CN106842818A - Photosensitive composition, the colour filter and image display device that are manufactured using it - Google Patents

Photosensitive composition, the colour filter and image display device that are manufactured using it Download PDF

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CN106842818A
CN106842818A CN201610983003.0A CN201610983003A CN106842818A CN 106842818 A CN106842818 A CN 106842818A CN 201610983003 A CN201610983003 A CN 201610983003A CN 106842818 A CN106842818 A CN 106842818A
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mentioned
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alkyl
chemical formula
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柳廷昊
金泰完
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Dongwoo Fine Chem Co Ltd
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Dongwoo Fine Chem Co Ltd
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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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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

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  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Optical Filters (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)

Abstract

The present invention relates to photosensitive composition, the colour filter and image display device that are manufactured using it, the present invention relates to following photosensitive compositions, the colour filter and image display device that are manufactured using it, the photosensitive composition is included：Alkali soluble resin；Photopolymerizable compound；And Photoepolymerizationinitiater initiater, above-mentioned alkali soluble resin contains the construction unit represented by chemical formula 1 and the construction unit represented by chemical formula 2, and above-mentioned Photoepolymerizationinitiater initiater includes the compound represented by chemical formula 3.

Description

Photosensitive composition, the colour filter manufactured using it and image are shown Device
Technical field
The present invention relates to photosensitive composition, the colour filter and image display device that are manufactured using it.
Background technology
Colour filter is widely used in the various display devices such as photographing element, liquid crystal display device (LCD), and its range of application is in urgency Expand fastly.Above-mentioned colour filter is made up of the colored pattern of red (Red), green (Green) and blue (Blue) this three color, or Person is made up of the colored pattern of yellow (Yellow), magenta (Magenta) and cyan (Cyan) this three color.
Each colored pattern of above-mentioned colour filter is typically using comprising the colouring agent such as pigment or dyestuff, resin glue, light The photosensitive composition of polymerizable compound, Photoepolymerizationinitiater initiater and solvent is formed.Make use of above-mentioned colored photosensitive Property resin combination colored pattern processing generally carried out by photo-mask process.
As such photosensitive composition, use more and contain photopolymerization together with pigment and resin glue The composition of property compound and Photoepolymerizationinitiater initiater.
For present display, in order to transmit more real image, high-resolution model is sharp increasing, special It is not the panel for being applied in mobile phone, the tablet PC as personal carrying equipment, it is desirable to which more than 500ppi's is high-precision Densification, or even require than from the TV, monitor for remotely watching small Pixel Dimensions.
As high-precision densification, in order to be put into substantial amounts of pixel in the space for limiting, the region of black matrix must become Greatly.But, if it does, aperture opening ratio reduction, it is impossible to produce sufficient brightness, further, since substantial amounts of black matrix pattern, Resist produces problem when being coated with flatness, it is possible to produce the part not being applied.
Such problem is considered as the problem for being produced in towards the way of the high-precision densification of display recently, on solving The problem stated, makes in addition to viscosity reduction, do not have special solution except simply reducing the content of resist solid constituent.
But, if the content for simply reducing solid constituent reduces viscosity, have the shortcomings that as follows：To using slit Flatness when coating machine is coated with produces numerous influences, produces brightness disproportionation, bad increase.For example, Patent Document 1 discloses About the content of photosensitive composition, but above-mentioned prior art has following problems：Because coating performance is poor, because This flatness is poor, and developing powder is also poor.
Prior art literature
Patent document
Patent document 1：KR published patent 10-2009-0008077 publications
The content of the invention
The invention problem to be solved
It is an object of the invention to provide coating, developing powder, adaptation and the excellent coloring phototonus resin of sensitivity Composition.
In addition, excellent it is an object of the invention to provide the brightness manufactured using above-mentioned photosensitive composition Colour filter and image display device.
Means for solving the problems
Photosensitive composition of the invention for realizing above-mentioned purpose, it is characterised in that include：Alkali is solvable Property resin；Photopolymerizable compound；And Photoepolymerizationinitiater initiater, above-mentioned alkali soluble resin contains and represented by following chemical formulas 1 Construction unit and the construction unit that is represented by chemical formula 2, above-mentioned Photoepolymerizationinitiater initiater includes what is represented by following chemical formulas 3 Compound.
[chemical formula 1]
[chemical formula 2]
[chemical formula 3]
In above-mentioned chemical formula 1, R1 be hydrogen, aliphatic hydrocarbon of the bag with or without heteroatomic carbon number 1~12 or comprising or Aromatic hydrocarbon without heteroatomic carbon number 6~12, n is 1~500 integer, in above-mentioned chemical formula 2, R2 be hydrogen or carbon number 1~ 12 alkyl, R3 is the linear alkyl of carbon number 2~20 or the branch-like alkyl of carbon number 2~20, and m is 1~500 integer, above-mentioned In chemical formula 3, R4~R7 is each independently hydrogen, halogen, the alkyl of carbon number 1~20, the aryl of carbon number 6~20, carbon number 1~20 Alkoxy, the aryl alkyl of carbon number 7~40, the hydroxy alkyl of carbon number 1~20, the hydroxy alkoxy alkyl of carbon number 2~40 or The cycloalkyl of carbon number 3~20, R8~R14 is each independently hydrogen, the alkyl of carbon number 1~20, the aryl of carbon number 6~20, carbon number 1 ~20 alkoxy, the aryl alkyl of carbon number 7~40, the hydroxy alkyl of carbon number 1~20, the hydroxy alkoxy base alkane of carbon number 2~40 Base, the cycloalkyl of carbon number 3~20, amino, nitro, cyano group or hydroxyl, p are 0 or 1.
In addition, the present invention provides the colour filter that is manufactured with above-mentioned photosensitive composition and the image comprising it is aobvious Showing device.
The effect of invention
It is excellent that photosensitive composition of the invention can provide coating, developing powder, adaptation and sensitivity Photosensitive composition.
In addition, having using the colour filter and image display device of photosensitive composition of the invention manufacture bright The excellent characteristic of degree.
Brief description of the drawings
Fig. 1 is to carry out sensitivity evaluation using the photosensitive composition manufactured by embodiments of the present invention Accompanying drawing.
Specific embodiment
Illustrated in more detail below for the present invention.
Make in the present invention certain component be located at other components " on " when, its feelings for not only connecting with other components comprising certain component Shape, the situation that also there are other components between being also contained in two components.
When making certain part in the present invention comprising certain inscape, if without especially opposite record, itself and it is non-excluded other Inscape, but be meant to also comprising other inscapes.
The present invention provides photosensitive composition and utilizes its colour filter.
Alkali soluble resin
Alkali soluble resin of the invention contains the construction unit that is represented by following chemical formulas 1 and by following chemical formulas 2 construction units for representing.
[chemical formula 1]
[chemical formula 2]
In above-mentioned chemical formula 1, R1 be hydrogen, aliphatic hydrocarbon of the bag with or without heteroatomic carbon number 1~12 or comprising or Aromatic hydrocarbon without heteroatomic carbon number 6~12, n is 1~500 integer, and in above-mentioned chemical formula 2, R2 is hydrogen or carbon number 1 ~12 alkyl, R3 is the linear alkyl of carbon number 2~20 or the branch-like alkyl of carbon number 2~20, and m is 1~500 integer.
Specifically, in above-mentioned chemical formula 2, R2 is hydrogen or methyl.
Form for the alkali soluble resin of the construction unit containing above-mentioned chemical formula 1 and chemical formula 2 is simultaneously unrestricted. I.e., it is possible to be the block copolymer form for making said structure unit definitely repeat, or make said structure unit randomly The random copolymer form for repeating.
The monomer associated with the construction unit of above-mentioned chemical formula 1, specifically, for example, can include (methyl) acrylic acid epoxy Change bicyclic last of the ten Heavenly stems ester, (methyl) acrylic acid 3,4- epoxy tristane -8- base esters, (methyl) acrylic acid 3,4- epoxies tristane - 8- base esters, the bicyclic amoxy ethyl ester of (methyl) acrylic acid epoxyization, (methyl) acrylic acid 2- (3,4- epoxy tristane -9- bases Oxygen) ethyl ester, (methyl) acrylic acid 2- (3,4- epoxy tristane -8- bases oxygen) ethyl ester, (methyl) acrylic acid epoxyization bicyclic penta Own ester of epoxide etc..In these, particularly preferably, the bicyclic last of the ten Heavenly stems ester of (methyl) acrylic acid epoxyization, (methyl) propylene can be included Sour bicyclic amoxy ethyl ester of epoxidation etc..Wherein, (methyl) acrylate means acrylate and/or methacrylate.
The monomer associated with the construction unit of above-mentioned chemical formula 2, specifically, for example, can include ethyl acrylate, methyl Ethyl acrylate, n-propyl, n propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, acrylic acid N-butyl, n-BMA, isobutyl acrylate, Isobutyl methacrylate, sec-butyl acrylate, methacrylic acid Secondary butyl ester, tert-butyl acrylate, Tert-butyl Methacrylate, acrylic acid n-pentyl ester, n-amylmethacrylate, acrylic acid 2- first Base butyl ester, methacrylic acid 2- methylbutyl butenoates, acrylic acid 2- ethylpropyls, methacrylic acid 2- methylbutyl butenoates, acrylic acid just oneself Ester, acrylic acid 2- ethyls butyl ester, 2-EHA, 2-Ethylhexyl Methacrylate, the positive heptyl ester of acrylic acid, acrylic acid Positive last of the ten Heavenly stems ester, acrylic acid n-dodecane base ester, acrylic acid n-tridecane base ester, acrylic acid hexadecane base ester, acrylic acid positive 17 Arrcostab, stearyl acrylate ester, stearyl methacrylate, acrylic acid 2,2,3,3- tetrafluoros propyl ester, acrylic acid 3- trimethoxies Silicyl propyl ester, acrylic acid 2- hydroxy methacrylates, 2-hydroxyethyl methacrylate, acrylic acid 2- hydroxy propyl esters, metering system Sour 2- hydroxy propyl esters, acrylic acid 3- hydroxy propyl esters, methacrylic acid 3- hydroxy propyl esters, acrylic acid 2- hydroxybutyls, metering system Sour 2- hydroxybutyls, acrylic acid 3- hydroxybutyls, methacrylic acid 3- hydroxybutyls, acrylic acid 4- hydroxybutyls, metering system Sour 4- hydroxybutyls, allyl acrylate, allyl methacrylate, methacrylic acid 2- methoxy acrylates, acrylic acid 2- benzene Epoxide ethyl ester, methacrylic acid 2- phenoxy ethyls, methoxyl group diethylene glycol (DEG) acrylate, methoxyl group diethylene glycol (DEG) methacrylic acid Ester, methoxy triglycol acrylate, methoxy triglycol methacrylate, MPEG acrylate, methoxyl group Propylene glycol methyl acrylate, methoxyl group DPG acrylate, methoxyl group dipropylene glycol methyl acrylate, acrylic acid 2- Hydroxyl -3- phenoxy-propyls, methacrylic acid 2- hydroxyl -3- phenoxy-propyls, glycerol mono-acrylate and glycerine monomethyl third The unsaturated carboxylate types such as olefin(e) acid ester；
Acrylic acid 2- amino ethyl esters, methacrylic acid 2- amino ethyl esters, acrylic acid 2- dimethylamino ethyl esters, metering system Sour 2- dimethylamino ethyl esters, acrylic acid 2- amino propyl ester, methacrylic acid 2- amino propyl ester, acrylic acid 2- dimethylaminos third Ester, methacrylic acid 2- dimethylaminos propyl ester, acrylic acid 3- amino propyl ester, methacrylic acid 3- amino propyl ester, acrylic acid 3- The unsaturated carboxylic acid aminoalkyl esters such as dimethylamino propyl ester and methacrylic acid 3- dimethylamino propyl ester；
The unsaturated carboxylic acid glycidol esters such as glycidyl acrylate and GMA；And
In PMA, polymethyl methacrylate, polyacrylic acid N-butyl, Vinalac 5920, poly- The end of the polymer branches chain of siloxanes has huge monomer class of single acryloyl group or monomethacrylate acyl group etc..
