CN104007612A - Coloring photosensitive resin composite - Google Patents
Coloring photosensitive resin composite Download PDFInfo
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- CN104007612A CN104007612A CN201410049223.7A CN201410049223A CN104007612A CN 104007612 A CN104007612 A CN 104007612A CN 201410049223 A CN201410049223 A CN 201410049223A CN 104007612 A CN104007612 A CN 104007612A
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- JKNCOURZONDCGV-UHFFFAOYSA-N CC(C(OCCN(C)C)=O)=C Chemical compound CC(C(OCCN(C)C)=O)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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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- 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
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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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
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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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- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention discloses a coloring photosensitive resin composite, comprising a colorant (A), a compound alkali soluble resin (B) represented by the following chemical formula 1, a light polymerized compound (C), a photoinitiator (D) and a solvent (E). The acid value of the compound alkali soluble resin (B) is 30-150 mg KOH/g, and has high sensitivity and adhesive force, thus short circuit is difficult to generate in a developing process, and accordingly the productivity of a color filter is high and the color filter using the composite is excellent in the aspects of contrast ratio, light transmittance, chemical resistance and sensitivity. In the chemical formula 1, R1 is hydrogen or C1-6 alkyl, R2 is C1-20 alkyl, alkenyl or aryl, and R3 and R4 are independently C1-12 alkyl, alkenyl or aryl; A1 is divalent linking group and C1-4 alkyl or alkenyl; X is carboxylate radical (-COO-), sulfonic acid root (-SO3) or sulfate radical (-OSO3-).
Description
The cross reference of related application
The application requires the rights and interests of the korean patent application KR10-2013-0018678 that submits on February 21st, 2013, thereby is incorporated in the application by quoting in full.
Technical field
The present invention relates to a kind of photosensitive composition.
Background technology
In conventional liquid crystal display, with silica bead or the plastic bead with predetermined diameter, keep the preset space length between upper substrate and infrabasal plate.Yet these integuments are dispersed on substrate randomly and the situation that therefore may be arranged in pixel is problematic, because aperture (aperture) may reduce and light leak may occur.
Take and address these problems as target, the spacer forming by photoetching process has started to use in liquid crystal display.At present, the spacer using in most liquid crystal display is to form by photoetching process.
By photoetching process, forming spacer is by photosensitive composition being coated on substrate, via photomask, UV being irradiated on substrate, and uses developing process to form spacer according to the pattern of mask needed position on substrate.Therefore, after forming spacer, develop residue or dirt may be stayed in the situation in the part of the substrate not irradiated by UV, may cause the heterogencity of alignment liquid crystal displays.
Meanwhile, the recent trend improving along with throughput rate, while manufacturing liquid crystal display, introduces and is called ODF(liquid crystal and drips in advance (One Drop Fill)) technique, this technique, before the glass of slurry crystal panel, allows liquid crystal material to flow on the surface of glass.By the method, can shorten significantly and manufacture the required time period of liquid crystal display.
When the bonding tft array of routine and colored filter, use bonding load, thereby thus spacer by Load Balanced press the height homogeneous that keeps spacer.Yet, in ODF, because initial adhesion is only by carrying out based on substrate weight and atmospheric load, so the load of initial adhesion duty factor conventional method is little.Even when spacer is pressed by low load, spacer is pressed to guarantee that height homogeneous is also very important equably.When spacer has the height of non-homogeneous, the homogeneity of cell pitch can not be kept and therefore the gap in structure cell may be created in, undesirably cause non-homogeneous demonstration.The spacer that therefore, need to have flexible and high elastic modulus is to realize excellent height homogeneity.
For this reason, by adding the conventional photosensitive composition with photo-curable alkali solubility (being total to) polymers, attempted using resin combination.Korean patent application publication number 10-2010-0060562 discloses a kind of alkali soluble resins, comprises, have unsaturated double-bond monomer, there is the monomer of epoxy radicals and there is the monomer of long side chain and acidic-group as the reaction product of repetitive; But it is problematic, because low developing rate, low susceptibility and the adhesion differing from undesirably cause that pattern is separated.
[quoted passage list]
[patent documentation]
(patent documentation 1) korean patent application publication number 10-2010-0060562
Summary of the invention
Therefore, the object of this invention is to provide a kind of photosensitive composition, it has high developing rate and excellent susceptibility and adhesion, therefore and in developing process, do not have a figuratum separation, and when this photosensitive composition is applied to photoetching material for flat-panel monitor (such as column spacer, colored filter, colorama resist etc.) time, it also can show high developability and excellent susceptibility and adhesion, make in developing process, to be difficult to produce the short circuit of pattern, thereby improve the throughput rate of colored filter, wherein, use the colored filter of said composition manufacture comprising contrast, transmittance, the properties of chemical-resistant and susceptibility is all enhanced.
To achieve these goals, the invention provides a kind of photosensitive composition, comprise: colorant (A), comprise alkali soluble resins (B), optical polymerism compound (C), light trigger (D) and solvent (E) by the represented compound of Chemical formula 1 below, wherein, the acid number of described alkali soluble resins (B) is 30～150mgKOH/g
[Chemical formula 1]
In Chemical formula 1, R
1hydrogen or C1～6 alkyl; R
2c1～20 alkyl, thiazolinyl, or aryl; R
3and R
4c1～12 alkyl, thiazolinyl independently of one another, or aryl; A1 is divalent linker and is C1～4 alkyl, or thiazolinyl; And X is carboxylate radical (COO
-), sulfonate radical (SO
3 -) or sulfate radical (OSO
3 -).
Embodiment
Hereinafter, the detailed description of photosensitive composition according to the specific embodiment of the invention and preparation method thereof will be provided.
The present invention relates to photosensitive composition, comprising: substantially comprise the alkali soluble resins (B) by the represented compound of following Chemical formula 1; And comprise the colorant (A) that substantially comprises at least one pigment and at least one dyestuff; Optical polymerism compound (C); Light trigger (D); Solvent (E) or adjuvant (F), wherein, the acid number of described alkali soluble resins (B) is 30～150mgKOH/g,
[Chemical formula 1]
In Chemical formula 1, R
1hydrogen or C1～6 alkyl; R
2c1～20 alkyl, thiazolinyl, or aryl; R
3and R
4c1～12 alkyl, thiazolinyl independently of one another, or aryl; A1 is divalent linker and is C1～4 alkyl, or thiazolinyl; And X is carboxylate radical (COO
-), sulfonate radical (SO
3 -) or sulfate radical (OSO
3 -).
According to the component of composition of the present invention, be described in detail in hereinafter.
