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CN110095936A - Photosensitive composition, colour filter and image display device - Google Patents

Photosensitive composition, colour filter and image display device Download PDF

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Publication number
CN110095936A
CN110095936A CN201910059478.4A CN201910059478A CN110095936A CN 110095936 A CN110095936 A CN 110095936A CN 201910059478 A CN201910059478 A CN 201910059478A CN 110095936 A CN110095936 A CN 110095936A
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CN
China
Prior art keywords
viscosity
solvent
vapour pressure
photosensitive composition
mentioned
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910059478.4A
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Chinese (zh)
Inventor
曺升铉
权宁竖
李贤普
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongwoo Fine Chem Co Ltd
Samyang Biopharmaceuticals Corp
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Dongwoo Fine Chem Co Ltd
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Application filed by Dongwoo Fine Chem Co Ltd filed Critical Dongwoo Fine Chem Co Ltd
Publication of CN110095936A publication Critical patent/CN110095936A/en
Pending legal-status Critical Current

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133512—Light shielding layers, e.g. black matrix
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G02F1/13394—Gaskets; Spacers; Sealing of cells spacers regularly patterned on the cell subtrate, e.g. walls, pillars
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)
  • Optical Filters (AREA)

Abstract

The present invention provides photosensitive composition, colour filter and image display device.Photosensitive composition of the invention is characterized in that the viscosity of each solvent is 2.0mPas at 20 DEG C hereinafter, the vapour pressure of each solvent is 3.0mmHg at 20 DEG C hereinafter, whole solvent meets following formula 1.In following formula 1, AiFor the viscosity (mPas) of solvent each at 20 DEG C, BiFor the vapour pressure (mmHg) of solvent each at 20 DEG C, MiFor weight ratio of each solvent in whole solvent.The advantage that photosensitive composition of the invention has levelability excellent, is capable of forming the difference of height to be designed, and effectively inhibits the black matrix, the surface defect of column spacer or the one-piece type column spacer of black matrix, surface roughness that are formed.[formula 1] ∑ [(| Ai‑Bi|)×Mi] < 1.5.

Description

Photosensitive composition, colour filter and image display device
Technical field
The present invention relates to photosensitive compositions, the black square manufactured using the photosensitive composition Battle array, column spacer or the one-piece type column spacer of black matrix and colour filter, image display device comprising them.
Background technique
In display industry, have occurred aobvious with plasma from cathode-ray tube (CRT, Cathode-ray tube) steering Show panel (PDP, plasma display panel), Organic Light Emitting Diode (OLED, organic light-emitting Diode), liquid crystal display (LCD, Liquid-crystal display) etc. is the great variety of the flat-panel monitor of representative. In particular, primary articles of the LCD as flat panel display market, by being equipped with the upper plate of colour filter, equipped with thin film transistor (TFT) (TFT) Lower plate and the liquid crystal being injected between them are constituted.
Colour filter is that the core component of performance color in an lcd is used for notebook along with the universal of flat-panel monitor The extensive purposes such as computer, monitor, portable terminal.Such colour filter passes through red (R), green (G), the indigo plant on substrate The pattern of color (B) and so that Picture Showing is gone out diversified color, by being located at each red (R), green (G), blue (B) pattern Between and prevent difference of height between the black matrix of light leakage between pixel, each pixel of amendment and improve the outer covering layer (OC of flatness； Over coat) and maintain two substrates between cell gap (cell gap) column spacer (CS；column Spacer it) constitutes.
In recent years, it is desirable that a kind of material for display interior plays diversified effect simultaneously.It is representative to have The one-piece type column spacer of black matrix does not require nothing more than uniform optical density (OD) (the Optical density required in black matrix； OD), and excellent electrical insulating property etc. is required.
Korean Patent Publication No. 2012-0033893 discloses comprising adhesive resin, multi-functional monomer, photopolymerization Initiator or photosensitizer and solvent, and the black pigments such as nigrosine, black, metal oxide are added wherein as coloring The technology of agent.
In addition, Korean Patent Publication No. 2013-0081019 discloses, by alkali soluble resins, multi-functional monomer, The copolymerization with specific polymerized unit is further included in the photosensitive polymer combination that Photoepolymerizationinitiater initiater and solvent are constituted Object, and the copolymer changes with the increased reactive functional groups of the degree of cross linking are made when forming black matrix and black column spacer The method of kind storage stability and chemical resistance.
However, forming black matrix, column spacer or black columnar interval using previous photosensitive polymer combination In the case where object, it may occur that levelability (flatness, DOP；Degree of Planarization) it is insufficient and be difficult to form target Difference of height, in vacuum drying (VCD；Vacuum dry) problem that causes surface bad in process.
It is therefore desirable to develop following photosensitive composition: levelability is excellent, the height easy to form to be designed Low difference can be such that surface defect minimizes, and thus, it is possible to increase output.
Existing technical literature
Patent document
Patent document 1: Korean Patent Publication No. 2013-0081019 bulletin
Patent document 2: Korean Patent Publication No. 2012-0033893 bulletin
Summary of the invention
Project to be solved
Present invention offer levelability is excellent, is capable of forming the photosensitive composition of target difference of height.
In addition, the present invention provides surface defect, surface roughness minimizes black matrix, column spacer or black matrix one Figure column spacer and colour filter, image display device comprising them.
The method used for solving the problem
The present invention provides a kind of photosensitive composition, the viscosity of each solvent at 20 DEG C for 2.0mPas with Under, the vapour pressure of each solvent is 3.0mmHg at 20 DEG C hereinafter, whole solvent meets following formula 1.
[formula 1]
∑[(|Ai-Bi|)×Mi] < 1.5
In above-mentioned formula 1,
AiFor the viscosity (mPas) of solvent each at 20 DEG C,
BiFor the vapour pressure (mmHg) of solvent each at 20 DEG C,
MiFor weight ratio of each solvent in whole solvent.
In addition, the present invention provides black matrix, column comprising the solidfied material containing above-mentioned photosensitive composition The colour filter of spacer or the one-piece type column spacer of black matrix.
In addition, the present invention provides the image display device comprising above-mentioned colour filter.
Invention effect
Photosensitive composition of the invention has low viscosity, therefore has the advantages that levelability is excellent, energy The difference of height to be designed enough is formed, can effectively inhibit to be formed by black matrix, column spacer or the one-piece type column of black matrix Surface defect, the surface roughness of shape spacer.
In addition, manufacturing black matrix, column spacer or black square using photosensitive composition of the invention In the case where the one-piece type column spacer of battle array, have the advantages that productivity is got higher.
In addition, the black matrix, column spacer or the black square that are manufactured using photosensitive composition of the invention The one-piece type column spacer of battle array has the advantages that surface defect, surface roughness minimize, and includes their colour filter and image Display device has the advantages that physical property and performance improve.
