WO2013115268A1 - 着色感光性組成物、ブラックフォトスペーサー、及びカラーフィルター - Google Patents
着色感光性組成物、ブラックフォトスペーサー、及びカラーフィルター Download PDFInfo
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- WO2013115268A1 WO2013115268A1 PCT/JP2013/052082 JP2013052082W WO2013115268A1 WO 2013115268 A1 WO2013115268 A1 WO 2013115268A1 JP 2013052082 W JP2013052082 W JP 2013052082W WO 2013115268 A1 WO2013115268 A1 WO 2013115268A1
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229940110337 pigment blue 1 Drugs 0.000 description 1
- 229940099800 pigment red 48 Drugs 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- HWWXSNHZGYWXEE-UHFFFAOYSA-N propyl 2-prop-2-enoylperoxycarbonylbenzoate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OOC(=O)C=C HWWXSNHZGYWXEE-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
Definitions
- the present invention relates to a colored photosensitive composition and the like.
- a colored photosensitive composition preferably used for forming a black photo spacer in a color filter such as a liquid crystal display, a black photo spacer formed using the colored photosensitive composition, and a color including the black photo spacer Regarding filters.
- Liquid crystal display utilizes the property that the arrangement of liquid crystal molecules is switched by turning on / off the voltage to the liquid crystal.
- each member constituting the LCD cell is often formed using a photosensitive composition typified by photolithography.
- the range of application of the photosensitive composition tends to further expand in the future because it is easy to form a fine structure and it is easy to process a substrate for a large screen.
- Patent Document 1 describes that a spacer is made light-shielding.
- a coloring agent including ordinary pigment in the photosensitive composition, curable spacer layer by a decrease in the clear component as the addition of a colorant
- Patent Document 2 discloses that spacer shapes and steps having different desired heights can be realized by controlling the exposure amount and the remaining film ratio.
- Patent Document 2 relates to a spacer to which no pigment is added, and when applied to the batch formation of colored spacers to which a pigment is added, the pigment absorbs light in the ultraviolet region contributing to photopolymerization, and thus the light transmittance of the opening. It has been found that a pattern having a small amount has poor curability, and it is difficult to achieve characteristics such as desired spacer shape and step difference in height and adhesion to a substrate.
- a main object of the present invention is a method of collectively forming different black photospacer height by photolithography, after securing the light shielding property and a voltage holding ratio of the liquid crystal, can control the shape or steps,
- An object of the present invention is to provide a colored photosensitive composition capable of forming a black photospacer excellent in adhesion to a substrate.
- Another object of the present invention is to provide a black photospacer formed from such a colored photosensitive composition.
- Still another object of the present invention is to provide a color filter having such a black photo spacer.
- the present inventors have found that the above problems can be solved by using a specific pigment as a colorant, and have completed the present invention. That is, the gist of the present invention is as follows.
- a colored photosensitive composition containing a pigment, a binder resin, a photopolymerizable monomer, and a photopolymerization initiator, wherein the pigment contains a pigment shown in (A) below and a pigment shown in (B) Photosensitive composition.
- the pigment is C.I. I. Pigment orange 64 and C.I. I.
- the pigment is C.I. I.
- pigment types having different light absorption characteristics are appropriately combined to ensure a balance between light absorption in the ultraviolet region and visible region.
- the light shielding property and the voltage holding ratio of the liquid crystal it is possible to control the shape and the level difference and realize high adhesion with the substrate.
- Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of the embodiments of the present invention, and the present invention does not exceed the gist thereof. It is not limited to the contents of.
- (meth) acryl and the like mean “at least one of acryl and methacryl”, and “(meth) acrylate” and the like mean “at least one of acrylate and methacrylate”.
- Etc. and “(meth) acrylic acid” means “at least one of acrylic acid and methacrylic acid”. The same applies to “(meth) acryloyl”.
- (acid) anhydride” and “(anhydrous)... Acid” mean that both an acid and its anhydride are included.
- total solid content means all components other than the solvent components described later, which are contained in the colored photosensitive composition or the pigment dispersion.
- a weight average molecular weight refers to the weight average molecular weight (Mw) of standard polystyrene conversion by GPC (gel permeation chromatography).
- C.I.” means a color index (c.I.).
- the “amine value” means an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the amount of base and the equivalent weight of KOH per 1 g of the solid content of the dispersant. is there. The measuring method will be described later.
- the “acid value” represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.
- the term “monomer” means a so-called high-molecular substance and includes a dimer, a trimer, an oligomer and the like in addition to a monomer (monomer) in a narrow sense.
- the colored photosensitive composition of the present invention includes a pigment, a binder resin, a photopolymerizable monomer, and a photopolymerization initiator, and includes the following (A) and (B) as the pigment: In particular, it is preferably used as a colored photosensitive composition for collectively forming black photo spacers having different heights by photolithography.
- A C.I. I. Pigment orange 43, C.I. I. Pigment orange 64, and C.I. I. One selected from the group consisting of CI Pigment Orange 72
- B C.I. I. Pigment Blue 60
- the exposure mask has a light shielding layer that blocks light transmission and a plurality of openings that transmit light, and the average light transmittance of some openings is smaller than the average light transmittance of other openings.
- a method of using is known. This has a light shielding layer (light transmittance of 0%) and a plurality of openings, and has the highest average light transmittance (usually light transmittance of 100%, hereinafter referred to as “completely transmissive opening”). And using an exposure mask having an opening having a small average light transmittance (average light transmittance exceeding 0% and less than 100%, preferably exceeding 5% and less than 50%, hereinafter referred to as “intermediate transmission opening”). is there.
- the degree of cure of the formed pattern depends on the difference in average light transmittance between the intermediate transmission opening and the complete transmission opening, that is, the difference in exposure amount. Differences can be made, and then black photo spacers of different heights can be formed through development and thermosetting processes.
- Pigment refers to one that colors the colored photosensitive composition of the present invention.
- various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used.
- organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, perylene, and various inorganic pigments can be used. is there.
- the colored photosensitive composition of the present invention contains the following (A) and (B) as essential components as pigments.
- the pigment to be used is not particularly limited, except that it contains the above-mentioned (A) and (B) as essential components, and it depends on the mixing of each color such as red, green, and blue.
- a black color material can be used.
- black pigments, other inorganic or organic pigments, and dyes can be appropriately selected and used in combination.
- C.I. I. Pigment Red 48 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 179, 209, 224, 254.
- C.I. I. And CI Pigment Red 254 (R254).
- C.I. I. Pigment Blue 1 As blue pigment, C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. And CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, and 15: 6.
- Green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.
- ⁇ As yellow pigment C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183,
- C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.
- C.I. I. Pigment Orange 1 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79.
- black pigments examples include perylene black (BA0084, K0084, K0086), cyanine black, first black HB (CI. 26150), Irgaphor Black S 0100 CF (BASF), carbon black, and titanium black. it can.
- Examples of commercially available carbon black include the following brands. Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45 , # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31 Degussa: Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex
- Examples of commercially available titanium black include the following brands. Mitsubishi Materials Corporation: 10S, 12S, 13R, 13M, 13M-C, 14M, 15M, L-15M, etc. Akaho Kasei Co., Ltd .: TilacD M, M-50, M-50A, M-AM, V, UV-3 , UV-6, F, S, C, X, etc.
- the colored photosensitive composition of the present invention includes C.I. as a pigment from the viewpoint of light shielding properties, voltage holding ratio of liquid crystal, control of shape and level difference, and adhesion to a substrate.
- C.I. as a pigment from the viewpoint of light shielding properties, voltage holding ratio of liquid crystal, control of shape and level difference, and adhesion to a substrate.
- I. Pigment orange 64 and C.I. I. Pigment Blue 60 is preferably included.
- the colored photosensitive composition of the present invention may further contain C.I. I. Pigment red 254, C.I. I. Pigment violet 23, and C.I. I. It is preferable to include one selected from the group consisting of CI Pigment Violet 29.
- the colored photosensitive composition of the present invention has, as a pigment, the following (1) to (1) to the following to improve the light shielding property, the voltage holding ratio of liquid crystal, the control of shape and level difference, and the adhesion to the substrate. It is preferable to include the three types of pigments shown in any one of (3), and in particular, from the viewpoint of the voltage holding ratio of the liquid crystal, it is preferable to include the three types of pigments shown in (1) or (2). (1) C.I. I. Pigment orange 64, C.I. I. Pigment blue 60, C.I. I. Pigment Red 254 (2) C.I. I. Pigment orange 64, C.I. I. Pigment blue 60, C.I. I. Pigment Violet 29 (3) C.I. I. Pigment orange 64, C.I. I. Pigment blue 60, C.I. I. Pigment Violet 23
- the proportion of the pigment in the colored photosensitive composition of the present invention is usually 5 to 50% by weight, preferably 10 to 45% by weight, more preferably 20 to 42% by weight, based on the total solid content. If there is more pigment than this range, the spacer shape and level difference, adhesion to the substrate may deteriorate, or the curable component may decrease and the pigment etc. may elute into the liquid crystal layer may cause a decrease in voltage holding ratio. is there. On the other hand, if it is less than this range, sufficient light shielding properties as a black photo spacer may not be ensured.
- the ratio of (A) and (B) in the pigment may be either too much or too little, and the light shielding property and voltage holding ratio, shape, and level difference of the liquid crystal according to the present invention by using these in combination. Control and the effect of improving the adhesion to the substrate may not be sufficiently obtained, so that (A) is 25 to 70 wt% with respect to 100 wt% of (A) and (B) in total. %, Particularly 30 to 60% by weight, especially 35 to 60% by weight. That is, in (A), the absorption of light in the vicinity of wavelengths from 330 nm to 380 nm is relatively small, and the absorption of light in the vicinity of wavelengths from 400 nm to 550 nm is large.
- the pigment used in the present invention may contain various pigments other than (A) and (B).
- the total proportion of (A) and (B) in the total 100% by weight of the pigments contained in the colored photosensitive composition of the present invention is 50% by weight or more, particularly 60 to 95% by weight, especially 70 to 90%. It is preferable that it is weight%.
- (A) in a total of 100% by weight of (A), (B) and R254, (A) is 20 to 40% by weight, (B) is 45 to 65% by weight, R254 is 5 to 25% by weight, In particular, it is preferable to use (A) in a proportion of 25 to 35% by weight, (B) in a proportion of 50 to 60% by weight, and R254 in a proportion of 10 to 20% by weight.
- pigments other than (A), (B) and R254 may be used, the total ratio of (A), (B) and R254 in all pigments in the colored photosensitive composition is 70% by weight or more, In particular, it is preferably used so as to be 90 to 100% by weight.
- (A) is 30 to 50% by weight
- (B) is 30 to 50% by weight
- V23 is 10 to 30% by weight
- (B) in a proportion of 35 to 45% by weight
- V23 in a proportion of 15 to 25% by weight.
- pigments other than (A), (B), and V23 may be used, the total ratio of (A), (B), and V23 in all pigments in the colored photosensitive composition is 70% by weight or more. In particular, it is preferably used in an amount of 90 to 100% by weight.
- (A) is 30 to 50% by weight
- (B) is 30 to 50% by weight
- V29 is 10 to 30% by weight
- (B) in a proportion of 35 to 45% by weight
- V29 in a proportion of 15 to 25% by weight.
- pigments other than these (A), (B), and V29 may be used, the total ratio of (A), (B), and V29 in all pigments in the colored photosensitive composition is 70% by weight or more. In particular, it is preferably used in an amount of 90 to 100% by weight.
- the pigments used in the present invention are (A) and (B), and C.I. I. Pigment Red 272 (R272) is preferably included. Since R272 has a large absorption in the visible region, it is advantageous for high OD. *
- the binder resin used in the colored photosensitive composition of the binder resin present invention if the resin member used for the color filter can be used without particular limitations, epoxy acrylate examples based resin, novolac resin , Polyvinyl phenol resin, acrylic resin, carboxyl group-containing epoxy resin, carboxyl group-containing urethane resin, etc., from the viewpoint of shape and step control, adhesion to the substrate, epoxy acrylate resin having a carboxyl group, It is preferable to use an acrylic resin, and it is more preferable to use an epoxy acrylate resin having a carboxyl group.
- the above-mentioned epoxy acrylate resin means that an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin (or epoxy compound), and further a polybasic It is synthesized by reacting an acid or its anhydride.
- an epoxy resin or epoxy compound
- Such a reaction product has substantially no epoxy group in terms of chemical structure and is not limited to “acrylate”, but epoxy resin (or epoxy compound) is a raw material, and “acrylate” is representative. Since it is an example, it is named in this way according to common usage.
- the raw material epoxy resin includes (o, m, p-) cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, or Examples thereof include epoxy resins (or epoxy compounds) represented by the general formulas (1-a) to (1-a ′ ′′) described.
- the particularly preferable binder resin in the present invention will be described below.
- One particularly preferable binder resin in the present invention is a reaction product of an epoxy compound (a ′′) represented by the following general formula (1-a ′′) and an unsaturated group-containing carboxylic acid (b ′′). And an alkali-soluble resin (A ′′) obtained by reacting at least one of a polybasic acid and its anhydride (c ′′).
- X represents a linking group represented by the following general formula (2a), (2b) or (3).
- adamantane structures are included in the molecular structure.
- l represents an integer of 2 or 3.