Colorant (A)
Colorant (A) comprises at least one pigment (a1) and at least one dyestuff (a2) substantially.
pigment (a1)
Pigment (a1) can comprise organic pigment usually used in this field or inorganic pigment.Organic pigment can comprise the different pigment for printing-ink, jetted ink etc., and its instantiation can comprise: water-soluble azo pigment, insoluble azo colour, phthalocyanine color, quinacridone pigment, isoindolinone pigment, isoindoline pigment, perylene dye, purple cyclic ketones pigment, triazine dioxin pigment, anthraquinone pigment, DIANTHRAQUINONE pigment, anthrapyrimidine pigment, anthanthrone pigment, indanthrone pigment, flavanthrone pigment, pyranthrone pigments, diketopyrrolo-pyrrole pigment etc.Inorganic pigment can comprise metallic compound, such as metal oxide or metal complex, and its concrete example comprises: metal oxide, and such as the oxide of iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black etc., or composite metal oxide.Particularly, organic pigment and inorganic pigment can specifically comprise the compound that is classified as pigment by color index (dyers and colorist association publish), its more specifically example can comprise, but be not necessarily limited to the pigment of following color index (C.I.) number: C.I. pigment yellow 13,20,24,31,53,83,86,93,94,109,110,117,125,137,138,139,147,148,150,153,154,166,173,180 and 185; C.I. pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65 and 71; C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,215,216,224,242,254,255 and 264; C.I. pigment violet 14,19,23,29,32,33,36,37 and 38; C.I. pigment blue 15 (15:3,15:4,15:6 etc.), 21,28,60,64 and 76, C.I. pigment Green 7,10,15,25,36,47 and 58; C.I. pigment brown 28; With C.I. pigment black 1 and 7.
These pigment (a1) can be used singly or in a combination of two or more kinds.
C.I. pigment listed above, is preferably usefully selected from C.I. pigment orange 38, C.I. pigment red 122, C.I. paratonere 166, C.I. paratonere 177, C.I. paratonere 208, C.I. paratonere 242, C.I. paratonere 254, C.I. paratonere 255, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 185, C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 58, C.I. pigment Violet 23, C.I. pigment blue 15: 3 and pigment blue 15: any pigment in 6.
About pigment, what preferably use is to make granules of pigments be dispersed in Pigments solution wherein.The example of the homodisperse method of granules of pigments can comprise the dispersion treatment of using pigment dispersing agent (a3), thereby can obtain pigment homodisperse Pigments solution in solution.
The instantiation of pigment dispersing agent can comprise: cationic surfactant, anionic surfactant, non-ionic surfactant, amphoteric surfactant, polyesters surfactant, polyamine class surfactant etc., they can be used singly or in a combination of two or more kinds.
The gross mass of the solid content based on pigment dispensing composition, the amount of pigment (a1) is 20～90 quality %, is preferably 30～70 quality %.When pigment is used with the amount based on aforesaid 20～90 quality %, can produce bin stability and the high dispersive efficiency of low viscosity, excellence, thereby effectively increase contrast.
As spreading agent (a3), can use the resin type pigment dispersing agent except acrylic dispersants.Such resin type pigment dispersing agent can comprise: known resin type pigment dispersing agent, oiliness spreading agent particularly, for example, such as (part) amine salt, the ammonium salt of poly carboxylic acid, the alkylamine salt of poly carboxylic acid, polysiloxane, long-chain polyaminoamide phosphate, the polycarboxylate of hydroxyl and the product of modification thereof of polyurethane, polycarboxylate (polyacrylate), unsaturated polyester acid amides, poly carboxylic acid, poly carboxylic acid, by the acid amides or its salt that form by poly-(low-grade alkylidene imines) and the pet reaction with free carboxy; Water soluble resin or water-soluble polymeric compounds, such as, (methyl) acrylic acid-styrol copolymer, (methyl) acrylic acid-(methyl) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol (PVA) or polyvinylpyrrolidone; Polyester, modified polyacrylate; The adduct of ethylene oxide/propylene oxide; And phosphate.The commercially available prod of resin type spreading agent described above can comprise cation type resin spreading agent, for example, DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184(are the commercially available trade name of BYK Chemie); EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800(are the commercially available trade name of BASF); SOLSPERS-24000, SOLSPERS-32550 and NBZ-4204/10(are the commercially available trade name of Lubirzol); HINOACT T-6000, HINOACT T-7000 and HINOACT T-8000(are the commercially available trade name of Kawaken Fine Chemicals); AJISPUR PB-821, AJISPUR PB-822 and AJISPUR PB-823(are the commercially available trade name of Ajinomoto); FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44(are the commercially available trade name of Kyoeisha Chemical).Resin type pigment dispersing agent except acrylic dispersants can be used singly or in a combination of two or more kinds, and can use together with acrylic dispersants.
The solid content of the pigment based on 100 mass parts (a1), the amount of pigment dispersing agent (a3) is 5～60 mass parts, is preferably 15～50 mass parts.If the amount of spreading agent (a3) surpasses 60 mass parts based on above-mentioned, viscosity may increase so.In contrast, if its amount is less than 5 mass parts, be difficult to so make pigment meticulous or after dispersion treatment, gelation may occur.
dyestuff (a2)
Dyestuff (a2) can be used and not restriction, as long as it dissolves in organic solvent.Preferably usefully in organic solvent, dissolve, and can guarantee the solubleness in alkaline-based developer, and the dyestuff of reliabilities such as thermotolerance, solvent resistance.
Dyestuff can be selected from the salt of acid dyes, acid dyes and the nitrogen-containing compound with acidic-groups such as sulfonic acid or carboxylic acid, sulfonamide product and the derivant thereof of acid dyes, and also can be selected from azo acid dye, xanthene acid dye, phthalocyanines acid dyes and derivant thereof.Dyestuff preferably includes the compound that is classified as dyestuff by color index (dyers and colorist association publish), or the known dyestuff described in dyestuff notes (Dyeing Note, Shikisensha publishes).
The instantiation of dyestuff can comprise C.I. solvent dye, and for example, orchil, such as C.I. solvent red 8,45,49,89,111,122,125,130,132,146,179; Blue dyes, such as C.I. solvent blue 5,35,36,37,44,59,67,70; Cudbear, such as C.I. solvent purple 8,9,13,14,36,37,47,49; Weld, such as C.I. solvent yellow 4,14,15,23,24,38,62,63,68,82,94,98,99,162; Orange, such as C.I. solvent orange 2,7,11,15,26,56; And green colouring material, such as C.I. solvent green 1,3,4,5,7,28,29,32,33,34,35.
In C.I. solvent dye, preferably usefully in organic solvent, there is high-dissolvability: C.I. solvent red 8,49,89,111,122,132,146,179; C.I. solvent blue 35,36,44,45,70; With C.I. solvent violet 13.And more preferably C.I. solvent red 8,122,132 usefully.
In addition, C.I. the example of acid dyes is as follows: orchil, such as C.I. azogeramine, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426, weld, such as C.I. Indian yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251, orange, such as C.I. acid orange 6,7,8,10,12,26,50,51,52,56,62,63,64,74,75,94,95,107,108,169,173, blue dyes, such as C.I. Blue VRS, 7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103,112,113,120,129,138,147,150,158,171,182,192,210,242,243,256,259,267,278,280,285,290,296,315,324:1,335,340, cudbear, such as C.I. acid violet 6B, 7,9,17,19,66, and green colouring material, such as C.I. acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106,109.
In acid dyes, C.I. acid red 92, C.I. acid blue 80,90 and the C.I. acid violet 66 in organic solvent with high-dissolvability is preferably to use.
