into by Dongdu system of changing into; As biphenyl type; Can enumerate out 3,5,3 '; 5 '-tetramethyl-4; 4 '-diglycidyl biphenyl etc. as the alicyclic epoxy compound, can be enumerated out (above by Dongdu system of changing into), Epiclon 430, Epiclon 673, Epiclon695, Epiclon 850S, Epiclon 4032 (above by the DIC system) etc. such as Celloxide 2021,2081,2083,2085, Epolead GT-301, GT-302, GT-401, GT-403, EHPE-3150 (above by Daicel chemistry system), Sun Tohto ST-3000, ST-4000, ST-5080, ST-5100.
In addition; Also can use 1; 1; 2,2-four (to glycidyl oxygen base phenyl) ethane, three (to glycidyl oxygen base phenyl) methane, triglycidyl group three (hydroxyethyl) isocyanuric acid ester, o-phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester and as the Epo Tohto YH-434 of amine type epoxy resin, YH-434L (above) by the Nagase system of changing into, in the skeleton of bisphenol A type epoxy resin modification the ethylene oxidic ester etc. of dimer acid.
Wherein, preferred " number of molecular weight/epoxide ring " is more than 100, more preferably 130～500.If " number of molecular weight/epoxide ring " is less, then curable is high, and the contraction during curing is big, and in addition, if excessive, then curable is not enough, lacks reliability, the flatness variation.
As concrete preferred compound; Can enumerate out Epo Tohto YD-115,118T, 127, YDF-170, YDPN-638, YDPN-701 (above), PLAXEL GL-61, GL-62,3 by the Nagase system of changing into; 5; 3 ', 5 '-tetramethyl-4,4 ' diglycidyl biphenyl, Celloxide 2021,2081, Epolead GT-302, GT-403, EHPE-3150 (above) etc. by Daicel chemistry system.
About the content of the auxiliary curing agent among the present invention, be preferably about 0.1～5.0 quality % with respect to all solids composition of coloring photosensitive combination, further be preferably 0.2～4.0 quality %, more preferably 0.5～2.0 quality %.When being 0.1 quality % when following, can not get solidifying facilitation effect, when being 5.0 quality % when above, photostability worsens and is a problem.
(thermal polymerization)
In the coloring photosensitive combination of the present invention, it also is effective containing thermal polymerization.As thermal polymerization; Can enumerate out for example various azo based compounds, superoxide based compound; As above-mentioned azo based compound; The two based compounds of azo can be enumerated out,, ketone peroxide, ketal peroxide, hydroperoxides, dialkyl peroxide, diacyl peroxide, peroxyester, peroxy dicarbonate etc. can be enumerated out as above-mentioned superoxide based compound.
(surfactant)
In the coloring photosensitive combination of the present invention,, preferably use various surfactants to constitute from the viewpoint of improvement coating.Utilize surfactant, can improve the characteristics of liquids (particularly mobile) when processing coating fluid, and can improve the homogeneity and joint fluidity of coating thickness.Promptly; Owing to the surface tension that can reduce substrate and coating fluid is improved the wetting state on substrate; The coating of raising on substrate; Even, be effective in this respect so, also can form the film of the little uniform thickness of difference in thickness forming with a spot of liquid measure under the situation of the film about several μ m.In addition, in the slot coated that causes the liquid cutout easily, also be effective.
As surfactant, can use the various surfactants of nonionic system, kation system, negative ion system.Wherein, preferred nonionic is that the fluorine that has perfluoroalkyl in the surfactant is a surfactant.
Fluorine is that the fluorine containing ratio of surfactant is preferably 3～40 quality %, and more preferably 5～30 quality % are preferably 7～25 quality % especially.When the fluorine containing ratio is in above-mentioned scope, be that effectively the dissolubility in composition is also good aspect coating thickness homogeneity, the joint fluidity.
As fluorine is surfactant, can enumerate out for example MEGAFAC F171, MEGAFACF172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F141, MEGAFACF142, MEGAFAC F143, MEGAFAC F144, MEGAFAC R30, MEGAFAC F437 (above by Dainippon Ink Chemicals's system), FLUORAD FC430, FLUORAD FC431, FLUORAD FC171 (above by Sumitomo 3M Co., Ltd. system), SURFLON S-382, SURFLON SC-101, SURFLON SC-103, SURFLON SC-104, SURFLONSC-105, SURFLON SC1068, SURFLON SC-381, SURFLON SC-383, SURFLON S393, SURFLON KH-40 (above by Asahi Glass Co., Ltd's system) etc.
As the example of the surfactant beyond the defluorination system, can enumerate out phthalocyanine derivates (commercially available article EFKA-745 (gloomy industry corporate system down)), organic siloxane polymer KP341 (chemical industrial company of SHIN-ETSU HANTOTAI system), (methyl) acrylic acid series (being total to) polymer P OLYFLOW No.75, No.90, No.95 (oil chemistry industrial group of common prosperity society system), W001 kations such as (abundant merchant's corporate systems) is surfactant; (nonionics such as the system PLURONIC L10 of BASF AG, L31, L61, L62,10R5,17R2,25R2, TETRONIC 304,701,704,901,904,150R1 are surfactant for polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether, NONIN HS 240, polyoxyethylene nonylplenyl ether, polyethylene glycol dilaurate, polyglycol distearate, sorbitan fatty acid ester; W004, W005, W017 negative ion such as (abundant merchant's corporate systems) are surfactant.