- R 1 to R 4 and R 13 to R 15 each independently have an adamantyl group optionally having a substituent, a hydrogen atom, and a substituent. And an optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted phenyl group.
- R 5 to R 12 may each independently have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a substituent.
- Y represents a divalent linking group containing an adamantane structure, which may have a substituent.
- * represents a bonding site with the glycidyloxy group in the general formula (1-a ′′).
- Epoxy compound (a ′′) represented by general formula (1-a ′′) First, the group X in the epoxy compound (a ′′) represented by the general formula (1-a ′′) (hereinafter sometimes referred to as “component (a ′′)”) will be described.
- the general formulas (2a) and (2b) each have an adamantane structure of 2 or more and 4 or less.
- the adamantane structure is 1, the developer resistance tends to decrease and the resolution tends to be inferior.
- Y in the general formula (3) is “a divalent linking group including an adamantyl structure which may have a substituent”. If it is, there is no restriction
- the epoxy compound (a ′′) represented by the general formula (1-a ′′) is preferably represented by the following general formula (6) or (7).
- the adamantane ring represented by the general formula (6) and the adamantyl group represented by (7) may have a substituent.
- R 16 to R 23 each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted phenyl group. Indicates a group.
- R 24 and R 25 are each independently an adamantyl group which may have a substituent, a hydrogen atom, or an alkyl group having 1 to 12 carbon atoms which may have a substituent. Or a phenyl group which may have a substituent.
- the alkyl group having 1 to 12 carbon atoms of R 1 to R 25 is preferably an alkyl group having 1 to 10 carbon atoms.
- substituents that these alkyl groups may have include a halogen atom, a hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, a sulfanyl group, A phosphino group, an amino group, a nitro group, etc. are mentioned.
- examples of the substituent that the phenyl group of R 1 to R 25 in the general formulas (2a), (2b), (3), (6), and (7) may have include a halogen atom, a hydroxyl group, examples thereof include an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, a sulfanyl group, a phosphino group, an amino group, and a nitro group.
- the adamantyl group in the general formula (7), the adamantyl group of R 24 and R 25 in the general formula (7), and the adamantane ring in the general formulas (4) and (5) may have a halogen Examples thereof include an atom, a hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, a sulfanyl group, a phosphino group, an amino group, and a nitro group.
- R 16 to R 23 are particularly preferably an alkyl group, a halogen atom, an alkoxyl group, an alkenyl group, or a phenyl group.
- R 24 and R 25 are particularly preferably an alkyl group, a halogen atom, an alkoxyl group, an alkenyl group, or a phenyl group.
- the molecular weight of X represented by the general formula (1-a ′′) is preferably 200 or more and 1000 or less. When the molecular weight of X is 200 or more, sufficient chemical resistance can be secured, and when it is 1000 or less, good sensitivity can be secured.
- the epoxy equivalent of the epoxy compound (a ′′) represented by the general formula (1-a ′′) is preferably 210 or more, and more preferably 230 or more.
- the epoxy equivalent is preferably 450 or less, and more preferably 400 or less.
- epoxy compound (a ′′) one type may be used alone, or two or more types may be used in combination.
- epoxy compound (a ′′) a commercially available product may be used, or it may be synthesized from a phenol compound as described below by a known method.
- an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added in advance to a dissolved mixture of the compound represented by the general formula (9a) or (9b) and an excess of epihalohydrin such as epichlorohydrin or epibromhydrin.
- X in the general formula (1-a ′′) is represented by the general formula (2a) or (2b).
- An epoxy compound (a ′′) as a group can be obtained.
- an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added in advance or added to a dissolved mixture of the compound represented by the general formula (10) and an epihalohydrin such as excess epichlorohydrin or epibromohydrin.
- the epoxy compound (a ′′) in which X in the general formula (1-a ′′) is represented by the general formula (3) is obtained by reacting at a temperature of 20 to 120 ° C. for 1 to 10 hours. Can do.
- an aqueous solution thereof may be used as an alkali metal hydroxide.
- the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure. Epihalohydrin may be continuously returned to the reaction system.
- a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or the like is catalyzed to a dissolved mixture of the compound represented by the general formula (9a), (9b) or (10) and epihalohydrin.
- a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or the like is catalyzed to a dissolved mixture of the compound represented by the general formula (9a), (9b) or (10) and epihalohydrin.
- To the halohydrin etherified product of the compound represented by the general formula (9a), (9b), or (10) obtained by reacting at 50 to 150 ° C. for 1 to 5 hours.
- the epoxy compound represented by the general formula (1-a ′′) can also be obtained by adding a solid or aqueous solution of the product and react
- the amount of epihalohydrin used in such a reaction is usually 1 to 20 mol, preferably 2 to 10 mol, relative to 1 equivalent of the hydroxyl group of the compound represented by formula (9a), (9b), or (10). It is.
- the amount of the alkali metal hydroxide used is usually 0.8 to 15 mol, preferably 0.9 to 0.1 mol per 1 equivalent of the hydroxyl group of the compound represented by the general formula (9a), (9b), or (10). 11 moles.
- an aprotic polar solvent such as dimethyl sulfone and dimethyl sulfoxide may be added to carry out the reaction smoothly.
- the amount used is 2 to 20% by weight, preferably 4 to 15% by weight, based on the amount of epihalohydrin.
- the amount used is 5 to 100% by weight, preferably 10 to 90% by weight, based on the amount of epihalohydrin.
- Unsaturated group-containing carboxylic acid (b ′′) examples include unsaturated carboxylic acids having an ethylenically unsaturated group.
- (Meth) acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, cinnamic acid, ⁇ -position is haloalkyl group, alkoxyl group, halogen atom, nitro group, or cyano group monocarboxylic acids such as substituted (meth) acrylic acid in; 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl adipic acid, 2- (meth) acryloyloxyethyl phthalate 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2 (Meth) acryloyloxy propyl adipate, 2- (meth) acryloy
- anhydrous hydroxyl-containing unsaturated compounds such as pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane diacrylate, glycidyl methacrylate acrylic acid adduct, and glycidyl methacrylate methacrylic acid adduct.
- the compound which added acid anhydrides such as succinic acid, maleic anhydride, tetrahydrophthalic anhydride, and phthalic anhydride, is also mentioned. Particularly preferred is (meth) acrylic acid. These may be used alone or in combination of two or more.
- the component (a ′′) and the component (b ′′) are mixed with tertiary amines such as triethylamine and benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, benzyltriethylammonium chloride and the like.
- tertiary amines such as triethylamine and benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, benzyltriethylammonium chloride and the like.
- Carboxylic acid can be added to the epoxy compound by reacting with a quaternary ammonium salt, pyridine, triphenylphosphine or the like in an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours.
- the amount of the catalyst used is preferably 0.01 to 10% by weight, particularly preferably 0.3 to 5% by weight, based on the reaction raw material mixture (the sum of the components (a ′′) and (b ′′). %.
- a polymerization inhibitor for example, methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butylcatechol, phenothiazine, etc.
- the amount is preferably 0.01 to 10% by weight, particularly preferably 0.03 to 5% by weight, based on the reaction raw material mixture.
- the ratio of adding the (b ′′) component to the epoxy group of the (a ′′) component is usually 90 to 100 mol%. Since the remaining epoxy group tends to adversely affect the storage stability, the component (b ′′) is usually 0.8 to 1.5 equivalents relative to 1 equivalent of the epoxy group of the component (a ′′). In particular, the reaction is preferably carried out at a ratio of 0.9 to 1.1 equivalents.
- polybasic acid and its anhydride As at least one of the polybasic acid and its anhydride (c ′′) (hereinafter sometimes referred to as “component (c ′′)” or “polybasic acid (anhydride)”), a dibasic acid and as at least one of the anhydride (hereinafter referred to as “tribasic acid (anhydride)”) (hereinafter, referred to as “dibasic acid (anhydride)”), 3 at least one of the nucleotide acid and its anhydride, At least one of the 4-basic acid and its anhydride (hereinafter referred to as “4-basic acid (anhydride)”) or the like can be used.
- the 4-basic acid (anhydride) (at least one of tetracarboxylic acid and dianhydride thereof), known ones can be used, for example, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid. And tetracarboxylic acids such as these, or their dianhydrides. These may be used individually by 1 type and may be used in combination of 2 or more type.
- the 4-basic acid (anhydride) among the above exemplified compounds, biphenyltetracarboxylic acid or an anhydride thereof is particularly preferable.
- the molecular weight is increased by a crosslinking reaction. For this reason, there exist effects, such as an adhesive improvement to a board
- dibasic acid examples include, for example, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid , Chlorendic acid, methyltetrahydrophthalic acid, or anhydrides thereof.
- tetrahydrophthalic acid, succinic acid, or anhydrides thereof are preferable. These may be used individually by 1 type and may be used in combination of 2 or more type.
- tribasic acid anhydride
- trimellitic acid hexahydrotrimellitic acid
- anhydrides thereof Particularly preferred are trimellitic anhydride and hexahydrotrimellitic anhydride. These may be used individually by 1 type and may be used in combination of 2 or more type.
- the molecular weight of the alkali-soluble resin (A ′′) can be increased, branching can be introduced into the molecule, and the balance between molecular weight and viscosity can be improved. Can take. Moreover, the amount of acid groups introduced into the molecule can be increased, and a resin having a good balance of sensitivity, adhesion, and the like can be obtained.
- the addition rate of the 4-basic acid (anhydride) is usually 10 to 100 mol%, preferably 10 to 100 mol%, based on the hydroxyl group produced when the component (b ′′) is added to the component (a ′′). It is 20 to 100 mol%, more preferably 30 to 100 mol%.
- 4-basic acid is used. It is preferable to use at least one of (anhydride) and dibasic acid (anhydride) in combination with tribasic acid (anhydride).
- the total addition rate of the component (c ′′) is usually 10 to 100 mol%, preferably 20 to 20%, based on the hydroxyl group produced when the component (b ′′) is added to the component (a ′′). 100 mol%, more preferably 30 to 100 mol%.
- the component (c ′′) can be added to the component (a ′′) (b ′) in addition to reacting with the hydroxyl group produced when the component (b ′′) is added to the component (a ′′).
- a component is added and a polyhydric alcohol (d ′′) described later is mixed, it may be reacted with any hydroxyl group present in the mixture.
- a known method can be used as a method of adding the component (c ′′) after adding the component (b ′′) to the component (a ′′) or mixing the polyhydric alcohol (d ′′) described later to this component.
- the reaction temperature is usually 80 to 130 ° C, preferably 90 to 125 ° C.
- the reaction temperature exceeds 130 ° C.
- polymerization of a part of unsaturated groups in the component (b ′′) occurs, which may lead to a rapid increase in molecular weight.
- the temperature is lower than 80 ° C., the reaction does not proceed smoothly, and the component (c ′′) may remain.
- the binder resin used in the present invention is obtained by adding a polyhydric alcohol (d ′′) (hereinafter referred to as “(d ′′)” to the reaction product obtained by adding the component (b ′′) to the component (a ′′) described above.
- An alkali-soluble resin (A1 ′′) obtained by mixing the above component (c ′′) with any hydroxyl group present in the mixture. It may be.
- Examples of the component (d ′′) include one or two or more kinds selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol.
- a monohydric alcohol is preferred.
- the molecular weight of the alkali-soluble resin (A1 ′′) can be increased, branching can be introduced into the molecule, and the molecular weight and the viscosity can be balanced. Moreover, the rate of introduction of acid groups into the molecule can be increased, and an organic binder having a good balance of sensitivity and adhesion can be obtained.
- component (d ′′) used is usually 0.01 to 0.5 times by weight, preferably 0.02 to 0.2 times by weight.
- Acid value and molecular weight of alkali-soluble resins (A ′′) and (A1 ′′) are usually 10 mg ⁇ KOH / g or more, preferably 50 mg-KOH / g or more.
- the acid value is preferably not less than the above lower limit value, and sufficient alkali resistance of the colored photosensitive composition is ensured (that is, the rough surface of the pattern surface by the alkaline developer).
- the acid value is preferably 200 mg-KOH / g or less, and more preferably 150 mg-KOH / g or less.
- the weight average molecular weight (Mw) in terms of standard polystyrene as measured by gel permeation chromatography (GPC) of the alkali-soluble resins (A ′′) and (A1 ′′) is preferably 1,500 or more, and 2,000. More preferably. Moreover, it is preferable that it is 20,000 or less, and it is more preferable that it is 10,000 or less.
- GPC gel permeation chromatography
- the alkali-soluble resin (A) is obtained by reacting a reaction product of a specific epoxy resin (a) with an unsaturated group-containing carboxylic acid (b) with at least one of a polybasic acid and its anhydride (c). Is obtained.
- Epoxy resin (a) The epoxy resin (a) is represented by the following general formula (1-a).
- n represents an average value and represents a number from 0 to 10.
- R 41 represents any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, and a biphenyl group. A plurality of R 41 present in one molecule may be the same or different.
- G represents a glycidyl group.
- R 41 in the general formula (1-a) represents any of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group.
- R 41 is particularly preferably a hydrogen atom or a methyl group.
- a plurality of R 41 present in one molecule may be the same or different.
- the epoxy resin (a) represented by the general formula (1-a) includes, for example, a compound represented by the following general formula (1-a-1) and an epihalohydrin in the presence of an alkali metal hydroxide. It can be obtained by reacting.