In addition, C.I. the example of direct dyes comprises: orchil, such as C.I. direct red 79,82,83,84,91,92,96,97,98,99,105,106,107,172,173,176,177,179,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246,250, weld, such as C.I. direct yellow 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129,136,138,141, orange, such as C.I. direct orange 34,39,41,46,50,52,56,57,61,64,65,68,70,96,97,106,107, blue dyes, such as C.I. direct blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, cudbear, such as C.I. direct purple 47,52,54,59,60,65,66,79,80,81,82,84,89,90,93,95,96,103,104, and green colouring material, such as C.I. direct green 25,27,31,32,34,37,63,65,66,67,68,69,72,77,79,82.
In addition, the example of C.I. mordant dyes comprises: weld, such as C.I. medium Huang 5,8,10,16,20,26,30,31,33,42,43,45,56,61,62,65; Orchil, such as C.I. medium red 1,2,3,4,9,11,12,14,17,18,19,22,23,24,25,26,30,32,33,36,37,38,39,41,43,45,46,48,53,56,63,71,74,85,86,88,90,94,95; Orange, such as C.I. medium orange 3,4,5,8,12,13,14,20,21,23,24,28,29,32,34,35,36,37,42,43,47,48; Blue dyes, such as C.I. medium indigo plant 1,2,3,7,8,9,12,13,15,16,19,20,21,22,23,24,26,30,31,32,39,40,41,43,44,48,49,53,61,74,77,83,84; Cudbear, such as C.I. medium purple 1,2,4,5,7,14,22,24,30,31,32,37,40,41,44,45,47,48,53,58; With green colouring material such as C.I. medium green 1,3,4,5,10,15,19,26,29,33,34,35,41,43,53.
These dyestuffs can be used singly or in a combination of two or more kinds.
The general assembly (TW) of the solid content based on colorant (A), the amount of the dyestuff of colorant (A) is preferably 0.5～80wt%, more preferably 0.5～60wt%, more preferably 1～50wt%.In the time of in the amount of the dyestuff of colorant (A) falls into based on aforesaid above-mentioned scope, can prevent from occurring after pattern forms because dyestuff dissolves the problem of the reliability deterioration causing in organic solvent, and can produce high sensitive.
The weight of the solid content based on photosensitive composition, the amount of colorant (A) is set to 5～60wt%, is preferably set to 10～45wt%.The consumption of colorant (A) is that the situation based on aforesaid 5～60wt% is desirable, because even pixel portion also has sufficient color depth when forming film, and when developing, do not reduce coming off of non-pixel portion, advantageously make to be difficult to produce residual.
As used in this article, the total solid content of photosensitive composition represents that photosensitive composition desolventizes the total amount of outer composition.
Alkali soluble resins (B)
According to the acid number of alkali soluble resins of the present invention (B), be 30～150mgKOH/g, to guarantee compatibility and the bin stability of photosensitive composition.If the acid number of alkali soluble resins is less than 30mgKOH/g, photosensitive composition is difficult to guarantee sufficient developing rate so.In contrast, if its acid number, higher than 150mgKOH/g, reduces the adhesion of substrate so, make to be easy to produce the short circuit of pattern, and cause the problem relevant with compatibility and bin stability, undesirably increase viscosity.
Alkali soluble resins (B) can be provided with the form of the multipolymer of the structural unit that represented by Chemical formula 1 and at least one extra monomer.Extra monomer is not particularly limited.Preferably, alkali soluble resins (B) is with the structural unit by Chemical formula 1 with have the form of the multipolymer that at least one compound (b1) of unsaturated link forms and be provided.
The compound (b1) with unsaturated link is not particularly limited, as long as it has polymerism unsaturated double-bond.Its instantiation can comprise: have the monomer of carboxylic acid, such as (methyl) acrylic acid, the alkyl ester compound of the unsaturated carboxylic acid replacing, such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid ammonia ethyl ester etc., there is alicyclic substituent unsaturated carboxylic ester compound, such as (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic methyl cyclohexyl, (methyl) acrylic acid ring heptyl ester, (methyl) acrylic acid ring monooctyl ester, (methyl) methyl acrylate, (methyl) acrylic acid cyclopentene ester, (methyl) acrylic acid cyclohexene ester, (methyl) acrylic acid cycloheptene ester, (methyl) acrylic acid cyclooctene ester, (methyl) acrylic acid pentadiene ester, (methyl) isobornyl acrylate, (methyl) acrylic acid pinane ester, (methyl) acrylic acid diamantane ester, (methyl) acrylic acid norborneol ester, (methyl) glycidyl acrylate, (methyl) acrylic acid 3, 4-epoxy cyclohexyl, (methyl) acrylic acid 3, 4-epoxycyclohexyl methyl esters, (methyl) acrylic acid methyl ethylene oxidic ester etc., the cholesterol carbonate of glycol, such as the few glycol monoalkyl ester of (methyl) acrylic acid etc., there is the substituent unsaturated carboxylic ester compound of aromatic rings, such as (methyl) benzyl acrylate, (methyl) acrylic acid benzene oxygen ester etc., aromatic ethylene compound, such as styrene, α-methyl styrene, vinyltoluene etc., vinyl carboxylates, such as vinyl acetate, propionate etc., ethene nitrile compound, such as (methyl) vinyl cyanide, α-chloro-acrylonitrile etc., and maleimide compound, such as N-N-cyclohexylmaleimide, N-phenylmaleimide etc.
In the situation that alkali soluble resins (B) with the structural unit of Chemical formula 1 with have unsaturated link at least one compound (b1) multipolymer form and be provided, preferably, total mole of structural unit based on containing in alkali soluble resins (B), the use amount of the structural unit of Chemical formula 1 is 2～98mol%; And total mole of the structural unit based on containing in alkali soluble resins (B), the use amount with the compound (b1) of unsaturated link is 10～90mol%.
Especially, more preferably, based on total mole, the use amount of the structural unit of Chemical formula 1 is 20～70mol%; And based on total mole, the use amount with the compound (b1) of unsaturated link is 30～80mol%.
The in the situation that of in mole fraction is arranged on above-mentioned scope, developability, dissolubility and thermotolerance be by balance effectively, thereby obtain preferred multipolymer.
In addition, preparation is as follows according to the method for alkali solubility adhesive resin of the present invention.
First step is the multipolymer of preparing the monomer being represented by Chemical formula 1.
This reaction can be by being selected from any the carrying out in multiple polymerization as known in the art, such as free radical polymerization, cationic polymerization, anionic polymerisation, condensation polymerization etc., but with regard to being easy to preparation or economic benefit, free radical polymerization is most preferred.
For example, the multipolymer of expectation can be produced by this way: monomer is mixed with polymer solvent, be heated to suitable temperature, and carry out deoxygenation via nitrogen blowing.In addition, it also can be by adding radical polymerization initiator and chain-transferring agent (if desired) and keeping polymerization temperature to be produced.Consider the half life period of the temperature that depends on polymerization initiator used, can determine polymerization temperature and polymerization time in said method.
For example, 2,2 '-azoisobutyronitrile (AIBN) is 4.8 hours 70 ℃ of half-life, the polymerization time while therefore using AIBN is preferably set to 6 hours or longer.Conventionally, polymerization temperature is 50～150 ℃, and polymerization time preferably falls in the scope of 30 minutes to 48 hours.
