CN104345559A - Colored photosensitive resin composition, color filter and liquid crystal display having the same - Google Patents
Colored photosensitive resin composition, color filter and liquid crystal display having the same Download PDFInfo
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- CN104345559A CN104345559A CN201410389639.3A CN201410389639A CN104345559A CN 104345559 A CN104345559 A CN 104345559A CN 201410389639 A CN201410389639 A CN 201410389639A CN 104345559 A CN104345559 A CN 104345559A
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- 0 C*(C)O[N+]([N+]([N-]N=C)=C)[O-] Chemical compound C*(C)O[N+]([N+]([N-]N=C)=C)[O-] 0.000 description 1
Classifications
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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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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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
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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
- G02F1/133514—Colour filters
- G02F1/133516—Methods for their manufacture, e.g. printing, electro-deposition or photolithography
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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
- G03F7/0005—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
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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
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Optics & Photonics (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention discloses a colored photosensitive resin composition. The colored photosensitive resin composition comprises: coloring agent (A), alkaline soluble resin (B), photo-polymerizing compound (C), photo-initiator (D),solvent (E) and additive agent (F), wherein the photo-initiator (D) is a compound represented by the chemical formula (1), and the additive agent (F) is a compound represented by the chemical formula (3), wherein, in the chemical formula (1), R1 is represented by the chemical formula (2), R2 is C1-C8 alkyl group, substituted phenyl group or unsubstituted phenyl group, or substituted benzyl group or unsubstituted benzyl group, R3 is substituted diphenyl sulfide group or unsubstituted diphenyl sulfide group, and in the chemical formula (2), R4 is C1-C4 alkyl group, and R5 is C3-C8 alicyclic alkyl group or aromatic alkyl group, and in the chemical formula (3), n is an integer from 1 to 12, the chemical formula (2) -R4-R5.
Description
This application claims the rights and interests of the Korean Patent Application No. 10-2013-0094691 submitted on August 9th, 2013, at this, it is incorporated in the application by the mode quoted in full.
Technical field
The present invention relates to a kind of photosensitive composition, comprise the colored filter of this photosensitive composition and comprise the liquid crystal display of this photosensitive composition.
Background technology
Colored filter can be built in imageing sensor, and in the coloured image register instrument of such as CMOS (Complementary Metal Oxide Semiconductor) (CMOS) or charge-coupled image sensor (CCD), and in fact it can be used to obtain coloured image.In addition, its range of application expands to rapidly for image sensor element, plasma display panel (PDP), liquid crystal display (LCD), Field Emission Display (FEL) and active display (LED) etc.
Particularly, recently, the purposes of LCD expands further, and thus has assert that colored filter is one of most important assembly of form and aspect (hue) for reappearing LCD.
Usually; in colour liquid crystal display device; namely the surface of dyed layer is equipped with diaphragm for protect the rear technique-chemical treatment technology of chromatograph (also pixel portion) from the manufacturing process of colored filter (such as acid or alkali etc.) and high temperature sputtering technology, and for making the discrepancy evens of generation according to each pixel of dyed layer.Therefore, the diaphragm of colored filter needs the physical properties such as the transparency, thermotolerance, chemical resistance, flatness.
Particularly, excellent thermotolerance is needed.
This is because, when being prepared the transparency electrode of such as ITO (indium tin oxide) etc. on diaphragm by sputtering method, need the technique of the heating temperatures diaphragm more than 200 DEG C; Or, when preparing liquid crystal orientation film on ITO, need the technique of the heating temperatures diaphragm more than 250 DEG C.
When utilize manufacture colored filter comprising the photosensitive composition of the dyestuff in toner time, owing to lacking and the compatibility of the material used and produce foreign material in the formation of dyed layer.In addition, when manufacturing colored filter, the problem produced is: because developing powder is slow and light sensitivity inadequate, the pattern therefore formed during developing process is often peeled off by alkaline-based developer.
Thus, need to develop a kind of photosensitive composition, its be applicable to photoetching process and can solve when comprise dyestuff as colorant or only use dyestuff as the problem produced during colorant.
In order to solve this problem, Korean Patent Publication No. 10-2012-0123930 discloses a kind of photosensitive polymer combination containing dyestuff for colored filter.
But with regard to light sensitivity and adhesiveness, said composition still needs to improve.
[quoted passage list]
[patent documentation]
(patent document 1) Korean Patent Publication No 10-2012-0123930A
Summary of the invention
In order to solve foregoing problems, the object of this invention is to provide a kind of photosensitive composition, even if described photosensitive composition also has high light sensitivity characteristic under the pixel formation condition of low exposure dose, and can form the coloring film of less defect.
In addition, another object of the present invention is to provide a kind of colored filter, and described colored filter can not produce the surface imperfection of such as projection in pixel portion.
In addition, other object of the present invention is to provide a kind of liquid crystal display being equipped with above-mentioned colored filter.
To achieve these goals, the invention provides a kind of photosensitive composition, described photosensitive composition comprises: colorant (A), alkali soluble resins (B), photopolymerizable compound (C), light trigger (D), solvent (E) and adjuvant (F), wherein, described light trigger (D) is the compound represented by following chemical formula 1, and described adjuvant (F) is the compound represented by following chemical formula 3:
[chemical formula 1]
[chemical formula 3]
Wherein, in described chemical formula 1, R
1represented by following chemical formula 2, R
2for the phenyl of C1 ~ C8 alkyl, replacement or unsubstituted phenyl or the benzyl replaced or unsubstituted benzyl, R
3diphenyl sulfide based or unsubstituted diphenyl sulfide based for what replace, and
In following chemical formula 2, R
4for C1 ~ C4 alkyl, and R
5for C3 ~ C8 alicyclic hydrocarbon radical or aromatic hydrocarbyl, and
In above-mentioned chemical formula 3, n is the integer of 1 ~ 12,
[chemical formula 2]
——R
4——R
5。
According to the present invention, a kind of photosensitive composition can be obtained, even if described photosensitive composition also has high light sensitivity characteristic under the pixel formation condition of low exposure dose, form the coloring film of less defect, and the surface imperfection of such as projection (bumping) can not be produced in pixel portion.
Embodiment
Configuration of the present invention and effect will be described in detail below.
The invention provides a kind of photosensitive composition, described photosensitive composition comprises: colorant (A), alkali soluble resins (B), photopolymerizable compound (C), light trigger (D), solvent (E) and adjuvant (F)
Wherein, described light trigger (D) is the compound represented by following chemical formula 1, and described adjuvant (F) is the compound represented by following chemical formula 3:
[chemical formula 1]
[chemical formula 3]
Wherein, in chemical formula 1, R
1represented by following chemical formula 2, R
2for the phenyl of C1 ~ C8 alkyl, replacement or unsubstituted phenyl or the benzyl replaced or unsubstituted benzyl, R
3the diphenyl sulfide based or unsubstituted diphenyl sulfide based of replacement, and
In following chemical formula 2, R
4c1 ~ C4 alkyl, and R
5c3 ~ C8 alicyclic hydrocarbon radical or aromatic hydrocarbyl, and
In above-mentioned chemical formula 3, n is the integer of 1 ~ 12,
[chemical formula 2]
——R
4——R
5。
Colorant (A)
In the present invention, the tone (tone) of colorant (A) is also unrestricted, and can select according to the purposes of colored filter.