In addition, above-mentioned alkali soluble resin additionally can also contain the construction unit of following chemical formulas 4.
[chemical formula 4]
In above-mentioned chemical formula 4, R15 and R17 is each independently the alkyl of hydrogen or carbon number 1~6, and R16 is comprising by acid anhydrides The residue of derivative carboxylic acid, q is 1~500 integer.
Above-mentioned acid anhydrides is comprising selected from phthalic anhydride (Phthalic anhydride), (2- dodecylene -1- bases) amber Amber acid anhydrides ((2-Dodecen-1-yl) succinic anhydride), maleic anhydride (Maleic anhydride), butanedioic acid Acid anhydride (Succinic anhydride), citraconic anhydride (Citraconic anhydride), glutaric anhydride (Glutaric Anhydride), methyl succinic acid anhydrides (Methylsuccinic anhydride), 3,3- dimethylated pentanedioic acid acid anhydrides (3,3- Dimethylglutaric anhydride), phenylsuccinic acid acid anhydride (Phenylsuccinic anhydride), itaconic anhydride (Itaconic anhydride), 3,4,5,6- tetrabydrophthalic anhydrides (3,4,5,6-Tetrahydrophthalic Anhydride), trimellitic anhydride (Trimellitic anhydride), hexahydrophthalic anhydride More than a kind in (Hexahydrophthalic anhydride) and carbic anhydride (Carbic anhydride).
In the present invention, in the case that above-mentioned alkali soluble resin additionally contains the construction unit of above-mentioned chemical formula 4, can With the glass transition temperature less than 0 DEG C, therefore the transparency is excellent, and brightness increases, while when being coated with slit coater Coatability is improved, and suppresses brightness disproportionation and uncoated phenomenon, can manufacture the colour filter of excellent quality.
Above-mentioned alkali soluble resin, can be with 1 relative to the total content of the construction unit for constituting above-mentioned alkali soluble resin ~99 moles of % contain the construction unit represented by above-mentioned chemical formula 1.In addition, relative to the knot for constituting above-mentioned alkali soluble resin The total content of structure unit, the construction unit that can be represented by above-mentioned chemical formula 2 containing 1~99 mole of %.Relative to the above-mentioned alkali of composition The total content of the construction unit of soluble resin, the construction unit that can be represented by above-mentioned chemical formula 4 containing 1~99 mole of %.
Containing the construction unit that is represented by above-mentioned chemical formula 1, represented by above-mentioned chemical formula 2 in the range of above-mentioned mole of % In the case of construction unit or the construction unit represented by above-mentioned chemical formula 4, have the following advantages that：Can obtain developability, can Dissolubility and the well-balanced alkali soluble resin with dyestuff.
In addition, above-mentioned alkali soluble resin can additionally use the monomer comprising unsaturated double-bond, make its copolymerization and manufacture.
Species to the above-mentioned monomer comprising unsaturated double-bond is not particularly limited, and specifically, there is such as styrene, ethene Base toluene, AMS, p- chlorostyrene, o- methoxy styrene, m- methoxy styrene, p- methoxybenzene second Alkene, o- vinyl benzyl methyl ether, m- vinyl benzyl methyl ether, p- vinyl benzyl methyl ether, o- vinyl benzyl The aromatic vinyls such as glycidyl ether, m- vinylbenzyl glycidyl base ether and p- vinylbenzyl glycidyl base ether Based compound；
The o- hydroxy phenyl horse of N- N-cyclohexylmaleimides, N- benzyl maleimides, N-phenylmaleimide, N- Come the m- hydroxyphenyl-maleimides of acid imide, N-, the p- hydroxyphenyl-maleimides of N-, N- ortho-methyl phenyl Malaysia acyl The m- methylphenylmaleimide of imines, N-, the p- methylphenylmaleimides of N-, the o- methoxyphenyl maleimides of N- The N- substituted maleimide amine systems such as the m- methoxyphenyl maleimide of amine, N- and the p- methoxyphenyl maleimides of N- Compound；
(methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, the ring [5.2.1.O of (methyl) acrylic acid three2,6] last of the ten Heavenly stems The bicyclic amoxy ethyl ester of alkane -8- base esters, (methyl) acrylic acid 2- and (methyl) isobornyl acrylate etc. alicyclic (methyl) third Olefin(e) acid esters；And
3- (methacryloxymethyl) oxetanes, 3- (methacryloxymethyl) -3- ethyl oxa- rings Butane, 3- (methacryloxymethyl) -2- trifluoromethyls oxetanes, 3- (methacryloxymethyl) -2- benzene Base oxetanes, 2- (methacryloxymethyl) oxetanes and 2- (methacryloxymethyl) -4- trifluoros Unsaturation oxygen heterocycle butane such as methy oxetane etc..
The above-mentioned monomer comprising unsaturated double-bond can each be used alone or two or more kinds mixed.
Content to the above-mentioned monomer comprising unsaturated double-bond is not particularly limited, relative to the above-mentioned alkali-soluble tree of composition The total content of the construction unit of fat, preferably comprises 5~50 moles of %.
In addition, the acid number of above-mentioned alkali soluble resin, in order to ensure the compatibility with dyestuff and coloring phototonus resin group The storage stability of compound, preferably 30~150mgKOH/g.
The acid number of above-mentioned alkali soluble resin be above range in the case of, above-mentioned photosensitive composition energy Enough ensure sufficient developing powder, be prevented from substrate and reduce with the adaptation of photosensitive composition, pattern occurs Short-circuit phenomenon, due to the excellent compatibility with dyestuff, therefore, it is possible to the phenomenon for preventing dyestuff from separating out.In addition, having as follows Advantage：The phenomenon for preventing the storage stability of photosensitive composition from reducing, is prevented from the problem of viscosity rising Occur.
In the present invention, above-mentioned alkali soluble resin, relative to feline amount in photosensitive composition, Preferably comprise 10~80 weight %, further preferably 10~70 weight %.When in the range of above-mentioned 10~80 weight %, development Fully, pattern is formed and becomes easy dissolubility in liquid, and the film of the pixel portion of exposure portion is reduced when preventing development, non-pixel portion The leaks divided can become good.
Photopolymerizable compound
Photopolymerizable compound is the compound that can be polymerized in the presence of Photoepolymerizationinitiater initiater described later in the present invention, Monofunctional monomer, 2 functional monomers or polyfunctional monomer can be used, specifically, multifunctional lists more than 2 functions can be used Body.
As the specific example of above-mentioned monofunctional monomer, nonyl phenyl carbitol acrylate, acrylic acid can be included 2- hydroxyl -3- phenoxy-propyls, 2- ethylhexyl carbitols acrylate, acrylic acid 2- hydroxy methacrylates or N- vinyl pyrroles Alkanone etc., but it is not limited to this.
Above-mentioned 2 functional monomer can for example include 1,6-HD two (methyl) acrylate, ethylene glycol two (methyl) third Olefin(e) acid ester, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, double (acryloxy second of bisphenol-A Base) ether or 3- methyl pentanediols two (methyl) acrylate etc., but it is not limited to this.
Above-mentioned polyfunctional monomer, specifically, there is trimethylolpropane tris (methyl) acrylate, ethoxylation trihydroxy methyl Propane three (methyl) acrylate, propoxylation trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) third Olefin(e) acid ester, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, ethoxylated dipentaerythritol Six (methyl) acrylate, (methyl) acrylate of propoxylated dipentaerythritol six or dipentaerythritol six (methyl) acrylic acid Ester etc., but it is not limited to this.
Relative to feline amount in photosensitive composition of the invention, preferably with 5~45 weight % Containing above-mentioned photopolymerizable compound, more preferably contain above-mentioned photopolymerizable compound with 7~45 weight %.Above-mentioned optical polymerism Compound can make the intensity of pixel portion, flatness become good when being above-mentioned 5~45 weight % scopes.
Photoepolymerizationinitiater initiater
The oxime ester fluorenes series initiators as feature of the invention are used to make together with being resin glue with aforesaid propylene acid The sensitivity for stating photosensitive composition is improved.Above-mentioned Photoepolymerizationinitiater initiater is for triggering above-mentioned photopolymerizable compound Compound, in the present invention by using the oxime ester fluorenes series initiators represented by following chemical formulas 3, so that above-mentioned coloring Photosensitive polymer combination high sensitivity, shortens the time for exposure, and the pattern that it is produced is improved, while high-resolution can be had Rate.