- n and R 41 represent the same meaning as in formula (1-a).
- the compound represented by the general formula (1-a-1) is obtained, for example, by subjecting a compound represented by the following general formula (1-a-2) and a phenol to a condensation reaction in the presence of an acid catalyst. be able to.
- Z represents a halogen atom, a hydroxyl group, or a lower alkoxy group.
- R 41 represents the same meaning as in the general formula (1-a).
- the halogen atom is preferably a chlorine atom, a bromine atom or the like
- the lower alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group. As a group.
- phenols are aromatic compounds having one phenolic hydroxyl group per molecule. Specific examples thereof include phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t-butylphenol, octylphenol.
- the amount of phenol used is preferably 0.5 to 20 mol, particularly preferably 2 to 15 mol, per 1 mol of the compound represented by the general formula (1-a-2). .
- an acid catalyst is preferably used, and various acid catalysts can be used, such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous aluminum chloride, zinc chloride, etc.
- p-toluenesulfonic acid, sulfuric acid, and hydrochloric acid are preferable.
- the amount of the acid catalyst used is not particularly limited, but it is preferably 0.1 to 30% by weight based on the compound represented by the general formula (1-a-2).
- the above condensation reaction can be carried out in the absence of a solvent or in the presence of an organic solvent.
- an organic solvent include toluene, xylene, methyl isobutyl ketone and the like.
- the amount of the organic solvent used is preferably 50 to 300% by weight, particularly preferably 100 to 250% by weight, based on the total weight of the charged raw materials.
- the reaction temperature is preferably in the range of 40 to 180 ° C., and the reaction time is preferably 1 to 8 hours.
- neutralization treatment or water washing treatment is performed to adjust the pH value of the product to 3-7, preferably 5-7.
- alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
- alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide
- ammonia sodium dihydrogen phosphate, diethylenetriamine
- organic amines such as a triethylenetetramine, aniline, and phenylenediamine
- the epoxy resin (a) represented by the general formula (1-a) As a method for obtaining the epoxy resin (a) according to the present invention represented by the general formula (1-a) from the compound represented by the general formula (1-a-1), a known method can be employed. For example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is previously added to a dissolved mixture of the compound represented by the general formula (1-a-1) and an excess of epihalohydrin such as epichlorohydrin or epibromohydrin. Alternatively, the epoxy resin (a) represented by the general formula (1-a) can be obtained by reacting at a temperature of 20 to 120 ° C. for 1 to 10 hours while being added.
- an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide
- epihalohydrin such as epichlorohydrin or epibromohydrin.
- the epoxy resin (a) represented by the general formula (1-a) can be obtained by reacting at a temperature of 20 to 120 °
- an aqueous solution of the alkali metal hydroxide may be used.
- the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system and the pressure is reduced.
- water and epihalohydrin may be continuously distilled off under normal pressure, followed by liquid separation, water may be removed, and epihalohydrin may be continuously returned to the reaction system.
- a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or the like is added to a dissolved mixture of the compound represented by the general formula (1-a-1) and epihalohydrin as a catalyst
- a solid or aqueous solution of an alkali metal hydroxide is added, and again 20 Alternatively, the reaction may be carried out at a temperature of ⁇ 120 ° C. for 1 to 10 hours to dehydrohalogenate (ring closure).
- the amount of epihalohydrin used in such a reaction is usually 1 to 20 mol, preferably 2 to 10 mol, relative to 1 equivalent of the hydroxyl group of the compound represented by the general formula (1-a-1).
- the amount of the alkali metal hydroxide used is usually 0.8 to 15 mol, preferably 0.9 to 11 mol, per 1 equivalent of the hydroxyl group of the compound represented by the general formula (1-a-1).
- the reaction may be carried out by adding an aprotic polar solvent such as dimethylsulfone or dimethylsulfoxide in addition to alcohols such as methanol and ethanol.
- an aprotic polar solvent such as dimethylsulfone or dimethylsulfoxide
- the amount used is 2 to 20% by weight, preferably 4 to 15% by weight, based on the amount of epihalohydrin.
- the amount used is 5 to 100% by weight, preferably 10 to 90% by weight, based on the amount of epihalohydrin.
- Epihalohydrin and other added solvents can be obtained after washing the reaction product of such an epoxidation reaction with or without washing with water under reduced pressure by heating, for example, at 110 to 250 ° C. and a pressure of 1.3 kPa (10 mmHg) or less. Are removed to obtain the desired epoxy resin (a).
- the obtained epoxy resin is dissolved again in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is dissolved.
- the reaction can be carried out by adding an aqueous solution to ensure ring closure.
- the amount of the alkali metal hydroxide used is preferably 0.01 to 0.3 mol, particularly with respect to 1 equivalent of the hydroxyl group of the compound represented by the general formula (1-a-1) used for epoxidation.
- the amount is preferably 0.05 to 0.2 mol.
- the reaction temperature is 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.
- Resin (a) can be obtained.
- unsaturated group-containing carboxylic acid examples include unsaturated carboxylic acids having an ethylenically unsaturated double bond, and specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p -Monocarboxylic acids such as vinyl benzoic acid, ⁇ -position haloalkyl, alkoxyl, halogen, nitro, and cyano substituents of (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2-acryloyloxyethyl adipic acid , 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleate, 2- (meth) acryloyloxy propyl acid 2- (meth)
- (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity. These may be used alone or in combination of two or more.
- Carboxylic acid can be added to the epoxy resin by reacting in an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours using a quaternary ammonium salt, pyridine or triphenylphosphine as a catalyst.
- the amount of the catalyst used is preferably from 0.01 to 10% by weight, particularly preferably from 0.3 to 10% by weight based on the reaction raw material mixture (total of epoxy resin (a) and unsaturated group-containing carboxylic acid (b)). 5% by weight.
- a polymerization inhibitor for example, methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butylcatechol, phenothiazine, etc.
- the amount is preferably 0.01 to 10% by weight, particularly preferably 0.1 to 5% by weight, based on the reaction raw material mixture.
- the proportion of the unsaturated group-containing carboxylic acid (b) added to the epoxy group of the epoxy resin (a) is usually 90 to 100 mol%. Residual epoxy groups adversely affect storage stability. Therefore, the unsaturated group-containing carboxylic acid (b) is usually 0.8 to 1.5 equivalents, particularly 0, to 1 equivalent of the epoxy group of the epoxy resin (a). It is preferable to carry out the reaction at a ratio of 9 to 1.1 equivalents.
- polybasic acid and its anhydride As the polybasic acid to be added to the hydroxyl group of the reaction product of the epoxy resin (a) and the unsaturated group-containing carboxylic acid (b) and its anhydride (c), known ones can be used, maleic acid, succinic acid, Itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, 5-norbornene-2,3-dicarboxylic acid, methyl-5-norbornene-2,3 A dibasic carboxylic acid such as dicarboxylic acid or an anhydride thereof; a polybasic carboxylic acid such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, or an anhydride thereof. Among these, t
- the addition rate of at least one of the polybasic acid and its anhydride (c) is usually 10 to 100 of the hydroxyl group produced when the unsaturated group-containing carboxylic acid (b) is added to the epoxy resin (a).
- the mol% preferably 20 to 100 mol%, more preferably 30 to 100 mol%. If the addition rate is too high, the remaining film rate during development may decrease, and if it is too low, the solubility may be insufficient or the adhesion to the substrate may be insufficient.
- the said addition rate represents the total addition rate of a polybasic acid and its anhydride.
- the epoxy group-containing compound (d) may be added to a part of the generated carboxyl group.
- the epoxy group-containing compound (d) in order to improve photosensitivity, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, glycidyl ether compound having a polymerizable unsaturated group, etc.
- a glycidyl ether compound having no polymerizable unsaturated group can be added, or both of them may be used in combination.
- the glycidyl ether compound having no polymerizable unsaturated group include a glycidyl ether compound having a phenyl group or an alkyl group (manufactured by Nagase Chemical Industries, Ltd., trade names: Denacol EX-111, Denacol EX-121, Denacol). EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192) and the like.
- the alkali-soluble resin (A) according to the present invention is a reaction product of the epoxy resin (a) and the unsaturated group-containing carboxylic acid (b), and at least one of a polybasic acid and its anhydride (c). It may be a resin obtained by adding such an epoxy group-containing compound (d) to a part of the carboxyl group of a resin obtained by reacting with.
- the weight-average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the alkali-soluble resin (A) used in the present invention is usually 1500 or more, preferably Is 2000 or more, usually 50000 or less, preferably 30000 or less, more preferably 10,000 or less. If the weight average molecular weight of the alkali-soluble resin (A) is too small, the sensitivity is inferior, and if it is too large, the solubility in the developer is insufficient, which is not preferable.
- the acid value (mgKOH / g) of the alkali-soluble resin (A) used in the present invention is usually 10 or more, preferably 50 or more, and usually 200 or less, preferably 150 or less. If the acid value of the alkali-soluble resin (A) is too low, sufficient solubility may not be obtained. If the acid value is too high, curability is insufficient and the surface properties of the coating film tend to deteriorate.
- the condensation reaction of the compound represented by the general formula (1-a-2) and the phenol compound, and the compound represented by the general formula (1-a-1) obtained by the condensation reaction and the epihalohydrin The synthesis reaction of the alkali-soluble resin (A) such as reaction, addition reaction with at least one of the unsaturated group-containing carboxylic acid (b) and the polybasic acid and its anhydride (c) can be performed by a known method. For example, it can be performed by the method described in Japanese Patent Application Laid-Open No. 2005-55814.
- Alkali-soluble resin (A ' ) As the binder resin in the present invention, particularly preferred other examples of things, 'epoxy compound represented by (a following general formula (1-a)' and), the reaction product of an unsaturated group-containing carboxylic acid (b ') And an alkali-soluble resin (A ′ ) obtained by reacting with at least one of a polybasic acid and its anhydride (c ′ ).
- p and q each independently represent an integer of 0 to 4, and R 31 and R 32 each independently represent an alkyl group or a halogen atom. R 33 and R 34 each independently represents an alkylene group. x and y each independently represents an integer of 0 or more. ]
- the alkyl group of R 31 and R 32 is preferably an alkyl group having 1 to 10 carbon atoms, and the halogen atom includes Cl, Br, F and the like.
- R 31 and R 32 are particularly preferably each independently an alkyl group having 1 to 5 carbon atoms.
- the bonding position of R 31 and R 32 to the benzene ring is not particularly limited,
- the o-position is preferred.
- R 31 and R 32 may be the same group or different groups, but are preferably the same group from the viewpoint of production cost.
- Examples of the alkylene group for R 33 and R 34 include an alkylene group having 1 to 10 carbon atoms, and it is particularly preferable that they are each independently an ethylene group or a propylene group.
- X and y each independently represents an integer of 0 or more, but is usually 0 to 6, preferably 0 to 3. In general, the larger x and y, the higher the solubility, but if it is too large, the sensitivity may decrease.
- R 33 and R 34 may be the same group or different groups, but are preferably the same group from the viewpoint of production cost.
- the molecular weight of these components (a ′ ) is usually in the range of 200 to 200,000, preferably 300 to 100,000, as the weight average molecular weight (Mw) in terms of standard polystyrene as measured by gel permeation chromatography (GPC). .
- Mw weight average molecular weight
- GPC gel permeation chromatography
- Unsaturated carboxylic acid (b ' ) examples include those in ⁇ Alkali-soluble resin (A ′′), Alkali-soluble resin (A1 ′′)>.
- the same compounds as those mentioned as the saturated group-containing carboxylic acid (b ′′) can be used.
- (meth) acrylic acid is preferred among ⁇ , ⁇ -unsaturated carboxylic acids, and acrylic acid is particularly preferred because of its high reactivity.
- ⁇ ⁇ -unsaturated carboxylic acid esters having a carboxyl group in the ester moiety
- 2- (meth) acryloyloxyethyl phthalic acid and 2- (meth) acryloyloxyethyl maleic acid are preferred.
- the amount of component (b ′ ) used is preferably in the range of 0.5 to 1.2 equivalents, more preferably in the range of 0.7 to 1.1 equivalents, relative to 1 equivalent of the epoxy group of component (a ′ ). .
- B ' By making the usage-amount of a component more than a lower limit, a sufficient quantity of unsaturated groups can be introduce
- polybasic acid and its anhydride (c ′ ) As the polybasic acid and its anhydride (c ′ ), those listed as the polybasic acid and its anhydride (c ′′ ) in ⁇ Alkali-soluble resin (A ′′), Alkali-soluble resin (A1 ′′)> And the like, and tetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof are preferable.
- the addition rate of at least one of the polybasic acid and its anhydride (c ′) should be such that the final alkali-soluble resin (A ′) has an acid value of 10 to 150 mg-KOH / g. More preferably, it is 20 to 140 mg-KOH / g.
- the acid value By setting the acid value to be equal to or higher than the above lower limit, alkali developability is improved, and by setting the acid value to be equal to or lower than the upper limit, sufficient photocurability is obtained.
- transduced polyfunctional alcohol (d ' ) such as a trimethylol propane, a pentaerythritol, a dipentaerythritol, and introduce
- the polyhydric alcohol (d ′) include compounds similar to those described above as the polyhydric alcohol (d ′′ ) in ⁇ Alkali-soluble resin (A ′′), Alkali-soluble resin (A1 ′′)>. The same applies to the preferred compounds and preferred amounts.