Detailed description of the invention
Fig. 1 is to illustrate the figure of the uneven evaluation image in the surface VCD.
Specific embodiment
Hereinafter, the present invention is described in more detail.
It not only include a certain component and another structure when pointing out that a certain component is located at another component "upper" in the present invention The case where part contacts, include thes case where that there are other components between two components.
In the present invention, when pointing out a certain constituent element of certain a part of "comprising", it means that as long as no especially opposite Record, then can further include other constituent elements, rather than other constituent elements are excluded.
< photosensitive composition >
A mode of the invention is related to a kind of photosensitive composition, and the viscosity of each solvent is at 20 DEG C 2.0mPas is hereinafter, the vapour pressure of each solvent is 3.0mmHg at 20 DEG C hereinafter, whole solvent meets following formula 1.
[formula 1]
∑[(|Ai-Bi|)×Mi] < 1.5
In above-mentioned formula 1,
AiFor the viscosity (mPas) of solvent each at 20 DEG C,
BiFor the vapour pressure (mmHg) of solvent each at 20 DEG C,
MiFor weight ratio of each solvent in whole solvent.
In addition to this photosensitive composition of the invention can further include usually used in this field Adhesive resin, photopolymerizable compound, Photoepolymerizationinitiater initiater, solvent or additive etc..
Solvent
In photosensitive composition of the invention, the viscosity of each solvent is 2.0mPas at 20 DEG C hereinafter, each The vapour pressure of solvent is at 20 DEG C for 3.0mmHg hereinafter, whole solvent includes the solvent for meeting following formula 1.
[formula 1]
∑[(|Ai-Bi|)×Mi] < 1.5
In above-mentioned formula 1,
AiFor the viscosity (mPas) of solvent each at 20 DEG C,
BiFor the vapour pressure (mmHg) of solvent each at 20 DEG C,
MiFor weight ratio of each solvent in whole solvent.
Photosensitive composition of the invention includes the solvent for meeting above-mentioned viscosity, vapour pressure and above-mentioned formula 1, because This, which has an advantage in that, is capable of forming target pattern difference of height, is able to carry out high-speed coating, can shorten the production time, this Outside, it is able to suppress bad, surface roughness in issuable surface etc. in VCD process, productivity can be greatly increased.
As long as specifically, solvent of the invention meet above-mentioned viscosity, vapour pressure and above-mentioned formula 1 and with can further wrap Composition contained in photosensitive composition has compatibility and does not react, then can be without particular limitation using usual Photosensitive composition used in solvent.For example, above-mentioned solvent can be the ethers met the above range, acetic acid The various organic solvents such as esters, aromatic hydrocarbon, ketone, alcohols or esters.
In one embodiment of the present invention, above-mentioned solvent may be to select free methyl -3- methoxy propyl acid esters (viscosity 1.1mPas, vapour pressure 1.8mmHg), methyl proxitol acetate (viscosity 1.3mPas, vapour pressure 2.8mmHg), the third two Alcohol list monoethyl ether acetate (viscosity 1.3mPas, vapour pressure 2.8mmHg), ethylene glycol monomethyl ether acetate (viscosity 1.3mPas, vapour pressure 1.2mmHg), methyl amyl ketone (viscosity 0.8mPas, vapour pressure 2.1mmHg), ethylene glycol list ethyl Ether (viscosity 1.3mPas, vapour pressure 1.2mmHg), methyl proxitol propionic ester (viscosity 1.2mPas, vapour pressure 0.9mmHg), diethylene glycol dimethyl ether (viscosity 2.0mPas, vapour pressure 3.0mmHg), valerone (viscosity 0.9mPas, vapour pressure 1.7mmHg), amyl propionate (viscosity 1.0mPas, vapour pressure 1.5mmHg), ethyl -3- ethyoxyl Propionic ester (viscosity 1.3mPas, vapour pressure 0.7mmHg), 3- methoxybutyl acetic acid esters (viscosity 0.7mPas, vapour pressure 1.1mmHg), dipropylene glycol dimethyl ether (viscosity 1.1mPas, vapour pressure 0.6mmHg), diethylene glycol ethyl methyl ether are (viscous Spend 1.2mPas, vapour pressure 0.7mmHg), diethylene glycol isopropyl methyl ether (viscosity 1.3mPas, vapour pressure 0.8mmHg) With one or more of the group of diethylene glycol diethyl ether (viscosity 1.4mPas, vapour pressure 0.4mmHg) composition.
It if above-mentioned solvent is met the above range, can be used alone, can also be use mixing two or more. For example, above-mentioned solvent meets viscous in the case where including a kind of independent above-mentioned solvent in above-mentioned photosensitive composition Degree at 20 DEG C be 2.0mPas hereinafter, vapour pressure be 3.0mmHg at 20 DEG C hereinafter, | viscosity-solvent steam of solvent Pressure | value be lower than 1.5.
Above-mentioned solvent includes the first solvent and the second solvent in the case where both, above-mentioned first solvent and above-mentioned second molten Agent meet viscosity be 2.0mPas at 20 DEG C hereinafter, vapour pressure be 3.0mmHg at 20 DEG C hereinafter, | the first solvent it is viscous Spend the-the first solvent vapour pressure | the ratio of the × the first solvent and | the vapour pressure of the-the second solvent of viscosity of the second solvent | × the second The total of the ratio of solvent is lower than 1.5.
Above-mentioned solvent viscosity at 20 DEG C is 2.0mPas hereinafter, preferably 1.8mPas is hereinafter, more preferably 0.8mPas~1.6mPas.In this case, the viscosity of solvent is low viscosity, there is the high-speed coating on enlarged production line When also inhibit the generation of crawling etc., be easy mass production, planarization characteristics are also excellent, are capable of forming the height to be designed The advantage of difference, therefore preferably.Specifically, being able to suppress as the viscosity of resist becomes very low, it has to increase solid Ingredient increases the problem of discharge-amount is to form sufficient film, and is able to suppress as the viscosity of resist becomes very Height, it is bad and can not form desired difference of height that when high-speed coating, leads to the problem of uneven or planarization characteristics.
Above-mentioned solvent vapour pressure at 20 DEG C is 3.0mmHg hereinafter, preferably 2.9mmHg is hereinafter, more preferably 0.5mmHg ~2.8mmHg.In this case, when the vapour pressure of solvent within the above range when, existing can obtain going out when no VCD process The uniform film of existing patterned surfaces defect shortens VCD activity time and improves the tendency of mass production, therefore preferably.
In another embodiment of the present invention, above-mentioned entirety solvent can satisfy following formula 2.
[formula 2]
∑[(|Ai-Bi|)×Mi] < 1.38
In above-mentioned formula 2,
Ai、Bi、MiAs defined in above-mentioned formula 1.