[chemical formula 3]
In above-mentioned chemical formula 3, R4~R7 is each independently hydrogen, halogen, the alkyl of carbon number 1~20, the virtue of carbon number 6~20 Base, the alkoxy of carbon number 1~20, the aryl alkyl of carbon number 7~40, the hydroxy alkyl of carbon number 1~20, the hydroxyl of carbon number 2~40 The cycloalkyl of alkoxyalkyl or carbon number 3~20, R8~R14 be each independently hydrogen, the alkyl of carbon number 1~20, carbon number 6~ 20 aryl, the alkoxy of carbon number 1~20, the aryl alkyl of carbon number 7~40, the hydroxy alkyl of carbon number 1~20, carbon number 2~40 Hydroxy alkoxy alkyl, the cycloalkyl of carbon number 3~20, amino, nitro, cyano group or hydroxyl, p is 0 or 1.
The halogen referred in the present invention is fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
The alkyl referred in the present invention mean only be made up of carbon and hydrogen atom, without degree of unsaturation, with singly-bound with point Straight chain or the alkyl of side chain type that the remainder of son is combined.The straight chain type or branched alkyl of the preferred carbon number 1~20 of alkyl, more It is preferred that the straight chain type or branched alkyl of the straight chain type or branched alkyl of carbon number 1~10, most preferably carbon number 1~6.As so Non-substituted alkyl example, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, uncle can be included Butyl, amyl group, isopentyl, hexyl etc..In abovementioned alkyl contained more than one hydrogen atom can by halogen atom, hydroxyl, Mercapto (- SH), nitro, cyano group, amino, amidino groups, hydrazine or hydrazone group, carboxyl, sulfonic group, phosphate, the alkyl of carbon number 1~20, The alkyl of the halo of carbon number 1~20, the alkenyl of carbon number 1~20, the alkynyl of carbon number 1~20, the miscellaneous alkyl of carbon number 1~20, carbon number 6 The heteroaryl alkyl substitution of~20 aryl, the aryl alkyl of carbon number 6~20, the heteroaryl of carbon number 6~20 or carbon number 6~20.
The alkoxy referred in the present invention preferably each the moieties with carbon number 1~20 containing aerobic straight chain type or Branching type alkoxy.The more preferably alkoxy of carbon number 1~10, the most preferably alkoxy of carbon number 1~4.As such alkoxy Example, methoxyl group, ethyoxyl, propoxyl group, butoxy and tert-butoxy can be included.Above-mentioned alkoxy can also by fluorine, Halogen atom more than chlorine or bromine is such a is further substituted with and provides halogenated alkoxy.As such example, can be with Include fluorine methoxyl group, chloromethane epoxide, trifluoromethoxy, trifluoro ethoxy, fluorine ethyoxyl and fluorine propoxyl group etc..Above-mentioned alkoxy In more than one hydrogen atom can be replaced by the substitution base same with the situation of abovementioned alkyl.
The cycloalkyl referred in the present invention not only comprising monocyclic system, and comprising polycyclic system hydrocarbon, in above-mentioned cycloalkyl The hydrogen atom of at least more than one can be replaced by the substitution base same with the situation of abovementioned alkyl.Above-mentioned cycloalkyl is preferably carbon The cycloalkyl of number 3~20, the more preferably cycloalkyl of carbon number 3~10, the most preferably cycloalkyl of carbon number 3~8.
The aryl referred in the present invention means aromatic monocyclic or the polycyclic hydrocarbon ring system being only made up of hydrogen and carbon, now, Ring system can partially or even wholly saturation.Hydrogen atom more than at least one of aryl can be by same with the situation of abovementioned alkyl Substitution base substitution.Above-mentioned aryl be by remove a hydrogen and as derived from aromatic hydrocarbon organic group, comprising in each ring fit Local single containing 4~7, preferably 5 or 6 annular atoms condenses ring system, or even is linked with singly-bound comprising multiple aryl Form.Above-mentioned aryl is preferably carbon number 6~20, more preferably with carbon number 6~18.
The hydroxy alkyl referred in the present invention means hydroxy combining in the OH- alkyl of alkyl defined above, hydroxyl alkane Epoxide alkyl means that above-mentioned hydroxy alkyl and alkyl are linked to the hydroxy alkyl-O- alkyl of oxygen.Above-mentioned hydroxy alkyl is preferred It is carbon number 1~20, more preferably carbon number 1~10, most preferably carbon number 1~6.Above-mentioned hydroxy alkoxy alkyl is preferably carbon number 2 ~40, more preferably carbon number 2~20, most preferably carbon number 2~9.
The aryl alkyl referred in the present invention means that the more than one hydrogen atom of abovementioned alkyl is replaced by above-mentioned aryl. Aryl alkyl is preferably carbon number 7~40, more preferably carbon number 7~28, most preferably carbon number 7~24.
For the oxime ester fluorenes series initiators represented by above-mentioned chemical formula 3, p can be 0 or in the case that 1, p be 0, can be with Represented by following chemical formulas 5, in the case that p is 1, can be represented by following chemical formulas 6.
[chemical formula 5]
In above-mentioned chemical formula 5, R18~R21 is each independently hydrogen, halogen, the alkyl of carbon number 1~20, carbon number 6~20 Aryl, the alkoxy of carbon number 1~20, the aryl alkyl of carbon number 7~40, the hydroxy alkyl of carbon number 1~20, the hydroxyl of carbon number 2~40 The cycloalkyl of base alkoxyalkyl or carbon number 3~20；A be hydrogen, the alkyl of carbon number 1~20, the aryl of carbon number 6~20, carbon number 1~ 20 alkoxy, the aryl alkyl of carbon number 7~40, the hydroxy alkyl of carbon number 1~20, the hydroxy alkoxy alkyl of carbon number 2~40, The cycloalkyl of carbon number 3~20, amino, nitro, cyano group or hydroxyl.
Above-mentioned R18~R21, can be specifically hydrogen, bromine, chlorine, iodine, methyl, ethyl, n-propyl, isopropyl, normal-butyl, different Butyl, the tert-butyl group, n-pentyl, isopentyl, n-hexyl, isohesyl, phenyl, naphthyl, xenyl, terphenyl, anthryl, indenyl, Phenanthryl, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, hydroxymethyl, hydroxyl Ethyl, hydroxy-n-propyl, hydroxy-n-butyl, hydroxyisobutyl, hydroxyl n-pentyl, hydroxyl isopentyl, hydroxyl n-hexyl, hydroxyl are different Hexyl, hydroxymethoxy methyl, hydroxymethoxy ethyl, hydroxymethoxy propyl group, hydroxymethoxy butyl, hydroxyl-oxethyl first Base, hydroxyl ethoxy ethyl, hydroxyethoxypropyl, hydroxyl-oxethyl butyl, hydroxyethoxypentyl or hydroxyl-oxethyl oneself Base；A can be hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, phenyl, naphthyl, xenyl, three Phenyl, anthryl, indenyl, phenanthryl, methoxyl group, ethyoxyl, propoxyl group, butoxy, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxyl Base butyl, hydroxymethoxy methyl, hydroxymethoxy ethyl, hydroxymethoxy propyl group, hydroxymethoxy butyl, hydroxyl-oxethyl Methyl, hydroxyl ethoxy ethyl, hydroxyethoxypropyl, hydroxyl-oxethyl butyl, amino, nitro, cyano group or hydroxyl, do not limit Due to this.
Preferably, above-mentioned R18 and R19 can be independently of one another hydrogen or normal-butyl；R20 can be methyl；R21 can for methyl, Normal-butyl or phenyl；A can be hydrogen or nitro.It is preferred that above-mentioned R18 is identical with R19.
As the oxime ester fluorenes series initiators of chemical formula 5, following compounds can be typically included, but do not limit In following examples, the known oxime ester fluorenes series initiators for being adapted to above-mentioned condition all can be used.
[chemical formula 6]
In above-mentioned chemical formula 6, R22~R32 is each independently hydrogen, halogen, the alkyl of carbon number 1~20, carbon number 6~20 Aryl, the alkoxy of carbon number 1~20, the aryl alkyl of carbon number 7~40, the hydroxy alkyl of carbon number 1~20, the hydroxyl of carbon number 2~40 The cycloalkyl of base alkoxyalkyl or carbon number 3~20.
Above-mentioned R22~R32, can be specifically hydrogen, bromine, chlorine, iodine, methyl, ethyl, n-propyl, isopropyl, normal-butyl, different Butyl, the tert-butyl group, n-pentyl, isopentyl, n-hexyl, isohesyl, phenyl, naphthyl, xenyl, terphenyl, anthryl, indenyl, Phenanthryl, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, hydroxymethyl, hydroxyl Ethyl, hydroxy-n-propyl, hydroxy-n-butyl, hydroxyisobutyl, hydroxyl n-pentyl, hydroxyl isopentyl, hydroxyl n-hexyl, hydroxyl are different Hexyl, hydroxymethoxy methyl, hydroxymethoxy ethyl, hydroxymethoxy propyl group, hydroxymethoxy butyl, hydroxyl-oxethyl first Base, hydroxyl ethoxy ethyl, hydroxyethoxypropyl, hydroxyl-oxethyl butyl, hydroxyethoxypentyl or hydroxyl-oxethyl oneself Base.
Preferably, above-mentioned R22 and R23 can be each independently hydrogen, methyl, ethyl, propyl group or butyl；R24 can be first Base, ethyl or propyl group；R25 can be methyl, ethyl, propyl group or butyl；R26~R32 can be hydrogen.It is preferred that above-mentioned R22 and R23 phases Together.
As the oxime ester fluorenes series initiators of above-mentioned chemical formula 6, following compounds can be typically included, but not Following examples are defined in, the oxime ester fluorenes series initiators as known in the art for being adapted to above-mentioned condition all can be used.
Content to above-mentioned Photoepolymerizationinitiater initiater is not particularly limited, complete relative to above-mentioned photosensitive composition Body, preferably 0.1~10 weight %, more preferably 0.1~5 weight %, can further preferably be contained with 0.1~1 weight %.It is right For the content of above-mentioned Photoepolymerizationinitiater initiater, in the case of containing within the above range, sensitivity reduction, development work are prevented from There is the phenomenon for coming off of pattern in sequence, be prevented from excessive cross-linking reaction due to excessive reaction, produce fold Film physical property reduction phenomenon.
Photoepolymerizationinitiater initiater other than the above can be additionally used in the range of effect of the invention not damaging.It is above-mentioned The Photoepolymerizationinitiater initiater that can additionally use, for example, it is preferable to using selected from acetophenone based compound, benzophenone based compound, More than a kind in triazine based compound, bisglyoxaline based compound and thioxanthones based compound of compound.