Colorant (A) can single use pigment, dyestuff and natural colouring matter (natural color) or select in pigment, dyestuff and natural colouring matter two or more combinationally use, and pigment can comprise: the organic pigment being classified as the compound of pigment in color index (Color Index) (being published by dyers and colorist association (The society of Dyers and Colourists)), or the inorganic pigment of metal oxide, metallic complex salt and barium sulphate.Particularly, just have with regard to excellent thermotolerance and colour development, organic pigment is preferred.
The instantiation of organic pigment comprises: yellow pigment is C.I. pigment yellow 1 such as, C.I. pigment yellow 3, C.I. pigment Yellow 12, C.I. pigment yellow 13, C.I. pigment Yellow 14, C.I. pigment yellow 15, C.I. pigment yellow 16, C.I. pigment yellow 17, C.I. pigment yellow 20, C.I. pigment yellow 24, C.I. pigment yellow 31, C.I. pigment yellow 53, C.I. pigment yellow 83, C.I. pigment yellow 86, C.I. pigment yellow 93, C.I. pigment yellow 94, C.I. pigment yellow 109, C.I. pigment yellow 110, C.I. pigment yellow 117, C.I. pigment Yellow 12 5, C.I. pigment Yellow 12 8, C.I. pigment yellow 13 7, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 147, C.I. pigment Yellow 14 8, C.I. pigment yellow 150, C.I. pigment yellow 153, C.I. pigment yellow 154, C.I. pigment yellow 166, C.I. pigment yellow 17 3, C.I. pigment yellow 194, C.I. pigment yellow 214 etc.,
Orange pigment such as C.I. pigment orange 13, C.I. pigment orange 31, C.I. pigment orange 38, C.I. pigment orange 40, C.I. pigment orange 42, C.I. pigment orange 43, C.I. pigment orange 51, C.I. pigment orange 55, C.I. pigment orange 59, C.I. pigment orange 61, C.I. pigment orange 64, C.I. pigment orange 65, C.I. pigment orange 71, C.I. pigment orange 73 etc.;
Red is C.I. Pigment Red 9 such as, C.I. Pigment Red 97, C.I. paratonere 105, C.I. pigment red 122, C.I. pigment red 123, C.I. paratonere 144, C.I. pigment red 149, C.I. paratonere 166, C.I. paratonere 168, C.I. paratonere 176, C.I. paratonere 177, C.I. paratonere 180, C.I. paratonere 192, C.I. paratonere 209, C.I. pigment red 21 5, C.I. pigment red 21 6, C.I. paratonere 224, C.I. paratonere 242, C.I. paratonere 254, C.I. paratonere 264, C.I. paratonere 265 etc.,
Blue pigment such as C.I. pigment blue 15, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6, C.I. pigment blue 60 etc.;
Purple dye is C.I. pigment violet 1, C.I. pigment violet 19, C.I. pigment Violet 23, C.I. pigment violet 29, C.I. pigment violet 32, C.I. pigment violet 36, C.I. pigment violet 38 etc. such as;
Green pigment is C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 58 etc. such as;
Palm fibre pigment such as C.I. pigment brown 23, C.I. pigment brown 25 etc.; Or mineral black is C.I. pigment black 1, C.I. pigment black 7 etc. such as.
Preferably, organic pigment comprises one or more and is selected from C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. paratonere 177, C.I. paratonere 209, C.I. paratonere 254, C.I. pigment Violet 23, C.I. pigment blue 15: 06 and C.I. pigment green 36.
To can be used alone or two or more combinationally use organic pigment and inorganic pigment.Particularly, the combination of preferred C.I. paratonere 254 and C.I. pigment yellow 13 9 forms red pixel; The combination of preferred C.I. pigment green 36 and C.I. pigment yellow 150 or the combination of C.I. pigment green 36 and C.I. pigment yellow 13 8 form green pixel; And preferably include pigment blue 15: 06 to form blue pixel.
Based on the general assembly (TW) of the solid of photosensitive composition, the content of colorant (A) is set to 5% to 60% weight, and preferred 10% to 50% weight.The colorant (A) of aforementioned quantities is preferred, even if because pixel portion also has sufficient color depth when forming film, and owing to not reducing (missing) degree that comes off of non-pixel portion when developing, is difficult to produce residue.
As used in this article, the total weight of solids of photosensitive composition represents the total amount of the composition in addition to the solvents of photosensitive composition.
When pigment is used as colorant (A), preferably use the pigment of uniform particle sizes.One of example of the method for uniform particle sizes be can be by adding the method for surfactant as the process distribution process of pigment dispersing agent, and the pigment dispersing solution of homodisperse pigment state can be obtained according to the method.
Pigment dispersing agent can single use surfactant such as cationic surfactant, anionic surfactant, non-ionic surfactant and gentle surfactant, or two or more being selected from the group of Free Surface activating agent such as cationic surfactant, anionic surfactant, non-ionic surfactant and gentle surfactant composition combinationally use, wherein, these surfactants can be used alone or combinationally use with two or more.
Based on the colorant (A) of 1 weight portion, the consumption of pigment dispersing agent is less than 1 weight portion usually, is preferably 0.05 to 0.5 weight portion.The pigment dispersing agent of aforementioned quantities is preferred, because there is the tendency that can obtain the pigment of even mean grain size.
Alkali soluble resins (B)
In the present invention, any acrylic copolymer just can be used as alkali soluble resins (B) and unrestricted, as long as this acrylic copolymer may be dissolved in solvent of the present invention, there is the reactivity of the effect to light or heat, have the function of the solvable adhesive resin of colorant (A) and may be dissolved in alkali developing solution.
Acrylic copolymer can comprise, and such as, has the monomer of carboxyl and the multipolymer of other monomer, and other monomer can have the monomer generation interpolymerization of carboxyl with this.
The instantiation with the monomer of carboxyl can be: unsaturated carboxylic acid, such as unsaturated monocarboxylic; Or there is the unsaturated polyvalent carboxylic acid (polyvalentcarboxylic acid) of one or more carboxyl in the molecule, such as unsaturated dicarboxylic or unsaturated tricarboxylic acids etc.
Unsaturated monocarboxylic can comprise, such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid etc.
Unsaturated dicarboxylic can comprise, such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc.
Unsaturated polyvalent carboxylic acid can be acid anhydrides, and especially comprises, such as maleic anhydride, itaconic anhydride, citraconic anhydride etc.
Unsaturated polyvalent carboxylic acid can be its list (2-methylacryoyloxyethyl alkyl) ester, and especially comprise, such as mono succinate (2-acryloyl-oxyethyl) acid, mono succinate (2-methacryloxyethyl), single (2-acryloyl-oxyethyl) phthalic ester, list (2-methacryloxyethyl) phthalic ester etc.
In addition, unsaturated polyvalent carboxylic acid can be list (methyl) acrylate that its two ends have polymkeric substance dicarboxyl, and especially comprises, such as ω-carboxy-polycaprolactone mono acrylic ester, ω-carboxy-polycaprolactone monomethacrylates etc.