Solvent of the invention meets above-mentioned formula 1, preferably satisfies above-mentioned formula 2, thus has the high speed on enlarged production line Also film uniformity height is applied when coating, does not generate uneven and uncoated, not will increase the solvent volatilization sharply as caused by VCD process The advantages of caused surface defect, VCD activity time, thus with can mass production there is institute's uniform height to be formed The advantage that film of difference.
If solvent of the invention is met the above range, can independently be used with boiling point, thus have make low viscosity VCD process when solvent strong volatilization caused by the bad minimum in surface the advantages of.
In another embodiment of the invention, relative to whole 100 parts by weight of above-mentioned photosensitive composition, The content of above-mentioned solvent can be 60~90 parts by weight, preferably can be 65~85 parts by weight.It is in the content of above-mentioned solvent In the case where in above range, levelability is excellent, institute's difference of height to be formed easy to form, can effectively inhibit film, i.e. by The black matrix of above-mentioned photosensitive composition manufacture and/or surface defect, the surface roughness of column spacer.This Outside, when forming cured layer using the photosensitive composition comprising solvent of the invention, it can satisfy developability, resistance to molten Agent and electrical characteristics etc. or even process and reliability, therefore preferably.
Colorant
In another embodiment of the invention, photosensitive composition of the invention can be further included Toner.
Above-mentioned colorant may include Colored organic pigments, can according to circumstances be used in mixed way black organic-inorganic pigment.
In another embodiment of the invention, above-mentioned colorant can be further included selected from by orange pigment, purple The pigment of one or more of the group of pigment and blue pigment composition.
In another embodiment of the invention, above-mentioned colorant can further include black pigment.
Above-mentioned colorant can further include viridine green etc., and above-mentioned black, orange, blue, green, violet pigment are only If pigment that can be usually used in this field, then can be used without limiting ground.It is, for example, possible to use be classified as in colour index The compound of pigment can further include well known dyestuff.
Above-mentioned orange pigment for example it is preferable to use selected from by C.I. pigment orange 1,2,5,13,16,17,19,20,21,22, 23,24,34,36,38,43,46,48,49,61,62,64,65,67,68,69,70,71,72,73,74,75,77,78 and 79 groups At one or more of group, most preferably comprise C.I. pigment orange 64,72 to use.
Above-mentioned orange pigment can play to be reduced transmitance and improves the work of optical density (OD) in the region of 400~550nm With.
Whole 100 parts by weight of solid component relative to above-mentioned colorant, the content of above-mentioned orange pigment can be 5~40 Parts by weight preferably can be 8~30 parts by weight, can be more preferably 10~20 parts by weight, in this case, purple can be obtained by having The light absorption in outside line region is few, excellent as pattern form, the control of difference of height and the excellent film of closing force, optical density (OD) Point.
As above-mentioned violet pigment, can enumerate C.I. pigment violet 1,1:1,2,2:2,3,3:1,3:3,5,5:1,14,15, 16,19,23,25,27,29,31,32,37,39,42,44,47,49,50.Wherein, it from the aspect of light-proofness, can preferably lift C.I. pigment violet 19,23,29 out, more preferably using the low C.I. pigment Violet 23 of absorption of UV, 29.
Whole 100 parts by weight of solid component relative to above-mentioned colorant, the content of above-mentioned violet pigment can for 10~ 40 parts by weight preferably can be 15~35 parts by weight, can be more preferably 20~35 parts by weight, but not limited to this.Upper In the case where stating the content of violet pigment within the above range, the excellent coloring phototonus resin of light-proofness can be obtained by having The advantage that composition.
As above-mentioned blue pigment, C.I. pigment blue 1,9,14,15,15:1,15:2,15:3,15:4,15 can be enumerated: 6、16、17、19、25、27、28、29、33、35、36、56、56:1、60、61、61:1、62、63、66、67、68、71、72、73、 74,75,76,78,79.C.I. pigment blue 15,15:1,15:2,15:3,15:4,15:6,16,60 wherein can be preferably enumerated, from From the aspect of dispersibility, light-proofness, the more preferable C.I. pigment blue 15 that uses: 6,16,60.
Whole 100 parts by weight of solid component relative to above-mentioned colorant, the content of above-mentioned blue pigment can for 10~ 40 parts by weight preferably can be 15~40 parts by weight, can be more preferably 20~40 parts by weight, but not limited to this.But In the case where meeting the above range, the excellent photosensitive composition of dispersibility, light-proofness can be manufactured, therefore excellent Choosing.
Above-mentioned viridine green it can be cited for example that C.I. naphthol green 1,2,4,7,8,10,13,14,15,17,18,19,26, 36,45,48,50,51,54,55,58,59 etc.., it is preferable to use C.I. naphthol green from the viewpoint of light-proofness and color sensation correction 7,36,54,58,59, it is contemplated that electrical characteristics more preferably use C.I. naphthol green 54.
By the pigment combinations of different colours, the combination of color is not particularly limited, but from light-proofness, From the viewpoint of 950nm transmitance, reliability, blue pigment, viridine green, orange pigment and violet pigment can be used for example Combination, in this case, shielding is excellent, therefore preferably.
Specifically, in order to adjust optical characteristics, photosensitive composition of the invention can be further included Black pigment.It more specifically can be enumerated for inorganic or organic pigment about above-mentioned black pigment as colorant Carbon black, acetylene black, lampblack, bone ink, graphite, iron oxide black, nigrosine, cyanine ink, titanium ink, lactams are black, black etc., according to purpose, Inorganic pigment and organic pigment can be used alone, but also also mix together.
Wherein, from the aspect of improving uniform light-proofness and chemical resistance with few dosage, it is preferable to use Carbon black, whole 100 parts by weight of solid component relative to above-mentioned colorant, the content of above-mentioned carbon black can be for greater than 0 and 20 weights Part is measured hereinafter, it is preferred that can be 4~20 parts by weight.
Above-mentioned black pigment can further include it is organic black, in this case, the solid component relative to above-mentioned colorant The content of whole 100 parts by weight, above-mentioned Organic Black can be 3~25 parts by weight, more preferably can be 8~20 parts by weight.Upper In the case where stating the content of Organic Black within the above range, has and be capable of forming that optical density (OD) is excellent and product reliability is excellent The advantage that different film.
Whole 100 parts by weight of solid component relative to above-mentioned photosensitive composition, above-mentioned colorant contain Amount can be 20~55 parts by weight, preferably can be 23~50 parts by weight.Above-mentioned colorant content within the above range In the case where, have can obtain excellent shielding (optical density (OD), OD) and patternability and it is excellent in reliability in this way The advantages of, therefore preferably.