- the weight average molecular weight in terms of standard polystyrene by gel permeation chromatography (GPC) of the alkali-soluble resin (A ') (Mw) is usually 1,000 or more, preferably 1,500 or more, usually 30,000 or less , Preferably 20,000 or less, more preferably 10,000 or less, particularly preferably 8,000 or less.
- GPC gel permeation chromatography
- Other examples of particularly preferable binder resins in the present invention include an epoxy resin (a ′ ′′) represented by the following general formula (1-a ′ ′′) and an unsaturated group-containing carboxylic acid (b ′ ′′). And an alkali-soluble resin (A ′ ′′) obtained by reacting the reaction product with at least one of a polybasic acid and its anhydride (c ′ ′′).
- R 51 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- R 52 represents a divalent polycyclic hydrocarbon group having 5 to 16 carbon atoms
- R 53 and R 54 each independently represents a hydrogen atom or a glycidyl group.
- s represents 1 or 2.
- t and z represent the proportion of each repeating unit, and t ⁇ z ⁇ 0.5t.
- R 51 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Among them, a hydrogen atom or a methyl group is preferable from the viewpoint of photocurability.
- S represents 1 or 2, and is preferably 1.
- R 52 represents a divalent polycyclic hydrocarbon group having 5 to 16 carbon atoms. Such a group refers to an unsaturated polycyclic hydrocarbon ring compound having the same skeleton and at least two carbon-carbon double bonds (hereinafter sometimes simply referred to as “unsaturated polycyclic hydrocarbon compound”). It can be formed by using the raw material and carrying out the reaction described below.
- Examples of the unsaturated polycyclic hydrocarbon ring compound as a raw material include the following compounds, but are not limited thereto.
- a bridged carbocycle is more preferable, and dicyclopentadiene is particularly preferable.
- the epoxy resin (a ′ ′′) represented by the general formula (1-a ′ ′′) is a polyaddition of the unsaturated polycyclic hydrocarbon compound described above and a phenol compound represented by the following general formula. It can be obtained by glycidylation of the hydroxyl group of the reaction product.
- R 51 and s are as defined in the general formula (1-a ′ ′′).
- epoxy resin (a ′ ′′) a compound represented by the following general formula (1-a ′ ′′-1) obtained by glycidylation of a polyaddition reaction product of dicyclopentadiene and the above-described phenol compound is used. Particularly preferred.
- the introduction ratio of the glycidyl group in the general formula (1-a ′ ′′) and the general formula (1-a ′ ′′-1) is 50 to 100 mol of the phenolic hydroxyl group in the phenol resin before glycidylation.
- % That is, t and z in the general formula (1-a ′ ′′) and the general formula (1-a ′ ′′-1) must have a relationship of t ⁇ z ⁇ 0.5t, preferably It is preferable that 70 to 100 mol% is substituted with a glycidyl group.
- the alkali-soluble resin (A ′ ′′) is a reaction product of the epoxy resin (a ′ ′′) represented by the general formula (1-a ′ ′′) and the unsaturated group-containing carboxylic acid (b ′ ′′). Is a resin obtained by reacting at least one of a polybasic acid and its anhydride (c ′ ′′).
- unsaturated group-containing carboxylic acid (b ′ ′′) those listed as unsaturated group-containing carboxylic acid (b ′′) in ⁇ Alkali-soluble resin (A ′′), alkali-soluble resin (A1 ′′)>
- a ′′ alkali-soluble resin
- A1 ′′ alkali-soluble resin
- the proportion of the unsaturated group-containing carboxylic acid (b ′ ′′) added to the epoxy group of the epoxy resin (a ′′ ′′) is usually 90 to 100 mol%. Since the remaining epoxy group adversely affects storage stability, the unsaturated group-containing carboxylic acid (b ′ ′′) is usually 0.8 to 1 with respect to 1 equivalent of the epoxy group of the epoxy resin (a ′′ ′). It is preferable to carry out the reaction at a ratio of 0.5 equivalent, particularly 0.9 to 1.1 equivalent.
- Polybasic acid and its anhydride (c ′ ′′) are also exemplified as polybasic acid and its anhydride (c ′′) in ⁇ Alkali-soluble resin (A ′′), Alkali-soluble resin (A1 ′′)>.
- a ′′ Alkali-soluble resin
- A1 ′′ Alkali-soluble resin
- the addition rate of at least one of the polybasic acid and its anhydride is generated when an unsaturated group-containing carboxylic acid (b ′ ′′) is added to the epoxy resin (a ′ ′′).
- the hydroxyl group is usually 15 to 100 mol%, preferably 20 to 90 mol%, and the final acid-soluble resin (A ′ ′′) has an acid value of 45 to 160 mg-KOH / g. Is preferred.
- this addition rate not more than the above upper limit value, it is possible to prevent a decrease in the remaining film rate during development, and by making it not less than the above lower limit value, good solubility and adhesion to the substrate can be obtained. Can do.
- the said addition rate represents the total addition rate of a polybasic acid and its anhydride.
- the weight average molecular weight of the alkali-soluble resin (A '' ') is usually 1,500 to 4,000, preferably 2,000 to 3,500, more preferably 2,500 to 3,000. If the weight average molecular weight is too small, there may be a problem that the developing solubility is too high, and if it is too large, there may be a problem that the developing solubility is too low.
- these binder resins may be used alone or in combination of two or more.
- the binder resin in the colored photosensitive composition of the present invention among the above alkali-soluble resins (A), (A ′), (A ′′), (A ′ ′′), (A1 ′′), the shape Alkali-soluble resins (A) and (A ′ ′′) are preferable from the viewpoints of control of the level difference and the balance of adhesion to the substrate.
- the content of the binder resin is usually 5% by weight or more, preferably 10% by weight or more, and usually 80% by weight or less, preferably 70% by weight or less, based on the total solid content of the colored photosensitive composition of the present invention. It is.
- the content of the binder resin is usually 5% by weight or more, preferably 10% by weight or more, and usually 80% by weight or less, preferably 70% by weight or less, based on the total solid content of the colored photosensitive composition of the present invention. It is.
- the content of the binder resin is usually 5% by weight or more, preferably 10% by weight or more, and usually 80% by weight or less, preferably 70% by weight or less, based on the total solid content of the colored photosensitive composition of the present invention. It is.
- Photopolymerizable monomer In the present invention, the photopolymerization initiator is used together with a photopolymerizable monomer such as an ethylenically unsaturated compound.
- an ethylenically unsaturated compound means a compound having at least one ethylenically unsaturated bond in the molecule, but it is polymerizable, crosslinkable, and a developer for exposed and non-exposed areas associated therewith.
- a compound having two or more ethylenically unsaturated bonds in the molecule is preferable from the viewpoint that the difference in solubility can be expanded, and the ethylenically unsaturated bond is derived from a (meth) acryloyloxy group. More preferred are (meth) acrylate compounds.
- a compound having three or more ethylenically unsaturated bonds in the molecule for example, (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, unsaturated carboxylic acids such as citraconic acid, and their alkyl esters , (Meth) acrylonitrile, (meth) acrylamide, styrene and the like.
- the compounds having two or more ethylenically unsaturated bonds are typically esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, hydroxy (meth) acrylates.
- esters of unsaturated carboxylic acids and polyhydroxy compounds include (meth) acryloyloxy group-containing phosphates, hydroxy (meth) acrylates.
- examples include urethane (meth) acrylates of a compound and a polyisocyanate compound, and epoxy (meth) acrylates of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound.
- esters of an unsaturated carboxylic acid and a polyhydroxy compound include the following compounds.
- sugar alcohol includes ethylene glycol, polyethylene glycol (addition number 2-14), propylene glycol, polypropylene glycol (addition number 2-14), trimethylene glycol, Examples include tetramethylene glycol, hexamethylene glycol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol and the like.
- Reaction product of unsaturated carboxylic acid and alkylene oxide adduct of sugar alcohol; sugar alcohol is the same as above.
- Specific examples of the alkylene oxide adduct include an ethylene oxide adduct and a propylene oxide adduct.
- Reaction product of unsaturated carboxylic acid and alcohol amine; specific examples of alcohol amines include diethanolamine and triethanolamine.
- esters of unsaturated carboxylic acid and polyhydroxy compound are as follows. Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide addition tri (meta) ) Acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (me
- esters of unsaturated carboxylic acids and polyhydroxy compounds include unsaturated carboxylic acids and aromatic polyhydroxy compounds such as hydroquinone, resorcinol, pyrogallol, bisphenol F, bisphenol A, or their ethylene oxide adducts. And the reaction product.
- (meth) acryloyloxy group-containing phosphates those represented by the following general formulas (6), (7) and (8) are preferable.
- R A represents a hydrogen atom or a methyl group
- e and g are integers of 1 to 25, and f is 1, 2 or 3.
- e and g are preferably 1 to 10, particularly 1 to 4. Specific examples thereof include (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, ( (Meth) acryloyloxyethylene glycol phosphate and the like, and these may be used alone or as a mixture.
- urethane (meth) acrylates of a hydroxy (meth) acrylate compound and a polyisocyanate compound examples include hydroxy (meth) acrylates such as hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and tetramethylolethane tri (meth) acrylate.
- aliphatic polyisocyanate such as hexamethylene diisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptanetri Cycloaliphatic polyisocyanates such as isocyanate, 4,4-diphenylmethane diisocyanate, tri Aromatic polyisocyanates such as (isocyanate phenyl) thiophosphate, heterocyclic polyisocyanates such as isocyanurate, a reaction product of a polyisocyanate compounds and the like.
- aliphatic polyisocyanate such as hexamethylene diisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, cyclohexane
- Examples of such products include trade names “U-4HA”, “UA-306A”, “UA-MC340H”, “UA-MC340H”, “U6LPA” manufactured by Shin-Nakamura Chemical Co., Ltd., and the like.
- a compound having 4 or more urethane bonds [—NH—CO—O—] and 4 or more (meth) acryloyloxy groups in one molecule is preferable, and examples of the compound include pentaerythritol, poly A compound obtained by reacting a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate with a compound having 4 or more hydroxyl groups in one molecule such as glycerin, or ethylene glycol
- Biuret type A compound having 3 or more isocyanate groups in one molecule such as adduct type such as “Duranate P-301-75E”, “Duranate E-402-90T” and “Duranate E-405-80T” is reacted.
- a compound having 4 or more, preferably 6 or more isocyanate groups in one molecule such as a compound obtained by polymerizing or copolymerizing isocyanate ethyl (meth) acrylate or the like,
- a compound obtained by polymerizing or copolymerizing isocyanate ethyl (meth) acrylate or the like For example, “Duranate ME20-100” manufactured by Asahi Kasei Kogyo Co., Ltd., pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc.
- One or more hydroxyl groups in one molecule and FOB can preferably be obtained by a compound having three or more (meth) acryloyloxy group, it is reacted.
- epoxy (meth) acrylates of (meth) acrylic acid or a hydroxy (meth) acrylate compound and a polyepoxy compound examples include (meth) acrylic acid, or a hydroxy (meth) acrylate compound as described above, and (poly) Ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene Glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether Aliphatic polyepoxy compounds such as ruthenium,
- ethylenically unsaturated compounds include, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, vinyl group-containing compounds such as divinyl phthalate, ether bonds Thioether bond-containing compounds in which the ether bond of the ethylenically unsaturated compound is sulfurized with phosphorus pentasulfide or the like to change to a thioether bond to improve the crosslinking rate, and for example, Japanese Patent No.
- a polyfunctional (meth) acrylate compound and a silica sol having a particle diameter of 5 to 30 nm for example, isopropanol-dispersed organosilica sol (“IPA-ST” manufactured by Nissan Chemical Co., Ltd.)), methyl ethyl ketone-dispersed organo described in JP-A-9-100111, etc.
- Silica sol (Nissan Chemical Co., Ltd.) MEK-ST ”), methyl isobutyl ketone-dispersed organosilica sol (“ MIBK-ST ”manufactured by NISSAN CHEMICAL CO., LTD.)] And the like, and the like, by using an isocyanate group or a mercapto group-containing silane coupling agent.
- silica sol Nisan Chemical Co., Ltd.) MEK-ST
- MIBK-ST methyl isobutyl ketone-dispersed organosilica sol
- MIBK-ST methyl isobutyl ketone-dispersed organosilica sol
- examples thereof include compounds in which the strength and heat resistance as a cured product are improved by reacting and bonding a silica sol with a functional unsaturated compound via a silane coupling agent.
- ester (meth) acrylates or urethane (meth) acrylates are preferable, and among them, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like. Those having 5 or more functional groups are particularly preferred.
- ethylenically unsaturated compounds may be used alone or in combination of two or more.
- the proportion of the photopolymerizable monomer in the colored photosensitive composition of the present invention is usually 1 to 60% by weight, preferably 5 to 40% by weight, particularly preferably 12 to 30% by weight, based on the total solid content. If the proportion of the photopolymerizable monomer is too much within this range, the degree of curing tends to decrease as the proportion of the other components decreases, so the voltage holding ratio tends to deteriorate. On the other hand, if the amount is too small, the amount of the alkali resin increases, so that the developability tends to decrease.