Above-mentioned acetophenone based compound, for example, can include diethoxy acetophenone, 2- hydroxy-2-methyl -1- phenyl third Alkane -1- ketone, benzil dimethyl ketal, 2- hydroxyls -1- [4- (2- hydroxyl-oxethyls) phenyl] -2- methylpropane -1- ketone, 1- hydroxyls Butylcyclohexyl phenyl ketone, 2- methyl isophthalic acids-(4- methyl mercaptos phenyl) -2- morpholino propane -1- ketone, 2- benzyl -2- dimethylaminos - 1- (4- morphlinophenyls) butane -1- ketone, 2- hydroxy-2-methyls -1- [4- (1- methyl ethylenes) phenyl] propane -1- ketone and 2- (4- methyl-benzyls) -2- (dimethylamino) -1- (4- morphlinophenyls) butane -1- ketone etc..
Above-mentioned benzophenone based compound, for example, can include benzophenone, 0- benzoyls methyl benzoate, 4- phenyl - four (tert-butyl crosses oxygen carbonyl) benzophenone of benzophenone, -4 '-dimethyl diphenyl sulfide of 4- benzoyls, 3,3 ', 4,4 " and 2,4,6- tri-methyl benzophenones etc..
Above-mentioned triazine based compound, for example, can include double (the trichloromethyl) -6- (4- methoxyphenyls) -1,3,5- of 2,4- Double (trichloromethyl) -6- (4- methoxyl groups the naphthyl) -1,3,5- triazines of triazine, 2,4-, double (the trichloromethyl) -6- piperonyls of 2,4- - Double (trichloromethyl) -6- (4- the methoxyl-styrenes) -1,3,5- triazines of 1,3,5- triazines, 2,4-, 2,4- double (trichloromethyls) - Double (trichloromethyl) -6- [2- (furans -2- bases) second of 6- [2- (5- methylfuran -2- bases) vinyl] -1,3,5- triazines, 2,4- Alkenyl] -1,3,5- triazines, double (the trichloromethyl) -6- [2- (4- diethylamino -2- aminomethyl phenyls) vinyl] -1,3 of 2,4-, 5- triazines and double (trichloromethyl) -6- [2- (3,4- Dimethoxyphenyls) the vinyl] -1,3,5- triazines of 2,4- etc..
Above-mentioned united imidazole, for example, can include 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl connection miaow Azoles, 2,2 '-bis- (2,3- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 ' - Four (alkoxyl phenyl) bisglyoxalines, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxalines, 2,2- Double (2,6- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxaline and 4,4 ', the phenyl of 5,5 ' positions taken by alkoxy carbonyl group The imidazolium compounds in generation etc..In above-mentioned united imidazole, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four benzene are preferably used Base bisglyoxaline, 2,2 '-bis- (2,3- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline and 2,2- double (2,6- dichlorophenyls) - 4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxaline.
Above-mentioned thioxanthones based compound, for example, can include ITX, 2,4- diethyl thioxanthones, 2,4- bis- Chloro- 4- propoxythioxanthones of clopenthixal ketone, 1- etc..
In addition, above-mentioned Photoepolymerizationinitiater initiater, in order to improve the sensitivity of photosensitive composition of the invention, can be with Further trigger adjuvant comprising photopolymerization.Photosensitive composition of the present invention triggers by comprising photopolymerization Adjuvant, can further improve sensitivity, by increasing capacitance it is possible to increase productivity ratio.
Above-mentioned photopolymerization triggers adjuvant, preferably uses and is selected from amines, carboxylic acid compound and with mercaptan More than a kind in the organic sulfur compound of base of compound.
Above-mentioned amines, for example, can include the aliphatic such as triethanolamine, methyl diethanolamine and triisopropanolamine Amines；4- dimethylaminobenzoic acids methyl esters, EDMAB, 4- dimethylaminobenzoic acid isoamyls Ester, 4- dimethylaminobenzoic acid 2- Octyl Nitrites, benzoic acid 2- dimethylamino ethyl esters, N, N- dimethyl-p-toluidines, 4, 4 '-bis- (dimethylamino) benzophenone (common names：Michler's keton) and the aromatic amine such as 4,4 '-bis- (diethylamino) benzophenone Compound, as above-mentioned amines, preferably uses aromatic amines compound.
Above-mentioned carboxylic acid compound, for example, can include phenyl acetic acid, aminomethyl phenyl thioacetic acid, ethylphenyl sulphur For acetic acid, Methylethyl phenyl thioacetic acid, 3,5-dimethylphenyl thioacetic acid, methoxyphenylthio acetic acid, dimethoxy benzene Base thioacetic acid, chlorophenylthio acetic acid, dichlorophenyl thioacetic acid, N-phenylglycine, phenoxyethanoic acid, naphthylthio vinegar The miscellaneous acetate types of aromatic series such as acid, N- naphthyls glycine and naphthoxy acetic acid.
The above-mentioned organic sulfur compound with mercapto, for example, can include 2-mercaptobenzothiazole, Isosorbide-5-Nitrae-bis- (3- sulfydryls Butyryl acyloxy) butane, 1,3,5- tri- (3- sulfydryls butoxyethyl group) -1,3,5- triazines -2,4,6 (1H, 3H, 5H)-triketone, three hydroxyls Methylpropane three (3-thiopropionate), pentaerythrite four (3- mercaptobutylates), pentaerythrite four (3-thiopropionate), two Pentaerythrite six (3-thiopropionate) and tetraethylene glycol double (3-thiopropionates) etc..
Such photopolymerization triggers adjuvant, more excellent preferably with less than 10 moles relative to 1 mole of Photoepolymerizationinitiater initiater Choosing is used with 0.01~5 mole of scope.In the case of triggering adjuvant using photopolymerization within the above range, it is possible to increase poly- Efficiency is closed, expects that productivity ratio improves effect.
Solvent
Solvent is used to dissolve the other compositions of photosensitive composition of the invention, as long as usually used Photosensitive composition in the solvent that uses, then can use with no particular limitation, preferably ethers, aromatic hydrocarbon Class, ketone, alcohols, esters, amide-type etc..
If enumerating the specific example of above-mentioned solvent, can include ethylene glycol single methyl ether, ethylene glycol monomethyl ether, The ethylene glycol monoalkyl ether class such as ethylene glycol monopropyl ether, ethylene glycol monobutyl ether；Propylene glycol monomethyl ether, propane diols list ethyl The propylene-glycol monoalky lether class such as ether, propylene glycol monopropyl ether, glycol monobutyl ether；Diethylene glycol dimethyl ether, diethylene glycol diethyl The diethylene glycol (DEG) dialkyl ethers such as base ether, diethylene glycol (DEG) dipropyl ether, diethylene glycol dibutyl ether；Methylcellosolve acetate, ethyl are molten The ethylene glycol alkyl ether acetate esters such as fine agent acetic acid esters；Propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, third The aklylene glycol alkylether acetates classes such as glycol list propyl ether acetic acid esters, methoxy butyl acetate, acetic acid methoxyl group pentyl ester； Benzene,toluene,xylene, mesitylene etc. are aromatic hydrocarbon；Methyl ethyl ketone, acetone, methyl amyl ketone, methyl iso-butyl ketone (MIBK), The ketones such as cyclohexanone；The alcohols such as ethanol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerine；3- ethoxyl ethyl propionates, 3- Ring-type esters such as the esters such as methyl propionate, gamma-butyrolacton etc..
Above-mentioned solvent is 100 DEG C~200 DEG C of organic solvent at coating and the aspect of drying property, preferably boiling point, for example Propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, cyclohexanone, ethyl lactate, butyl lactate, 3- can be included Ethoxyl ethyl propionate, 3- methyl propionates etc..Foregoing illustrative solvent can each be used alone or make two or more mixing With.
Foregoing illustrative solvent can each be used alone or two or more kinds mixed.In addition, above-mentioned solvent is relative In photosensitive composition gross weight of the invention, further preferably preferably 60~90 weight %, 70~85 weight %. If containing above-mentioned solvent with the scope of 60~90 weight %, using roll coater, spin coater, slit and spin coater, narrow Seam coating machine (being otherwise referred to as molded coating machine), flush coater, reversal printing, intaglio printing, silk-screen printing, bat printing and ink-jet etc. Coating when apparatus for coating is coated with becomes good.
Colouring agent
In the present invention, colouring agent can include more than a kind of pigment, more than a kind of dyestuff or their mixture.
Above-mentioned pigment can use the organic pigment or inorganic pigment generally used in the field.In addition, for above-mentioned face Material, can implement resin treatment, make use of the surface of the pigment derivative that has imported acidic-group or basic group etc. as needed Process, processed using the grafting of the surface of pigments of macromolecular compound etc., processed using the micronized of sulfuric acid particles method etc., used The removing of the ionic impurity in the cleaning treatment of use organic solvent, the water for removing impurity etc. or using ion-exchange etc. Treatment etc..
Above-mentioned organic pigment specifically, be able to can be enumerated using the middle various pigment for using such as printing-ink, jetted ink Water outlet insoluble azo pigment, insoluble azo colour, phthalocyanine color, quinacridone pigment, isoindolenone pigments, isoindoline Pigment, perylene dye, perylene ketone pigment, triazine dioxin pigments, anthraquinone pigment, dianthraquinone pigment, anthracene pyrimidine pigment, anthrone pigment, the moon Red ketone pigment, yellow anthrone pigment, pyranthrone pigments, diketo-pyrrolo pyrrole pigments etc..
In addition, as above-mentioned inorganic pigment, the metallic compounds such as metal oxide, metallic complex salt can be used, specifically, Can enumerate iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black, organic black pigments, titanium it is black and by red, green and Cyan mixes and is in oxide or metal composite oxide of the metals such as the pigment of black etc..
Particularly as above-mentioned organic pigment and inorganic pigment, specifically, colour index (The society can be included Of Dyers and Colourists publish) in be categorized as the compound of pigment, more specifically, following colour index can be enumerated (C.I.) pigment of sequence number, but these may not be defined in.
Can include：
C.I. pigment yellow 13,20,24,31,53,83,86,93,94,109,110,117,125,137,138,139,147, 148th, 150,153,154,166,173,180 and 185；
C.I. pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65 and 71；
C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,208,215, 216th, 224,242,254,255 and 264；
C.I. pigment violet 14,19,23,29,32,33,36,37 and 38；
C.I. pigment blue 15 (15：3、15：4、15：6 etc.), 21,28,60,64 and 76；
C.I. pigment Green 7,10,15,25,36,47,58,59,62 and 63；
C.I pigment browns 28；
The grade pigment of C.I pigment blacks 1 and 7.