With respect to the gross mass of coloring photosensitive combination, the addition of surfactant is preferably 0.001～2.0 quality %, more preferably 0.005～1.0 quality %.
(bonding auxiliary agent)
Among the present invention in the used photosensitive polymer combination,, can add bonding auxiliary agent from improving the viewpoint with the cementability of substrate.As bonding auxiliary agent, can use alkoxysilane compound containing trialkylsilyl group in molecular structure, especially silane coupling agent.
Silane coupling agent preferably have alkoxysilyl as can with the hydrolization group as the inorganic material chemical bonding of substrate; Preferably have and organic resin between produce to interact or form key and show the silane coupling agent of the groups such as (methyl) acryloyl group, phenyl, secondary or three grades of sulfydryls, epoxy radicals, amino silane base of compatibility; Wherein, more preferably (methyl) acryloyl group propyl trimethoxy silicane, glycidyl trimethoxy silane.As such material, can enumerate out KBM-303, KBM-403, KBM-503 (above) by Shin-Etsu Chemial Co., Ltd's system.
Addition when using silane coupling agent is preferably the scope of 0.2 quality %～5.0 quality %, more preferably 0.5 quality %～3.0 quality % in all solids composition in coloring photosensitive combination of the present invention.
(development accelerant)
In addition, in uncured the alkali dissolution property that promotes the coloring photosensitive combination layer, seek can in coloring photosensitive combination, use development accelerant under the situation of further raising of development property of coloring photosensitive combination.
As such development accelerant, be preferably organic carboxyl acid, preferred molecular weight is the low-molecular-weight organic carboxyl acid below 1000.Particularly, for example can enumerate out formic acid, acetate, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetate, enanthic acid, aliphatics monocarboxylic acid such as sad; Aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, tridecandioic acid, methylmalonic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl succinic acid, citraconic acid; Aliphatics tricarboxylic acids such as tricarballylic acid, aconitic acid, norcamphor three acid; Benzoic acid, toluic acid, cumfrey, 2,3-mesitylenic acid, 3, aromatic series monocarboxylic acids such as 5-mesitylenic acid; Aromatic series polybasic carboxylic acids such as phthalic acid, m-phthalic acid, terephthalic acid (TPA), trimellitic acid, trimesic acid, mellophanic acid, PMA; Other carboxylic acid such as the inferior cinnamic ester of phenylacetate, hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, acetate, coumaric acid, umbellic acid.
(hot polymerization inhibitor)
The hot polymerization inhibitor of preferred further interpolation in the coloring photosensitive combination of the present invention; For example quinhydrones, p methoxy phenol, di-t-butyl-paracresol, pyrogallol, tert-butyl catechol, benzoquinones, 4; 4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), 2-mercaptobenzimidazole etc. are useful.
(spreading agent)
Except that above-mentioned, can be added on the pigment dispersing agent of describing in the item of pigment dispensing composition in the coloring photosensitive combination.
(other adjuvant)
Can enumerate out filling agents such as glass, aluminium oxide; Ultraviolet light absorbers such as 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, alkoxy benzophenone; Reach anti-agglutinants such as sodium polyacrylate.
Coloring photosensitive combination of the present invention can be prepared as follows: contain each composition of above description, promptly (A) zinc halide phthalocyanine color, (B) have analiphatic sulphur alcoholic compound and (F) solvent, (or further (G) sensitizer) of polymerizable monomer, (C) adhesive resin, (D) Photoepolymerizationinitiater initiater, (E) secondary or three grades of acidic group, and further add other adjuvant and mixing such as surfactant as required and prepare.
< color filter and manufacturing approach thereof >
Color filter of the present invention is to form through painted film (colored pattern) on substrates such as glass through the coloring photosensitive combination that uses the invention described above to make, and for example makes through the manufacturing approach that comprises following operation: coloring photosensitive combination of the present invention is applied on the substrate forms operation with the dyed layer that forms dyed layer; This dyed layer is made public to form the exposure process of sub-image with pattern appearance; Dyed layer after the exposure is developed to form the developing procedure of colored pattern.
Dyed layer can directly or be situated between and is imparted on the substrate by other layer, as the method for bestowing dyed layer, forms through methods such as rotary coating, slot coated, curtain coating coating, roller coat, ink-jet application or transfer printings.For formed dyed layer; Make public or make public across mask pattern with pattern-like; Make exposure portion solidify the back and unexposed (uncured portion) development is removed, form the colored pattern of (for example 3 looks or 4 looks) of all kinds thus, thereby can make color filter with developer solution.
Thus, can technologic difficulty less, high-quality and make the color filter that is used for liquid crystal indicator or solid-state imager at low cost.
At this moment, as the radioactive ray that are used to make public, except g ray, h ray, i ray, j ray etc. the ultraviolet ray, preferred ultraviolet laser etc.
In addition, as the mode of exposure,, can also suitably use the Exposure mode that has adopted LASER Light Source except the close induction type Exposure mode, sputter-Exposure mode.