- Photopolymerization initiator is usually used as a mixture (photopolymerization initiator system) with an accelerator, and a sensitizing dye added as necessary is used in combination.
- the photopolymerization initiator system is a component that directly absorbs light or is photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.
- photopolymerization initiator constituting the photopolymerization initiator system component
- various compounds described in International Publication No. 2008/153000 can be used.
- the photopolymerization initiator used in the colored photosensitive composition of the present invention is particularly preferably an oxime ester compound from the viewpoint of good generation efficiency of polymerization active radicals.
- the compounds exemplified below are preferably used. Can do.
- Examples of the accelerator and the sensitizing dye constituting the photopolymerization initiator component include, for example, various compounds described in International Publication No. 2008/153000, and preferable compounds are also described in International Publication No. 2008/153000. It is the same as the prepared compound.
- the content ratio of the photopolymerization initiator system component is usually 0.1 to 40% by weight, preferably 0.8% in the total solid content in the colored photosensitive composition of the present invention. 5 to 30% by weight. If this content is extremely low, the sensitivity to exposure light may be reduced. On the other hand, if it is extremely high, the solubility of the unexposed portion in the developer may be reduced, leading to poor development.
- the content of the sensitizing dye in the colored photosensitive composition of the present invention is usually 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 0 to 0% by weight based on the total solid content in the colored photosensitive composition. 10% by weight.
- Dispersant / dispersion aid In the colored photosensitive composition of the present invention, at least one of a pigment dispersant and a dispersion aid is used in combination in order to improve the dispersibility and dispersion stability of the pigment. Is preferred. Among them, it is particularly preferable to use a polymer dispersant as the pigment dispersant because it is excellent in dispersion stability with time.
- the polymer dispersant is a polymer having a completely different structure from the pigment for ensuring the dispersion stability of the pigment, and the dispersion aid means a pigment derivative or the like for enhancing the dispersibility of the pigment. .
- polymer dispersant examples include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester. And the like, and the like.
- Specific examples of these dispersants are trade names of EFKA (manufactured by BASF), DisperBYK (manufactured by Big Chemie), Disparon (manufactured by Enomoto Kasei Co., Ltd.), SOLPERSE (manufactured by Geneca), KP (Shin-Etsu Chemical Co., Ltd. Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
- These polymer dispersants can be used singly or in combination of two or more.
- pigment derivatives azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine
- Derivatives such as quinophthalone are preferable, among which quinophthalone is preferable.
- Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc.
- pigment skeleton or alkyl groups, aryl groups, and complex groups examples thereof include those bonded via a ring group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton.
- pigment derivatives include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives.
- These pigment derivatives can be used alone or in combination of two or more.
- the content of at least one of the dispersant and the dispersion aid is usually 5% by weight to 120% by weight, preferably 5% by weight to 90% by weight, based on the pigment.
- it is 5 wt% or more and 60 wt% or less, and a particularly preferred range is 5 wt% or more and 40 wt% or less. If the content of the dispersant and the dispersion aid is too small, sufficient dispersibility may not be obtained. If the content is too large, the ratio of other components may be relatively decreased, and the voltage holding ratio may be decreased.
- the said content represents content of the sum total of a dispersing agent and a dispersing aid.
- the amount used is usually 0.1 to 30% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, based on the pigment in the colored photosensitive composition. More preferably, it is 0.1 to 5% by weight.
- the colored photosensitive composition of the present invention generally contains the above-described pigment, binder resin, photopolymerizable monomer, photopolymerization initiator, dispersant and dispersion aid, and the solid content of other components described below as a solvent. It is prepared by dissolving or dispersing in.
- the solvent has a function of adjusting the viscosity by dissolving or dispersing the pigment, binder resin, photopolymerizable monomer, photopolymerization initiator, and the like in the colored photosensitive composition of the present invention.
- a solvent having a boiling point in the range of 100 to 300 ° C. is preferably selected.
- a solvent having a boiling point of 120 to 280 ° C. is more preferable. Examples of such a solvent include various solvents described in International Publication No. 2008/153000.
- solvents may be used alone or in combination of two or more.
- a solvent having a boiling point in the range of 100 to 200 ° C. (under a pressure of 101.25 [hPa], the same applies to the boiling points hereinafter) is selected. More preferably. Particularly preferred are those having a boiling point of 120 to 170 ° C.
- glycol alkyl ether acetates are preferred from the viewpoint of good balance of coating properties, surface tension, etc., and relatively high solubility of constituents in the composition. .
- glycol alkyl ether acetates may be used alone or in combination with other solvents.
- glycol monoalkyl ethers are particularly preferable.
- propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition.
- Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment is likely to aggregate, and the storage stability such as the viscosity of the colored photosensitive composition tends to increase over time tends to decrease.
- the proportion of glycol monoalkyl ethers in the solvent is preferably 5 to 30% by weight, more preferably 5 to 20% by weight.
- a solvent having a boiling point of 150 ° C. or higher (hereinafter sometimes referred to as “high boiling point solvent”).
- high boiling point solvent a solvent having a boiling point of 150 ° C. or higher
- diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred. preferable.
- the content of the high boiling point solvent in the solvent is preferably 3% to 50% by weight, more preferably 5% to 40% by weight, and particularly preferably 5% to 30% by weight.
- the high boiling point solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a high boiling point solvent having a boiling point of 150 ° C. or higher is not separately contained. It doesn't matter.
- Preferred high boiling solvents include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.
- the content of the solvent in the entire colored photosensitive composition of the present invention is not particularly limited, but is usually 99% by weight or less, usually 50% by weight or more, preferably 55% by weight or more, more preferably 60% by weight or more. It is.
- the ratio of the solvent to the above upper limit or less, the colored photosensitive composition can contain a necessary and sufficient amount of solids such as a pigment, a binder resin, and a photopolymerizable monomer.
- thickening can be suppressed and favorable applicability
- the colored photosensitive composition of the present invention is prepared by using a solvent so that the solid content concentration is usually 5 to 50% by weight, preferably 10 to 30% by weight.
- the colored photosensitive composition of the present invention further includes a polymerization accelerator, a sensitizing dye, a surfactant, a photoacid generator, a crosslinking agent, an adhesion improver, A plasticizer, a storage stabilizer, a surface protective agent, an organic carboxylic acid, an organic carboxylic acid anhydride, a development improver, a thermal polymerization inhibitor and the like may be contained.
- Photoacid generator is a compound capable of generating an acid by ultraviolet rays, and there is a crosslinking agent such as a melamine compound by the action of the acid generated upon exposure. As a result, the crosslinking reaction proceeds.
- a crosslinking agent such as a melamine compound by the action of the acid generated upon exposure.
- the crosslinking reaction proceeds.
- photoacid generators those having a high solubility in a solvent, particularly in a solvent used in a colored photosensitive composition, are preferred.
- a photoacid generator When a photoacid generator is used, its content is preferably 0 to 20% by weight, particularly preferably 2 to 15% by weight, based on the total solid content of the colored photosensitive composition.
- crosslinking agent To the colored photosensitive composition of the present invention, a crosslinking agent can be further added.
- a crosslinking agent can be further added.
- a melamine or guanamine compound can be used.
- these crosslinking agents include melamine or guanamine compounds represented by the following general formula (XI).
- R 61 represents a —NR 66 R 67 group or an aryl group, and when R 61 is a —NR 66 R 67 group, one of R 62 , R 63 , R 64 , R 65 , R 66 and R 67 And when R 61 is an aryl group, one of R 62 , R 63 , R 64 and R 65 represents a —CH 2 OR 68 group, and R 62 , R 63 , R 64 , R 65 , R 66 and R 65
- the rest of 67 independently of each other, represents a hydrogen atom or a —CH 2 OR 68 group, where R 68 represents a hydrogen atom or an alkyl group.
- the aryl group is typically a phenyl group, a 1-naphthyl group, or a 2-naphthyl group, and a substituent such as an alkyl group, an alkoxy group, or a halogen atom is bonded to the phenyl group or naphthyl group. It may be.
- the alkyl group and the alkoxy group can each have 1 to 6 carbon atoms.
- Alkyl group represented by R 68 is, among the above, methyl group or ethyl group, especially common that a methyl group.
- Melamine compounds corresponding to the general formula (XI), that is, compounds of the following general formula (XI-1) include hexamethylol melamine, pentamethylol melamine, tetramethylol melamine, hexamethoxymethyl melamine, pentamethoxymethyl melamine, tetra Methoxymethyl melamine, hexaethoxymethyl melamine and the like are included.
- R 62 , R 63 , R 64 , R 65 , R 66 and R 67 is an aryl group
- one of R 62 , R 63 , R 64 and R 65 represents a —CH 2 OR 68 group.
- the remainder of R 62 , R 63 , R 64 , R 65 , R 66 and R 67 independently of one another represents a hydrogen atom or a —CH 2 OR 68 group, wherein R 68 represents a hydrogen atom or alkyl.
- guanamine compounds corresponding to the general formula (XI), that is, compounds in which R 61 in the general formula (XI) is an aryl group include tetramethylol benzoguanamine, tetramethoxymethyl benzoguanamine, trimethoxymethyl benzoguanamine, tetraethoxymethyl. Benzoguanamine and the like are included.
- a crosslinking agent having a methylol group or a methylol alkyl ether group can also be used. Examples are given below. 2,6-bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-2,6-bis (hydroxymethyl) phenol, 5-ethyl-1,3-bis (hydroxymethyl) perhydro-1,3 , 5-triazin-2-one (commonly known as N- ethyl-dimethylol triazone) or its dimethyl ether thereof, dimethylol trimethylene urea or dimethyl ether thereof, 3,5-bis (hydroxymethyl) perhydro-1,3,5 Oxadiazin-4-one (commonly called dimethyloluron) or a dimethyl ether thereof, tetramethylol glyoxal diurein or a tetramethyl ether thereof.
- crosslinking agents may be used individually by 1 type, or may be used in combination of 2 or more type.
- the amount when the crosslinking agent is used is preferably from 0.1 to 15% by weight, particularly preferably from 0.5 to 10% by weight, based on the total solid content of the colored photosensitive composition.
- the colored photosensitive composition of the present invention may contain an adhesion improving agent in order to sufficiently adhere fine lines and dots.
- a compound containing a nitrogen atom, a phosphoric acid group-containing compound, a silane coupling agent and the like are preferable.
- the compound containing a nitrogen atom include diamines (described in Japanese Patent Application Laid-Open No. 11-184080).
- other azoles are preferred. Among them, azoles are preferable, and in particular, imidazoles (adhesion improvers described in JP-A-9-236923, etc.), benzimidazoles, benzotriazoles (adhesion improvement described in JP-A-2000-171968). Agents, etc.) are preferred, and imidazoles and benzimidazoles are most preferred.
- 2-hydroxybenzimidazole, 2-hydroxyethylbenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole, 2-mercaptoimidazole, 2 are less likely to cause fogging and greatly improve the adhesion.
- -Aminoimidazole is preferred, and 2-hydroxybenzimidazole, benzimidazole, 2-hydroxyimidazole, and imidazole are particularly preferred.
- silane coupling agents such as epoxy, methacrylic, amino, etc. can be used, and epoxy and isocyanate silane coupling agents are particularly preferred.
- the blending ratio varies depending on the type of the adhesion improver used, but is 0.01 to 5% by weight, particularly 0.05%, based on the total solid content of the colored photosensitive composition. It is preferable to set it to 3% by weight. If it is less than this, sufficient adhesion improving effect may not be obtained, and if it is too much, developability may be lowered.
- Sensitizing dyes examples include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, JP-A-3-239703, and Japan.
- Japanese Laid-Open Patent Publication No. 60-88005 Japanese Laid-Open Patent Publication No. 59-56403, Japanese Laid-Open Patent Publication No.
- the content of the sensitizing dye in the total solid content in the colored photosensitive composition is usually 0.01 to 5% by weight, preferably 0.05 to 3% by weight. If it is less than this, the sensitization effect may not be obtained, and if it is too much, developability may be lowered.
- surfactant As the surfactant, one or more of anionic, cationic, nonionic, amphoteric surfactants and the like can be used, but they adversely affect various properties. In view of low possibility, it is preferable to use a nonionic surfactant. In addition, fluorine-based and silicon-based materials are effective in terms of coating properties.
- the blending ratio is usually 0.001 to 10% by weight, preferably 0.005 to 1% by weight, more preferably 0.8%, based on the total solid content in the colored photosensitive composition.
- the range is from 01 to 0.5% by weight, most preferably from 0.03 to 0.3% by weight. If the addition amount of the surfactant is less than the above range, the smoothness and uniformity of the coating film may not be expressed. If the addition amount is large, the smoothness and uniformity of the coating film may not be expressed, and other characteristics may be exhibited. It may get worse.
- the colored photosensitive composition of the present invention contains at least one of an organic carboxylic acid and an organic carboxylic anhydride for the purpose of improving developability and improving background stains. You may go out.
- organic carboxylic acids include aliphatic carboxylic acids and aromatic carboxylic acids.
- aliphatic carboxylic acid include monoacids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid, glycolic acid, acrylic acid, and methacrylic acid.
- dicarboxylic acids such as succinic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, and fumaric acid
- tricarboxylic acids such as tricarbaryl acid, aconitic acid, and camphoric acid.