The monomer with carboxyl can be used alone or combinationally use with two or more.
Can be with the instantiation of other monomer of the monomer generation copolymerization with carboxyl: aromatic vinyl compound, such as styrene, α-methyl styrene, adjacent vinyltoluene, a vinyltoluene, to vinyltoluene, to chlorostyrene, o-methoxystyrene, meta-methoxy styrene, to methoxy styrene, adjacent vinyl benzyl methyl ether, a vinyl benzyl methyl ether, to vinyl benzyl methyl ether, adjacent vinylbenzyl glycidyl ether, a vinylbenzyl glycidyl base ether, to vinylbenzyl glycidyl ether, indenes etc.;
Esters of unsaturated carboxylic acids, such as methyl acrylate, methyl methacrylate, ethyl acrylate, β-dimethyl-aminoethylmethacrylate, n-propyl, n propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-BMA, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, the secondary butyl ester of methacrylic acid, tert-butyl acrylate, Tert-butyl Methacrylate, acrylic acid 2-hydroxyl ethyl ester, HEMA, acrylic acid 2-hydroxypropyl acrylate, methacrylic acid 2-hydroxypropyl acrylate, acrylic acid 3-hydroxypropyl acrylate, methacrylic acid 3-hydroxypropyl acrylate, hydroxyl butylacrylic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxy butyl ester, acrylic acid 3-hydroxy butyl ester, methacrylic acid 3-hydroxy butyl ester, acrylic acid 4-hydroxy butyl ester, methacrylic acid 4-hydroxy butyl ester, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, 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 diethylene glycol acrylate, methoxyl diethylene glycol methacrylate, methoxy triethylene acrylate, methoxy triethylene methacrylate, MPEG acrylate, MPEG methacrylate, methoxyl dipropylene glycol acrylate, methoxyl dipropylene glycol methyl acrylate, isobornyl acrylate, isobornyl methacrylate, acrylic acid bicyclopentadiene ester, methacrylic acid bicyclopentadiene ester, acrylic acid 2-hydroxyl-3-phenoxy-propyl, methacrylic acid 2-hydroxyl-3-phenoxy-propyl, acrylic acid monoglyceride, metering system monoglyceride etc.,
Unsaturated carboxylic acid aminoalkyl ester, such as acrylic acid 2-amino ethyl ester, methacrylic acid 2-amino ethyl ester, acrylic acid 2-dimethylamino ethyl ester, methacrylic acid 2-dimethylamino ethyl ester, the amino propyl ester of acrylic acid 2-, methacrylic acid 2-amino propyl ester, acrylic acid 2-dimethylamino propyl ester, methacrylic acid 2-dimethylamino propyl ester, acrylic acid 3-aminopropyl ester, methacrylic acid 3-aminopropyl ester, acrylic acid 3-dimethylaminopropyl ester, methacrylic acid 3-dimethylaminopropyl ester etc.;
Unsaturated carboxylic acid ethylene oxidic ester, such as glycidyl acrylate, glycidyl methacrylate etc.;
Vinyl carboxylates, such as vinyl acetate, propionate, vinyl butyrate, vinyl benzoate etc.;
Unsaturated ethers, such as vinyl methyl ether, EVE, allyl glycidyl ether etc.;
Vinyl nitrile compounds, such as vinyl cyanide, methacrylonitrile, α-chloroacrylonitrile, ethenylidene nitrile compound etc.;
Unsaturated amides, such as acrylamide, Methacrylamide, alpha-chloro acrylamide, N-2-hydroxyethyl acrylamide, N-2-hydroxyethyl methacrylamide etc.;
Unsaturated acyl imines, such as maleimide, N-phenylmaleimide, N-N-cyclohexylmaleimide etc.;
Aliphatic conjugated diene, such as 1,3-butadiene, isoprene, chlorbutadiene etc.; And
There is the polymeric monomer of single acryloyl or monomethacrylate acyl, such as polystyrene, polymethyl acrylate, polymethylmethacrylate, the positive butyl ester of polyacrylic acid, Vinalac 5920, polysiloxane etc. at the end of polymer molecular chain.These monomers can be used alone or combinationally use with two or more.
The amount in alkali soluble resins (B) with the monomer of carboxyl is generally 10% to 50% weight, is preferably 15% to 40% weight, is more preferably 25% to 40% weight.The monomer with carboxyl of 10% to 50% weight is preferred, because solubleness is good in developing solution, and is easy to accurately form developing pattern simultaneously.
Unsaturated polyvalent carboxylic acid can be acid anhydrides, and especially comprises, such as maleic anhydride, itaconic anhydride, citraconic anhydride etc.
Acrylic copolymer can such as comprise: (methyl) acrylic acid/(methyl) methyl acrylate copolymer, (methyl) acrylic acid/(methyl) benzyl acrylate multipolymer, (methyl) acrylic acid/(methyl) acrylic acid 2-hydroxyl ethyl ester/(methyl) benzyl acrylate multipolymer, (methyl) acrylic acid/(methyl) methyl acrylate/polystyrene macromer multipolymer, (methyl) acrylic acid/(methyl) methyl acrylate/poly-(methyl) methyl acrylate polymeric monomer multipolymer, (methyl) acrylic acid/(methyl) benzyl acrylate/polystyrene macromer multipolymer, (methyl) acrylic acid/(methyl) benzyl acrylate/poly-(methyl) methyl acrylate polymeric monomer multipolymer, (methyl) acrylic acid/(methyl) acrylic acid 2-hydroxyl ethyl ester/(methyl) benzyl acrylate/polystyrene macromer multipolymer, (methyl) acrylic acid/(methyl) acrylic acid 2-hydroxyl ethyl ester/(methyl) benzyl acrylate/poly-(methyl) methyl acrylate polymeric monomer multipolymer, (methyl) acrylic acid/styrene/(methyl) benzyl acrylate/N-phenylmaleimide multipolymer, (methyl) acrylic acid/mono succinate (2-acryloxy)/styrene/(methyl) benzyl acrylate/N-phenylmaleimide multipolymer, (methyl) acrylic acid/mono succinate (2-acryloyl-oxyethyl)/styrene/(methyl) allyl acrylate/N-phenylmaleimide multipolymer, (methyl) acrylic acid/(methyl) benzyl acrylate/N-phenylmaleimide/styrene/glycerine list (methyl) acrylate copolymer etc.In this article, (methyl) acrylate refers to acrylate or methacrylate.
Wherein, preferably (methyl) acrylic acid/(methyl) benzyl acrylate multipolymer, (methyl) acrylic acid/(methyl) benzyl acrylate/styrol copolymer, (methyl) acrylic acid/(methyl) methyl acrylate copolymer and (methyl) acrylic acid/(methyl) methyl acrylate/styrol copolymer is used.
The mean molecular weight (polystyrene converted average molecular weight) of the polystyrene conversion of alkali soluble resins is generally 5000 to 50000, and be preferably 8000 to 40000, be more preferably 10000 to 35000, and most preferably be 10000 to 30000.The alkali soluble resins with the molecular weight of 5000 to 50000 is desirable, this is because the hardness of coat film is improved, residual film ratio is high, and in developing solution, the solubleness of unexposed portion is good, and resolution (resolution) trends towards increasing.