In the case where using photosensitive composition of the invention as black matrix, above-mentioned colorant can be sent out Wave and assign light-proofness and prevent the effect of the light leakage of black matrix, use photosensitive composition of the invention as column In the case where shape spacer, the effect for being able to maintain that certain elasticity modulus and cell gap can be played.
Above-mentioned black matrix and column spacer may be one-piece type.For example, coloring phototonus resin combination of the invention Object can be used for the manufacture of the one-piece type column spacer of black matrix.The above-mentioned one-piece type spacer of black matrix can be sent out with a pattern The effect of black matrix and column spacer is waved, rather than is respectively formed black matrix and column spacer, can be used of the invention Photosensitive composition.
In another embodiment of the invention, above-mentioned photosensitive composition can further include selected from by One or more of alkali soluble resins, photopolymerizable compound, Photoepolymerizationinitiater initiater and group of additive composition.
Alkali soluble resins
Photosensitive composition of the invention may include alkali soluble resins.
Above-mentioned alkali soluble resins can have the reactivity and alkali solubility of the effect based on light, heat, be as with colorant The decentralized medium of the solid component of representative and play a role, and play binder resin function.
Alkali soluble resins of the invention can choose the alkali soluble resins using the acid value with 50~200 (mgKOH/g). Acid value is the value that measures as the amount (mg) of required potassium hydroxide when neutralizing acrylic acid series polymeric compounds 1g, is had with dissolubility It closes.If the acid value of above-mentioned alkali soluble resins is lower than above range, it is difficult to ensure sufficient developing powder, on the contrary, if big In above range, then it can generate and stablize with the reduction of the adaptation of substrate, the short circuit for being easy to happen pattern, the preservation of entire combination object Property reduce, viscosity rise the problem of.
In addition, being used as surface hardness when colour filter in order to improve about above-mentioned alkali soluble resins, it may be considered that limit and divide Son amount and molecular weight distribution degree Mw/Mn.Preferably, 3,000~40,000 can be reached according to weight average molecular weight, preferably reaches 5, 000~20,000, and molecular weight distribution degree with 1.5~6.0, preferably with 1.8~4.0 range mode direct polymerization or Person buys and uses.The alkali soluble resins of molecular weight and molecualr weight distribution degree with above range can be improved above-mentioned refer to Hardness, not only membrane left rate is high, and dissolubility is also excellent in developer solution for non-exposed portion, to improve resolution ratio.
Above-mentioned alkali soluble resins include selected from by the unsaturated monomer containing carboxyl polymer or with the tool that can be copolymerized with it One or more of the group being made of the copolymer and their combination of the monomer of unsaturated bond.
At this point, unsaturated monomer containing carboxyl can be unsaturated monocarboxylic, unsaturated dicarboxylic, unsaturated tricarboxylic acids etc.. Specifically, as unsaturated monocarboxylic, it can be cited for example that acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, meat Cinnamic acid etc..As unsaturated dicarboxylic, it can be cited for example that maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc..Insatiable hunger With polybasic carboxylic acid or acid anhydrides, specifically, maleic anhydride, itaconic anhydride, citraconic anhydride etc. can be enumerated.In addition, not Saturation polybasic carboxylic acid may be its single (2- methacryloxyalkyl) ester, it can be cited for example that mono succinate (2- propylene Trimethylammonium) ester, mono succinate (2- methacryloxyethyl) ester, phthalic acid list (2- acryloyl-oxyethyl) Ester, phthalic acid list (2- methacryloxyethyl) ester etc..Unsaturated polybasic carboxylic acid can also be its two ends dicarboxyl List (methyl) acrylate of based polyalcohol, it can be cited for example that ω-carboxy-polycaprolactone mono acrylic ester, ω-carboxyl gather oneself Caprolactone monomethacrylate etc..Above-mentioned carboxyl group-containing monomer can respectively individually or be use mixing two or more.
Furthermore it is possible to unsaturated monomer containing carboxyl copolymerization monomer can for selected from by aromatic ethenyl compound, Unsaturated carboxylic ester compound, unsaturated carboxylic acid aminoalkyl ester compounds, unsaturated carboxylic acid epihydric alcohol ester compound, carboxylic acid Ethylene ester compounds, unsaturated ether compound, vinyl cyanide based compound, unsaturated acyl imine compound, aliphatic are total Polymeric monomer, large volume monomer of the end with single acryloyl group or monomethacrylate acyl group of yoke diolefinic compounds, strand And one of the group of their combination composition.
More specifically, styrene, α-methylstyrene, adjacent vinyl first can be used in the above-mentioned monomer that can be copolymerized Benzene, vinyltoluene, to vinyltoluene, p-chlorostyrene, o-methoxystyrene, meta-methoxy styrene, to methoxy Base styrene, adjacent vinyl benzyl methyl ether, vinyl benzyl methyl ether, to vinyl benzyl methyl ether, adjacent vinyl benzyl Base glycidyl ether, vinylbenzyl glycidyl base ether, to aromatic series second such as vinylbenzyl glycidyl base ether, indenes Alkenyl compound；Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl, N propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-BMA, The secondary butyl ester of isobutyl acrylate, Isobutyl methacrylate, sec-butyl acrylate, methacrylic acid, tert-butyl acrylate, methyl Tert-butyl acrylate, acrylic acid 2- hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid 2- hydroxy propyl ester, metering system Sour 2- hydroxy propyl ester, acrylic acid 3- hydroxy propyl ester, methacrylic acid 3- hydroxy propyl ester, acrylic acid 2- hydroxybutyl, metering system Sour 2- hydroxybutyl, acrylic acid 3- hydroxybutyl, methacrylic acid 3- hydroxybutyl, acrylic acid 4- hydroxybutyl, metering system Sour 4- hydroxybutyl, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, acrylic acid ring Own ester, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, acrylic acid 2- methoxy acrylate, methacrylic acid 2- methoxy acrylate, acrylic acid 2- phenoxy ethyl, methacrylic acid 2- phenoxy ethyl, methoxyl group diethylene glycol acrylic acid Ester, methoxyl group diethylene glycol methacrylate, methoxy triethylene acrylate, methoxy triethylene methacrylic acid Ester, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxyl group dipropylene glycol acrylate, methoxy Base dipropylene glycol methyl acrylate, isobornyl acrylate, isobornyl methacrylate, acrylic acid bicyclopentadiene ester, Methacrylic acid bicyclopentadiene ester, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (methyl) acrylic acid norbornyl ester, acrylic acid 2- hydroxyl Base -3- phenoxy-propyl, methacrylic acid 2- hydroxyl -3- phenoxy-propyl, glycerol mono-acrylate, glycerol monomethacrylate The esters of unsaturated carboxylic acids such as ester；Acrylic acid 2- amino ethyl ester, methacrylic acid 2- amino ethyl ester, acrylic acid 2- dimethylaminoethyl Ester, methacrylic acid 2- dimethylamino ethyl ester, acrylic acid 2- amino propyl ester, methacrylic acid 2- amino propyl ester, acrylic acid 2- Dimethylamino propyl ester, methacrylic acid 2- dimethylamino propyl ester, acrylic acid 3- amino propyl ester, methacrylic acid 3- aminopropan The esterification of the unsaturated carboxylic acids aminoalkyls such as ester, acrylic acid 3- dimethylamino propyl ester, methacrylic acid 3- dimethylamino propyl ester Close species；The unsaturated carboxylic acids epihydric alcohol ester compound such as glycidyl acrylate, glycidyl methacrylate；Acetic acid The generating vinyl carboxylates ester compounds such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate；Vinyl methyl ether, ethylene The unsaturated ethers compound such as benzyl ethyl ether, allyl glycidyl ether；Acrylonitrile, methacrylonitrile, α-chloro-acrylonitrile, sub- second The vinyl cyanides based compound such as alkenyl dicyan；Acrylamide, Methacrylamide, α-chloroacrylamide, N-2- hydroxyethyl third The unsaturated acyls amines such as acrylamide, N-2- hydroxyethyl methacrylamide；Maleimide, benzyl maleimide, N- benzene The unsaturated acyls group with imine moiety such as base maleimide, N- N-cyclohexylmaleimide；1,3- butadiene, isoprene, neoprene The aliphatic conjugated dienes class such as diene；And polystyrene, polymethyl acrylate, polymethyl methacrylate, polyacrylic acid are just Butyl ester, Vinalac 5920, polysiloxanes the end of polymer molecular chain there is single acryloyl group or monomethyl third The polymeric monomer class of enoyl-；It can reduce the monomer with norborny skeleton of relative permittivity value, there is adamantane bone The large volumes monomers such as the monomer of frame, monomer with rosin skeleton.