In the laser explosure mode, use ultraviolet laser as light source.Laser is the initial of English Light Amplification by Stimulated Emission of Radiation (carrying out the amplification of light through stimulated emission).Can use oscillator and amplifier; They are utilized in the phenomenon of the stimulated emission that takes place in the material with counter-rotating distribution; Amplification, vibration through light wave produce interference capability and the stronger monochromatic light of directivity; As exciting media, crystal, glass, liquid, pigment, gas etc. are arranged, can use the known laser that have oscillation wavelength at the ultraviolet light place such as Solid State Laser from these media, liquid laser, gas laser, semiconductor laser.Wherein, from the viewpoint of output power of laser and oscillation wavelength, preferred Solid State Laser, gas laser.
As the wavelength that can be used for laser explosure of the present invention; The scope of optimal wavelength is the ultraviolet laser of 300nm～380nm scope; Consider that from the aspect consistent further optimal wavelength is the ultraviolet laser of the scope of 300nm～360nm with the wavelength photoreceptor of coloring photosensitive combination.
Particularly, be particularly suitable for using the 3rd higher hamonic wave (355nm) or XeCl (308nm), the XeF (353nm) of PRK of the Nd:YAG laser of big, the less expensive Solid State Laser of output power.
Exposure by exposure thing (pattern) is 1mJ/cm 2～100mJ/cm 2Scope, 1mJ/cm more preferably 2～50mJ/cm 2Scope.When exposure is this scope, preferred from the throughput rate angle that pattern forms.
As being used for exposure device of the present invention; Not special restriction; As commercially available exposure device, can use Callisto (V Technology Co., Ltd. system), EGIS (V Technology Co., Ltd. system) or DF2200G (big Japanese Screen Co., Ltd. system) etc.In addition, also can suitably use above-mentioned device in addition.
In addition, can also use light emitting diode (LED) and laser diode (LD) as active radiation source.Particularly when the needs ultraviolet source, can use ultraviolet LED and ultraviolet LD.For example, Ri Ya KCC sells has the purple LED that main emission spectrum is the wavelength between 365nm and the 420nm.In addition, when the shorter wavelength of needs, U.S. Patent number the 6th, 084, but No. 250 instructionss disclose the LED of the active radioactive ray of launching centre between 300nm and 370nm.In addition, also other ultraviolet LEDs can be obtained, the radiation of different ultraviolet bandwidth can be shone.Preferred especially active radiation source is UV-LED among the present invention, has the UV-LED of peak wavelength particularly preferably in 340～370m place.
Ultraviolet laser is because the depth of parallelism is good, so even exposure the time is not used mask, also can carry out pattern exposure.But when using mask to come exposing patterns, the rectilinearity of pattern further improves, so more preferably.
Can use heating plate, baking oven etc. in 50～140 ℃ temperature range, under 10～300 seconds the condition, to carry out by the drying (prebake conditions) of bestowing the film that (being preferably coating) form to the coloring photosensitive combination of the present invention on the substrate.
In development, make uncured stripping after the exposure in developer solution and only make solidified portion residual.As development temperature, be generally 20～30 ℃, as development time, be 20～90 seconds.
As developer solution, so long as the film of the coloring photosensitive combination in uncured of the solubilized but do not dissolve the developer solution of solidified portion then can use developer solution arbitrarily.Particularly, can use the combination of various organic solvents or the WS of alkalescence.
As above-mentioned organic solvent, operable above-mentioned solvent in the time of can enumerating out as preparation pigment dispensing composition of the present invention or coloring photosensitive combination and the solvent enumerated.
As above-mentioned alkaline aqueous solution; Can enumerate out for example with NaOH, potassium hydroxide, sodium carbonate, soda mint, sodium silicate, sodium metasilicate, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, TMAH, tetraethyl ammonium hydroxide, choline, pyrroles, piperidines, 1; 8-diazabicyclo-[5; 4,0]-alkali compounds such as 7-hendecene is so that concentration reaches 0.001～10 quality %, the mode that preferably reaches 0.01～1 quality % is dissolved and the alkaline aqueous solution that obtains.
In addition, when using alkaline aqueous solution as developer solution, water washs (flushing) after development usually.
After the development, remaining developer solution is removed in washing, and implements dryly, implements heat treated (back baking) being generally under 100～250 ℃ the temperature then.
Back baking is the heating that is used for making after the development of completion of cure, under about 200 ℃～250 ℃, heats (hard baking) usually.This back baking processing can use heating plate or heater meanses such as convection oven (heated air circulation type dryer), high frequency heating machine to carry out with continous way or batch-type according to above-mentioned condition the coated film after developing.
According to desirable form and aspect number, successively each color is repeated above operation, can make the color filter that is formed with polychrome thus through painted cured film.
Coloring photosensitive combination of the present invention is imparted on the substrate when forming film,, is generally 0.3 μ m～5.0 μ m, be preferably 0.5 μ m～3.5 μ m, most preferably be 1.0 μ m～2.5 μ m as the dry thickness of film.
As substrate, for example can enumerate out the alkali-free glass that is used for liquid crystal indicator etc., soda-lime glass, Pyrex (registered trademark) glass, quartz glass, and at these photo-electric conversion element substrates that adhered to the substrate of nesa coating or be used for solid-state imager etc. on glass for example silicon substrate etc. and plastic base.Usually, can on these substrates, be formed for isolating the blackstreak of each pixel.
Preferably have gas-barrier layer and/or solvent resistance layer on the surface of plastic base.
Other layers when bestowing coloring photosensitive combination as on substrate, being situated between by other layers can be enumerated out gas-barrier layer, solvent resistance layer etc.