Above-mentioned radical polymerization initiator can comprise radical polymerization initiator as known in the art, and its instantiation can comprise: 2,2 '-azoisobutyronitrile (AIBN), 2,2 '-azo two (2,4-methyl pentane nitrile), 2,2 '-azo two (4-methoxyl-2,4-methyl pentane nitrile), benzoyl peroxide, lauroyl peroxide, tert-Butyl peroxypivalate, 1,1 '-bis--(two-tert-butyl hydroperoxide) cyclohexane etc.
With chain-transferring agent, adjust weight-average molecular weight, its instantiation can comprise, but be not limited to: n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tertiary lauryl mercaptan, mercaptoacetic acid, 3-mercaptopropionic acid, α-methyl styrene dimer etc., and also can use chain-transferring agent well known in the prior art.
For the preparation of the not restriction of monomer of multipolymer, as long as it has polymerism unsaturated double-bond, its instantiation can comprise: have the monomer of carboxylic acid, such as (methyl) acrylic acid, the alkyl ester compound of the unsaturated carboxylic acid replacing, such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid ammonia ethyl ester etc., there is alicyclic substituent unsaturated carboxylic ester compound, such as (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic methyl cyclohexyl, (methyl) acrylic acid ring heptyl ester, (methyl) acrylic acid ring monooctyl ester, (methyl) methyl acrylate, (methyl) acrylic acid cyclopentene ester, (methyl) acrylic acid cyclohexene ester, (methyl) acrylic acid cycloheptene ester, (methyl) acrylic acid cyclooctene ester, (methyl) acrylic acid pentadiene ester, (methyl) isobornyl acrylate, (methyl) acrylic acid pinane ester, (methyl) acrylic acid diamantane ester, (methyl) acrylic acid norborneol ester, (methyl) glycidyl acrylate, (methyl) acrylic acid 3, 4-epoxy cyclohexyl, (methyl) acrylic acid 3, 4-epoxycyclohexyl methyl esters, (methyl) acrylic acid methyl ethylene oxidic ester etc., the cholesterol carbonate of glycol, such as the few glycol monoalkyl ester of (methyl) acrylic acid etc., there is the substituent unsaturated carboxylic ester compound of aromatic rings, such as (methyl) benzyl acrylate, (methyl) acrylic acid benzene oxygen ester etc., aromatic ethylene compound, such as styrene, α-methyl styrene, vinyltoluene etc., vinyl carboxylates, such as vinyl acetate, propionate etc., ethene nitrile compound, such as (methyl) vinyl cyanide, α-chloro-acrylonitrile etc., and maleimide compound, such as N-N-cyclohexylmaleimide, N-phenylmaleimide etc.
In the present invention, with regard to polystyrene standard, comprise that the weight average molecule of the alkali soluble resins (B) of Chemical formula 1 is 3000～100000, more preferably 5000～50000.When the weight-average molecular weight of alkali soluble resins (B) falls in above-mentioned scope, when developing, film is difficult to shrink and non-pixel portion comes off equably.
The molecular weight distribution of alkali soluble resins (B) [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] is preferably set to 1.0～6.0, and more preferably 1.3～4.0.When molecular weight distribution [Mw/Mn] falls in 1.5～6.0 scope, it is excellent that developability can become.
Optical polymerism compound (C)
Optical polymerism compound is the compound that can carry out polymerization by the effect of light trigger (D), can comprise simple function group monomer, bifunctional monomer or polyfunctional monomer.Preferably usefully bifunctional monomer or more polyfunctional monomer.
The instantiation of simple function group monomer includes, but are not limited to: nonyl phenyl carbitol acrylate, 2-hydroxyl-3-phenoxy propyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxy ethyl methacrylate, N-vinylpyrrolidone etc.
Bifunctional monomer's instantiation comprises, but be not limited to: two (acryloxy ethyl) ethers of 1,6-hexanediol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, bisphenol-A, 3-methyl pentanediol two (methyl) acrylate etc.
The instantiation of polyfunctional monomer includes, but are not limited to: trimethylolpropane tris (methyl) acrylate, ethoxylated trimethylolpropane three (methyl) acrylate, propoxylation trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, ethoxylation dipentaerythritol six (methyl) acrylate, propoxylation dipentaerythritol six (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc.
The weight of the solid content based on photosensitive composition, the consumption of optical polymerism compound (C) is 5～45wt%, and is preferably 7～45wt%.When the amount of optical polymerism compound (C) falls in the scope based on aforesaid 5～45wt%, the intensity of pixel portion or its smoothness improve.
Light trigger (D)
Light trigger (D) is used and is not particularly limited, as long as it makes optical polymerism compound (C) polymerization.Especially, from viewpoints such as polymerization property, efficiency of initiation, absorbing wavelength, value of purchase, prices, light trigger (D) preferably includes at least one compound in the group of selecting free acetophenone compounds, benzophenone compound, compound in triazine class, bisglyoxaline compounds, oxime compound and thioxanthones compounds composition.
The instantiation of acetophenone compounds can comprise: diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzyl dimethyl ketal, 2-hydroxyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-2-methylpropane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-morpholinyl propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butane-1-ketone, 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] propane-1-ketone, 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholinyl phenyl) butane-1-ketone etc.
The example of benzophenone compound comprises: benzophenone, o-benzoylbenzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 3; 3 ', 4,4 '-tetra-(t-butyl peroxy carbonyl) benzophenone, 2; 4,6-tri-methyl benzophenone etc.
The instantiation of compound in triazine class comprises: 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-of 4-piperonyl-1, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1 of 4-, 3, 5-triazine, 2, two (trichloromethyl)-6-[2-(5-methylfuran-2-yl) vinyl of 4-]-1, 3, 5-triazine, 2, two (trichloromethyl)-6-[2-(furans-2-yl) vinyl of 4-]-1, 3, 5-triazine, 2, two (trichloromethyl)-6-[2-(4-lignocaine-2-aminomethyl phenyl) vinyl of 4-]-1, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(3 of 4-, 4-Dimethoxyphenyl) vinyl]-1, 3, 5-triazine etc.
The instantiation of bisglyoxaline compounds comprises 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 '-tetra-(alkoxyl phenyl) bisglyoxaline, 2,2 '-bis-(2-chlorphenyls)-4,4 ', 5,5 '-tetra-(tri-alkoxy phenyl) bisglyoxaline, 2, two (2, the 6-dichlorophenyls)-4,4 ' of 2-, 5,5 '-tetraphenyl-1,4,4 ' of 2 '-bisglyoxaline, phenyl, 5,5 ' imidazolium compounds being replaced by alkoxy carbonyl group etc.In these united imidazoles, preferred 2,2 '-bis-(2-chlorphenyls)-4 usefully, 4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2,3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline and 2,2-two (2,6-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline.
The instantiation of oxime compound can comprise: o-ethoxy carbonyl-α-oxygen imido grpup-1-phenyl-propane-1-ketone etc., and commercially available prod, for example OXE01 and OXE02(buy from BASF).
The example of thioxanthones compounds comprises ITX, 2,4-diethyl thioxanthone, 2,4-bis-clopenthixal ketones, the chloro-4-propoxyl group of 1-thioxanthones etc.
In order to improve the susceptibility according to photosensitive composition of the present invention, light trigger (D) may further include light-initiated auxiliary agent (d2).Light-initiated auxiliary agent (d2) due to wherein contained, can have the susceptibility of further raising, thereby improve throughput rate according to photosensitive composition of the present invention.