The acid number of alkali soluble resins (B) is generally 50 to 150mgKOH/g, is preferably 60 to 140mgKOH/g, is more preferably 80 to 135mgKOH/g, and most preferably is 80 ~ 130mgKOH/g.Acid number is the alkali soluble resins of 50 ~ 150mgKOH/g is desirable, this is because solubleness in developing solution increases thus unexposed portion is easy to dissolve, and light sensitivity uprises thus when developing, maintain the pattern of exposure area, and residual film ratio also trends towards uprising.
Acid number is herein the value measured like this: in and the amount (mg) of potassium hydroxide needed for 1g acrylate copolymer, and usually can utilize the titration of the aqueous solution of potassium hydroxide to determine.
Based on the general assembly (TW) of the solid of photosensitive composition, the content of alkali soluble resins (B) is set to 5% to 85% weight, is preferably 10% to 70% weight.The alkali soluble resins (B) of aforementioned quantities is preferred, because be difficult to produce development residues in the substrate of non-pixel portion due to solubleness enough in developing solution, and owing to probably there is the reduction of film when developing in the pixel portion of exposure area, because of but not the omission of pixel portion (omission) trend towards well.
Photopolymerizable compound (C)
In the present invention, photopolymerizable compound (C) is by by the photopolymerizable compound irradiating the living radical, acid etc. that produce from light trigger and carry out being polymerized.In this application, " photopolymerizable compound " refers to the monomer with one or more functional groups, and is registered as simple function polymerizable compound, difunctionality polymerizable compound or trifunctional polymerizable compound according to the number of functional group.
The instantiation of simple function polymerizable compound can comprise: nonyl phenyl carbitol acrylate, acrylic acid 2-hydroxyl-3-phenoxy-propyl, 2-ethylhexyl carbitol acrylate, acrylic acid 2-hydroxyl ethyl ester, NVP etc.
The instantiation of difunctionality polymerizable compound can comprise: 1, 6-hexanediol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, two (acryloyl-oxyethyl) ethers of bisphenol-A, 3-methyl pentanediol two (methyl) acrylate, butanediol dimethylacrylate, hexanediol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, polyglycol two (methyl) acrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, ethoxylated neopentyl, ethoxylated neopentylglycol diacrylate etc.
The instantiation of trifunctional polymerizable compound can comprise: trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, ethoxylated trimethylolpropane three (methyl) acrylate, propoxylation trimethylolpropane tris (methyl) acrylate, glyceryl propoaylate triacrylate, isocyanurate triacrylate etc.
The instantiation of four sense polymerizable compounds can comprise: pentaerythrite four (methyl) acrylate, dihydroxy methylpropane four (methyl) acrylate etc.
The instantiation of face energy polymerizable compound can comprise: dipentaerythritol five (methyl) acrylate; And six the instantiation of sense polymerizable compound can comprise: dipentaerythritol six (methyl) acrylate.
Wherein, preferably use the multifunctional polymerizable compound with two or more functional groups, and especially more preferably use there is the multifunctional polymerizable compound that five kinds or more plant functional group.
In this application, based on the general assembly (TW) of the solids content of photosensitive composition, the consumption of photopolymerizable compound (C) is preferably 5% to 50% weight, and more preferably 7% to 45% weight.
The photopolymerizable compound (C) of aforementioned quantities is preferred, because when the amount of photopolymerizable compound (C) falls within the scope of this, the intensity of pixel portion or its smoothness trend towards being improved.
Light trigger (D)
Light trigger (D) comprises the light trigger (d1) of the structure with chemical formula 1.
[chemical formula 1]
Wherein, in chemical formula 1, R
1represented by following chemical formula 2, R
2c1 ~ C8 alkyl, the phenyl of replacement or the benzyl of unsubstituted phenyl or replacement or unsubstituted benzyl, R
3the diphenyl sulfide based or unsubstituted diphenyl sulfide based of replacement, and
In following chemical formula 2, R
4c1 ~ C4 alkyl, and R
5c3 ~ C8 alicyclic hydrocarbon radical or aromatic hydrocarbyl,
[chemical formula 2]
——R
4——R
5。
In addition, in the scope not being unfavorable for effect of the present invention, use capable of being combined light trigger apart from the above (d2).Typically, at least one compound in the group being selected from and being made up of acetophenone compounds, benzoin compounds, benzophenone compound, compound in triazine class, oxime compound, bisglyoxaline compounds and thioxanthones compounds can be preferably used to come for light trigger (d2).
The instantiation of acetophenone compounds is: the oligomer etc. of diethoxy acetophenone, 2-methyl-2-morpholinyl-1-(4-methyl thio phenyl) propane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxy ethoxy) phenyl] propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] propane-1-ketone; And more preferably 2-methyl-2-morpholinyl-1-(4-methyl mercapto phenyl) propane-1-ketone.Acetophenone compounds can be used alone or combinationally uses with two or more, and it can combinationally use with other light trigger.
The instantiation of benzoin compounds is: benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether etc.
The instantiation of benzophenone compound is: benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 3; 3 '; 4; 4 '-four (t-butyl peroxy carbonyl) benzophenone, 2; 4,6-tri-methyl benzophenone etc.
The instantiation of compound in triazine class is: 2, two (the trichloromethyl)-6-(4-methoxyphenyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl naphthyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1 of 4-, 3, 5-triazine, 2, two (trichloromethyl the methyl)-6-[2-(5-methylfuran-2-base) vinyl]-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(furans-2-base) vinyl]-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(4-lignocaine-2-aminomethyl phenyl) vinyl]-1 of 4-, 3, 5-triazine, 2, two (trichloromethyl)-6-[2-(3 of 4-, 4-Dimethoxyphenyl) vinyl]-1, 3, 5-triazine etc.
The instantiation of oxime compound is: 2-(O-benzoyl oxime)-1-[4-(thiophenyl) phenyl]-1; 2-acetyl caproyl, 1-(4-first sulphur l-phenvl)-butane-1,2-butane-2-oxime-O-acetic acid esters, 1-(4-first sulphur l-phenvl)-butane-1-ketoxime-O-acetic acid esters, oxyimino-(4-sulphur l-phenvl)-ethylhexoate-O-acetic acid esters, oxyimino-(4-sulphur l-phenvl)-ethyl acetate-O-benzoic ether etc.
The instantiation of bisglyoxaline compounds is: 2, 2 '-bis-(2-chlorphenyl)-4, 4 ', 5, 5 '-tetraphenyl bisglyoxaline, 2, 2 '-bis-(2, 3-dichlorophenyl)-4, 4 ', 5, 5 '-tetraphenyl bisglyoxaline, 2, 2 '-bis-(2-chlorphenyl)-4, 4 ', 5, 5 '-four (alkoxyl phenyl) bisglyoxaline, 2, 2 '-bis-(2-chlorphenyl)-4, 4 ', 5, 5 '-four (tri-alkoxy phenyl) bisglyoxaline, 2, 2-two (2, 6-dichlorophenyl)-4, 4 ', 5, 5 '-tetraphenyl-1, 4 of 2 '-bisglyoxaline or wherein phenyl, 4 ', 5, the imidazolium compounds etc. that 5 ' position is replaced by alkoxy carbonyl group.In these bisglyoxaline compounds, preferably use 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2,3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2-two (2,6-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline.