[liquid crystal indicator]
Color filter of the present invention is particularly suitable for the color filter used as liquid crystal indicator.The liquid crystal indicator that possesses this color filter can show high-grade image.
About the display device definition and each display device description, such as "Electron イ su plastic Rei terrestrial Buses イ su (Junior Wood? Akio book, (strain) Industrial Research Council? 1990 issuance) "," terrestrial イ su plastic Rei terrestrial Buses イ su (Ibuki? shun chapter book, industrial Charts book (strain) Heisei issuance) ", etc. There are documented.In addition, the liquid crystal display device, for example, in "the next generation of LCD terrestrial イ su plastic Rei Technology (Uchida? Tatsuo compilation, (strain) Industrial Research Council? 1994 issuance)" in the records.The liquid crystal indicator that the present invention can be suitable for is not particularly limited, and for example can be useful in the liquid crystal indicator of the variety of way of record in above-mentioned " inferior generation liquid crystal デ イ ス プ レ イ technology ".
Wherein, color filter of the present invention is effective especially for the liquid crystal indicator of colored TFT mode.About the liquid crystal indicator of colored TFT mode, for example on the books in " カ ラ one TFT liquid crystal デ イ ス プ レ イ (upright altogether publication (strain) 1996 Nian development are capable) ".In addition, the present invention can also be applicable to liquid crystal indicator or the liquid crystal indicators such as STN, TN, VA, OCS, FFS and R-OCB that visual angles such as pixel partitioning scheme such as transverse electric field type of drive, MVA such as IPS enlarge.
In addition, color filter of the present invention can also supply in liquid crystal indicator bright and COA (Color-filter On Array, the color filter array) mode that height is meticulous.In the liquid crystal indicator of COA mode, the characteristic that color-filter layer is required need be low-k and stripper patience to the characteristic that interlayer dielectric requires also except above-mentioned common requiring the characteristic.
Coloring photosensitive combination of the present invention is because the curable raising of colored pixels; Can form and not have pixel damaged or that peel off, twist; So particularly improved the stripper patience that is arranged on the dyed layer on the TFT substrate directly or indirectly, also be useful for the liquid crystal indicator of COA mode.In order to satisfy the characteristic that requires of low-k, also resin coating can be set on color-filter layer.
And then; For the driving that makes the ITO electrode that is configured on the dyed layer and dyed layer below terminal conducting with the TFT substrate; The length that forms a limit on the dyed layer that forms in need using at the color filter of COA mode is the through hole of the rectangle about 1～15 μ m or the guiding paths such as depression of コ font; Preferably the size (i.e. the length on a limit) with guiding path is set at below the 5 μ m, and the coloring photosensitive combination of the application of the invention can also form the guiding path below the 5 μ m.
About these images displayed, for example, in "EL, PDP, LCD terrestrial イ su plastic Rei - Technology and market Full latest trends - (Toray re Thermopreg チ Center for a research department in 2001 issuance)," The first 43 such in the records.
Liquid crystal indicator of the present invention also is made up of various parts such as electrode base board, polarizing coating, phase retardation film, backlight, sept, visual angle guarantee films except that color filter of the present invention.Color filter of the present invention goes for the liquid crystal indicator that is made up of these known parts.
About these parts, for example, in "'94 LCD terrestrial イ su plastic Rei Surrounding materials · Kelly mini Cal Season Full Market (Island Kentaro (strain) Shin a ェ Rousseau Shin a 1994 issuance)", "2003 LCD-related market Current Status and Future Prospects (scroll down) (Table? Liang Ji (strain) Fuji キ Mera AIST 2003 issuance) "in the records.
About backlight, on the books in SID meeting Digest 1380 (2005) (A.Konno et.al), monthly magazine デ イ ス プ レ イ in December, 2005 number 18～24 ペ, one ジ (the island health is abundant), monthly magazine デ イ ス プ レ イ in December, 2005 number 25～30 ペ, one ジ (Yagi spark gap is grand bright) etc.
When color filter of the present invention is used for liquid crystal indicator; Through realizing high-contrast with the three-wavelength pipe combination of known cold-cathode tube in the past; And through with the led light source (RGB-LED) of red, green, blue as backlight, can provide the high colorrendering quality of brightness height and colour purity good liquid crystal indicator.
Embodiment
Below, through embodiment the present invention is explained more specifically, but be not limited to following embodiment.In addition, short of special instruction, " % ", " part " they are quality criteria.
-zinc halide phthalocyanine color synthetic-
Make the zinc phthalocyanine with phthalonitrile, zinc chloride as raw material.
Halogenation is described below and carries out: 1 part of 3.1 parts of chlorosulfuric acid, 3.7 parts of anhydrous Aluminum chlorides, 0.46 part in sodium chloride, zinc phthalocyanine mixed down at 40 ℃, and 2.2 parts of dripping bromine.Reacted 15 hours down at 80 ℃, then, reaction mixture is put in the water, the thick pigment of part zinc bromide phthalocyanine is separated out.This water paste is filtered, wash with 80 ℃ hot water, dry under 90 ℃, obtain 2.6 parts of purified thick pigment of part zinc bromide phthalocyanine.