Light-initiated auxiliary agent (d2) preferably includes choosing freely for example amines, carboxylic acid compound and have at least one in the group that the organosulfur compound of sulfydryl forms.
Amines is aromatic amine compound preferably, and the instantiation of amines comprises: aliphatic amine compound, such as triethanolamine, methyldiethanolamine, triisopropanolamine etc.; 4-dimethylaminobenzoic acid methyl esters, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, 2-dimethylaminoethyl benzoic ether, N, N-dimethyl-p-toluidine, 4,4 '-bis-(dimethylamino) benzophenone (being commonly referred to Michler's keton), 4,4 '-bis-(lignocaine) benzophenone etc.
Carboxylic acid compound is the assorted acetic acid of aromatics preferably, and its instantiation comprises: phenyl thioacetic acid, aminomethyl phenyl thioacetic acid, ethylphenyl thioacetic acid, Methylethyl phenyl thioacetic acid, 3,5-dimethylphenyl thioacetic acid, methoxyphenyl thioacetic acid, Dimethoxyphenyl thioacetic acid, chlorphenyl thioacetic acid, dichlorophenyl thioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthyl thioacetic acid, N-naphthyl glycocoll, naphthoxy acetic acid etc.
The instantiation with the organosulfur compound of sulfydryl comprises: 2-mercaptobenzothiazole, 1, two (the 3-sulfydryl butyryl acyloxy) butane, 1 of 4-, 3,5-tri-(3-sulfydryl butoxyethyl group)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-triketone, trimethylolpropane tris (3-mercaptopropionic acid ester), pentaerythrite four (3-sulfydryl butyric ester), pentaerythrite four (3-mercaptopropionic acid ester), dipentaerythritol six (3-mercaptopropionic acid ester), TEG two (3-mercaptopropionic acid ester) etc.
Based on according to the alkali soluble resins of 100 weight portions of the present invention (B) and optical polymerism compound (C), the amount of light trigger (D) can be set to 0.1～40 weight portion, is preferably 1～30 weight portion.When the amount of light trigger (D) falls in the scope of 0.1～40 weight portion, can improve the susceptibility of photosensitive composition and therefore can reduce the time shutter, thereby boost productivity and keep high-res.And, state in the use in the situation of the composition under condition, can improve intensity and the surface smoothness thereof of formed pixel portion.In addition, the solid content of the light trigger based on 100 weight portions, the use amount of light-initiated auxiliary agent should be 10～100 weight portions, and preferred 20～100 weight portions.If the amount of light-initiated auxiliary agent is less than the 10wt% of the total amount based on light trigger, can not overcome the short circuit that the susceptibility causing with dyestuff reduces relevant problem and may be easy to produce pattern in developing process so.
In the situation that in addition using light-initiated auxiliary agent (d2), based on according to the alkali soluble resins of 100 weight portions of the present invention (B) and optical polymerism compound (C), its amount can be set to 0.1～40 weight portion, is preferably 1～30 weight portion.When the amount of light-initiated auxiliary agent falls in the scope of 0.1～40 weight portion, can further improve the susceptibility of photosensitive composition, and improve the throughput rate of using the formed colored filter of above-mentioned composition.
Solvent (E)
As solvent (E), as long as it can dissolve other component comprising in photosensitive composition effectively, can use for any solvent of common photosensitive composition and be not particularly limited.Its example comprises: ether, aromatic hydrocarbons, ketone, alcohol, ester and acid amides.
The instantiation of solvent comprises: ethylene glycol monoalkyl ether, such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether etc.; Diethylene glycol dialkyl ether, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, dibutyl ethylene glycol ether etc.; Ethylene glycol alkyl ether acetic acid esters, such as methylcellosolve acetate, ethyl cellosolve acetate etc.; Aklylene glycol alkyl ether acetic acid esters, such as propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, methoxyl butylacetic acid ester, methoxyl amyl group acetic acid esters etc.; Aromatic hydrocarbons, such as benzene,toluene,xylene, 1,3,5-trimethylbenzene etc.; Ketone, such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone etc.; Alcohol, such as ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, glycerine etc.; Ester, such as 3-ethoxyl ethyl propionate, 3-methoxy methyl propionate etc.; And cyclic ester, such as gamma-butyrolacton etc.
With regard to coating and drying capacity, solvent preferably boiling point is the organic solvent of 100～200 ℃, and more preferably, can use propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, 3-ethoxyl ethyl propionate, 3-methoxy methyl propionate etc.
The above-mentioned solvent of enumerating can be used singly or in a combination of two or more kinds.Based on according to the general assembly (TW) of photosensitive composition of the present invention, the consumption of solvent can be 60～90wt%, and is preferably 70～85wt%.When the amount of solvent falls in the scope of 60～90wt%, use coating machines 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 can improve coating degree.
Adjuvant (F)
Add alternatively if desired adjuvant, the example can comprise: another kind of polymer compound, hardening agent, surfactant, adhesion promotor, antioxidant, UV absorbing agent, agglutination inhibitor etc.
The instantiation of other polymer compound can comprise: curable resin, such as epoxy resin, maleimide resin etc.; Thermoplastic resin, such as polyvinyl alcohol (PVA), polyacrylic acid, polyalkylene glycol monoalkyl ether, perfluoroalkyl acrylate, polyester, polyurethane etc.
Hardening agent is that its instantiation can comprise: epoxy compound, polyfunctional isocyanate's compound, melamine compound, oxetane compound etc. for solidifying core and improving physical strength.
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, aliphatic series except epoxy resin and brominated derivative thereof, alicyclic or aromatic ring oxygen compound, epoxidation butadiene (being total to) polymers, epoxidized isoprene (being total to) polymers, (methyl) glycidyl acrylate (being total to) polymers, triglycidyl group isocyanuric acid ester etc.
In hardening agent, the instantiation of oxetane compound can comprise: the two oxetanes of carbonic ester, the two oxetanes of dimethylbenzene, the two oxetanes of adipate, the two oxetanes of terephthalate, the two oxetanes of cyclohexane dicarboxylic acid etc.
Hardening agent may further include Curing compound, and Curing compound makes the epoxy radicals of epoxy compound and the oxetanes main chain of oxetane compound carry out ring-opening polymerization together with hardening agent.Curing compound can comprise such as polybasic carboxylic acid, polybasic acid anhydride, acid producing agent etc.Polybasic acid anhydride can comprise commercially available those as epoxy curing agent.The example of commercially available epoxy curing agent comprises: Adeka hardener EH-700(buys from Adeka), Rikacid HH(buys from New Japan Chemicals), MH-700(buys from New Japan Chemicals) etc.The above-mentioned hardening agent of enumerating can be used singly or in a combination of two or more kinds.
Surfactant can be used for further strengthening the film forming of photosensitive composition, and preferably includes fluorine class surfactant or polysiloxane-based surfactant.
Polysiloxane-based surfactant can comprise, for example, DC3PA, DC7PA, SH11PA, SH21PA, SH8400 etc. (being the commercially available trade name of Dow Corning Toray Silicone), and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 etc. (being the commercially available trade name of GE Toshiba Silicones).Fluorine class surfactant can comprise, for example, and MEGAFAC F-470, F-471, F-475, F-482, F-489 etc. (from Dainippon Ink Kagaku Kogyo, buying).The above-mentioned surfactant of enumerating can be used singly or in a combination of two or more kinds.