Above-mentioned pigment can be used alone or be used in mixed way two or more.
Additionally, it is preferred that using selected from C.I pigment oranges 38；C.I paratoneres 166,177,208,242,255；C.I pigment yellows 138、139、150、185；C.I pigment Green 7s, 36,58；C.I pigment Violet 23s；C.I pigment blue 15s：3、15：More than a kind in 6.
Above-mentioned pigment relative to feline amount in photosensitive composition, preferably 5~60 weight %, more Preferably comprise 10~45 weight %.If the above-mentioned pigment containing 5~60 weight %, even if forming film, the colour saturation of pixel Also fully, the deciduous of non-pixel portion will not be reduced during development, thus do not produce residue and it is preferred that.
Above-mentioned pigment preferably uses the scattered dispersible pigment dispersion in uniform particle sizes ground of pigment.As for making the particle diameter of pigment The example of the method being uniformly dispersed, can include carries out method of decentralized processing etc. containing pigment dispersing agent, using above-mentioned Method, can obtain the dispersible pigment dispersion of the state that pigment is uniformly dispersed in the solution.
Above-mentioned pigment dispersing agent in order to maintain pigment de- cohesion and stability and add, as the specific of pigment dispersing agent Example, can include surfactant of cation system, anion system, nonionic system, both sexes system, Polyester, many amine systems etc. etc., this Can each be used alone a bit or be applied in combination two or more.
As the concrete example of above-mentioned cation system surfactant, stearyl amine hydrochloride and lauryl trimethyl can be included The amine salt such as ammonium chloride or quaternary ammonium salt etc..
As the concrete example of above-mentioned anion system surfactant, laruyl alcohol sodium sulfovinate and oleyl sulfate can be included Alkylsurfuric acid salt, the detergent alkylates such as the higher alcohol sulfate such as sodium salt, lauryl sodium sulfate and ammonium lauryl sulfate Alkylaryl sulfonates class such as sodium sulfonate and dodecyl sodium naphthalene sulfonate etc..
As the concrete example of above-mentioned nonionic surfactants, polyoxyethylene alkyl ether, polyoxyethylene virtue can be included Base ether, polyoxyethylene alkylaryl ether, other polyoxyethylene derivs, ethylene oxide/propylene oxide block copolymer, sorbose Alcohol acid anhydride fatty acid ester, polyoxyethylene sorbitan fatty acid ester, Polyoxyethylene Sorbitol Fatty Acid Esters, fatty acid glyceride, Polyoxyethylene fatty acid ester and polyoxyethylene alkyl amine etc..
Additionally, polyoxyethylene alkyl ether class, polyoxyethylene alkyl phenyl ether class, polyethylene glycol di class, mountain can be included Pears sugar alcohol acid anhydride fatty acid ester, fatty acid modified polyesters, tertiary-amine modified polyurethanes and polyethyleneimine amine etc..
In addition, above-mentioned pigment dispersing agent is preferably comprised comprising butyl methacrylate (BMA) or methacrylic acid N, N- bis- The acrylic ester dispersant (hereinafter referred to as acrylic ester dispersant) of methylamino ethyl ester (DMAEMA).As aforesaid propylene The commercially available product of sour ester system dispersant, can include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070 Or DISPER BYK-2150 etc., aforesaid propylene acid ester system dispersant can each be used alone or make two or more mixing With.
Above-mentioned pigment dispersing agent is in addition to acrylic ester dispersant, it is possible to use the pigment dispersion of other resin types Agent.As the pigment dispersing agent of above-mentioned other resin types, the pigment dispersing agent of known resin type can be included, particularly poly- ammonia Ester, polyacrylate are polycarboxylate, unsaturated polyamide, polycarboxylic acids, (part) amine salt of polycarboxylic acids, the polycarboxylic acids of representative Ammonium salt, the alkylamine salt of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate, the ester of the polycarboxylic acids of hydroxyl and Their modified product or the reaction with the polyester by the carboxyl with free (free) and poly- (rudimentary alkyleneimines) The dispersant of the acid amides of formation or their salt identical oil；(methyl) acrylic-styrene copolymer, (methyl) propylene As acid-(methyl) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or PVP Water-soluble resin or water-soluble polymeric compounds；Polyester；Modified polyacrylate；The addition life of ethylene oxide/propylene oxide Into thing；With phosphate etc..
As the commercially available product of the pigment dispersing agent of above-mentioned other resin types, as cation system pitch dispersant, for example may be used Include the trade name of BYK chemical companies：DISPER BYK-160、DISPER BYK-161、DISPER BYK-162、DISPER BYK-163、DISPER BYK-164、DISPER BYK-166、DISPER BYK-171、DISPER BYK-182、DISPER BYK-184；The trade name of BASF AG：EFKA-44、EFKA-46、EFKA-47、EFKA-48、EFKA-4010、EFKA-4050、 EFKA-4055、EFKA-4020、EFKA-4015、EFKA-4060、EFKA-4300、EFKA-4330、EFKA-4400、EFKA- 4406、EFKA-4510、EFKA-4800；The trade name of Lubirzol companies：SOLSPERS-24000、SOLSPERS-32550、 NBZ-4204/10；The trade name of Chuan Yan fine chemistries Co., Ltd.：ヒノアクト(HINOACT)T-6000、ヒノアクトT- 7000、ヒノアクトT-8000；The trade name of Ajincomoto Co., Inc：アジスパー(AJISPUR)PB-821、アジス パーPB-822、アジスパーPB-823；The trade name of Kyoeisha Chemical Co., Ltd.：フローレン(FLORENE) DOPA-17HF, フ ロ ー レ Application DOPA-15BHF, フ ロ ー レ Application DOPA-33, フ ロ ー レ Application DOPA-44 etc..
In addition to above-mentioned acrylic ester dispersant, the pigment dispersing agent of other resin types can each be used alone Or two or more is used in mixed way, can with acrylic ester dispersant and use and use.
Above-mentioned pigment dispersing agent, relative to the weight portion of solid constituent 100 in pigment, preferably comprises 5~60 weight portions, more Preferably comprise 15~50 weight portions.The content of above-mentioned pigment dispersing agent is if it exceeds 60 weight portions, then viscosity rising, less than 5 In the case of weight portion, it is possible to which the micronized of pigment is difficult, or the problems such as cause gelation after dispersion.
As long as above-mentioned dyestuff then can be used unrestrictedly with the dissolubility for organic solvent.Preferably, preferably make With with the dissolubility for organic solvent and being able to ensure that dissolubility and heat resistance, solvent resistance for alkaline developer Deng reliability dyestuff.
As above-mentioned dyestuff, it is possible to use selected from the acid dyes with acidic-groups such as sulfonic acid, carboxylic acids, acid dyes with Dyestuff in the salt of nitrogen-containing compound, sulphonyl amine system of acid dyes etc. and their derivative, in addition it is also possible to select azo System, xanthene system, the acid dyes of phthalocyanine system and their derivative.Preferably, above-mentioned dyestuff can enumerate colour index (The Society of Dyers and Colourists publish) in be categorized as the compound of dyestuff or dyeing notes (Se Ran societies) in The known dyestuff recorded.
As the specific example of above-mentioned dyestuff, as C.I. solvent dyes, can include
C.I. solvent red 8,45,49,89,111,122,125,130,132,146 and 179；
C.I. solvent blue 5,35,36,37,44,59,67 and 70；
C.I. solvent purple 8,9,13,14,36,37,47 and 49；
C.I. solvent yellow 4,14,15,23,24,38,62,63,68,82,94,98,99 and 162；
C.I. solvent orange 2,7,11,15,26 and 56；
C.I. the grade dyestuff of solvent green 1,3,4,5,7,28,29,32,33,34 and 35.
In above-mentioned C.I. solvent dyes, preferably C.I. solvent red 8s, 49,89,111,122,132,146 and 179；C.I. it is molten Agent indigo plant 35,36,44,45 and 70；C.I. solvent violet 13, more preferably C.I. solvent red 8s, 122 and 132.
In addition, as C.I. acid dyes, can include
C.I. azogeramine, 4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66, 73、80、87、88、91、92、94、97、103、111、114、129、133、134、138、143、145、150、151、158、176、 182、183、195、198、206、211、215、216、217、227、228、249、252、257、258、260、261、266、268、 270th, 274,277,280,281,308,312,315,316,339,341,345,346,349,382,383,394,401,412, 417th, 418,422 and 426；
C.I. Indian yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98, 99、111、112、113、114、116、119、123、128、134、135、138、139、140、144、150、155、157、160、 161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、203、204、205、207、 212nd, 214,220,221,228,230,232,235,238,240,242,243 and 251；
C.I. acid orange 6,7,8,10,12,26,50,51,52,56,62,63,64,74,75,94,95,107,108,169 With 173；
C.I. Blue VRS, 7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87, 90、92、96、103、112、113、120、129、138、147、150、158、171、182、192、210、242、243、256、259、 267、278、280、285、290、296、315、324：1st, 335 and 340；
C.I. acid violet 6B, 7,9,17,19 and 66；
C.I. the dyestuff such as acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106 and 109.
In above-mentioned C.I. acid dyes, C.I. acid red 92s；C.I. acid blue 80,90；With C.I. acid violets 60 for having The solubility of machine solvent is excellent and preferred.
In addition, as C.I. direct dyess, can include
C.I. directly red 79,82,83,84,91,92,96,97,98,99,105,106,107,172,173,176,177, 179th, 181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246 and 250；
C.I. directly yellow 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98, 102nd, 108,109,129,136,138 and 141；
C.I. direct orange 34,39,41,46,50,52,56,57,61,64,65,68,70,96,97,106 and 107；
C.I. directly blue 38,44,57,70,77,80,81,84,85,86,90,93,94,95,97,98,99,100,101, 106、107、108、109、113、114、115、117、119、137、149、150、153、155、156、158、159、160、161、 162、163、164、166、167、170、171、172、173、188、189、190、192、193、194、196、198、199、200、 207、209、210、212、213、214、222、228、229、237、238、242、243、244、245、247、248、250、251、 252nd, 256,257,259,260,268,274,275 and 293；
C.I. direct purple 47,52,54,59,60,65,66,79,80,81,82,84,89,90,93,95,96,103 and 104；
C.I. the dyestuff such as direct green 25,27,31,32,34,37,63,65,66,67,68,69,72,77,79 and 82.