- aromatic carboxylic acid examples include benzoic acid, toluic acid, cumic acid, hemellitic acid, mesitylene acid, phthalic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, and melophane. Acids, pyromellitic acid, phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropaic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, umberic acid, etc. Examples thereof include carboxylic acids in which a carboxyl group is directly bonded to a phenyl group, and carboxylic acids in which a carboxyl group is bonded to the phenyl group through a carbon bond.
- organic carboxylic acids monocarboxylic acids and dicarboxylic acids are preferable, among which malonic acid, glutaric acid, and glycolic acid are more preferable, and malonic acid is particularly preferable.
- the molecular weight of the organic carboxylic acid is usually 1000 or less and usually 50 or more. If the molecular weight of the organic carboxylic acid is too large, the effect of improving background stains may be insufficient. If the molecular weight is too small, the addition amount may decrease or process contamination may occur due to sublimation or volatilization.
- organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides.
- aliphatic carboxylic acid anhydrides include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, Tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, glutaric anhydride, 1,2-cyclohexenedicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3- Aliphatic carboxylic acid anhydrides such as dicarboxylic acids are mentioned.
- aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride.
- maleic anhydride succinic anhydride, itaconic anhydride, and citraconic anhydride are preferable, and maleic anhydride is more preferable.
- the molecular weight of the organic carboxylic acid anhydride is usually 800 or less, preferably 600 or less, more preferably 500 or less, and usually 50 or more. If the molecular weight of the organic carboxylic acid anhydride is too large, the effect of improving scumming may be insufficient. If the molecular weight is too small, the amount added may be reduced or process contamination may occur due to sublimation or volatilization.
- organic carboxylic acids and organic carboxylic acid anhydrides may be used alone or in combination of two or more.
- the amount added is usually 0.01% by weight to 5% by weight, preferably 0%, based on the total solid content of the colored photosensitive composition of the present invention. 0.03% to 3% by weight. If the addition amount is too small, a sufficient addition effect may not be obtained. If the addition amount is too large, surface smoothness and sensitivity may be deteriorated, and undissolved peeling pieces may be generated.
- thermal polymerization inhibitor examples include one or two of hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, ⁇ -naphthol and the like. More than seeds are used.
- the blending ratio of the thermal polymerization inhibitor is preferably in the range of 0 to 2% by weight with respect to the total solid content in the colored photosensitive composition, and if it is more than this, the light shielding property and the sensitivity of the colored photosensitive composition are improved. It may cause a decrease.
- Plasticizers examples include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. Species or two or more are used.
- the blending ratio of these plasticizers is preferably in the range of 0 to 5% by weight with respect to the total solid content of the colored photosensitive composition, and if it is more than this, the curing point of the black photospacer is lowered.
- the colored photosensitive composition of the present invention is prepared according to a conventional method. Hereinafter, examples will be described in detail, but the method for preparing the colored photosensitive composition in the present invention is not limited to this method.
- the colored photosensitive composition of the present invention is preferably prepared by preparing a pigment dispersion in advance and mixing other components thereto as described below.
- the dispersion treatment is performed using a sand grinder or a paint shaker, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to 8 mm.
- the temperature during the dispersion treatment is usually set in the range of 0 to 100 ° C., preferably in the range of room temperature to 80 ° C.
- the dispersion time needs to be appropriately adjusted because the appropriate time varies depending on the composition of the pigment dispersion (pigment, solvent, dispersant, etc.) and the size of the apparatus.
- the standard of dispersion is to control the gloss of the pigment dispersion so that the 20 ° specular gloss in JIS Z8741 (1997) is in the range of 100 to 200.
- the dispersion treatment is not sufficient and rough pigment particles often remain, which may be insufficient in terms of developability, adhesion, resolution, and the like. Further, when the dispersion treatment is performed until the gloss value exceeds the above range, a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.
- the binder resin or the dispersion aid may be appropriately used in combination.
- the binder resin By including the binder resin, it is possible to improve the dispersion stability when producing the pigment dispersion.
- the addition amount of the binder resin is usually 5 to 100% by weight, preferably 10 to 60% by weight, based on the pigment in the pigment dispersion.
- the addition amount of the binder resin By making the addition amount of the binder resin more than the above lower limit value, it can have higher dispersion stability and patterning characteristics, and by making it less than the above upper limit value, it is possible to ensure a high pigment concentration and higher light shielding properties. Is preferable.
- the solid content concentration of the pigment dispersion is usually 10 to 40% by weight.
- total solid content refers to all components of the pigment dispersion other than the solvent.
- the colored photosensitive composition of the present invention is prepared by adding the other components contained in the colored photosensitive composition to the pigment dispersion obtained by the above steps and mixing them. It is prepared by making a uniform solution.
- blended as a coloring photosensitive composition simultaneously has a possibility that a highly reactive component may modify
- fine dust is often mixed in the liquid in the manufacturing process, it is desirable that the obtained colored photosensitive composition solution is filtered by a filter or the like.
- the colored photosensitive composition of the present invention is used in the same applications as known colored photosensitive compositions for color filters.
- the colored photosensitive composition of the present invention is used as a black photospacer. This will be described according to a specific example of a method for forming a black photospacer using.
- a colored photosensitive composition solution is supplied in a film shape or a pattern shape by a method such as coating on a substrate on which a black photospacer is to be provided, and the solvent is dried. Subsequently, pattern formation is performed by a method such as exposure-development photolithography. Thereafter, a black photo spacer is formed on the substrate by performing additional exposure or thermosetting treatment as necessary.
- the colored photosensitive composition of the present invention is usually supplied onto a substrate in a state dissolved or dispersed in a solvent.
- a conventionally known method such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like can be used. Further, it may be supplied in a pattern by an inkjet method or a printing method.
- the reduction of consumption is much coating liquid, and there is no influence of mist adhering upon by a spin coating method, a foreign substance generation is suppressed, a comprehensive It is preferable from the viewpoint.
- the coating amount varies depending on the application, but in the case of a black photospacer, for example, the dry film thickness is usually in the range of 0.5 ⁇ m to 10 ⁇ m, preferably 1 ⁇ m to 9 ⁇ m, particularly preferably 1 ⁇ m to 7 ⁇ m.
- the dry film thickness or the height of the finally formed spacer is uniform over the entire area of the substrate. When the variation is large, a nonuniformity defect occurs in the liquid crystal panel.
- the final height of the black photosensitive spacers is different.
- a known substrate such as a glass substrate can be used as the substrate.
- the substrate surface is preferably a flat surface.
- Drying method The drying after supplying the colored photosensitive composition solution onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Moreover, you may combine the reduced pressure drying method of drying in a reduced pressure chamber, without raising temperature.
- Drying conditions can be appropriately selected according to the type of solvent component and the performance of the dryer used.
- the drying time is usually selected within a range of 15 seconds to 5 minutes at a temperature of 40 ° C. to 130 ° C., preferably 50 ° C. to 110 ° C., depending on the type of solvent component and the performance of the dryer used.
- the temperature is selected in the range of 30 seconds to 3 minutes.
- Exposure is performed by superimposing a negative mask pattern on the coating film of the colored photosensitive composition and irradiating an ultraviolet light source or a visible light source through this mask pattern.
- the exposure mask is placed close to the coating film of the colored photosensitive composition, or the exposure mask is placed at a position away from the coating film of the colored photosensitive composition, and the exposure is performed.
- a method of projecting exposure light through a mask may be used. Further, a scanning exposure method using a laser beam without using a mask pattern may be used.
- the exposure is performed in a deoxygenated atmosphere or after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer. Or you may.
- a light shielding portion (light transmittance of 0%) and a plurality of openings are used as an average light.
- An exposure mask having an opening (intermediate transmission opening) having a small average light transmittance relative to an opening having the highest transmittance (complete transmission opening) is used.
- a method of creating the intermediate transmission opening by a matrix-shaped light shielding pattern having a minute polygonal light shielding unit is known. Also known is a method of controlling the light transmittance with a film of a material such as chromium, molybdenum, tungsten, or silicon as the absorber.
- the light source used for the above exposure is not particularly limited.
- the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, an argon ion laser, a YAG laser,
- laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, blue-violet semiconductor laser, and near infrared semiconductor laser.
- An optical filter can also be used when used by irradiating light of a specific wavelength.
- the optical filter may be of a type that can control the light transmittance at the exposure wavelength with a thin film, for example, and the material in that case is, for example, a Cr compound (Cr oxide, nitride, oxynitride, fluoride, etc.), Examples include MoSi, Si, W, and Al.
- a Cr compound Cr oxide, nitride, oxynitride, fluoride, etc.
- Energy of exposure generally, 1 mJ / cm 2 or more, preferably 5 mJ / cm 2 or more, more preferably 10 mJ / cm 2 or more, usually 300 mJ / cm 2 or less, preferably 200 mJ / cm 2 or less, more preferably 150 mJ / cm 2 or less.
- the distance between the exposure target and the mask pattern is usually 10 ⁇ m or more, preferably 50 ⁇ m or more, more preferably 75 ⁇ m or more, and usually 500 ⁇ m or less, preferably 400 ⁇ m or less, more preferably 300 ⁇ m or less.
- an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent.
- This aqueous solution may further contain a surfactant, an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.
- Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate
- Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine , Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc.
- Organic alkaline compounds. These alkaline compounds may be a mixture of two or more.
- surfactant examples include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters; Anionic surfactants such as acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; amphoteric surfactants such as alkylbetaines and amino acids.
- nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters
- Anionic surfactants such as acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfon
- organic solvent examples include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like.
- the organic solvent can be used alone or in combination with an aqueous solution.
- the development processing method is not particularly limited, but is usually performed at a development temperature of 10 ° C. to 50 ° C., preferably 15 ° C. to 45 ° C., by a method such as immersion development, spray development, brush development, or ultrasonic development. .
- thermosetting treatment The substrate after development may be subjected to additional exposure by a method similar to the above exposure method, if necessary, or may be subjected to thermosetting treatment.
- the thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 ° C. to 280 ° C., preferably in the range of 150 ° C. to 250 ° C., and the time is selected in the range of 5 minutes to 60 minutes.
- the size, shape, etc. of the black photospacer of the present invention are appropriately adjusted according to the specifications of the color filter to which the black photospacer is applied, but the colored photosensitive composition of the present invention is particularly suitable for the spacer and sub-spacer by photolithography. It is useful for forming black photo spacers with different heights at the same time, in which case the height of the spacer is usually 2-7 ⁇ m and the sub-spacer is usually 0.2-1.5 ⁇ m lower than the spacer Have
- the color filter of the present invention comprises the black photo spacer of the present invention as described above.
- a black matrix, red, green, and blue pixel coloring layers, and an overcoat are laminated to form a black photo spacer, and then an alignment film is formed.
- a liquid crystal cell is formed by bonding the color filter of the present invention having the black photo spacer of the present invention and the liquid crystal driving side substrate, and a liquid crystal is injected into the formed liquid crystal cell to manufacture a liquid crystal display device. it can.
- the components of the colored photosensitive composition used in the following examples and comparative examples are as follows.
- the binder resin-1 corresponds to the “alkali-soluble resin (A)” in the present invention.
- the binder resin-2 corresponds to the “alkali-soluble resin (A)” in the present invention.
- the binder resin-3 can be synthesized according to the following method.
- ⁇ Synthesis Example 1 Synthesis of Binder Resin-3> 50 g of the epoxy compound having the structure (11) (epoxy equivalent 264), 13.65 g of acrylic acid, 60.5 g of methoxybutyl acetate, 0.936 g of triphenylphosphine, and 0.032 g of paramethoxyphenol were added to a thermometer, a stirrer, and cooling. It puts into the flask which attached the pipe
- TMP trimethylolpropane
- BPDA biphenyltetracarboxylic dianhydride
- THPA tetrahydrophthalic anhydride
- This binder resin-3 corresponds to the “alkali-soluble resin (A1”) ”in the present invention.
- DPHA Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.
- pigment dispersions 1 to 10 The pigment, dispersant, dispersion aid, binder resin, and solvent described in Table 1 were mixed at a weight ratio described in Table 1. Here, 80% of the volume of the dispersion container is mixed with zirconia beads (average particle size 0.3 mm), and then filled into a picomil dispersion container and dispersed at the necessary retention time (RT) shown in Table 1. Each pigment dispersion was prepared.
- the exposure gap (distance between the mask and the coated surface) was 250 ⁇ m.
- the light Shako, intensity at a wavelength of 365nm is used ultraviolet is 32 mW / cm 2, the exposure amount was 6 levels of 40 ⁇ 90mJ / cm 2.
- ultraviolet irradiation was performed under air.
- a developer composed of an aqueous solution containing 0.05% by weight of potassium hydroxide and 0.08% by weight of a nonionic surfactant (“A-60” manufactured by Kao Corporation) was used.
- the development was stopped with pure water and washed with a water spray.
- the shower development time was adjusted between 10 and 120 seconds, and was 1.5 times as long as the unexposed coating film was dissolved and removed.
- substrate with which the said pattern was formed was heated at 230 degreeC for 20 minute (s) in oven, the pattern was hardened, and the substantially cylindrical spacer pattern was obtained.
- step ⁇ H The height difference (step ⁇ H) between the complete transmission opening of the circular pattern with a diameter of 15 ⁇ m and the intermediate transmission opening of the circular pattern with a diameter of 35 ⁇ m is calculated, and the maximum value at an exposure amount of 40 to 90 mJ / cm 2 is obtained.