The instantiation of adhesion promotor can comprise: vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, APTES, 3-glycidyl ether oxygen propyl trimethoxy silicane, 3-glycidyl ether oxygen propyl methyl dimethoxysilane, 2-(3, 4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane, 3-sulfydryl propyl trimethoxy silicane, 3-isocyanate group propyl trimethoxy silicane, 3-isocyanate group propyl-triethoxysilicane etc.The above-mentioned adhesion promotor of enumerating can be used singly or in a combination of two or more kinds.The weight of the solid content based on photosensitive composition, the use amount of adhesion promotor is 0.01～10wt%, is preferably 0.05～2wt%.
The instantiation of antioxidant can comprise: 2, and 2 '-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methy phenol etc.
The instantiation of UV absorbing agent includes but not limited to: 2-(the 3-tert-butyl group-2-hydroxy-5-methyl base phenyl)-5-chlorobenzotriazole, alkoxy benzophenone etc.
The instantiation of agglutination inhibitor can comprise sodium polyacrylate etc.
Preparation is as described below according to the method for photosensitive composition of the present invention.
Particularly, the pigment of colorant (A) (a1) mixed with solvent (E) and use bowl mill by its dispersion until the mean grain size of pigment is 0.2 μ m or less.Like this, can by pigment dispersing agent (a3), alkali soluble resins (B) partly or entirely, or dyestuff (a2) mixes with solvent (E), as needs, their dissolved or dispersion.
Further by the remainder of dyestuff (a2), alkali soluble resins (B), optical polymerism compound (C) and light trigger (D) and optional adjuvant (F), and solvent (E) is added in mixed dispersion soln with the concentration of being scheduled to, thereby preparation is according to photosensitive composition of the present invention.
Below by for setting forth but be not interpreted as restriction following embodiment of the present invention and carry out more detailed description the present invention.Scope of the present invention is shown in claims, and comprises the implication that is equivalent to the record of claims and all modification within the scope of it.Except as otherwise noted, " % " providing in following examples and comparative example and " part " are all in mass.
the preparation of pigment dispensing composition
< pigment dispensing composition M1>
By make 12.0 mass parts as the C.I. pigment blue 15 of pigment with bowl mill: 6,4.0 mass parts are buied from BYK as the DISPERBYK-2001(of pigment dispersing agent) and the solvent being formed by the propylene glycol methyl ether acetate of 44 mass parts and the propylene glycol monomethyl ether of 40 mass parts mix/disperse and within 12 hours, prepare Pigments solution M1.
synthesizing of alkali soluble resins
(1) compound of Chemical formula 1 (M2 and M3) is synthetic
The synthetic > of <M2
The tetrahydrofuran of the compound of 33.96 parts 1 and 500 parts is added in the four neck round-bottomed flasks of being furnished with condenser and stirrer, and under agitation add the PS of 31.6 parts.The internal temperature of reactor is elevated to 50 ℃, and continues reaction 48 hours.Generated white depositions, by filtration under diminished pressure, carried out separation, then at room temperature carried out vacuum drying, thereby obtained the white product M2(productive rate 80% of 48.28 parts).
1H-NMR（300MHz，DMSO-d
6）：1.93(3H，CH
3)，2.31(2H?CH
2)，3.23(2H，CH
2)，3.31(6H，2CH
3N)，3.40(2H)，3.51(2H，CH
2)，4.59(2H，CH
2)，5.58(1H)，6.15(1H)。
The synthetic > of <M3
The tetrahydrofuran of the compound of 33.96 parts 1 and 500 parts is added in the four neck round-bottomed flasks of being furnished with condenser and stirrer, and under agitation add the beta-propiolactone of 18.68 parts.At room temperature reaction is proceeded to 24 hours.Generated white depositions, by filtration under diminished pressure, carried out separation, then at room temperature carried out vacuum drying, thereby obtained the white product M3(productive rate 86% of 42.59g).
1H-NMR(300MHz，DMSO-d
6)：1.92(3H，CH
3)，2.85(2H，CH
2)，3.30(6H，2CH
3N)，3.51(2H)，3.57(2H，CH
2)，4.60(2H，CH
2)，5.59(1H)，6.16(1H)。
(2) alkali soluble resins is synthetic
[synthesis example 1]
The n-dodecyl mercaptan of the propylene glycol methyl ether acetate of 120 parts, the propylene glycol monomethyl ether, the AIBN of 2 parts, the M2 of 20 parts, the methyl methacrylate of 15 parts, the 4-methyl styrene of 30 parts, the benzyl methacrylate of 25 parts, the methacrylic acid of 10 parts of 80 parts and 3 parts is added be furnished with stirrer, in the flask of thermometer, reflux condenser, dropping liquid divider and nitrogen gas supply pipe, and with the inside of nitrogen blowing flask., stir the potpourri that obtain, the temperature of reaction mixture is increased to 80 ℃, and reaction is carried out 8 hours thereafter.Then, the temperature of reaction solution is reduced to room temperature.The acid number of the solid content of so synthetic alkali soluble resins is 67.2mgKOH/g, and its weight-average molecular weight (Mw) of being measured by gel permeation chromatography (GPC) is approximately 12560.
[synthesis example 2]
The n-dodecyl mercaptan of the propylene glycol methyl ether acetate of 120 parts, the propylene glycol monomethyl ether, the AIBN of 1.8 parts, the M2 of 30 parts, the methyl methacrylate of 15 parts, the 4-methyl styrene of 25 parts, the benzyl methacrylate of 15 parts, the methacrylic acid of 15 parts of 80 parts and 3 parts is added be furnished with stirrer, in the flask of thermometer, reflux condenser, dropping liquid divider and nitrogen gas supply pipe, and with the inside of nitrogen blowing flask., stir the potpourri that obtain, the temperature of reaction mixture is increased to 80 ℃, and reaction is carried out 8 hours thereafter.Then, the temperature of reaction solution is reduced to room temperature.The acid number of the solid content of so synthetic alkali soluble resins is 100.5mgKOH/g, and is approximately 15940 by its Mw of gpc measurement.
[synthesis example 3]
The n-dodecyl mercaptan of the propylene glycol methyl ether acetate of 120 parts, the propylene glycol monomethyl ether, the AIBN of 2 parts, the M3 of 10 parts, the methyl methacrylate of 15 parts, the 4-methyl styrene of 37 parts, the benzyl methacrylate of 25 parts, the methacrylic acid of 13 parts of 80 parts and 3 parts is added be furnished with stirrer, in the flask of thermometer, reflux condenser, dropping liquid divider and nitrogen gas supply pipe, and with the inside of nitrogen blowing flask., stir the potpourri that obtain, the temperature of reaction mixture is increased to 80 ℃, and reaction is carried out 8 hours thereafter.Then, the temperature of reaction solution is reduced to room temperature.The acid number of the solid content of so synthetic alkali soluble resins is 96.3mgKOH/g, and is approximately 13580 by its Mw of gpc measurement.