In addition, as C.I. mordant dyes, can include
C.I. mordant yellow 5,8,10,16,20,26,30,31,33,42,43,45,56,61,62 and 65；
C.I. mordant rouge 1,2,3,4,9,11,12,14,17,18,19,22,23,24,25,26,30,32,33,36,37, 38th, 39,41,43,45,46,48,53,56,63,71,74,85,86,88,90,94 and 95；
C.I. mordant dyeing orange 3,4,5,8,12,13,14,20,21,23,24,28,29,32,34,35,36,37,42,43,47 With 48；
C.I. mordant dyeing indigo plant 1,2,3,7,8,9,12,13,15,16,19,20,21,22,23,24,26,30,31,32,39, 40th, 41,43,44,48,49,53,61,74,77,83 and 84；
C.I. mordant dyeing purple 1,2,4,5,7,14,22,24,30,31,32,37,40,41,44,45,47,48,53 and 58；
C.I. the dyestuff such as viridon 1,3,4,5,10,15,19,26,29,33,34,35,41,43 and 53.
Above-mentioned dyestuff can each be used alone or be applied in combination two or more.
The content of the dyestuff in above-mentioned colouring agent, relative to feline amount in colouring agent, preferably 0.5~80 weight Amount %, more preferably 0.5~70 weight %, further preferred 1~70 weight %.For the content of dyestuff in above-mentioned colouring agent, If contained with above-mentioned 0.5~80 weight %, be prevented from after pattern is formed making due to organic solvent dyestuff separates out can By property reduction problem, sensitivity is improved.
In the present invention, solids by weight means above-mentioned coloring phototonus resin group in photosensitive composition The gross weight of the residual components after the removing solvent of compound.
The content of above-mentioned colouring agent, relative to feline amount, preferably 5 in above-mentioned photosensitive composition ~60 weight %, are more preferably contained with 10~45 weight %.In the case of containing above-mentioned colouring agent with above-mentioned 5~60 weight %, In the presence of following advantage：Fully, the deciduous of non-pixel portion will not be reduced the colour saturation of pixel during development when foring film, therefore It is difficult to produce residue.
Additive
Additive can be optionally added in photosensitive composition of the invention as needed, for example can be with Comprising selected from other macromolecular compounds, curing agent, surfactant, closely sealed accelerator, antioxidant, ultra-violet absorber and More than a kind in anti-flocculating agent.
As the concrete example of above-mentioned other macromolecular compounds, epoxy resin, maleimide resin etc. can be included solid The heat such as the property changed resin, polyvinyl alcohol, polyacrylic acid, polyalkylene glycol monoalkyl ether, polyacrylic acid fluothane base ester, polyester and polyurethane Plastic resin etc..
Above-mentioned curing agent is used to improve deep solidification and mechanical strength, as the concrete example of curing agent, can be enumerated Go out epoxide, polyfunctional isocyanate compound, melamine compound and oxetane compound etc..
In above-mentioned curing agent, as the concrete example of epoxide, bisphenol-A system epoxy resin, hydrogenated bisphenol A can be included It is epoxy resin, Bisphenol F system epoxy resin, A Hydrogenated Bisphenol A F systems epoxy resin, phenolic resin varnish type epoxy resin, other aromatic series It is epoxy resin, alicyclic ring family epoxy resin, ethylene oxidic ester system resin, glycidol amine system resin or above-mentioned epoxy resin Brominated derivative, epoxy resin and its brominated derivative beyond aliphatic, alicyclic or aromatic epoxy compound, fourth two Alkene (co) polymer epoxide, isoprene (co) polymer epoxide, (methyl) glycidyl acrylate (co) polymer and triglycidyl isocyanurate etc..
In above-mentioned curing agent, as the concrete example of oxetane compound, can include carbonic ester dioxygen azetidine, Dimethylbenzene dioxygen azetidine, adipate ester dioxygen azetidine, terephthalate dioxygen azetidine, cyclohexane dicarboxylic acid Dioxygen azetidine etc..
For above-mentioned curing agent, epoxy radicals, the oxa- ring fourth of epoxide can will can be made together with curing agent The solidification auxiliary compounds that the oxetanes skeleton of hydride compounds carries out ring-opening polymerisation are used in combination.
Above-mentioned solidification auxiliary compounds for example have polybasic carboxylic acid class, polybasic carboxylic acid anhydride and acid agent etc..Above-mentioned polynary carboxylic Anhydrides can be used as the commercially available product of epoxy curing agent.As above-mentioned commercially available product, ADEKA can be included HARDENER, EH-700 (ADEKA industry (strain) manufactures), リ カ シ ッ De HH (new Japan Chemical (strain) manufacture), MH-700 (new days This physics and chemistry (strain) is manufactured) etc..Foregoing illustrative curing agent can be used alone or be used in mixed way two or more.
In order to the envelope for further improving photosensitive composition is formed, above-mentioned surfactant can be used, Preferably use silicon-type, fluorine system, ester system, cation system, anion system, nonionic system, amphoteric surfactant etc..
Above-mentioned silicone based surfactants, for example, as commercially available product, have DOW CORNING Dong Li organosilicons company DC3PA, DC7PA, SH11PA, SH21PA and SH8400 etc., have the TSF-4440 of organosilicon company of GE Toshiba, TSF-4300, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 etc..
Above-mentioned fluorine system surfactant, for example, as commercially available product, the メ ガ ピ ー of You great Japanese inks chemical industrial company ス F-470, F-471, F-475, F-482 and F-489 etc..
In addition, as other usable commercially available products, KP (SHIN-ETSU HANTOTAI's chemical industry (strain)), Port リ フ ロ ー can be included (POLYFLOW) (common prosperity society chemistry (strain)), エ Off ト ッ プ (EFTOP) (ト ー ケ system プ ロ ダ クツ companies), メ ガ Off ァ ッ Network (MEGAFAC) (big Japanese ink chemical industry (strain)), Off ロ ラ ー De (Flourad) (Sumitomo 3M (strain)), ア サ ヒ ガ ー De (Asahi guard), サ ー Off ロ Application (Surflon) (being above Asahi Glass (strain)), ソ Le ス パ ー ス (SOLSPERSE) (Lubrisol companies), EFKA (EFKA chemical companies), PB 821 (aginomoto (strain)), Disperbyk series (BYK-chemi Company) etc..
Foregoing illustrative surfactant can each be used alone or be applied in combination two or more.
Species to above-mentioned closely sealed accelerator is not particularly limited, as the concrete example of usable closely sealed accelerator, can Include vinyltrimethoxy silane, VTES, vinyl three (2- methoxy ethoxies) silane, N- (2- amino-ethyls) -3- amino propyl methyls dimethoxysilane, N- (2- amino-ethyls) -3- aminopropyl trimethoxy silicon Alkane, APTES, 3- glycidoxypropyltrimewasxysilanes, 3- glycidoxypropyl first Base dimethoxysilane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, 3- chloropropylmethyldimethoxysilanes, 3- R-chloropropyl trimethoxyl silane, 3- methacryloxypropyl trimethoxy silanes, 3-mercaptopropyi trimethoxy silane, 3- NCO propyl trimethoxy silicane and 3- NCO propyl-triethoxysilicanes etc..
Foregoing illustrative closely sealed accelerator can each be used alone or be applied in combination two or more.
Above-mentioned closely sealed accelerator, relative to the feline amount in photosensitive composition, preferably 0.01 ~10 weight %, can more preferably contain 0.05~2 weight %.
Species to above-mentioned antioxidant is not particularly limited, and can include 2,2 '-thiobis (4- methyl-6-terts-butyl Phenol), 2,6- di-tert-butyl -4- methylphenols etc..
Species to above-mentioned ultra-violet absorber is not particularly limited, and as usable concrete example, can include 2- (3- Tert-butyl -2- hydroxy-5-methyl bases phenyl) -5- chlorobenzotriazoles, alkoxy benzophenone etc..
Species to above-mentioned anti-flocculating agent is not particularly limited, and as usable concrete example, can include polyacrylic acid Sodium etc..
Above-mentioned additive, relative to all 100 weight % of above-mentioned photosensitive composition, can preferably contain 0.1~5 weight %.Above-mentioned additive is relative to above-mentioned photosensitive composition, situation about containing within the above range Under, have the following advantages that：The performance reduction of the colour filter not manufactured using above-mentioned photosensitive composition, while can To assign additive respective target capabilities.
Photosensitive composition of the invention can for example be fabricated as described below.
First, the pigment in above-mentioned colouring agent is mixed with solvent, dispersion putting down up to pigment is carried out using ball mill etc. Equal particle diameter turns into less than 0.2 μm Zuo You.Now, as needed, can make pigment dispersing agent, a part for alkali soluble resin or Whole or dyestuff is mixed together with solvent, dissolves or disperses.
Dyestuff, the remainder of alkali soluble resin, optical polymerism are further added in the dispersion liquid of above-mentioned mixing Compound, Photoepolymerizationinitiater initiater and the additive for using as needed and solvent are so that the concentration as regulation, can manufacture this hair The bright photosensitive composition being related to, but it is not limited to these.
Colour filter and image display device
The present invention provides the colour filter and the figure comprising above-mentioned colour filter manufactured with above-mentioned photosensitive composition As display device.
As the image display device can with such colour filter, can there are liquid crystal display device, OLED, Flexible Displays Device etc., but these are not limited to, applicable whole image display device as known in the art can be exemplified.
Colour filter can be coated with by by above-mentioned photosensitive composition of the invention on base material, carry out light Solidification and development, form pattern, so as to manufacture.
First, after photosensitive composition being coated into base material, it is thermally dried, so as to solvent etc. be volatilized Composition is removed, and obtains smooth film.
As coating method, for example, can use spin coating, cast coating method, roller rubbing method, slit and rotary coating or narrow Seam rubbing method etc. is implemented.Heated after application dries (prebake), or is heated after drying under reduced pressure, makes the volatile ingredients such as solvent Volatilization.
Wherein, preferably 0~200 DEG C of heating-up temperature, more preferably 80~130 DEG C.Coating thickness after heat drying is usual It is 1~8 μm or so.To the film for so obtaining, via the mask irradiation ultraviolet radiation for forming target pattern.Now, to exposing Light portion entirety equably irradiates parallel rays, in addition, the correct contraposition in order to implement mask and substrate, preferably uses mask pair The devices such as quasi- device, stepper.If irradiation ultraviolet radiation, the solidification at the position of ultraviolet has been irradiated.