Relative to whole 100 parts by weight of photosensitive composition, the content of above-mentioned alkali soluble resins can for 1~ 30 parts by weight preferably can be 3~20 parts by weight, more preferably can be 5~10 parts by weight.
Above-mentioned alkali soluble resins content within the above range in the case where, the dissolubility in developer solution is abundant, is easy Pattern is formed, when development, prevents the film of the pixel portion of exposure portion from reducing, and the deciduous of non-pixel portion is good, thus preferably.
In the case where above-mentioned alkali soluble resins content is lower than above range, non-pixel portion falls off sometimes, in above-mentioned alkali In the case that soluble resin content is greater than above range, the dissolubility in developer solution is reduced, and pattern formation may become difficult.
Photopolymerizable compound
Photopolymerizable compound included in photosensitive composition of the invention is by light and aftermentioned The effect of Photoepolymerizationinitiater initiater and the compound that can polymerize, can enumerate that monofunctional monomer, two functional monomers, other are multifunctional Monomer etc..
The type of above-mentioned monofunctional monomer is not particularly limited, it can be cited for example that nonyl phenyl carbitol acrylate, Acrylic acid 2- hydroxyl -3- phenoxy-propyl, 2- ethylhexyl carbitol acrylate, acrylic acid 2- hydroxy methacrylate, N- vinyl Pyrrolidones etc..
The type of above-mentioned two functional monomer is not particularly limited, it can be cited for example that 1,6- hexylene glycol two (methyl) acrylic acid Ester, ethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, Bis- (acryloyl-oxyethyl) ethers of bisphenol-A, 3- methyl pentanediol two (methyl) acrylate etc..
The type of above-mentioned polyfunctional monomer is not particularly limited, it can be cited for example that trimethylolpropane tris (methyl) propylene Acid esters, ethoxylated trimethylolpropane three (methyl) acrylate, propoxylation trimethylolpropane tris (methyl) acrylic acid Ester, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol three (methyl) acrylic acid Ester, dipentaerythritol five (methyl) acrylate, ethoxylated dipentaerythritol six (methyl) acrylate, two season of propoxylation Penta tetrol six (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc..
As the example of commercially available above-mentioned photopolymerizable compound, there is the DPHA etc. of Japanese chemical drug company, but is not limited to This.
On the basis of above-mentioned photosensitive composition overall weight, the content of above-mentioned photopolymerizable compound can be with It preferably can be 1~20 parts by weight for 1~30 parts by weight, can be more preferably 2~10 parts by weight, be in above-mentioned model in content In the case where in enclosing, there is the advantage that intensity of pixel portion, flatness aspect is excellent.
In the case where the content of above-mentioned photopolymerizable compound is lower than above range, the intensity of pixel portion can be reduced, In the case that the content of above-mentioned photopolymerizable compound is greater than above range, flatness can be reduced, therefore content is preferably in It states in range.
Photoepolymerizationinitiater initiater
Photosensitive composition of the invention may include Photoepolymerizationinitiater initiater.
The Photoepolymerizationinitiater initiater generally used in photosensitive composition can be used in above-mentioned Photoepolymerizationinitiater initiater. Such as acetophenone system, benzophenone series, triazine system, thioxanthones system, oxime system, benzoin system, bisglyoxaline based compound can be used Deng.
Acetophenone based compound can be even for diethoxy acetophenone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, benzene Acyl dimethyl ketal, 2- hydroxyl -1- [4- (2- hydroxyl-oxethyl) phenyl] -2- methylpropane -1- ketone, 1- hydroxycyclohexylphenyl Ketone, 2- methyl-1-(4- methylthiophenyi)-2- morpholino propane-1- ketone, 2- benzyl-2- dimethylamino-1- (4- morpholine For phenyl) butane -1- ketone, the oligomer of 2- hydroxy-2-methyl [4- (1- methyl ethylene) phenyl] propane -1- ketone etc., wherein It is preferred that 2- benzyl -2- dimethylamino -1- (4- morphlinophenyl) butane -1- ketone etc. can be used.
It can be benzophenone, o-benzoylbenzoic acid, o-benzoylbenzoic acid first as benzophenone based compound Ester, 4- phenyl benzophenone, dihydroxy benaophenonel, acrylated benzophenone, 4,4 '-bis- (dimethylamino) benzophenone, 4,4 '-bis- (diethylamino) benzophenone etc..
It can be 2,4,6- tri- chloro- s-triazine, 2- phenyl -4,6- bis- (trichloromethyls)-equal three as triazine based compound Piperazine, bis- (the trichloromethyl)-s-triazine of 2- (3 ', 4 "-dimethoxy-styryl) -4,6-, 2- (4 '-methoxyl group naphthalene) -4,6- Bis- (trichloromethyl)-s-triazine, bis- (the trichloromethyl)-s-triazine of 2- (p-methoxyphenyl) -4,6-, 2- (p-methylphenyl) -4, Bis- (the trichloromethyl)-s-triazine of 6-, bis- (the trichloromethyl)-s-triazine of 2- xenyl -4,6-, bis- (trichloromethyl) -6- styrene Base-s-triazine, bis- (the trichloromethyl)-s-triazine of 2- (naphthalene -1- base) -4,6-, 2- (4- methoxynaphthalene -1- base) bis- (trichlorines of -4,6- Methyl)-s-triazine, 2,4- trichloromethyl (piperonyl) -6- triazine, 2,4- trichloromethyl (4 '-methoxyl-styrene) -6- three Piperazine etc..