- step ⁇ H 0.5 ⁇ m or more: ⁇ 0.3 ⁇ m or more and less than 0.5 ⁇ m: ⁇ Less than 0.3 ⁇ m: ⁇
- ⁇ Evaluation of substrate adhesion> The pattern remains with good resolution at a completely transmissive aperture of a circular pattern of 5 to 50 ⁇ m and an intermediate transmissive aperture of 5 to 50 ⁇ m at an exposure amount that maximizes the height difference ( ⁇ H).
- the minimum opening diameter ( ⁇ m) is shown in Table 2 as the minimum adhesion. The smaller this value, the better the substrate adhesion. “Remaining with good resolution” means that 24 patterns of the same size are formed and all the patterns are formed normally.
- optical density (OD) ⁇ Evaluation of optical density (OD)>
- the optical density (OD) of the solid part was measured with a transmission densitometer (“D 200-II” manufactured by Gretag Macbeth). Furthermore, the film thickness at the measurement location was also measured, and the optical density per unit film thickness (unit OD) was calculated and evaluated according to the following criteria.
- the OD value is a numerical value indicating the light shielding ability, and the larger the numerical value, the higher the light shielding property. (Evaluation criteria for unit OD) 0.8 or more: ⁇ Less than 0.8: ⁇
- VHR Voltage holding ratio evaluation
- An extraction substrate having a width of 2 mm was connected to the center of one side of the 2.5 cm square glass substrate and the electrode substrate A (Ec Sea, glass ITO solid for evaluation) having an ITO film formed on the entire surface of a 5 cm square piece.
- An electrode substrate B manufactured by ECH, evaluation glass SZ-B111MIN (B)) on which a 1 cm square ITO film was formed was prepared.
- Each colored photosensitive composition was applied on the electrode substrate A, vacuum-dried for 1 minute, and then pre-baked on a hot plate at 90 ° C. for 1.5 minutes to obtain a coating film having a dry film thickness of 2.0 ⁇ m. . Thereafter, the outer edge portion was masked by 2 mm, and image exposure was performed using 3 kW high-pressure mercury under exposure conditions of 50 mJ / cm 2 . Next, a developer composed of an aqueous solution containing about 0.06% by weight of potassium hydroxide and about 0.14% by weight of a nonionic surfactant (“A-60” manufactured by Kao Corporation) was used at 25 ° C.
- A-60 nonionic surfactant
- the shower development time was adjusted between 10 and 120 seconds, and was about 1.5 times the time (break time) during which the non-photosensitive layer was dissolved and removed.
- the electrode substrate thus image-formed was post-baked at 230 ° C. for 20 minutes to obtain a resist-coated electrode substrate (resist substrate). Thereafter, a polyimide solution was applied to the resist substrate, pre-baked on a hot plate at 70 ° C. for 2 minutes, and post-baked at 220 ° C. for 24 minutes.
- the resist substrate thus obtained was cut into a 2.5 cm square substrate to complete an evaluation electrode substrate A.
- a polyimide solution was also applied onto the electrode substrate B, pre-baked at 70 ° C. for 2 minutes on a hot plate, and post-baked at 220 ° C. for 24 minutes to complete the evaluation electrode substrate B.
- an epoxy resin sealant containing silica beads having a diameter of 5 ⁇ m is applied on the outer periphery of the electrode substrate B using a dispenser, and then the electrode substrate A for evaluation is placed on the front side (the sealant side) of the electrode substrate B.
- the application surface was pasted and bonded to complete the empty cell. Heating was performed at 180 ° C. for 2 hours in a hot air circulating furnace.
- a liquid crystal (MLC-6608 manufactured by Merck Japan Co., Ltd.) was injected into the empty cell thus obtained, and the peripheral portion was sealed with a UV curable sealant to complete a voltage holding ratio liquid crystal cell.
- VHR voltage holding ratio
- the colored photosensitive composition of the present invention containing Or64 and B60 as essential components as pigments, and the colored photosensitive composition of the present invention containing Or72 and B60 as essential components as pigments have light shielding properties. It can be seen that it is useful for simultaneously forming cured products having different heights from the same material while maintaining adhesion and voltage holding ratio.
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Abstract
Description
しかしながら、スペーサーを遮光性にするためには、通常顔料を含めた着色剤等を感光性組成物に添加することが考えられるが、着色剤を添加するにつれクリア成分の減少によりスペーサー層の硬化性が減ること及び顔料に由来する不純物等の影響により、特性を損なう恐れがある。
また、本発明の他の課題は、このような着色感光性組成物により形成されたブラックフォトスペーサーを提供することにある。
また更に、本発明の他の課題は、このようなブラックフォトスペーサーを備えるカラーフィルターを提供することにある。
(A)C.I.ピグメントオレンジ43、C.I.ピグメントオレンジ64、及びC.I.ピグメントオレンジ72からなる群より選ばれる1つ
(B)C.I.ピグメントブルー60
[2] 前記顔料が、C.I.ピグメントオレンジ64及びC.I.ピグメントブルー60を含む上記[1]に記載の着色感光性組成物。
[3] 前記顔料が、C.I.ピグメントレッド254、C.I.ピグメントバイオレット23、及びC.I.ピグメントバイオレット29からなる群より選ばれる1つをさらに含む上記[1]又は[2]に記載の着色感光性組成物。
[4] 前記顔料が、下記(1)に示す顔料又は(2)に示す顔料を含む上記[1]に記載の着色感光性組成物。
(1) C.I.ピグメントオレンジ64、C.I.ピグメントブルー60、及びC.I.ピグメントレッド254
(2) C.I.ピグメントオレンジ64、C.I.ピグメントブルー60、及びC.I.ピグメントバイオレット29
[5] 上記[1]乃至[4]のいずれかに記載の着色感光性組成物を用いて形成されたブラックフォトスペーサー。
[6] 上記[5]に記載のブラックフォトスペーサーを含むカラーフィルター。
また、「全固形分」とは、着色感光性組成物又は顔料分散液に含まれる、後記する溶剤成分以外の全成分を意味するものとする。
更に、本発明において、「アミン価」とは、特に断りのない限り有効固形分換算のアミン価を表し、分散剤の固形分1gあたりの塩基量と当量のKOHの重量で表される値である。尚、測定方法については後述する。一方、「酸価」とは、特に断りのない限り有効固形分換算の酸価を表し、中和滴定により算出される。
(A)C.I.ピグメントオレンジ43、C.I.ピグメントオレンジ64、及びC.I.ピグメントオレンジ72からなる群より選ばれる1つ
(B)C.I.ピグメントブルー60
まず、本発明の着色感光性組成物が好適に使用されるフォトリソグラフィー法により高さの異なるブラックフォトスペーサーを一括形成する方法について説明する。この方法は、主として露光工程における露光マスクに特徴を有する。
以下に本発明の着色感光性組成物の構成材料について説明する。
顔料は、本発明の着色感光性組成物を着色するものをいう。
顔料としては青色顔料、緑色顔料、赤色顔料、黄色顔料、紫色顔料、オレンジ顔料、ブラウン顔料、黒色顔料等各種の色の顔料を使用することができる。また、その構造としてはアゾ系、フタロシアニン系、キナクリドン系、ベンズイミダゾロン系、イソインドリノン系、ジオキサジン系、インダンスレン系、ペリレン系等の有機顔料や、種々の無機顔料等が利用可能である。
(A)C.I.ピグメントオレンジ43、C.I.ピグメントオレンジ64、及びC.I.ピグメントオレンジ72からなる群より選ばれる1つ
(B)C.I.ピグメントブルー60
本発明の着色感光性組成物では、顔料として、上記(A)及び(B)を必須成分として含有する以外は、用いる顔料には特に制限はなく、赤、緑、青色等の各色の混合による黒色色材を用いることができる。更に、黒色顔料や、その他の無機又は有機の顔料、染料の中から適宜選択して併用することができる。
三菱化学社製:MA7、MA8、MA11、MA100、MA100R、MA220、MA230、MA600、#5、#10、#20、#25、#30、#32、#33、#40、#44、#45、#47、#50、#52、#55、#650、#750、#850、#950、#960、#970、#980、#990、#1000、#2200、#2300、#2350、#2400、#2600、#3050、#3150、#3250、#3600、#3750、#3950、#4000、#4010、OIL7B、OIL9B、OIL11B、OIL30B、OIL31
デグサ社製:Printex3、Printex3OP、Printex30、Printex30OP、Printex40、Printex45、Printex55、Printex60、Printex75、Printex80、Printex85、Printex90、Printex A、Printex L、Printex G、Printex P、Printex U、Printex V、PrintexG、SpecialBlack550、SpecialBlack350、SpecialBlack250、SpecialBlack100、SpecialBlack6、SpecialBlack5、SpecialBlack4、Color Black FW1、Color Black FW2、Color Black FW2V、Color Black FW18、Color Black FW18、Color Black FW200、Color Black S160、Color Black S170
キャボット社製:Monarch120、Monarch280、Monarch460、Monarch800、Monarch880、Monarch900、Monarch1000、Monarch1100、Monarch1300、Monarch1400、Monarch4630、REGAL99、REGAL99R、REGAL415、REGAL415R、REGAL250、REGAL250R、REGAL330、REGAL400R、REGAL55R0、REGAL660R、BLACK PEARLS480、PEARLS130、VULCAN XC72R、ELFTEX-8
コロンビヤン カーボン社製:RAVEN11、RAVEN14、RAVEN15、RAVEN16、RAVEN22RAVEN30、RAVEN35、RAVEN40、RAVEN410、RAVEN420、RAVEN450、RAVEN500、RAVEN760、RAVEN780RAVEN850、RAVEN890H、RAVEN1000、RAVEN1020、RAVEN1060U、RAVEN1080U、RAVEN1100URAVEN1040、RAVEN1060U、RAVEN1080U、RAVEN1170、RAVEN1190U、RAVEN1250、RAVEN1500、RAVEN2000、RAVEN2500U、RAVEN3500、RAVEN5000、RAVEN5250、RAVEN5750、RAVEN7000