Thioxanthones compounds such as comprises ITX, ITX, 2,4-diethyl thioxanthones, 2,4-bis-clopenthixal ketones, the chloro-4-propoxythioxanthone of 1-etc.
In the present invention, based on the general assembly (TW) of the solid of photosensitive composition, the content of light trigger (D) is 0.1% to 40% weight, is preferably 1% to 30% weight.The light trigger (D) of aforementioned quantities is preferred, because photosensitive composition has ISO, thus makes the time shutter shorter, and improves throughput rate, and can keep higher resolution.
In addition, in the present invention, in company with light trigger (D) together, light-initiated auxiliary agent can be comprised extraly.Light-initiated auxiliary agent and light trigger (D) combinationally use, and for promoting the polyreaction of photopolymerizable compound, this polyreaction is caused by light trigger.Light-initiated auxiliary agent is such as aminated compounds, alkoxy anthracene compounds, thioxanthones compounds etc.
The instantiation of aminated compounds is triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl esters, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid isopentyl ester, benzoic acid 2-dimethylamino ethyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, N, N-dimethyl-p-toluidine, 4,4 '-bis-(dimethylamino) benzophenone, 4,4 '-bis-(lignocaine) benzophenone, 4,4 '-bis-(ethylmethylamino) benzophenone etc.In these aminated compoundss, 4,4 '-bis-(lignocaine) benzophenone is preferred.
The instantiation of alkoxy anthracene compounds is 9,10-dimethoxy anthracene, EDMO, 9,10-diethoxy anthracenes, 2-ethyl-9,10-diethoxy anthracene etc.
The instantiation of thioxanthones compounds is ITX, ITX, 2,4-diethyl thioxanthones, 2,4-bis-clopenthixal ketones, the chloro-4-propoxythioxanthone of 1-etc.
Light-initiated auxiliary agent can be used alone or combinationally uses with two or more, and can use commercial product, such as, and EAB-F (can purchased from Hodogaya Chemical Co., Ltd.).
The preferred embodiment of the combination of light trigger and light-initiated auxiliary agent is as follows:
Diethoxy acetophenone and 4,4 '-bis-(lignocaine) benzophenone; 2-methyl-2-morpholinyl-1-(4-methyl mercapto phenyl) propane-1-ketone and 4,4 '-bis-(lignocaine) benzophenone; 2-hydroxy-2-methyl-phenyl-propane-1-ketone and 4,4 '-bis-(lignocaine) benzophenone; 2-hydroxy-2-methyl-1-[4-(2-hydroxy ethoxy) phenyl] propane-1-ketone and 4,4 '-bis-(lignocaine) benzophenone; 1-hydroxycyclohexylphenylketone and 4,4 '-bis-(lignocaine) benzophenone; The oligomer and 4 of 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] propane-1-ketone, 4 '-bis-(lignocaine) benzophenone; 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone and 4,4 '-bis-(lignocaine) benzophenone etc., and 2-methyl-2-morpholinyl-1-(4-methyl mercapto phenyl) propane-1-ketone and 4, the combination of 4 '-bis-(lignocaine) benzophenone is preferred.
When light trigger uses together with light-initiated auxiliary agent, for the light trigger of every 1 mole, the amount that preferred light causes auxiliary agent can be set as lower than 10 moles, and is more preferably 0.01 to 5 mole.Be preferred when the amount of light-initiated auxiliary agent falls in above-mentioned scope, because the light sensitivity of photosensitive composition can be increased further, and improve the throughput rate by the colored filter using above-mentioned composition to be formed.
Solvent (E)
As long as other component comprised in painted photosensitive polymer combination effectively can be dissolved, then any solvent for conventional photosensitive composition can be used as the solvent (E) of the application when being not particularly limited.Particularly, ether, aromatic hydrocarbons, ketone, alcohol, ester or amide-type are preferred.
The instantiation of ether is tetrahydrofuran, oxinane, 1, 4-dioxane, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, dibutyl ethylene glycol ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, methylcellosolve acetate, ethyl cellosolve acetate, ethylcarbitol acetate, acetate of butyl carbitol, propylene glycol methyl ether acetate, methoxy butyl acetate, acetic acid methoxyl pentyl ester, methyl phenyl ethers anisole, phenetol or methylanisole etc.
The instantiation of aromatic hydrocarbons is benzene,toluene,xylene or sym-trimethyl benzene etc.
The instantiation of ketone is acetone, 2-butanone, 2-HEPTANONE, 3-heptanone, 4-heptanone, 4-methyl-2 pentanone, cyclohexanone or cyclopentanone etc.
The instantiation of alcohols is methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol or glycerine etc.
The instantiation of ester class is ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl formate, isobutyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, Arrcostab, methyl lactate, ethyl lactate, ethoxyacetic acid methyl esters (methyl oxy acetate), ethoxyacetic acid ethyl ester (ethyl oxy acetate), ethoxyacetic acid butyl ester (butyl oxy acetate), methoxy menthyl acetate, ethyl methoxyacetate, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, methyl 3-oxygen base propionic ester, ethyl 3-oxygen base propionic ester, methyl 3-methoxy ethoxy propionic ester, ethyl 3-methoxy propyl acid esters, methyl 3-ethoxy-c acid esters, ethyl 3-ethoxy-c acid esters, methyl 2-oxygen base propionic ester, ethyl 2-oxygen base propionic ester, propyl group 2-oxygen base propionic ester, methyl 2-methoxy propyl acid esters, ethyl 2-methoxy propyl acid esters, propyl group 2-methoxy propyl acid esters, methyl 2-ethoxy-c acid esters, ethyl 2-ethoxy-c acid esters, methyl 2-oxygen base-2 Methylpropionic acid ester, ethyl 2-oxygen base-2 Methylpropionic acid ester, methyl 2-methoxyl-2 Methylpropionic acid ester, ethyl 2-methoxyl-2 Methylpropionic acid ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-Oxobutyric acid methyl esters, 2-Oxobutyric acid ethyl ester, acetic acid 3-methoxybutyl, acetic acid 3-methyl-3-methoxybutyl or gamma-butyrolacton etc.
The instantiation of amide-type is DMF or DMA etc.
The solvent of other kind is such as 1-METHYLPYRROLIDONE or dimethyl sulfoxide (DMSO) etc.Preferably, be selected from the one in 3-ethoxyl ethyl propionate, propylene glycol methyl ether acetate or propylene glycol monomethyl ether, or the combination of two or more.
In the present invention, based on the general assembly (TW) according to photosensitive composition of the present invention containing solvent, the consumption of solvent (E) can be 60% to 90% weight, and is preferably 70% to 85% weight.It is preferred that the amount of solvent (E) falls in above-mentioned scope, because when using that such as the coating apparatus such as roll coater, spin coater, seam end spin coater (slit end spin coater), slit coater (also referred to as mould coating machine), ink jet printer is coated with, the coating property of photosensitive composition can be improved.