[synthesis example 4]
The n-dodecyl mercaptan of the propylene glycol methyl ether acetate of 120 parts, the propylene glycol monomethyl ether, the AIBN of 2 parts, the M3 of 20 parts, the methyl methacrylate of 15 parts, the 4-methyl styrene of 38 parts, the benzyl methacrylate of 15 parts, the methacrylic acid of 12 parts of 80 parts and 3 parts is added be furnished with stirrer, in the flask of thermometer, reflux condenser, dropping liquid divider and nitrogen gas supply pipe, and with the inside of nitrogen blowing flask., stir the potpourri that obtain, the temperature of reaction mixture is increased to 80 ℃, and reaction is carried out 8 hours thereafter.Then, the temperature of reaction solution is reduced to room temperature.The acid number of the solid content of so synthetic alkali soluble resins is 80.2mgKOH/g, and is approximately 12550 by its Mw of gpc measurement.
[synthesis example 5]
The n-dodecyl mercaptan of the propylene glycol methyl ether acetate of 120 parts, the propylene glycol monomethyl ether, the AIBN of 2 parts, the M2 of 5.0 parts, the 4-methyl styrene of 55.0 parts, the benzyl methacrylate of 20 parts, the methyl methacrylate of 20 parts of 80 parts and 3 parts is added be furnished with stirrer, in the flask of thermometer, reflux condenser, dropping liquid divider and nitrogen gas supply pipe, and with the inside of nitrogen blowing flask., stir the potpourri that obtain, the temperature of reaction mixture is increased to 80 ℃, and reaction is carried out 8 hours thereafter.The acid number of the solid content of so synthetic alkali soluble resins is 17.4mgKOH/g, and is approximately 17370 by its Mw of gpc measurement.
[synthesis example 6]
The n-dodecyl mercaptan of the propylene glycol methyl ether acetate of 120 parts, the propylene glycol monomethyl ether, the AIBN of 2 parts, the M2 of 60.0 parts, the 4-methyl styrene of 10.0 parts, the benzyl methacrylate of 10 parts, the methyl methacrylate of 10 parts of 80 parts and 3 parts is added be furnished with stirrer, in the flask of thermometer, reflux condenser, dropping liquid divider and nitrogen gas supply pipe, and with the inside of nitrogen blowing flask., stir the potpourri that obtain, the temperature of reaction mixture is increased to 80 ℃, and reaction is carried out 8 hours thereafter.The acid number of the solid content of so synthetic alkali soluble resins is 172.3mgKOH/g, and is approximately 11874 by its Mw of gpc measurement.
With GPC, measure under the following conditions weight-average molecular weight (Mw) and the number-average molecular weight (Mn) of binder polymer.
Device: HLC-8120GPC(buys from Tosoh);
Post: TSK-GELG4000HXL+TSK-GELG2000HXL(series connection);
Column temperature: 40 ℃;
Mobile phase solvent: tetrahydrofuran;
Flow velocity: 1.0ml/min;
Injection volume: 50 μ l;
Detecting device: RI;
Measure sample concentration: 0.6wt%(solvent=tetrahydrofuran);
The standard material of proofreading and correct: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500(buys from Tosoh).
The ratio of the Mw so obtaining and Mn is set to molecular weight distribution (Mw/Mn).
the preparation of photosensitive composition
< embodiment 1>
By by the pigment dispensing composition M1 of 22.50 parts, the C.I. solvent blue 44(trade name of 0.3 part: VALIFAST BLUE2620, buy from Orient Kagaku Kogyo Kabushiki Kaisha), the resin of the synthesis example 1 of 16.5 parts, the KAYARAD DPHA(of 5.0 parts buy from Nippon Kayaku), the Irgacure907(of 0.3 part buys from BASF), the OXE-01(of 0.7 part buys from BASF), the propylene glycol methyl ether acetate of 20.5 parts and the propylene glycol monomethyl ether of 34.0 parts mix to prepare photosensitive composition.
< embodiment 2>
Except the resin that the alkali soluble resins of the synthesis example 2 with 16.5 parts replaces using in embodiment 1, in the mode identical with embodiment 1, prepare photosensitive composition.
< embodiment 3>
Except the resin that the alkali soluble resins of the synthesis example 3 with 16.5 parts replaces using in embodiment 1, in the mode identical with embodiment 1, prepare photosensitive composition.
< embodiment 4>
Except the resin that the alkali soluble resins of the synthesis example 4 with 16.5 parts replaces using in embodiment 1, in the mode identical with embodiment 1, prepare photosensitive composition.
< comparative example 1>
Except the resin that the alkali soluble resins of the synthesis example 5 with 16.5 parts replaces using in embodiment 1, in the mode identical with embodiment 1, prepare photosensitive composition.
< comparative example 2>
Except the resin that the alkali soluble resins of the synthesis example 6 with 16.5 parts replaces using in embodiment 1, in the mode identical with embodiment 1, prepare photosensitive composition.
< test case >
test case 1: the assessment of adhesion and developing rate
With the photosensitive composition that comprises alkali soluble resins of embodiment 1～4 and comparative example 1～2, manufacture colored filter.
Particularly, with spin-coating method, every kind of photosensitive composition is coated on the glass substrate (EAGLE XG, buys from Corning) of 2 inches, and this glass substrate is placed on heating plate and at 100 ℃ and is kept 3 minutes, thereby form film.Subsequently, by having, transmittance is placed on film in 1～100% scope with the test light mask of the pattern of step-wise manner change and lines/space pattern of 1～50 μ m, and is carrying out UV irradiation apart from the interval of this test light mask 100 μ m.Like this, use the high-pressure sodium lamp of the 1KW that contains g, h and all rays of i with 100mJ/cm
2dosage carry out UV irradiation, and do not use specific optical filter.In the KOH aqueous solution that it is 10.5 that film that UV was irradiated immerses as the pH of developer solution 2 minutes, thus make its development.The glass substrate that is coated with film with distilled water washing, is dried with nitrogen, and is heated 25 minutes in the baking oven of 200 ℃, thereby manufactures colored filter.The film thickness of the colored filter of so manufacturing is 2.0 μ m.
Use the colored filter of so manufacturing to carry out following assessment.
[assessment of adhesion]
Use the formed pattern of observation by light microscope, and assess by the number of the defect that causes due to pattern perk.The results are shown in table 1 below.
O: pattern-free defect
△: 1～3 pattern defect
X:4 or more pattern defects
[assessment of developing rate]
The colored filter that use is manufactured in the mode identical with test case 1, when developing, measure non-exposed portion is dissolved in to developing solution completely in the required time.The results are shown in table 1 below.
test case 2: the measurement of contrast
Except not having use test photomask, use the colored filter of manufacturing in the mode identical with test case 1 to measure contrast.
Measure in the following manner contrast: the substrate of above-mentioned colored filter is inserted between two deflectors (deflector), when using fluorescent light (wavelength 380～780nm) that post deflection device is illuminated, make front deflector rotation, use CS-2000 nitometer (buying from Konica Minolta) measure through maximal value and the minimum value of light intensity, and calculate contrast by minimum value except maximal value.Use tintmeter (OSP-200 buys from Olympus) to measure transmittance.The results are shown in table 1 below.
test case 3: the assessment of chemical-resistant
At room temperature the colored filter manufactured in the mode identical with test case 1 is immersed in nmp solution 30 minutes, with ultrapure water, clean and be heated on the hot plate of 120 ℃ dry 2 minutes, and before immersing and afterwards its color is assessed.Like this, change color (△ E*ab) be 3.0 or less situation be judged as O, and change color be 3.0 or larger situation be judged as X.The results are shown in table 1 below.
test case 4: the assessment of susceptibility
The colored filter that use is manufactured in the mode identical with test case 1, (film thickness * 100 afterwards of film thickness/developments before developing) be 90% or minimum exposure amount when larger by susceptibility, represented.The results are shown in table 1 below.