1.6 parts of 7 parts in sodium chloride, diethylene glycols, the xylene of 1 part of the thick pigment of this part zinc bromide phthalocyanine, pulverizing are joined in the both arms type kneader for 0.09 part, descended mixing 6 hours at 100 ℃.After mixing, be taken out in 80 ℃ 100 parts in the water, stir after 1 hour, filter, hot wash, drying, pulverizing, obtain part zinc bromide phthalocyanine color.
Content of halogen analysis by utilizing mass spectrophotometry can know that the average group of resulting part zinc bromide phthalocyanine color becomes ZnPcBr 10Cl 4H 2(Pc: phthalocyanine), on average contain 10 bromines in 1 molecule.
In addition, measuring the mean value that obtains primary particle size with transmission electron microscope (the system JEM-2010 of Jeol Ltd.) is 0.065 μ m.
-quinophthalone compound synthetic-
While stirring with quinophthalone pigment (4,5,6; [2-(4,5,6 for 7-tetrachloro-2-; 7-tetrachloro-2; 3-dihydro-1,3-dioxo-1H-indenes-2-yl)-the 8-quinolyl]-1H-iso-indoles-1,3 (2H)-diketone) (BASF AG's system " Paliotol " Yellow K0961HD) 10g puts into 15 ℃ oleum (25%SO 3) among the 130g.Stir after 3 hours, be added to 250g on ice.Place after 30 minutes,, resulting product is washed with the water of 50ml the suspension filtered that generates.Above-mentioned product is put among the water 330ml, with ammonia spirit neutralization (add ammonia spirit to pH reach 7).Interpolation ammonium chloride 75g also stirred 30 minutes under 80 ℃, and the sediment of separating out is filtered down at 60 ℃.With resulting wet crystal with water washing after, 80 ℃ down dry, obtain the ammonium salt of 17g quinophthalone derivatives sulfonated bodies.
The ammonium salt of this quinophthalone derivatives sulfonated bodies 180 ℃ of following thermal treatments 3 hours, is obtained the quinophthalone derivatives sulfonated bodies (compound 4 of following structure) that 16g (yield is 94%) has removed ammonium salt.
In chloroform, ice-cooledly down in sulfonated bodies (compound 4) 10g, add oxalyl chloride (with the pure medicine corporate system of light) 2.2g and N, dinethylformamide (with the pure medicine corporate system of light) 1ml stirred 2 hours down at 50 ℃.Reaction mixture is joined in ice bath among the water 150mL, filter the crystal of separating out, obtain sulfonyl chloride compound (compound 5 of following structure) 7.4g (yield is 72%).
Figure BDA0000084314610000371
In chloroform, ice-cooled 6-chloro-1-hexylamine (the Rare Chemicals corporate system) 0.9g that in 5.0g compound 5, adds down, at room temperature stirred 2 hours.Reaction mixture is joined among the water 150mL, and the crystal that filtration is separated out is also washed, and drying under reduced pressure obtains sulfonamide alkyl chloride compound (compound 6 of following structure) 4.3g (yield is 76%).
In 4.3g compound 6, add excessive water and excessive anhydrous sodium sulfite (Northeast chemistry system), in autoclave, heated 12 hours down at 180 ℃.Put cold after, filter crystal, obtain sulfonamide alkyl sulfonic acid compound (compound 7 of following structure) 3.7g (yield is 82%).
Figure BDA0000084314610000381
-resin (J-1) synthetic-
(1) resin (i-1) is synthetic
Caprylic acid 6.4g, 6-caprolactone 200g, four titanium butoxide (IV) 5g are mixed, be cooled to room temperature after 8 hours, obtain vibrin (i-1) in heating under 160 ℃.
Synthetic schemes is as follows.
Figure BDA0000084314610000382
(2) resin (J-1) is synthetic
Polyethyleneimine (SP-018, number-average molecular weight are 1800, Japanese catalyst system) 10g and vibrin (i-1) 100g are mixed,, obtain intermedium (J-1B) 120 ℃ of heating 3 hours down.Then, put and be chilled to 65 ℃, slowly add the methyl proxitol acetate contain succinic anhydride 3.8g (below be called PGMEA) 200g, stirred 2 hours.Then, add PGMEA, obtain PGMEA 10% solution of resin (J-1).Resin (J-1) has from the side chain of vibrin (i-1) with from the carboxyl of succinic anhydride.
Synthetic schemes is as follows.
Figure BDA0000084314610000391
-comprise the preparation of the dispersive composition of part zinc bromide phthalocyanine color-
With 11.9 parts, 3.1 parts chemical combination 7 of above-mentioned part zinc bromide phthalocyanine color (below be called PG58), as after 9.0 parts of the SOLSPERSE 24000GR (Japanese Lubrizol corporate system) of spreading agent, 76 parts of mixing of PGMEA as solvent as the quinophthalone compound; Disperseed 3 hours with sand mill, obtain comprising the pigment dispensing composition of part zinc bromide phthalocyanine color thus.In 23 ℃ of viscosity of measuring resulting pigment dispensing composition down of temperature, the result is 9.2mPas, highly stable, confirms to obtain good dispersion stabilization with E type viscosity meter RE-85L (Toki Sangyo Co., Ltd.'s system).Preservation condition: disperse back 14 days (storage temperature is 5 ℃)
-contain the preparation of the dispersive composition of yellow uitramarine PY150-
To mix with ball mill (zirconia bead 0.3mm) as the mixed liquor of 223 parts of PGMEA 10% solution of 40 parts of C.I. pigment yellows 150 (average 1 particle diameter is 60nm) of pigment (below be called PY150) and above-mentioned resin (J-1) (convert count 22.3 parts with solid constituent) and disperse 3 hours, thereby prepare the dispersive composition that contains yellow uitramarine PY150.