As above-mentioned ultraviolet, g line (wavelength can be used：436nm), h lines, i line (wavelength：365nm) etc..Ultraviolet Exposure can be selected as suitably desired, and there is no particular limitation as to it in the present invention.By the film for completing solidification Contacted with developer solution, dissolve non-exposed portion, developed such that it is able to form the shape of target pattern.
For above-mentioned developing method, it is possible to use any method such as liquid additive process, infusion process, spray-on process.In addition, development When substrate can be made to incline arbitrary angle.Above-mentioned developer solution is usually water-soluble containing alkali compounds and surfactant Liquid.
Above-mentioned alkali compounds can be any one of inorganic and organic basic compound.
As the concrete example of inorganic alkaline compound, NaOH, potassium hydroxide, disodium hydrogen phosphate, phosphoric acid can be included Sodium dihydrogen, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium metasilicate, potassium silicate, sodium carbonate, potassium carbonate, sodium acid carbonate, Saleratus, Boratex, potassium borate, ammonia etc..
In addition, as the concrete example of organic basic compound, TMAH, 2- hydroxyethyl front threes can be included Base ammonium hydroxide, monomethyl amine, dimethylamine, trimethylamine, monoethyl amine, diethylamine, triethylamine, Mono Isopropylamine, diisopropylamine, monoethanolamine Deng.
These inorganic and organic basic compounds can each be used alone or be applied in combination two or more.Alkali development The concentration of the alkali compounds in liquid, preferably 0.01~10 weight %, more preferably 0.03~5 weight %.
Surfactant in above-mentioned alkaline developer can be using selected from nonionic surfactants, anion system surface At least one in activating agent and cation system surfactant.
As the concrete example of above-mentioned nonionic surfactants, polyoxyethylene alkyl ether, polyoxyethylene virtue can be included Base ether, polyoxyethylene alkylaryl ether, other polyoxyethylene derivs, ethylene oxide/propylene oxide block copolymer, sorbose Alcohol acid anhydride fatty acid ester, polyoxyethylene sorbitan fatty acid ester, Polyoxyethylene Sorbitol Fatty Acid Esters, fatty acid glyceride, Polyoxyethylene fatty acid ester, polyoxyethylene alkyl amine etc..
As the concrete example of above-mentioned anion system surfactant, laruyl alcohol sodium sulfovinate, oleyl sulfate can be included The higher alcohol sulfate salt such as sodium；The alkylsurfuric acid salt such as lauryl sodium sulfate, ammonium lauryl sulfate；Detergent alkylate sulphur Alkylaryl sulfonates classes such as sour sodium, dodecyl sodium naphthalene sulfonate etc..
As the concrete example of above-mentioned cation system surfactant, stearyl amine hydrochloride, lauryl trimethyl can be included The amine salt such as ammonium chloride or quaternary ammonium salt etc..These surfactants can each be used alone or be applied in combination two or more.
The concentration of the surfactant in above-mentioned developer solution preferably 0.01~10 weight %, more preferably 0.05~8 weight Amount %, more preferably 0.1~5 weight %.After development, washed, in addition, as needed can also be at 150~230 DEG C The lower rear baking for implementing 10~60 minutes.
【Embodiment】
The present invention is illustrated in further detail below based on embodiment, but following disclosed embodiments of the present invention are only It is but to illustrate, the scope of the present invention is not limited to these implementation methods.The scope of the present invention represents by Patent right requirement, Also contain the whole deformation in the implication and scope impartial with the record of Patent right requirement.In addition, following embodiment, ratio Compared with example, " % " and " part " for representing content is as long as no special instructions, then weight basis.
＜ experimental examples ＞
Synthesis example 1：The manufacture of alkali soluble resin
Propane diols is put into the flask for possessing agitator, thermometer, backflow cooling tube, dropping funel and nitrogen ingress pipe Monomethyl ether acetate 100g and propylene glycol monomethyl ether 100g, after the atmosphere in flask is replaced into nitrogen from air, input is even Monomethacrylates (Hitachi's chemical conversion (strain) manufacture, FA-513M) 3.1g, third of nitrogen bis-isobutyronitrile 8.2g, tricyclodecane skeleton Olefin(e) acid 2- Octyl Nitrite 55.2g, 4- methyl styrenes 5.9g, GMA 85.2g and n-dodecane mercaptan 6.0g.Then, stir, the temperature of reaction solution is risen to 80 DEG C, reacted 4 hours.
The temperature of reaction solution is reduced to normal temperature, after the atmosphere of flask is replaced into air from nitrogen, 2 are lasted from dropping funel After hour instills triethylamine 0.2g, 4- metoxyphenol 0.1g, acrylic acid 43.2g and propylene glycol monomethyl ether 136g, Reacted at 100 DEG C 6 hours.Then, the temperature of reaction solution is reduced to normal temperature, succinyl oxide 6.0g is put into, at 80 DEG C Reaction 6 hours, has obtained the alkali soluble resin of synthesis example 1.
The alkali soluble resin of above-mentioned synthesis example 1 contains the construction unit of above-mentioned chemical formula 1, chemical formula 2 and chemical formula 4 All, the solid constituent acid number of above-mentioned alkali soluble resin is 36.2mgKOH/g, use the weight average molecular weight Mw that GPC is determined for About 7540.
Synthesis example 2：The manufacture of alkali soluble resin
Propane diols is put into the flask for possessing agitator, thermometer, reflux condensing tube, dropping funel and nitrogen ingress pipe Monomethyl ether acetate 100g and propylene glycol monomethyl ether 100g, after the atmosphere in flask is replaced into nitrogen from air, input is even Monomethacrylates (Hitachi's chemical conversion (strain) manufacture, FA-513M) 3.1g, third of nitrogen bis-isobutyronitrile 8.2g, tricyclodecane skeleton Olefin(e) acid N-butyl 38.4g, 4- methyl styrene 5.9g, GMA 85.2g and n-dodecane mercaptan 6.0g.Then, stir, the temperature of reaction solution is risen to 80 DEG C, reacted 4 hours.
The temperature of reaction solution is reduced to normal temperature, after being air from nitrogen displacement by the atmosphere of flask, is gone through from dropping funel When instill triethylamine 0.2g, 4- metoxyphenol 0.1g, acrylic acid 43.2g and propylene glycol monomethyl ether 136g within 2 hours Afterwards, reacted at 100 DEG C 6 hours.Then, the temperature of reaction solution is reduced to normal temperature, succinyl oxide 12.5g is put into, 80 Reacted at DEG C 6 hours.
The alkali soluble resin of above-mentioned synthesis example 2 contains the construction unit of above-mentioned chemical formula 1, chemical formula 2 and chemical formula 4 Whole, the solid constituent acid number of above-mentioned alkali soluble resin is 42.3mgKOH/g, the weight average molecular weight Mw determined using GPC For about 6020.
Synthesis example 3：The manufacture of alkali soluble resin
Propane diols is put into the flask for possessing agitator, thermometer, reflux condensing tube, dropping funel and nitrogen ingress pipe Monomethyl ether acetate 182g, after the atmosphere in flask is replaced into nitrogen from air, is warmed up to 100 DEG C.
Then, in above-mentioned flask, by benzyl methacrylate 70.5g, methacrylic acid 43.0g, tricyclodecane skeleton Monomethacrylates (Hitachi's chemical conversion (strain) manufacture, FA-513M) 22.0g, propylene glycol monomethyl ether 136g and even The mixed solution of nitrogen bis-isobutyronitrile 3.6g mixing is lasted in 2 hours instillation flasks from dropping funel, 5 has been carried out at 100 DEG C small When stirring.
Then, the atmosphere in flask is replaced into air from nitrogen, by GMA 35.5g, three (diformazans Base amino methyl) phenol 0.9g and quinhydrones 0.145g input flask in, it has been reacted at 110 DEG C 6 hours.
The alkali soluble resin of above-mentioned synthesis example 3 comprises only the construction unit of above-mentioned chemical formula 1, above-mentioned alkali soluble resin Solid constituent acid number be 79mgKOH/g, use GPC determine weight average molecular weight Mw be 13000.
Synthesis example 4：Photoepolymerizationinitiater initiater (C-1) synthesizes
Reaction 1.
2- nitrofluorenes 5.0g is dissolved in anhydrous nitrobenzene 100ml, after adding anhydrous Aluminum chloride 6.31g, will be reacted Thing is warmed up to 45 DEG C, and the solution for making chloroacetic chloride 2.79g be dissolved in anhydrous nitrobenzene 30ml was slowly added into 30 minutes, will react Thing is warmed up to 65 DEG C, has stirred 1 hour.Then, reactant is cooled to room temperature, adds distilled water 70ml, stir 30 minutes left sides Behind the right side, product is filtered.The solid product for obtaining is set to be scattered in the ether of 50ml, after being stirred at room temperature 30 minutes, mistake It is filtered dry dry, has obtained flaxen reactant 1 (1- (9,9-H-7- nitrofluorene -2- bases)-ethyl ketone) 5.08g.
Reaction 2.
The 1.5g of reactant 1 is set to be scattered in ethanol 30ml, after adding hydrochloric acid hydroxylamine 0.49g and sodium acetate 0.58g, will Reaction solution lentamente heats up, and makes its back flow reaction 2 hours.Reactant is cooled to room temperature, after adding distilled water 20ml, is stirred Mix 30 minutes or so, the solid product filtering that will be obtained after being cleaned several times with distilled water, is dried, and has obtained ash gray anti- Answer thing 2 (1- (9,9-H-7- nitrofluorene -2- bases)-acetophenone oxime) 1.38g.
Reaction 3.
The 1.20g of reactant 2 is set to be scattered in ethyl acetate 50ml, after adding acetic anhydride 0.69g, by reaction solution Lentamente heat up, make its back flow reaction 3 hours.Reactant is cooled to room temperature, by saturated sodium bicarbonate aqueous solution 20ml and steaming After the order cleaning of distilled water 20ml, the organic layer that will be reclaimed is dried with anhydrous magnesium sulfate, solvent under reduced pressure is distilled, the life that will be obtained Into thing with methyl alcohol 20ml recrystallize, obtained flaxen initiator C-1 (1- (9,9-H-7- nitrofluorene -2- bases)-acetophenone oxime - O- acetic acid esters) 1.22g.
Synthesis example 5：Photoepolymerizationinitiater initiater (C-2) synthesizes
Reaction 1.