Adjuvant (F)
Photosensitive composition according to the present invention comprises the projection inhibitor that represented by following chemical formula 3 as adjuvant, makes the surface imperfection that can not produce such as projection in the pixel portion of colored filter.
Based on the general assembly (TW) of the solid of photosensitive composition, the content of adjuvant can be 1% to 10% weight, is preferably 1% to 5% weight.
[chemical formula 3]
In above-mentioned chemical formula 3, n is the integer of 1 to 12.
The instantiation of projection inhibitor is what produced by BASF
hDDA etc.
Except projection inhibitor, it is such as other polymer compound, hardening agent, surfactant, tackifier, antioxidant, UV absorbing agent, anti gelling agent that alternative is added to other adjuvant of the present invention.
The instantiation of other polymer compound can comprise: curable resin, such as epoxy resin, maleimide resin etc.; And thermoplastic resin, such as polyvinyl alcohol (PVA), polyacrylic acid, polyalkylene glycol monoalkyl ether, perfluoroalkyl acrylate, polyester, polyurethane etc., but be not limited to this.
Hardening agent is used for core is solidified and enhance mechanical strength, and the instantiation of hardening agent can comprise: epoxy compound, polyfunctional isocyanate compound, melamine compound, oxetane compound etc., but is not limited to this.
In hardening agent, the instantiation of epoxy compound can comprise: bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol f type epoxy resin, A Hydrogenated Bisphenol A F type epoxy resin, novalac epoxy, other aromatic epoxy resin, cycloaliphatic epoxy resin, glycidyl ester resin, epihydric alcohol amine resin, or the brominated derivative of epoxy resin, except the aliphatic series of epoxy resin and latter bromide derivative beyond the region of objective existence thereof, alicyclic or aromatic ring oxygen compound, epoxidized butadiene (being total to) polymers, epoxidized isoprene (being total to) polymers, (methyl) glycidyl acrylate (being total to) polymers, triglycidyl group isocyanuric acid ester etc., but be not limited to this.
In hardening agent, the instantiation of oxetane compound can comprise: carbonic ester dioxygen azetidine, dimethylbenzene dioxygen azetidine, adipate dioxygen azetidine, terephthalate dioxygen azetidine, cyclohexane dicarboxylic acid dioxygen azetidine etc., but is not limited to this.
Hardening agent may further include the compound of Curing, and the compound of Curing enables the epoxy radicals of epoxy compound and the oxetanes skeleton of oxetane compound carry out ring-opening polymerization together with hardening agent.The compound of Curing can such as comprise polybasic carboxylic acid, polybasic acid anhydride, acid producing agent etc.Polybasic acid anhydride can comprise those as the commercially available polybasic acid anhydride of epoxy curing agent.The example of commercially available epoxy curing agent comprises: Adeka rigidizer EH-700 (buying from Adeka company), Rikacid HH (buying from New Japan Chemicals company), MH-700 (buying from New Japan Chemicals company) etc.The above-mentioned hardening agent enumerated can be used alone or combinationally uses with two or more.
Surfactant can be used for the filming performance strengthening photosensitive composition, and preferably uses fluorine system surfactant or polysiloxane series surfactant.
Polysiloxane series surfactant DC3PA, DC7PA, SH11PA, SH21PA, SH8400 etc. such as buying from the beautiful silicon in the healthy and free from worry east of Tao Shi (Dow Corning Toray silicon) company of commercially available surfactant; And from TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 etc. that general Toshiba silicon (GE Toshiba silicon) company buys.
Fluorine system surfactant MEGAFAC F-470, F-471, F-475, F-482, F-489 etc. such as buying from Dainippon Ink & Chemicals company limited of commercially available surfactant.
The above-mentioned surfactant enumerated can be used alone or combinationally use with two or more.
The instantiation of tackifier can comprise: vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-aminoethyl)-3-aminopropyltriethoxy dimethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-glycydoxy trimethoxy silane, 3-glycydoxy methyl dimethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane, 3-mercaptopropyi trimethoxy silane, 3-isocyanates propyl trimethoxy silicane, 3-isocyanate group propyl-triethoxysilicane etc.
The above-mentioned tackifier enumerated can be used alone or combinationally use with two or more.
Based on the weight of the solids content of photosensitive composition, the consumption of tackifier can be 0.01% to 10% weight, is preferably 0.05% to 2% weight.
The instantiation of antioxidant can comprise: 2,2 '-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methy phenols etc.
The instantiation of UV absorbing agent can comprise: 2-(the 3-tert-butyl group-2-hydroxy-5-methyl base phenyl)-5-chlorinated benzotriazole, alkoxy benzene ketone etc.
The instantiation of anti-coagulants comprises sodium polyacrylate etc.
Can such as manufacture according to following method according to photosensitive composition of the present invention.
Particularly, colorant mixes with solvent in advance, and uses bowl mill to carry out disperseing until the mean grain size of pigment is 0.2 μm or less.Similarly, if need to use pigment dispersing agent, and part or all of alkali soluble resins can mix with solvent.
If by further the extra solvent of remaining alkali soluble resins, photopolymerizable compound, light trigger, reactive silicon class surfactant, other composition used as required and needs being joined obtained dispersion liquid (hereinafter, refer in some cases " mill base ") in, so that presetting concentration, thus obtain required photosensitive composition.
In addition, the invention provides a kind of colored filter manufactured by this photosensitive composition.
The structure of colored filter and the manufacture method of this colored filter are known in the art, thus these methods can be utilized to manufacture colored filter of the present invention.
Such as, there is a kind of developing method and utilize the ink-jet apparatus not needing the method for photoresist method.Wherein, this developing method such as photosensitive composition of the present invention is coated in resin bed top or on independently substrate (such as, first independently substrate forms colored photosensitive resin composition etc.), form dyed layer by removing volatile material (such as solvent etc.), and expose dyed layer by photomask.
According to photosensitive composition of the present invention, the coat film with high brightness and ISO may be obtained.
In addition, the invention provides a kind of liquid crystal display comprising above-mentioned colored filter.
This liquid crystal display, except having above-mentioned colored filter, is also included in the configuration that the technician in field related to the present invention knows.
In other words, the whole liquid crystal display can applying colored filter of the present invention are comprised in the present invention.Such as, the present invention includes transmission type lcd device, this transmission type lcd device has liquid crystal layer, pixel electrode and to electrode base board, this liquid crystal layer has the liquid crystal material be injected in thin film transistor (TFT) (TFT element) gap portion, this to electrode base board be equipped with predetermined space and towards oriented layer.In addition, there is reflection LCD, wherein, between colored filter substrate and dyed layer, reflection horizon is installed.
As another example, a kind of liquid crystal display can be provided, this liquid crystal display comprises TFT (thin film transistor (TFT)) substrate and backlight, wherein, TFT substrate is combined on the top of the transparency electrode of colored filter, and backlight is fixed with TFT substrate on the position overlapping with colored filter.