-contain the preparation of the dispersive composition of yellow uitramarine PY138-
To mix with ball mill (zirconia bead 0.3mm) as the mixed liquor of PGMEA 10% solution 223 parts (being scaled 22.3 parts) of 40 parts of the C.I. pigment yellow 13s 8 (average 1 particle diameter is 60nm) of pigment (below be called PY138), above-mentioned resin (J-1) and disperse 3 hours, thereby preparation contains the dispersive composition of yellow uitramarine PY138 with solid constituent.
-as the compound 1 of Photoepolymerizationinitiater initiater synthetic-
(1) compd A is synthetic
At first, come synthetic compound A according to following scheme.
(100.0g, 0.512mol) is dissolved among the chlorobenzene 260ml with ethyl carbazole, be cooled to 0 ℃ after, add aluminum chloride (70.3g, 0.527mol).Then, drip ortho-chlorotolu'ene (81.5g, 0.527mol) with 40 minutes, stirred 3 hours after being warming up to room temperature.Then, be cooled to 0 ℃ after, add aluminum chloride (75.1g, 0.563mol).Drip 4-chlorobutanoylchloride (79.4g, 0.563mol) with 40 minutes, be warming up to room temperature and stirred 3 hours.The mixed solution of 35 quality % aqueous hydrochloric acid solution 156ml and distilled water 392ml is cooled to 0 ℃, dropwise reaction solution.Behind the solid suction filtration of separating out, wash with distilled water and methyl alcohol, behind the acetonitrile recrystallization, obtain the compd A (the receipts amount is that 164.4g, yield are 77%) of following structure.
Figure BDA0000084314610000401
(2) compd B is synthetic
Then, use compd A to come synthetic compound B according to following scheme.
(20.0g, 47.9mmol) is dissolved among the THF 64ml with compd A, adds 4-chlorobenzene mercaptan (7.27g, 50.2mmol) and sodium iodide (0.7g, 4.79mmol).Then in reactant liquor, add NaOH (2.0g, 50.2mmol), refluxed 2 hours.Then, be cooled to 0 ℃ after, drip SM-28 (11.1g, 57.4mmol) with 20 minutes, be warming up to room temperature and stirred 2 hours.Then, be cooled to 0 ℃ after, drip isoamyl nitrite (6.73g, 57.4mmol) with 20 minutes, be warming up to room temperature and stirred 3 hours.Reactant liquor is diluted among the acetone 120ml, is added drop-wise in the 0.1N aqueous hydrochloric acid solution that is cooled to 0 ℃.Behind the solid suction filtration of separating out, wash with distilled water.Then, use the acetonitrile recrystallization, obtain the compd B (the receipts amount is that 17.0g, yield are 64%) of following structure.
(3) Compound C is synthetic
Then, use compd B to synthesize Compound C as initiating agent according to following scheme.
(18.0g, 32.4mmol) is dissolved in the N-Methyl pyrrolidone of 90ml with compd B, adds triethylamine (3.94g, 38.9mmol).Then, be cooled to 0 ℃ after, after 20 minutes dripping acetyl chloride (3.05g, 38.9mmol), be warming up to room temperature and stirred 2 hours.Reactant liquor is added drop-wise among the distilled water 150ml that is cooled to 0 ℃, behind the solid suction filtration of separating out, washs, after the drying, obtain the Compound C (the receipts amount is that 19.5g, yield are 99%) of following structure with the isopropyl alcohol 200ml that is cooled to 0 ℃.
Figure BDA0000084314610000421
(embodiment 1)
< preparation of coloring photosensitive combination >
Composition shown in the following composition 1 is mixed, thus the coloring photosensitive combination of preparation embodiment 1.
(forming 1)
33.0 parts of pigment dispensing compositions that contain PG58
15.2 parts of pigment dispensing compositions that contain PY150
20.1 parts of solvents (PGMEA)
24.6 parts of solvents (propionic acid 3-ethoxy ethyl ester)
0.78 part of adhesive resin (allyl methacrylate-methacrylic acid (=copolymerization mol ratio is 8: 2) multipolymer, weight-average molecular weight are 30000)
Polymerizable monomer: 4.43 parts of ARONIX M-520 (Toagosei Co., Ltd's system)
Photoepolymerizationinitiater initiater: 2-chlorphenyl-4,0.14 part of the two phenylimidazole dipolymer (B-CIM, HODOGAYA KCC system) of 5-
Photoepolymerizationinitiater initiater: 1.47 parts of IRGACURE OXE01 (Ciba Specialty Chemicals Co., Ltd. system, following structure)
Analiphatic sulphur alcoholic compound: Karenz MT-BD1 (two (3-sulfydryl butyric ester, the Showa Denko K. K's systems) 0.19 part of butylene glycol
Light sensitizer: 0.042 part of compound 8 (following structure)
Surfactant (fluorine is surfactant, DIC corporate system MEGAFAC F781-F)
0.033 part
Figure BDA0000084314610000431
IRGACURE?OXE-01
Figure BDA0000084314610000432
< having used the formation of the colored pattern of coloring photosensitive combination >
The formation of-coloring photosensitive combination layer-
With resulting coloring photosensitive combination slot coated to glass substrate (Corning corporate system ミ レ ニ ア system, 0.7mm thick).Particularly, regulate interval, the discharge-amount of gap nozzle and substrate, make the thickness of the coloured composition layer after toast the back reach about 2.4 μ m, be coated with second with coating speed 120mm/.