It can be 2-isopropylthioxanthone, 2,4- diethyl thioxanthone, 2,4- dichloro thioxanthene as thioxanthones based compound Chloro- 4- propoxythioxanthone of ketone, 1- etc..
As oxime compound, adjacent ethoxy carbonyl-α-oxyimino group -1- phenyl-propane -1- ketone etc. can be enumerated, as Commercially available product, representative OXE-01, OXE-02 for having Ciba.
As benzoin based compound, can be used benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin isobutyl ether, benzil dimethyl ketal etc..
It can be 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 "-tetraphenyl bisglyoxalines, 2 as bisglyoxaline based compound, 2 '-bis- (2,3- dichlorophenyl) -4,4 ', 5,5 "-tetraphenyl bisglyoxalines, 2,2 '-bis- (2- chlorphenyl) -4,4 ', 5,5 "-four (alkane Phenyl) bisglyoxaline, 2,2 '-bis- (2- chlorphenyl) -4,4 ', 5,5 "-four (tri-alkoxy phenyl) bisglyoxalines, 4,4 ', 5,5 " The united imidazole etc. that the phenyl of position is replaced by alkoxy carbonyl group.
In above-mentioned 100 parts by weight of photosensitive composition, above-mentioned Photoepolymerizationinitiater initiater can be used 0.01~10 0.01~5 parts by weight preferably can be used in parts by weight.Such content range is the photopolymerization speed for considering photopolymerizable compound Depending on the physical property of degree and finally obtained film, if being lower than above range, polymerization speed is low, and whole activity time may Elongated, on the contrary, cross-linking reaction is excessive due to overreaction in the case where being greater than above range, the physical property of film instead may Decline, therefore appropriate use within the above range.
Furthermore, it is possible to be used together photopolymerization initiator with Photoepolymerizationinitiater initiater, with above-mentioned Photoepolymerizationinitiater initiater one With using in the case where photopolymerization initiator, photosensitive polymer combination high-sensitivity, productivity is improved, therefore preferably. As above-mentioned photopolymerization initiator, preferably can be used selected from one or more of the group being made of amine and carboxylic acid compound Compound.
Such photopolymerization initiator in terms of every 1 mole of Photoepolymerizationinitiater initiater usually using 10 moles hereinafter, it is preferred that It is used in the range of 0.01~5 mole.It is poly- using that in the case where photopolymerization initiator, can expect to be promoted within the above range It closes efficiency and proposes large-duty effect.
Additive
In order to increase coating or adaptation, photosensitive composition of the invention can further include dispersion The additive of agent, closely sealed promotor, levelling agent etc.
For example, photosensitive composition of the invention can further include dispersing agent so that manufactured colour filter The optics of device, physical qualities are excellent.Above-mentioned dispersing agent is not particularly limited as long as substance usually used in this field, can To enumerate such as polyacrylic dispersing agent, Polyester dispersant, polyethylene imine system dispersing agent, polyurethane series dispersing agent Deng SOLSPERSE5000/20000/24000 (Lubrizol Corp.'s manufacture) etc. can be used as commercially available dispersing agent.
Above-mentioned closely sealed promotor can add to improve the adaptation with substrate, and may include has selected from by carboxylic The silane for the reactive substituents in group that base, methylacryloyl, isocyanate group, epoxy group and their combination form Coupling agent, but not limited to this.For example, above-mentioned silane coupling agent can enumerate trimethoxysilyl benzoic acid, γ-first Base acryloyloxypropyltrimethoxysilane, vinyltriacetoxy silane, vinyltrimethoxysilane, γ-isocyanide Acid esters propyl-triethoxysilicane, γ-glycidoxypropyltrimethoxy silane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy Base silane etc., they can be independent or be used in combination of two or more.
In the case where photosensitive composition of the invention includes above-mentioned levelling agent, having can be improved coating The advantages of property.Such as BM-1000, BM-1100 (BM Chemie company), Fluorad FC-135/ can be used in above-mentioned levelling agent FC-170C/FC-430 (Sumitomo 3M company), SH-28PA/-190/SZ-6032 (Dong Li organosilicon company), DIC company F- 475, the fluorine systems levelling agent such as F554, but not limited to this.
In addition to this, photosensitive composition of the invention can be in a range that does not hinder the effect of the present invention The additive for further including antioxidant, ultraviolet absorbing agent, anticoagulant etc, for above-mentioned additive, same ability Field technique personnel suitably additional in a range that does not hinder the effect of the present invention can use.For example, with above-mentioned coloring phototonus On the basis of whole 100 parts by weight of resin combination, 0.05~10 parts by weight are can be used in above-mentioned additive, specifically can be used 0.1~5 parts by weight more specifically can be used in 0.1~10 parts by weight, and but not limited to this.
< colour filter >
Another way of the invention is related to the colour filter of the solidfied material comprising above-mentioned photosensitive composition Black matrix.
Another way of the invention is related to the colour filter of the solidfied material comprising above-mentioned photosensitive composition Column spacer.
Another way again of the invention is related to the colour filter of the solidfied material comprising above-mentioned photosensitive composition The one-piece type column spacer of black matrix.
In addition, another way of the invention is related to the solidfied material comprising above-mentioned photosensitive composition as black The colour filter of matrix, column spacer or the one-piece type column spacer of black matrix.
Specifically, above-mentioned colour filter may include the black square manufactured using above-mentioned photosensitive composition Battle array.
In addition, above-mentioned colour filter may include the columnar interval manufactured using above-mentioned photosensitive composition Object.
In addition, above-mentioned colour filter may include the one-piece type column of the black matrix manufactured using photosensitive composition Shape spacer.
Specifically, the one-piece type column spacer of above-mentioned black matrix, column spacer, black matrix can be to include the present invention Photosensitive composition solidfied material layer, or by above-mentioned photosensitive composition be coated with and with Scheduled pattern exposure, development and heat cure and the layer formed, it is one-piece type comprising above-mentioned black matrix, column spacer or black matrix The manufacturing method of the colour filter of column spacer can be formed by implementing method generally known in the art.