[table 1]
| Composition | Developing rate | Contrast | Adhesion | Chemical-resistant | Susceptibility |
| Embodiment 1 | 26 | 5874 | O | O | 20 |
| Embodiment 2 | 30 | 5885 | O | O | 15 |
| Embodiment 3 | 25 | 5875 | O | O | 20 |
| Embodiment 4 | 23 | 5860 | O | O | 35 |
| Comparative example 1 | 65 | 5815 | O | X | 35 |
| Comparative example 2 | 15 | 5865 | X | X | 40 |
As apparent from Table 1, according to of the present invention, comprise that the photosensitive composition of alkali soluble resins is excellent on developing rate, contrast, adhesion, chemical-resistant and susceptibility.
As described above, the invention provides a kind of photosensitive composition.According to the present invention, photosensitive composition comprises containing and can in molecule, form the adhesive resin of the monomer of salt, thereby realizes the colored filter that the homogeneous of dyestuff in photosensitive composite disperses and obtain having high reliability.Therefore, photosensitive composition according to the present invention is good on susceptibility and adhesion, thereby makes in developing process, to be difficult to produce pattern short circuit, thereby and the throughput rate of colored filter uprise.In addition, using the colored filter of this composition manufacturing is being excellent aspect contrast, transmittance, chemical-resistant and susceptibility.
Although disclose for illustrative purposes the preferred embodiment of the present invention, skilled person will appreciate that and can carry out multiple modification, interpolation and replacement, and do not deviate from as disclosed scope and spirit of the present invention in claims.
Claims (6)
1. a photosensitive composition, comprise: colorant (A), comprise alkali soluble resins (B), optical polymerism compound (C), light trigger (D) and solvent (E) by the represented compound of Chemical formula 1 below, wherein, the acid number of described alkali soluble resins (B) is 30～150mgKOH/g
[Chemical formula 1]
In Chemical formula 1, R
1hydrogen or C1～6 alkyl; R
2c1～20 alkyl, thiazolinyl, or aryl; R
3and R
4c1～12 alkyl, thiazolinyl independently of one another, or aryl; A1 is divalent linker and is C1～4 alkyl, or thiazolinyl; And X is carboxylate radical (COO
-), sulfonate radical (SO
3 -) or sulfate radical (OSO
3 -).
2. photosensitive composition according to claim 1 wherein, based on total mole of described alkali soluble resins (B), is 2～100mol% by the use amount of the represented described compound of Chemical formula 1.
3. photosensitive composition according to claim 1, wherein, described alkali soluble resins (B) is by Chemical formula 1 represented described compound and the multipolymer with the ethylenically unsaturated monomer of carboxyl.
4. photosensitive composition according to claim 3, wherein, described in there is carboxyl ethylenically unsaturated monomer be methyl methacrylate.
5. photosensitive composition according to claim 1, wherein, described colorant (A) comprises at least one pigment and at least one dyestuff.
6. photosensitive composition according to claim 1, further comprises adjuvant (F).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130018678A KR20140104768A (en) | 2013-02-21 | 2013-02-21 | Colored photosensitive resin composition comprising the same |
| KR10-2013-0018678 | 2013-02-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104007612A true CN104007612A (en) | 2014-08-27 |
Family
ID=51368340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410049223.7A Pending CN104007612A (en) | 2013-02-21 | 2014-02-12 | Coloring photosensitive resin composite |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20140104768A (en) |
| CN (1) | CN104007612A (en) |
| TW (1) | TW201433581A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016117873A (en) * | 2014-12-23 | 2016-06-30 | ベーイプシロンカー−シェミー ゲーエムベーハーBYK−Chemie GmbH | Colorant composition including dispersant together with water soluble pigment affinity group |
| CN107219726A (en) * | 2017-06-27 | 2017-09-29 | 浙江福斯特新材料研究院有限公司 | A kind of resin combination and purposes |
| JP2019066737A (en) * | 2017-10-03 | 2019-04-25 | 東洋インキＳｃホールディングス株式会社 | Color filter coloring composition and color filter |
| JP2019095548A (en) * | 2017-11-21 | 2019-06-20 | 東洋インキＳｃホールディングス株式会社 | Color filter coloring composition and color filter |
| CN116144233A (en) * | 2023-01-08 | 2023-05-23 | 珦盛新材料(珠海横琴)股份有限公司 | Photosensitive dry film coating, preparation method thereof and photosensitive dry film |
| WO2023245625A1 (en) * | 2022-06-24 | 2023-12-28 | 深圳市邦得凌半导体材料有限公司 | Dispersion resin, method for preparing same, and photoresist composition |
-
2013
- 2013-02-21 KR KR1020130018678A patent/KR20140104768A/en not_active Application Discontinuation
-
2014
- 2014-02-12 CN CN201410049223.7A patent/CN104007612A/en active Pending
- 2014-02-21 TW TW103105823A patent/TW201433581A/en unknown
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016117873A (en) * | 2014-12-23 | 2016-06-30 | ベーイプシロンカー−シェミー ゲーエムベーハーBYK−Chemie GmbH | Colorant composition including dispersant together with water soluble pigment affinity group |
| CN107219726A (en) * | 2017-06-27 | 2017-09-29 | 浙江福斯特新材料研究院有限公司 | A kind of resin combination and purposes |
| CN107219726B (en) * | 2017-06-27 | 2020-07-28 | 浙江福斯特新材料研究院有限公司 | Resin composition and application |
| JP2019066737A (en) * | 2017-10-03 | 2019-04-25 | 東洋インキＳｃホールディングス株式会社 | Color filter coloring composition and color filter |
| JP2019095548A (en) * | 2017-11-21 | 2019-06-20 | 東洋インキＳｃホールディングス株式会社 | Color filter coloring composition and color filter |
| WO2023245625A1 (en) * | 2022-06-24 | 2023-12-28 | 深圳市邦得凌半导体材料有限公司 | Dispersion resin, method for preparing same, and photoresist composition |
| CN116144233A (en) * | 2023-01-08 | 2023-05-23 | 珦盛新材料(珠海横琴)股份有限公司 | Photosensitive dry film coating, preparation method thereof and photosensitive dry film |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20140104768A (en) | 2014-08-29 |
| TW201433581A (en) | 2014-09-01 |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C53 | Correction of patent for invention or patent application | ||
| CB02 | Change of applicant information |
Address after: Jeonbuk, South Korea Applicant after: Tongwoo Fine Chemicals Co., Ltd. Address before: Jeonbuk, South Korea Applicant before: Dongwoo Fine Chem Co Ltd |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: DONGWOO FINE-CHEM CO., LTD. TO: TONGWOO FINE CHEMICALS CO., LTD. |
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| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140827 |