-prebake conditions operation-
Then, after the coloring photosensitive combination layer is dried to vacuum tightness and reaches 66Pa with Minton dryer, with heating plate 90 ℃ of heating (prebake conditions processing) 120 seconds down.
-exposure process (close induction type exposure)-
After prebake conditions is handled, use close induction type exposure machine (High-Technologies of Hitachi corporate system, LE5565A), with 40mJ/cm 2Make public.
-developing procedure, baking (back baking) operation-
Then; Use developing apparatus (High-Technologies of Hitachi corporate system); With potassium hydroxide is 1.0% developer solution (liquid that 1 part of CDK-1 is obtained with the dilution of 99 parts of pure water, 25 ℃) of developer solution CDK-1 (Fujifilm Electronic Materials Co., Ltd. system); To spray pressure and be set at 0.2MPa, and carry out for 60 seconds and develop, and wash with pure water.
Fully after the drying, the back baking is 40 minutes in 230 ℃ baking oven.
(embodiment 2～12, comparative example 1～8)
To as record in the table 1, change in the kind of the pigment dispensing composition in the composition 1 of embodiment 1, polymerizable monomer, Photoepolymerizationinitiater initiater, chain-transferring agent (analiphatic sulphur alcoholic compound), likewise prepare embodiment 2～12, and each coloring photosensitive combination of comparative example 1～8 with embodiment 1 in addition.
Use resulting each coloring photosensitive combination, the Exposure mode in the exposure process is changed as record in the table 1, likewise make colored pattern with embodiment 1 in addition.
In the table 1, pigment dispensing composition is the pigment dispensing composition of representing with the title of pigment.
In addition, the details that is recited as the Exposure mode of " close induction type " in the table 1 is the Exposure mode (close induction type exposure) that is applied to the exposure process among the embodiment 1.In addition, the details that is recited as the Exposure mode of " laser " is described below.
-exposure process (laser explosure)-
After prebake conditions is handled; As laser explosure device; Use EGIS (the 3rd higher hamonic wave of V Technology Co., Ltd., YAG laser, wavelength are 6nsec as 355nm, pulse height),, carry out about 1mJ/cm 20 times through photomask to the photosensitive polymer combination laminar surface 2Pulse irradiation.
Table 1
Figure BDA0000084314610000451
In the table 1, the structure of DPHA, Karenz MT-PE1 is as follows.
DPHA: Japanese chemical drug system dipentaerythritol acrylate
Karenz MT-PE1: Showa Denko K. K's system, pentaerythrite four (3-sulfydryl butyric ester)
In addition, in the table 1, OXE-01 is IRGACURE OXE-01.
< evaluation >
Projects to the ageing stability of resulting each coloring photosensitive combination and colored pattern, foul smell, development property, solvent resistance are estimated.Evaluation method and metewand below are shown.Resulting evaluation result is shown in Table 2 in the lump.
1. the evaluation of ageing stability-
Ageing stability is estimated with the viewpoint of solution viscosity stability and contrast stability.Solution viscosity stability changes according to the viscosity that coloring photosensitive combination is left standstill the solution of preserving 7 days front and back under 40 ℃ heat condition to be estimated.
Contrast stability is estimated in the following manner, will under 40 ℃ heat condition, leave standstill the coloring photosensitive combination preserved before and after 7 days and be applied to respectively on the substrate with the thickness of 2.3 μ m, calculates rate of change by the contrast value of each substrate.
Use E type viscosity meter RE-85L (Toki Sangyo Co., Ltd.'s system) in the viscosimetric analysis, contrast is used BM-5 (TOPCON Co., Ltd. system) in measuring.
-metewand-
Zero: under heat condition, leaving standstill and preserve front and back, is benchmark with the value before leaving standstill, and (1) viscosity rate of change is in 10%, and (2) contrast rate of change is in 10%.
*: do not meet more than any one in above-mentioned (1) and (2).
Value to leave standstill before preserving is a benchmark, coloring photosensitive combination through the time the viscosity rate of change and through the time the contrast rate of change be preferably in 10%.If the As time goes on marked change of above-mentioned project when then utilizing coloring photosensitive combination of the present invention to form the colored pattern (pattern of pixels) of color filter, can not get making stability, be inappropriate for the production of color filter.
2. the evaluation of foul smell
About the evaluation of foul smell, the 1ml coloring photosensitive combination is added drop-wise in the double dish, carry out through the sense evaluation under 23 ℃ according to following benchmark.Foul smell is serious, and is not only unhappy, and produces necessity of equipment reinforcement such as exhaust, so, not preferred in the practicality.
-metewand-
Zero: in 10 people's foul smell official can estimate, feel that undesirable number is 0～3 people.
*: in 10 people's foul smell official can estimate, feel that undesirable number is more than 4 people.