The one-piece type column spacer of above-mentioned black matrix, column spacer, black matrix due to using comprising viscosity at 20 DEG C It is 3.0mmHg or less at 20 DEG C for 2.0mPas or less, vapour pressure and meets the coloring phototonus tree of the solvent of above-mentioned formula 1 Oil/fat composition manufactures, therefore has the optical effect for basic shading performance excellent, and elasticity modulus and reliability The advantage that excellent, levelability is excellent, and the formation of difference of height is excellent, minimizes surface defect, surface roughness.
< image display device >
In addition, another way of the invention is related to the image display device comprising above-mentioned colour filter.
Colour filter of the invention can be applied not only to common liquid crystal display device, and can be applied to electroluminescent The various image display devices such as display device, plasm display device, field emission display device.
Image display device of the invention is due to comprising being 2.0mPas or less, steam at 20 DEG C using containing viscosity When being pressed in 20 DEG C for 3.0mmHg or less and meet above-mentioned formula 1 solvent photosensitive composition manufacture colour filter Device, therefore there is the advantage that process is excellent and excellent in reliability.
Hereinafter, being described in detail to illustrate this specification using embodiment.However, the reality in this specification Various other modes can be deformed by applying example, and the range of this specification will not be interpreted by being described below in detail The restriction of embodiment.Embodiment in this specification is to more completely illustrate this specification to those of ordinary skill in the art And provide.In addition, then " % " and " part " of following presentation content is weight basis as long as no specifically mentioned.
Synthesis example: the synthesis of alkali soluble resins (B)
In the divergence type for the internal volume 1L for having blender, thermometer, reflux condensing tube, dropping funel and nitrogen ingress pipe In flask, methoxybutyl acetic acid esters 277g is put into, after being warming up to 80 DEG C, was added dropwise through 5 hours by 3,4- epoxy group tricyclic [5.2.1.02,6] decane -9- base acrylate and 3,4- epoxy group tricyclic [5.2.1.02,6] decane -8- base acrylate it is mixed Close object [50:50 (molar ratio)] [compound represented by above-mentioned chemical formula 1, Ra=H] 301g, methacrylic acid 49g and azo Double methyl pentane nitrile 23g are dissolved in mixed solution made of methoxybutyl acetic acid esters 350g, and maturation 3 hours, thus To copolymer solution [35.0 weight % of solid component (NV)].The acid value (dry (dry)) of resulting copolymer is 69.8mgKOH/g, weight average molecular weight (Mw) are 9,500, and dispersion degree Mw/Mn is 1.9.
[chemical formula 1]
Embodiment and comparative example: the manufacture of photosensitive composition
Photosensitive composition is manufactured according to the composition of following table 1.At this point, the physicochemical characteristics of solvent is shown in In following table 2.
[table 1]
[table 2]
No. Type Viscosity (mPas) Vapour pressure (mmHg) | Δ (viscosity-vapour pressure) |
1 Methyl proxitol acetate (PGMEA) 1.3 2.8 1.5
2 Ethylene glycol monomethyl ether acetate (EGA) 1.3 1.2 0.1
3 3- methoxybutyl acetic acid esters (3-MBA) 0.7 1.1 0.4
4 Diethylene glycol ethyl methyl ether (MEDG) 1.2 0.7 0.5
5 1,2- propylene-glycol diacetate (PGDA) 2.9 0.2 2.6
6 Propylene glycol monomethyl ether (PGME) 1.9 8.7 6.8
Experimental example
(1) production of colored substrate
It is dry after the glass substrate (Corning Incorporated's manufacture) of 5cm × 5cm is cleaned with neutral lotion and water.In above-mentioned glass The coloring phototonus tree manufactured in spin coating embodiment and comparative example in such a way that final film thickness becomes 3.0 μm respectively on glass substrate Oil/fat composition, firing before carrying out at 100 DEG C is 90 seconds dry, removes solvent.Then, with 35mJ/cm2Light exposure is exposed and is formed Pattern is removed non-exposed portion using aqueous alkali.Then, rear firing in 30 minutes is carried out at 230 DEG C, manufactures colored substrate.
(2) measurement of viscosity
Fly viscosimeter (manufacture of Brookfield Viscometer DV-I+, Bo Lefei company) using rich strangle at 20 DEG C, surveys Determine solvent and embodiment, comparative example photosensitive composition viscosity.
(3) measurement (optical density (OD), UV-vis) of light characteristic
Cured film for the colored substrate manufactured by above-mentioned experimental example, using optical densitometer, (361T, X-rite are public Department manufacture) measurement 550nm at transmitance, find out the optical density (OD) for 1 μm of thickness, and be shown in following Table 3.
In addition, utilizing UV-vis (UV-2550 for the cured film of above-mentioned formation；Shimadzu Corporation's manufacture) evaluation light characteristic. At this point, evaluation criteria is as follows, and show the result in following Table 3.
> in the wave-length coverage of < light characteristic evaluation criteria 1:700~750nm
Zero: excellent, 10% or less translucency
△: insufficient, translucency is greater than 10% and 12% or less
×: deteriorate, translucency is greater than 12%
> in the wave-length coverage of < light characteristic evaluation criteria 2:950nm
Zero: excellent, 15% or more translucency
△: insufficient, translucency 13% is more than or lower than 15%
×: deteriorate, translucency is lower than 13%
(4) measurement of flatness (DOP:Degree of Planarization)
3.0 (± 0.2) μ are become with final film thickness respectively on forming figuratum substrate (5cm × 5cm glass substrate) The photosensitive composition manufactured in mode spin coating above-described embodiment and comparative example of m, firing before being carried out at 100 DEG C, It is 90 seconds dry, solvent is removed, to form pre-cured film.Later, with 35mJ/cm2Light exposure is exposed whole face and is formed Whole face pattern, is developed using aqueous alkali.Then, carry out rear firing in 130 minutes at 230 DEG C, manufacture whole face color base Plate.Lower part is measured using film thickness determination instrument (manufacture of DEKTAK6M, Veeco company) for manufactured whole face colored substrate Figuratum part and after not having the thickness of figuratum part, using the pattern thickness of the lower substrate of measured in advance, measurement is flat Smooth property (DOP), and be recorded in following Table 3.
The evaluation criteria > of < flatness (DOP)
In such a way that the thickness of lower part pattern becomes 1.17 μm on cut-and-dried substrate, with the flat of no lower part pattern The thickness in smoothization portion becomes 3.20 μm of modes and is coated, and measures flatness using following formula 3.
[formula 3]
In above-mentioned formula 3,
Refer to the thickness of lower part pattern,Refer toValue,Refer to by coloring phototonus resin group The film middle and lower part that conjunction object forms flatness does not have the thickness of figuratum part,Refer to from by coloring phototonus resin combination The highest point that object forms the film of flatness removes the thickness of the part of the highest point of lower part pattern.