TFT substrate can be equipped with: the outside framework be made up of the light tight resin of the outer surface around colored filter; The liquid crystal layer be made up of the nematic crystal be applied on outside framework; Be equipped in the multiple pixel electrodes in each region in liquid crystal layer; Form the transparent glass substrate of pixel electrode; And, be formed in the polarizer in the exposed of transparent glass substrate.
Embodiments of the invention are limited with more detailed description the present invention below by for setting forth but should not be construed as.Scope of the present invention illustrates in detail in the claims, and comprises the implication of the record that is equivalent to claims and all modification within the scope of it.Except as otherwise noted, " % " and " part " that provide in following examples and comparative example all by weight.
< embodiment 1>
The preparation > of < photosensitive composition
By using the C.I. paratonere 254 (A-1) of 5.57 parts as colorant, as the multipolymer of the methacrylic acid of 8.23 parts of alkali soluble resins and benzyl methacrylate, (mol ratio of methacrylic acid unit and benzyl methacrylate unit is 27:73, acid number is 83, and weight-average molecular weight is 18000) (B-1), as the dipentaerythritol acrylate (C-1) of 2.72 parts of photopolymerizable compound, as 2-methyl-2-morpholinyl-1-(the 4-methyl mercapto phenyl) propane-1-ketone (D-1) of 0.22 part of Photoepolymerizationinitiater initiater, as 0.16 part of light-initiated auxiliary agent 4,4 '-bis-(lignocaine) benzophenone (D-2), as TR-PBG-305 (buying from TRONLY) (D-3) that the following chemical formula 4 of 0.22 part of Photoepolymerizationinitiater initiater represents, as the 3-ethoxyl ethyl propionate (E-1) of 17.08 parts of solvent and the propylene glycol methyl ether acetate (E-2) of 65.63 parts, as the polyether-modified polysiloxane oil SH8400 (buying from Toray silicon company) (F-1) of 0.03 part of adjuvant and Mega packs (registered trade mark) F554 (F-2) of 0.01 part as adjuvant, and as the available from BASF of 0.14 part of projection inhibitor
(F-3) HDDA carries out mixing and disperse to prepare photosensitive composition,
[chemical formula 4]
< embodiment 2>
Use except the composition shown in table except lower, prepare photosensitive composition by the method identical with above-described embodiment 1.
< comparative example 1 to 4>
Use except the composition shown in table except lower, prepare photosensitive composition by the method identical with above-described embodiment 1.
[table 1]
(A-1) colorant: C.I. paratonere 254;
(B-1) alkali soluble resins: the multipolymer (mol ratio of methacrylic acid unit and benzyl methacrylate unit is 27:73, and acid number is 83, and weight-average molecular weight is 18000) of methacrylic acid and benzyl methacrylate;
(C-1) photopolymerizable compound: dipentaerythritol acrylate;
(D-1) light trigger: 2-methyl-2-morpholinyl-1-(4-methyl mercapto phenyl) propane-1-ketone;
(D-2) light-initiated auxiliary agent: 4,4 '-bis-(lignocaine) benzophenone;
(D-3) light trigger: TR-PBG-305 (buying from TRONLY company);
(E-1) solvent: ethyl-3-ethoxy-c acid esters;
(E-2) solvent: propylene glycol methyl ether acetate;
(F-1) surfactant: polyether-modified polysiloxane oil SH8400 (buying from Toray silicon company limited);
(F-2) surfactant: Mega packs (registered trade mark) F554 (buying from Dainippon Ink & Chemicals company limited);
(F-3) projection inhibitor: buy from BASF AG
(F-3) HDDA.
The preparation > of < colored filter
With spin-coating method, the often kind of photosensitive composition manufactured by above-described embodiment 1 to 2 and comparative example 1 to 4 is coated in glass substrate (the EAGLE XG at 2-inch angle, buy from Corning company), and placed on hot plate by this glass substrate after vacuum drying and keep 3 minutes at 100 DEG C, thus form film.Subsequently, be placed on having generation test light mask of the pattern of the transmissivity of step variation and lines/blank (line/space) pattern of 1 ~ 50 μm in the scope of 1 ~ 100% on film, and carry out UV irradiation at the interval apart from this test light mask 100 μm.Like this, use the high-pressure sodium lamp of the 1KW containing all g, h and i rays with 100mJ/cm
2dosage carry out UV irradiation, and do not use specific optical filter.The pH immersed by the film irradiated through UV as developer solution keeps 2 minutes in the KOH aqueous solution of 10.5, develops to make it.Be coated with the glass substrate of film with distilled water washing, with nitrogen drying, and heat 25 minutes at 200 DEG C in an oven, thus manufacture colored filter.
The film thickness of the colored filter of manufacture like this is 2.0 μm.For by above-mentioned prepared colored filter, assess light sensitivity, adhesiveness, developing performance and chemical resistance as follows.
< adhesiveness test >
Measured the pattern collapses degree of produced pattern according to standard below by optical microscope, and in following table 2, this result has been shown.
Zero: there is no pattern collapses
△: 1 to 3 pattern collapses
×: 4 or more pattern collapses
< projection test >
Measured pin-hole type flaw (stain) degree on the film of produced film (paint film) by optical microscope according to standard below, and in following table 2, this result has been shown.
Zero: film there is no pin-hole type flaw
△: film has 10 pin-hole type flaws
×: film there is the pin-hole type flaw more than 10
< production time per piece test >
Measure the time that dry solvent spends in vacuum drying process, and in following table 2, this result has been shown.
[table 2]
With reference to above-mentioned table 2, constructed in accordance according to embodiment 1 to 2, coloring photosensitive combination, even if also there is high light sensitivity characteristic under the pixel formation condition of low exposure dose, form the coloring film of less defect, and the surface imperfection of such as projection can not be produced in pixel portion.
In addition, adjuvant of the present invention (projection inhibitor is not used according to comparative example 2; (F), when coloring photosensitive combination), surface imperfection is created.
Not using in the situation of the coloring photosensitive combination of light trigger of the present invention (D) according to comparative example 3 and 4, adhesiveness is bad.
In addition, according to the use of comparative example 1 light trigger of the present invention (D) and adjuvant (projection inhibitor; (F)) but its coloring photosensitive combination outside preferable range of amount, adhesiveness and surface blemish good, but production time per piece is long.
Claims (16)
1. a photosensitive composition, comprise: colorant (A), alkali soluble resins (B), photopolymerizable compound (C), light trigger (D), solvent (E) and adjuvant (F)
Wherein, described light trigger (D) is the compound represented by following chemical formula 1, and described adjuvant (F) is the compound represented by following chemical formula 3:
[chemical formula 1]
[chemical formula 3]
Wherein, in described chemical formula 1, R
1represented by following chemical formula 2, R
2for the phenyl of C1 ~ C8 alkyl, replacement or unsubstituted phenyl or the benzyl replaced or unsubstituted benzyl, R
3diphenyl sulfide based or unsubstituted diphenyl sulfide based for what replace, and
In following chemical formula 2, R
4for C1 ~ C4 alkyl, and R
5for C3 ~ C8 alicyclic hydrocarbon radical or aromatic hydrocarbyl, and
In above-mentioned chemical formula 3, n is the integer of 1 ~ 12,
[chemical formula 2]
——R
4——R
5。
2. photosensitive composition according to claim 1, comprising: based on the general assembly (TW) of solid,
The described colorant (A) of 5% to 60% weight;
The described alkali soluble resins (B) of 5% to 85% weight;
The described photopolymerizable compound (C) of 5% to 50% weight;
The described light trigger (D) of 0.1% to 40% weight; And
The described adjuvant (F) of 1% to 10% weight.