3. the evaluation of development property
Estimate development tolerance and dissolves property when under these conditions the glass substrate after the exposure process end being developed.The development tolerance is narrow, in manufacturing process, can not get stable developing property, so not preferred.In addition, dissolves property shortage, when developing, producing demoulding becomes the reason that residue and technology are polluted with peeling off, become problem.
For resulting result, estimate through following metewand.The point that ftractures is meant the time (second number) that the unexposed portion of coloring photosensitive combination in developing procedure dissolving takes place and peels off, and is meant the unexposed portion generation dissolving of coloring photosensitive combination in developing procedure and the moment of peeling off during cracking.
-metewand-
Zero: (1) does not have peeling off of colored pattern from cracking point beginning more than 80 seconds, and (2) demoulding of when cracking, not seeing dyed layer in the developer solution with peel off.
*: do not meet more than any one in above-mentioned (1) and (2).
4. the evaluation of solvent resistance
The glass substrate that is formed with colored pattern after developing procedure finished carries out 230 ℃ * 30 minutes back baking through convection oven.Utilize the OSP-SP100 of Olympus Co., Ltd's system to measure the colourity of the substrate after the resulting baking; In N-N-methyl-2-2-pyrrolidone N-(below be called " NMP "), carry out 23 ℃ * 30 minutes dippings, obtain Δ E*ab by the colourity of the colored pattern before and after the dipping.The OSP-SP100 that chrominance passband is crossed Olympus Co., Ltd's system measures.
Δ E*ab surpasses at 3 o'clock, and in the making of liquid crystal indicator etc., the various soups solvent resistance down that panel handles is not enough being used for, and inscribes between becoming in the practicality.
In addition, through observation by light microscope, the shape variation that is impregnated into the colored pattern before and after the NMP is observed.
To resulting result, estimate through following metewand.
-metewand-
Zero: (1) Δ E*ab is below 3.0, and the colored pattern shape variation is not seen in (2).
*: do not meet more than any one in above-mentioned (1) and (2).
Table 2
Ageing stability Foul smell Development property Solvent resistance
Embodiment 1 ○ ○ ○ ○
Embodiment 2 ○ ○ ○ ○
Embodiment 3 ○ ○ ○ ○
Embodiment 4 ○ ○ ○ ○
Embodiment 5 ○ ○ ○ ○
Embodiment 6 ○ ○ ○ ○
Embodiment 7 ○ ○ ○ ○
Embodiment 8 ○ ○ ○ ○
Embodiment 9 ○ ○ ○ ○
Embodiment 10 ○ ○ ○ ○
Embodiment 11 ○ ○ ○ ○
Embodiment 12 ○ ○ ○ ○
Comparative example 1 × ○ ○ ○
Comparative example 2 × ○ ○ ○
Comparative example 3 × ○ ○ ○
Comparative example 4 × ○ ○ ○
Comparative example 5 ○ ○ × ○
Comparative example 6 ○ × ○ ×
Comparative example 7 ○ × ○ ×
Comparative example 8 × × ○ ○
That kind as shown in table 2, the ageing stability of the coloring photosensitive combination of embodiment is excellent, does not have undesirable foul smell, and solvent resistance is also good.Relative therewith, the coloring photosensitive combination of comparative example 1～4 through the time before and after performance variation big, poor stability.In addition, the development tolerance of the coloring photosensitive combination of comparative example 5 is narrow, existing problems.The foul smell that is caused by mercaptan compound of the coloring photosensitive combination of comparative example 6～8 is serious, can't be used for practicality.
In addition; According to the contrast of embodiment 2 with embodiment 1; The colored pattern that forms among any embodiment (coloring film) all obtains same good result about solvent resistance, and hence one can see that, even for the situation of having used the pattern exposure that utilizes the laser explosure machine; Also same with the exposure that utilizes high-pressure sodium lamp, can obtain the effect of excellence of the present invention.

Claims (8)

1. coloring photosensitive combination, it contains chain-transferring agent and (F) solvent in the analiphatic sulphur alcoholic compound that polymerizable monomer, (C) adhesive resin, (D) Photoepolymerizationinitiater initiater, (E) that (A) zinc halide phthalocyanine color, (B) have acidic group be selected from secondary or three grades.
2. coloring photosensitive combination according to claim 1, wherein, the analiphatic sulphur alcoholic compound of said secondary or three grades is the analiphatic sulphur alcoholic compound of simple function or two senses.
3. coloring photosensitive combination according to claim 1, wherein, said (D) Photoepolymerizationinitiater initiater is the hexa-aryl bi-imidazole compound.
4. coloring photosensitive combination according to claim 1, wherein, said (C) adhesive resin is the resin with acidic group.
5. coloring photosensitive combination according to claim 1 wherein, further contains (G) light sensitizer.
6. pattern formation method, it comprises following operation: each described coloring photosensitive combination in the claim 1～5 is imparted on the substrate forms operation with the dyed layer that forms dyed layer;
The exposure that formed dyed layer is carried out pattern appearance is so that the exposure process that solidify the exposure area; With,
With the exposure after dyed layer in unexposed development, remove with formation pattern developing procedure.
7. color filter, it is made through the described manufacturing approach of claim 6.
8. liquid crystal indicator, it possesses the described color filter of claim 7.
CN2011102379644A 2010-09-01 2011-08-18 Colored photosensitive composition, color filter manufacture method, color filter and liquid crystal display device Pending CN102385246A (en)

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