◎: very excellent, 30% more than or lower than 60%
Zero: it is excellent, 15% more than or lower than 30%, 60% more than or lower than 75%
△: it is insufficient, 10% more than or lower than 15%, 75% more than or lower than 85%
×: deteriorate, is lower than 10%, 85% or more
(5) evaluation of the surface VCD unevenness
It will be become respectively with final film thickness by the photosensitive composition of above-described embodiment and comparative example manufacture The mode spin coating of 3.0 (± 0.2) μm is dried under reduced pressure (Vacuum Dry:VCD) until 65Pa, measures until reaching 65Pa Time, later, with optical microscopy confirm coating surface, measurement VCD decompression caused by surface defect and produce away from time (Tact Time), and it is recorded in table 3.Fig. 1 is the uneven illustration for evaluating image in the surface VCD of being classified according to following evaluation criteria.
The evaluation criteria > of < VCD
◎: very excellent, surface unevenness is less than 5
Zero: excellent, surface is not 5 or more and is less than 10
△: insufficient, surface is not 10 or more and is less than 20
×: deteriorate, surface is not 20 or more
(6) measurement of reliability
The glass substrate manufactured in above-mentioned (2) is cut into 3 × 3cm, after being then impregnated in nmp solution, at 100 DEG C Heating 60 minutes.Later, nmp solution is only extracted, about the dissolution degree in nmp solvent, utilizes ultraviolet-visual spectrometer (UV- Vis spectrometer) measurement absorbance, and record its result in following Table 3.At this point, evaluation criteria is as follows.
<evaluation criteria of reliability>
Zero: excellent, absorbance is 0.5 or less
△: insufficient, absorbance is greater than 0.5 and is 0.8 or less
×: deteriorate, absorbance is greater than 0.8
(7) evaluation of elastic recovery rate
For the substrate that the manufacture by above-mentioned (1) colored substrate manufactures, existed using SNU (SIS-2000, SNU company) The thickness and width of pattern is measured under normal condition.Later, hardometer (Nano-indenter HM500, Fisher company is utilized Manufacture) plane pressure head, with the pressing of the speed of 2mN/sec until becoming until the position of 1 μm of deformation occurs for pattern occurring 1 μm The position of shape is kept for 5 seconds retention times (Holding Time).Later, using the thickness and width of SNU measurement pattern, by preceding The thickness change of pattern measures elastic recovery rate afterwards.Specific evaluation criteria is as follows, and evaluation result is recorded in following Table 3.
The evaluation criteria > of < elastic recovery rate
◎: it is very excellent, 98% or more
Zero: excellent, 96% more than or lower than 98%
△: insufficient, 94% more than or lower than 96%
×: deteriorate, is lower than 94%
[table 3]
Referring to above-mentioned table 3, it is known that in the case where meeting the value of formula 1, the flatness of film is excellent, advantageously forms and is wanted The difference of height of design will not increase surface unevenness and activity time etc. caused by VCD process, show suitable for mass production Characteristic.

Claims (12)

1. a kind of photosensitive composition,
The viscosity of each solvent at 20 DEG C be 2.0mPas hereinafter,
The vapour pressure of each solvent at 20 DEG C be 3.0mmHg hereinafter,
Whole solvent meets following formula 1,
Formula 1
∑[(|Ai-Bi|)×Mi] < 1.5
In the formula 1,
AiFor the viscosity of solvent each at 20 DEG C, unit mPas,
BiFor the vapour pressure of solvent each at 20 DEG C, unit mmHg,
MiFor weight ratio of each solvent in whole solvent.
2. photosensitive composition according to claim 1, the solvent includes selected from by viscosity 1.1mPas And the propylene glycol methyl of the methyl -3- methoxy propyl acid esters of vapour pressure 1.8mmHg, viscosity 1.3mPas and vapour pressure 2.8mmHg Ether acetic acid ester, viscosity 1.3mPas and vapour pressure 2.8mmHg propylene glycol monoethyl acetic acid esters, viscosity 1.3mPas and steam Press 1.2mmHg ethylene glycol monomethyl ether acetate, viscosity 0.8mPas and vapour pressure 2.1mmHg methyl amyl ketone, viscosity 1.3mPas and vapour pressure 1.2mmHg ethylene glycol monomethyl ether, viscosity 1.2mPas and vapour pressure 0.9mmHg propylene glycol methyl Ether propionic ester, the diethylene glycol dimethyl ether of viscosity 2.0mPas and vapour pressure 3.0mmHg, viscosity 0.9mPas and vapour pressure The valerone of 1.7mmHg, viscosity 1.0mPas and vapour pressure 1.5mmHg amyl propionate, viscosity 1.3mPas And the 3- methoxyl group fourth of the ethyl -3- ethoxy-c acid esters of vapour pressure 0.7mmHg, viscosity 0.7mPas and vapour pressure 1.1mmHg Yl acetate, the dipropylene glycol dimethyl ether of viscosity 1.1mPas and vapour pressure 0.6mmHg, viscosity 1.2mPas and vapour pressure The diethylene glycol isopropyl methyl of the diethylene glycol ethyl methyl ether of 0.7mmHg, viscosity 1.3mPas and vapour pressure 0.8mmHg One or more of the group of ether and viscosity 1.4mPas and vapour pressure 0.4mmHg diethylene glycol diethyl ether composition.
3. photosensitive composition according to claim 1, the entirety solvent meets following formula 2,
Formula 2
∑[(|Ai-Bi|)×Mi] < 1.38
In the formula 2,
Ai、Bi、MiAs defined in the formula 1.
4. photosensitive composition according to claim 1, further include containing selected from by orange pigment, The colorant of the pigment of one or more of the group of violet pigment and blue pigment composition.
5. photosensitive composition according to claim 4, the colorant further includes black pigment.
6. photosensitive composition according to claim 1, relative to the photosensitive composition Whole 100 parts by weight, the content of the solvent are 60~90 parts by weight.
7. photosensitive composition according to claim 1 is further included selected from by alkali soluble resins, light One or more of polymerizable compound, Photoepolymerizationinitiater initiater and group of additive composition.
8. a kind of black matrix of colour filter, it includes photosensitive compositions according to any one of claims 1 to 7 Solidfied material.
9. a kind of column spacer of colour filter, it includes coloring phototonus resin groups according to any one of claims 1 to 7 Close the solidfied material of object.
10. a kind of one-piece type column spacer of the black matrix of colour filter, it includes according to any one of claims 1 to 7 The solidfied material of color sensation photosensitive resin composition.
11. a kind of colour filter, it includes the solidifications of photosensitive composition according to any one of claims 1 to 7 Object is as black matrix, column spacer or the one-piece type column spacer of black matrix.
12. a kind of image display device, it includes the colour filters described in claim 11.
CN201910059478.4A 2018-01-31 2019-01-22 Photosensitive composition, colour filter and image display device Pending CN110095936A (en)

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