Fluorenes 200.0g, potassium hydroxide 268.8g and KI 19.9g is set to be dissolved in anhydrous dimethyl sulphoxide under nitrogen atmosphere In 1L, after reactant is maintained into 15 DEG C, bromoethane 283.3g was slowly added into 2 hours, reactant is stirred at 15 DEG C 1 hour.Then, distilled water 2L is added in reactant, after stirring 30 minutes, product is extracted with dichloromethane 2L Take, after the organic layer for extracting is cleaned into 2 times with distilled water 2L, the organic layer that will be reclaimed is dried with anhydrous magnesium sulfate, and solvent is entered Row vacuum distillation, the product that will be obtained separated under reduced pressure has been obtained as the flaxen anti-of high-viscosity liquid Answer thing 1 (9,9- diethyl -9H- fluorenes) 248.6g.
Reaction 2.
The 100.5g of reactant 1 is dissolved in dichloromethane 1L, after reactant is cooled into -5 DEG C, be slowly added into chlorine After changing aluminium 72.3g, note not making the temperature of reaction water to heat up, be slowly added into what is diluted in dichloromethane 50ml with 2 hours Propionyl chloride 50.1g, stirs reactant 1 hour at -5 DEG C.Then, reactant is lentamente injected in frozen water 1L, stirring 30 Minute, after organic layer is separated, being cleaned with distilled water 500ml, the organic layer vacuum distillation that will be reclaimed, the product that will be obtained is used Silica gel column chromatography (developing solvent；Ethyl acetate：N-hexane=1：4) refine, obtained as the reactant 2 of flaxen solid (1- (9,9- diethyl -9H- fluorenes -2- bases) -1- acetone) 75.8g.
Reaction 3.
The 44.5g of reactant 2 is dissolved in tetrahydrofuran (THF) 900ml, sequentially add and dissolved in the diox of Isosorbide-5-Nitrae- 4N HCl 150ml and isobutyl nitrite 24.7g, reactant is stirred 6 hours at 25 DEG C.Then, in reaction solution Ethyl acetate 500ml is added, is stirred 30 minutes, it is organic by what is reclaimed after being cleaned with distilled water 600ml after organic layer is separated Layer is dried with anhydrous magnesium sulfate, and solvent under reduced pressure is distilled, and the solid product that will be obtained uses ethyl acetate：Hexane (1：6) After mixed solvent 300ml is recrystallized, dry, obtained as ash gray solid reactant 3 (1- (9,9- diethyl- 9H- fluorenes -2- bases) -1,2- propanedione -2- oximes) 27.5g.
Reaction 4.
Reactant 3 is dissolved in METHYLPYRROLIDONE (NMP) 1L under nitrogen atmosphere, reactant is maintained -5 After DEG C, triethylamine 35.4g is added, after reaction solution has been stirred into 30 minutes, being slowly added into 30 minutes makes chloroacetic chloride 27.5g The solution of METHYLPYRROLIDONE 75ml is dissolved in, notes not making reactant heat up, stirred 30 minutes.Then, will distill Water 1L is slowly added into reactant, is stirred 30 minutes, after organic layer is separated, the organic layer of recovery is done with anhydrous magnesium sulfate It is dry, solvent under reduced pressure is distilled.For the solid product for obtaining, after being recrystallized using ethanol 1L, dry, obtained conduct The initiator C-2 (1- (9,9- diethyl -9H- fluorenes -2- bases) -1,2- propanedione -2- oxime-O- acetic acid esters) of ash gray solid 93.7g。
Embodiment 1~6 and comparative example 1~6：Photosensitive composition is manufactured
Use the composition and content (unit of following tables 1：Weight %) manufacture photosensitive composition.
【Table 1】
The pigment dispensing composition of Production Example 1. (D) is manufactured
Using the C.I. pigment blue 15s as pigment of 12.5 weight portions：6th, 7.5 weight portions as pigment dispersing agent DISPER BYK-2001 (manufacture of BYK companies), the C.I. pigment acid red 52 as dyestuff of 1.2 weight portions, 72 weight portions Mixed with ball mill as the methyl proxitol acetate of solvent and the propylene glycol monomethyl ether of 8 weight portions and dispersion 12 is small When, make paints dispersive composition D.
＜ test methods ＞
Experimental example 1：Coating is evaluated
For the photosensitive composition according to embodiment 1~6 and comparative example 1~6, using MUSASI companies SHOT mini 200s have carried out discharge experiment.Specifically, for embodiment 1~6 and the coloring phototonus tree of comparative example 1~6 Oil/fat composition, under pressure, using the head speed (head speed) of 250mm/s, in the glass base of 15 inch squares 10cm × 10 time are discharged on plate (Corning Incorporated's manufacture, " EAGLE XG "), coating is evaluated.
Evaluation criterion as described below, evaluation result is shown in following tables 2.
◎：Discharge is interrupted：Nothing
○：Discharge is interrupted：More than 1 time and less than 3 times
△：Discharge is interrupted：More than 3 times and less than 10 times
×：Discharge is interrupted：More than 10 times
Experimental example 2：Developing powder, adaptation and sensitivity evaluation
The photosensitive composition of embodiment 1~6 and comparative example 1~6 is respectively adopted into spin-coating method to see at 2 inches After being coated with the glass substrate (Corning Incorporated's manufacture, " EAGLE XG ") of side, it is positioned in heating plate, at a temperature of 100 DEG C Maintain 3 minutes, form film.Then, placing to have on the above-mentioned films makes transmissivity in the range of 1~100% with rank The pattern of scalariform change and the experiment photomask of 1 μm~100 μm of line/space pattern, make with experiment photomask at intervals of 300 μm, irradiate ultraviolet.Now, the light source of ultraviolet uses the high-pressure sodium lamp of the whole 1kW comprising g, h, i line, with 60mJ/ cm2Illumination be irradiated, particularly not use optical filter.The film of above-mentioned ultraviolet will have been irradiated pH10.5's Impregnated 2 minutes in KOH aqueous development solution, developed.The glass substrate that above-mentioned film will be coated with uses distilled water clear After washing, nitrogen is blown into, be dried, heated 25 minutes with 200 DEG C of heated ovens, manufactured each colour filter.Above-mentioned manufacture Colour filter thickness be 2.4 μm.
In developing procedure in above-mentioned operation, determine until non-exposed portion is completely dissolved the required time in developer solution (developing powder), is shown in following tables 2.
In addition, the pattern generated with observation by light microscope, with following standards to 20 μm of degree of the disruption of pattern Evaluated, adaptation evaluation result is shown in following tables 2.
○：Pattern is interrupted：Nothing
△：Pattern is interrupted：1~4
×：Pattern is interrupted：More than 5
In addition, in order to carry out sensitivity evaluation, observing the above-mentioned pixel portion for obtaining like that, see whether have under NaLamp Surface roughness, its is shown in Figure 1.
In Fig. 1, left part is the part with surface roughness, and right part is the portion without surface roughness Point.
Determine the minimum necessary light exposure (mJ/cm for forming the pattern without surface roughness2), it is shown in following In table 2.
【Table 2】
As being understood as above-mentioned table 2, used the embodiment 1 of photosensitive composition of the present invention~ In the case of 6, it is known that coating, developing powder, adaptation and sensitivity are all excellent.

Claims (8)

1. photosensitive composition, it includes alkali soluble resin；Photopolymerizable compound and Photoepolymerizationinitiater initiater, institute State alkali soluble resin and contain the construction unit represented by following chemical formulas 1 and the construction unit represented by chemical formula 2, it is described Photoepolymerizationinitiater initiater includes the compound represented by following chemical formulas 3：
[chemical formula 1]
[chemical formula 2]
[chemical formula 3]
In above-mentioned chemical formula 1,
R1 is hydrogen, bag aliphatic hydrocarbon or bag with or without heteroatomic carbon number 1~12 with or without heteroatomic carbon number 6 ~12 aromatic hydrocarbon,
N is 1~500 integer,
In above-mentioned chemical formula 2,
R2 is the alkyl of hydrogen or carbon number 1~12,
R3 for carbon number 2~20 linear alkyl or carbon number 2~20 branch-like alkyl,
M is 1~500 integer,
In above-mentioned chemical formula 3,
R4~R7 is each independently hydrogen, halogen, the alkyl of carbon number 1~20, the aryl of carbon number 6~20, the alcoxyl of carbon number 1~20 Base, the aryl alkyl of carbon number 7~40, the hydroxy alkyl of carbon number 1~20, the hydroxy alkoxy alkyl of carbon number 2~40 or carbon number 3 ~20 cycloalkyl,
R8~R14 be each independently hydrogen, the alkyl of carbon number 1~20, the aryl of carbon number 6~20, the alkoxy of carbon number 1~20, The aryl alkyl of carbon number 7~40, the hydroxy alkyl of carbon number 1~20, the hydroxy alkoxy alkyl of carbon number 2~40, carbon number 3~20 Cycloalkyl, amino, nitro, cyano group or hydroxyl,
P is 0 or 1.
2. photosensitive composition according to claim 1, wherein, the alkali soluble resin also contains under The construction unit that the chemical formula 4 stated is represented：
[chemical formula 4]
In above-mentioned chemical formula 4,
R15 and R17 are each independently the alkyl of hydrogen or carbon number 1~6,
R16 is the residue comprising the carboxylic acid as derived from acid anhydrides,
Q is 1~500 integer.
3. photosensitive composition according to claim 2, wherein, the acid anhydrides is comprising being selected from phthalic acid Acid anhydride, (2- dodecylene -1- bases) succinyl oxide, maleic anhydride, succinyl oxide, citraconic anhydride, glutaric anhydride, methylsuccinic acid Acid anhydride, 3,3- dimethylated pentanedioic acids acid anhydride, phenylsuccinic acid acid anhydride, itaconic anhydride, 3,4,5,6- tetrabydrophthalic anhydrides, trimellitic acid More than a kind in acid anhydride, hexahydrophthalic anhydride and carbic anhydride.
4. photosensitive composition according to claim 1, wherein, relative to the coloring phototonus resin group The all solids composition of compound, the alkali soluble resin comprising 10~80 weight %.
5. photosensitive composition according to claim 1, wherein, relative to the coloring phototonus resin group Compound is all, the Photoepolymerizationinitiater initiater comprising 0.1~10 weight %.
6. photosensitive composition according to claim 1, wherein, also comprising solvent and colouring agent.
7. colour filter, its solidification for including the photosensitive composition according to any one of claim 1~6 Thing.
8. image display device, it includes colour filter according to claim 7.
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