3. photosensitive composition according to claim 1, wherein, described colorant (A) is for being selected from a kind of in pigment, dyestuff and natural colouring matter or the combination of two or more.
4. photosensitive composition according to claim 1, wherein, described alkali soluble resins (B) is acrylic copolymer.
5. photosensitive composition according to claim 4, wherein, described acrylic copolymer is have the monomer of carboxyl and the multipolymer of other monomer, other monomer described can with the described monomer generation interpolymerization with carboxyl.
6. photosensitive composition according to claim 5, wherein, in described alkali soluble resins (B), the content described in contained with the monomer of carboxyl is 10% to 50% weight.
7. photosensitive composition according to claim 4, wherein, described acrylic copolymer is:
(methyl) acrylic acid/(methyl) benzyl acrylate multipolymer,
(methyl) acrylic acid/(methyl) benzyl acrylate/styrol copolymer,
(methyl) acrylic acid/(methyl) methyl acrylate copolymer or
(methyl) acrylic acid/(methyl) methyl acrylate/styrol copolymer.
8. photosensitive composition according to claim 1, wherein, the mean molecular weight of the polystyrene conversion of described alkali soluble resins (B) is 5000 to 50000.
9. photosensitive composition according to claim 1, wherein, the acid number of described alkali soluble resins (B) is 50 to 150.
10. photosensitive composition according to claim 1, wherein, except by except the compound shown in described chemical formula 1, described light trigger (D) comprises at least one compound in the group being selected from and being made up of acetophenone compounds, benzoin compounds, benzophenone compound, compound in triazine class, oxime compound, bisglyoxaline compounds and thioxanthones compounds extraly.
11. photosensitive compositions according to claim 1, wherein, described light trigger (D) and light-initiated auxiliary combination use,
Wherein, described light trigger and light-initiated auxiliary agent be combined as following combination:
Diethoxy acetophenone and 4,4 '-bis-(lignocaine) benzophenone; 2-methyl-2-morpholinyl-1-(4-methyl mercapto phenyl) propane-1-ketone and 4,4 '-bis-(lignocaine) benzophenone; 2-hydroxy-2-methyl-phenyl-propane-1-ketone and 4,4 '-bis-(lignocaine) benzophenone; 2-hydroxy-2-methyl-1-[4-(2-hydroxy ethoxy) phenyl] propane-1-ketone and 4,4 '-bis-(lignocaine) benzophenone; 1-hydroxycyclohexylphenylketone and 4,4 '-bis-(lignocaine) benzophenone; The oligomer and 4 of 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] propane-1-ketone, 4 '-bis-(lignocaine) benzophenone; Or 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone and 4,4 '-bis-(lignocaine) benzophenone.
12. photosensitive compositions according to claim 11, wherein, based on the described light trigger of 1 mole, the content of contained described light-initiated auxiliary agent is 0.01 mole to 5 moles.
13. photosensitive compositions according to claim 1, wherein, based on the general assembly (TW) of described photosensitive composition, the content of contained described solvent (E) is 60% to 90% weight.
14. photosensitive compositions according to claim 1, wherein, described solvent (E) is for being selected from least one compound in ethyl-3-ethoxy-c acid esters, propylene glycol methyl ether acetate and propylene glycol monomethyl ether.
15. 1 kinds of colored filters, described colored filter utilizes the described photosensitive composition of claim 1 to manufacture.
16. 1 kinds of liquid crystal display, described liquid crystal display comprises the described colored filter of claim 15.
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| KR1020130094691A KR101526678B1 (en) | 2013-08-09 | 2013-08-09 | Colored photosensitive resin composition, color filter and liquid crystal display having the same |
| KR10-2013-0094691 | 2013-08-09 |
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| CN107817652A (en) * | 2016-09-13 | 2018-03-20 | 东友精细化工有限公司 | Photosensitive polymer combination and the photocuring pattern being produced from it |
| CN108017730A (en) * | 2016-10-31 | 2018-05-11 | 固安鼎材科技有限公司 | A kind of photoetching compositions, colored filter and preparation method thereof |
| CN110308617A (en) * | 2018-03-20 | 2019-10-08 | 东友精细化工有限公司 | Photosensitive composition, colour filter and image display device comprising it |
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| TWI639889B (en) * | 2015-12-25 | 2018-11-01 | 旭化成股份有限公司 | Photosensitive resin composition, photosensitive resin laminate, resin pattern manufacturing method, cured film pattern manufacturing method, and display device |
| KR101935380B1 (en) * | 2016-05-17 | 2019-01-07 | 마이크로크래프트코리아 주식회사 | A method of ink jet resin composition |
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| WO2009145120A1 (en) * | 2008-05-30 | 2009-12-03 | 日立化成工業株式会社 | Photosensitive resin composition, photosensitive element, method of forming resist pattern and method of producing printed wiring board |
| JP2012013734A (en) * | 2010-06-29 | 2012-01-19 | Toppan Printing Co Ltd | Red photosensitive resin composition and color filter |
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| CN101548203B (en) * | 2007-06-11 | 2012-03-07 | 三菱化学株式会社 | Photosensitive color resin composition for color filter, color filter, liquid crystal display, and organic el display |
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| CN101086619A (en) * | 2006-06-08 | 2007-12-12 | 住友化学株式会社 | Color photosensitive resin compositions |
| CN101528682A (en) * | 2006-12-27 | 2009-09-09 | 株式会社艾迪科 | Oxime ester compound and photopolymerization initiator comprising the compound |
| WO2009145120A1 (en) * | 2008-05-30 | 2009-12-03 | 日立化成工業株式会社 | Photosensitive resin composition, photosensitive element, method of forming resist pattern and method of producing printed wiring board |
| CN102754032A (en) * | 2010-03-19 | 2012-10-24 | 日立化成工业株式会社 | Photosensitive resin composition and photosensitive element using same, resist pattern formation method and printed circuit board manufacturing method |
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| CN107817652B (en) * | 2016-09-13 | 2022-03-08 | 东友精细化工有限公司 | Photosensitive resin composition and photocured pattern produced therefrom |
| CN108017730A (en) * | 2016-10-31 | 2018-05-11 | 固安鼎材科技有限公司 | A kind of photoetching compositions, colored filter and preparation method thereof |
| CN110308617A (en) * | 2018-03-20 | 2019-10-08 | 东友精细化工有限公司 | Photosensitive composition, colour filter and image display device comprising it |
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| KR101526678B1 (en) | 2015-06-05 |
| KR20150018142A (en) | 2015-02-23 |
| CN104345559B (en) | 2018-10-19 |
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