三菱マテリアル社製:10S、12S、13R、13M、13M-C、14M、15M、L-15M等
赤穂化成社製:TilackD M、M-50、M-50A、M-AM、V、UV-3、UV-6、F、S、C、X等
本発明の着色感光性組成物は、顔料として、上記(A)及び(B)の他に、更にC.I.ピグメントレッド254、C.I.ピグメントバイオレット23、及びC.I.ピグメントバイオレット29からなる群より選ばれる1つを含むことが好ましい。
本発明の着色感光性組成物は、遮光性と液晶の電圧保持率、形状や段差のコントロール、及び基板との密着性をより良好なものとするために、顔料として、以下の(1)乃至(3)のいずれかに示す3種の顔料を含むことが好ましく、特に、液晶の電圧保持率の観点から、(1)又は(2)に示す3種の顔料を含むことが好ましい。
(1) C.I.ピグメントオレンジ64、C.I.ピグメントブルー60、C.I.ピグメントレッド254
(2) C.I.ピグメントオレンジ64、C.I.ピグメントブルー60、C.I.ピグメントバイオレット29
(3) C.I.ピグメントオレンジ64、C.I.ピグメントブルー60、C.I.ピグメントバイオレット23
即ち、(A)は波長330nmから380nm付近の光の吸収が比較的小さく、かつ波長400nmから550nm付近の光の吸収が大きい。一方で、(B)は同様に波長330nmから380nm付近の光の吸収が小さく、かつ波長550nmから700nm付近の光の吸収が大きい。従って、これらの2種の顔料をバランスよく組み合わせて用いることにより、紫外領域と可視領域の光吸収のバランスを良好なものとして、遮光性と液晶の電圧保持率、形状や段差のコントロール、及び基板との密着性を高めることができる。
本発明の着色感光性組成物に用いられるバインダー樹脂としては、カラーフィルターに使用される部材の樹脂であれば特に制限無く使用でき、例としてはエポキシアクリレート系樹脂、ノボラック系樹脂、ポリビニルフェノール系樹脂、アクリル系樹脂、カルボキシル基含有エポキシ樹脂、カルボキシル基含有ウレタン樹脂等が挙げられるが、形状や段差のコントロール、基板との密着性の観点から、カルボキシル基を有するエポキシアクリレート樹脂やアクリル樹脂を用いることが好ましく、カルボキシル基を有するエポキシアクリレート樹脂を用いることがさらに好ましい。
本発明におけるバインダー樹脂として、特に好ましいものの一つに、下記一般式(1-a’’)で示されるエポキシ化合物(a’’)と不飽和基含有カルボン酸(b’’)との反応物を、多塩基酸及びその無水物(c’’)のうち少なくとも一方と反応させて得られるアルカリ可溶性樹脂(A’’)が挙げられる。
上記一般式(3)において、R5~R12は、それぞれ独立に、水素原子、置換基を有していてもよい炭素数1~12のアルキル基、又は置換基を有していてもよいフェニル基を示す。Yは、置換基を有していてもよい、アダマンタン構造を含む2価の連結基を示す。
上記一般式(2a)、(2b)及び(3)において、*は、一般式(1-a’’)におけるグリシジルオキシ基との結合部位を示す。)〕
まず、前記一般式(1-a’’)で表されるエポキシ化合物(a’’)(以下、「(a’’)成分」と称することがある)における基Xについて説明する。
一般式(6)において、R16~R23は、それぞれ独立に、水素原子、置換基を有していてもよい炭素数1~12のアルキル基、又は置換基を有していてもよいフェニル基を示す。
一般式(7)において、R24及びR25は、それぞれ独立に、置換基を有していてもよいアダマンチル基、水素原子、置換基を有していてもよい炭素数1~12のアルキル基、又は置換基を有していてもよいフェニル基を示す。〕
また、これらのアルキル基が有していてもよい置換基としては、ハロゲン原子、水酸基、炭素数1~10のアルコキシル基、炭素数2~10のアルケニル基、フェニル基、カルボキシル基、スルファニル基、ホスフィノ基、アミノ基、及びニトロ基などが挙げられる。
不飽和基含有カルボン酸(b’’)(以下、「(b’’)成分」と称することがある)としては、エチレン性不飽和基を有する不飽和カルボン酸が挙げられ、具体例としては、(メタ)アクリル酸、クロトン酸、o-ビニル安息香酸、m-ビニル安息香酸、p-ビニル安息香酸、ケイヒ酸、α-位がハロアルキル基、アルコキシル基、ハロゲン原子、ニトロ基、又はシアノ基で置換された(メタ)アクリル酸などのモノカルボン酸;2-(メタ)アクリロイロキシエチルコハク酸、2-(メタ)アクリロイロキシエチルアジピン酸、2-(メタ)アクリロイロキシエチルフタル酸、2-(メタ)アクリロイロキシエチルヘキサヒドロフタル酸、2-(メタ)アクリロイロキシエチルマレイン酸、2-(メタ)アクリロイロキシプロピルコハク酸、2-(メタ)アクリロイロキシプロピルアジピン酸、2-(メタ)アクリロイロキシプロピルテトラヒドロフタル酸、2-(メタ)アクリロイロキシプロピルフタル酸、2-(メタ)アクリロイロキシプロピルマレイン酸、2-(メタ)アクリロイロキシブチルコハク酸、2-(メタ)アクリロイロキシブチルアジピン酸、2-(メタ)アクリロイロキシブチルヒドロフタル酸、2-(メタ)アクリロイロキシブチルフタル酸、2-(メタ)アクリロイロキシブチルマレイン酸などの、2塩基酸の(メタ)アクリロイロキシアルキルエステル;(メタ)アクリル酸にε-カプロラクトン、β-プロピオラクトン、γ-ブチロラクトン、δ-バレロラクトン等のラクトン類を付加させたものである単量体;(メタ)アクリル酸ダイマーなどが挙げられる。
また、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、トリメチロールプロパンジアクリレート、グリシジルメタクリレートのアクリル酸付加物、グリシジルメタクリレートのメタクリル酸付加物のような水酸基含有不飽和化合物に無水コハク酸、無水マレイン酸、無水テトラヒドロフタル酸、無水フタル酸などの酸無水物を付加させた化合物も挙げられる。
特に好ましいものは、(メタ)アクリル酸である。
これらは1種を単独で用いてもよく、2種以上を混合して用いてもよい。
多塩基酸及びその無水物(c’’)のうち少なくとも一方(以下、「(c’’)成分」又は「多塩基酸(無水物)」と称することがある)としては、2塩基酸及びその無水物のうち少なくとも一方(以下、「2塩基酸(無水物)」と称する)、3塩基酸及びその無水物のうち少なくとも一方(以下、「3塩基酸(無水物)」と称する)、4塩基酸及びその無水物のうち少なくとも一方(以下、「4塩基酸(無水物)」と称する)等を用いることができる。
4塩基酸(無水物)としては、上記例示化合物の中でも、特にビフェニルテトラカルボン酸、又はその無水物が好ましい。
(a’’)成分に(b’’)成分を付加させた後、或いはこれに、後述する多価アルコール(d’’)を混合した後、(c’’)成分を付加させる方法としては、公知の方法を用いることができる。
本発明で用いるバインダー樹脂は、前述した(a’’)成分に(b’’)成分を付加させてなる反応物に、更に多価アルコール(d’’)(以下、「(d’’)成分」と称することがある)を混合し、これら混合物中に存在するいずれかの水酸基に対して上述の(c’’)成分を付加反応させることにより得られる、アルカリ可溶性樹脂(A1’’)であってもよい。
このようにして得られるアルカリ可溶性樹脂(A’’)及び(A1’’)の酸価は、通常10mg-KOH/g以上、好ましくは50mg-KOH/g以上である。良好な現像性を確保するには、酸価が上記下限値以上であることが好ましく、また着色感光性組成物の十分なアルカリ耐性を確保する(すなわち、アルカリ性現像液による、パターン表面の粗面化や、膜減りを生じさせない)には、酸価は200mg-KOH/g以下であることが好ましく、150mg-KOH/g以下であることがより好ましい。
アルカリ可溶性樹脂(A)は、特定のエポキシ樹脂(a)と、不飽和基含有カルボン酸(b)との反応物を、更に多塩基酸及びその無水物(c)のうち少なくとも一方と反応させて得られるものである。
エポキシ樹脂(a)は下記一般式(1-a)で表される。
不飽和基含有カルボン酸(b)としては、エチレン性不飽和二重結合を有する不飽和カルボン酸が挙げられ、具体例としては、(メタ)アクリル酸、クロトン酸、o-、m-、p-ビニル安息香酸、(メタ)アクリル酸のα位ハロアルキル、アルコキシル、ハロゲン、ニトロ、シアノ置換体などのモノカルボン酸、2-(メタ)アクリロイロキシエチルコハク酸、2-アクリロイロキシエチルアジピン酸、2-(メタ)アクリロイロキシエチルフタル酸、2-(メタ)アクリロイロキシエチルヘキサヒドロフタル酸、2-(メタ)アクリロイロキシエチルマレイン酸、2-(メタ)アクリロイロキシプロピルコハク酸、2-(メタ)アクリロイロキシプロピルアジピン酸、2-(メタ)アクリロイロキシプロピルテトラヒドロフタル酸、2-(メタ)アクリロイロキシプロピルフタル酸、2-(メタ)アクリロイロキシプロピルマレイン酸、2-(メタ)アクリロイロキシブチルコハク酸、2-(メタ)アクリロイロキシブチルアジピン酸、2-(メタ)アクリロイロキシブチルヒドロフタル酸、2-(メタ)アクリロイロキシブチルフタル酸、2-(メタ)アクリロイロキシブチルマレイン酸、(メタ)アクリル酸にε-カプロラクトン、β-プロピオラクトン、γ-ブチロラクトン、δ-バレロラクトン等のラクトン類を付加させたものである単量体、或いはヒドロキシアルキル(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレートに(無水)コハク酸、(無水)フタル酸、(無水)マレイン酸などの酸(無水物)を付加させた単量体、(メタ)アクリル酸ダイマーなどが挙げられる。
エポキシ樹脂(a)中のエポキシ基と不飽和基含有カルボン酸(b)とを反応させる方法としては公知の手法を用いることができる。例えば、エポキシ樹脂(a)と不飽和基含有カルボン酸(b)とを、トリエチルアミン、ベンジルメチルアミン等の3級アミン、ドデシルトリメチルアンモニウムクロライド、テトラメチルアンモニウムクロライド、テトラエチルアンモニウムクロライド、ベンジルトリエチルアンモニウムクロライド等の4級アンモニウム塩、ピリジン、トリフェニルホスフィン等を触媒として、有機溶剤中、反応温度50~150℃で数~数十時間反応させることにより、エポキシ樹脂にカルボン酸を付加することができる。
エポキシ樹脂(a)と不飽和基含有カルボン酸(b)との反応物の水酸基に付加させる多塩基酸及びその無水物(c)としては、公知のものが使用でき、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、メチルエンドメチレンテトラヒドロフタル酸、クロレンド酸、メチルテトラヒドロフタル酸、5-ノルボルネン-2,3-ジカルボン酸、メチル-5-ノルボルネン-2,3-ジカルボン酸等の二塩基性カルボン酸又はその無水物;トリメリット酸、ピロメリット酸、ベンゾフェノンテトラカルボン酸、ビフェニルテトラカルボン酸等の多塩基性カルボン酸又はその無水物等が挙げられる。中でも好ましくは、テトラヒドロ無水フタル酸又は無水コハク酸が挙げられる。これらは1種を単独で用いてもよく、2種以上を併用してもよい。
本発明で用いるアルカリ可溶性樹脂(A)の、ゲルパーミエーションクロマトグラフィー(GPC)で測定したポリスチレン換算の重量平均分子量(Mw)は通常1500以上、好ましくは2000以上であり、通常50000以下、好ましくは30000以下、より好ましくは10000以下である。このアルカリ可溶性樹脂(A)の重量平均分子量が小さすぎると、感度が劣り、大きすぎると現像液に対する溶解性が不足するため好ましくない。
本発明におけるバインダー樹脂として、特に好ましいものの他の例として、下記一般式(1-a’)で示されるエポキシ化合物(a’)と、不飽和基含有カルボン酸(b’)との反応物を、多塩基酸及びその無水物(c’)のうち少なくとも一方と反応させて得られるアルカリ可溶性樹脂(A’)が挙げられる。
まず、前記一般式(1-a’)で示されるエポキシ化合物(a’)(以下、「(a’)成分」と称することがある)について説明する。
従って上記観点からは、前記一般式(1-a’)におけるp及びqはそれぞれ独立して0~4の整数を表すが、好ましくは1又は2である。
不飽和基含有カルボン酸(b’)(以下、「(b’)成分」と称することがある)としては、<アルカリ可溶性樹脂(A’’),アルカリ可溶性樹脂(A1’’)>における不飽和基含有カルボン酸(b’’)として挙げたものと同様の化合物が使用できる。これらの内、α,β-不飽和カルボン酸の中では(メタ)アクリル酸が好ましく、特にアクリル酸が反応性に富むため好ましい。またエステル部分にカルボキシル基を有するα,β-不飽和カルボン酸エステルの中では、2-(メタ)アクリロイロキシエチルフタル酸、及び2-(メタ)アクリロイロキシエチルマレイン酸が好ましい。
(b’)成分の使用量を下限値以上とすることにより、十分な量の不飽和基を導入することができ、また続く多塩基酸及びその無水物(c’)のうち少なくとも一方との反応も十分となる。また、多量のエポキシ基が残存しない点も好ましい。(b’)成分の使用量を上限値以下とすることにより、未反応物として残存しない点で好ましい。上記範囲を満たすことにより、高い光硬化特性を得ることができる。
多塩基酸及びその無水物(c’)としても、<アルカリ可溶性樹脂(A’’),アルカリ可溶性樹脂(A1’’)>における多塩基酸及びその無水物(c’’)として挙げたものと同様の化合物が挙げられ、中でもテトラヒドロフタル酸、ビフェニルテトラカルボン酸、及びこれらの無水物が好ましい。
本発明におけるバインダー樹脂として、特に好ましいものの他の例として、下記一般式(1-a’’’)で示されるエポキシ樹脂(a’’’)と不飽和基含有カルボン酸(b’’’)との反応物を、多塩基酸及びその無水物(c’’’)のうち少なくとも一方と反応させて得られるアルカリ可溶性樹脂(A’’’)が挙げられる。
本発明において、光重合開始剤は、エチレン性不飽和化合物等の光重合性モノマーと共に用いられる。
エチレン性不飽和結合を分子内に1個以上有する化合物としては、例えば、(メタ)アクリル酸、クロトン酸、イソクロトン酸、マレイン酸、イタコン酸、シトラコン酸等の不飽和カルボン酸、及びそのアルキルエステル、(メタ)アクリロニトリル、(メタ)アクリルアミド、スチレン等が挙げられる。
不飽和カルボン酸とアルコールアミンとの反応物;アルコールアミン類とは具体的にはジエタノールアミン、トリエタノールアミン等が挙げられる。
エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、トリメチロールプロパンジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、トリメチロールプロパンエチレンオキサイド付加トリ(メタ)アクリレート、グリセロールジ(メタ)アクリレート、グリセロールトリ(メタ)アクリレート、グリセロールプロピレンオキサイド付加トリ(メタ)アクリレート、ペンタエリスリトールジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート等、及び同様のクロトネート、イソクロトネート、マレエート、イタコネート、シトラコネート等
光重合開始剤は、通常、加速剤との混合物(光重合開始剤系)として用いられ、必要に応じて添加される増感色素等が併用される。
本発明の着色感光性組成物は、顔料の分散性の向上、分散安定性の向上のために、顔料分散剤及び分散助剤のうち少なくとも一方を併用する事が好ましい。中でも、特に顔料分散剤として高分子分散剤を用いると経時の分散安定性に優れるので好ましい。なお、ここで、高分子分散剤は顔料の分散安定性を確保するための、顔料とは全く構造の異なるポリマーであり、分散助剤とは顔料の分散性を高めるための顔料誘導体等をいう。
顔料誘導体を用いる場合、その使用量は着色感光性組成物中の顔料に対して通常0.1~30重量%、好ましくは0.1~20重量%、より好ましくは0.1~10重量%、さらに好ましくは0.1~5重量%である。
本発明の着色感光性組成物は、一般に上述の顔料、バインダー樹脂、光重合性モノマー、光重合開始剤、分散剤及び分散助剤や、後述のその他の成分の固形分を溶剤に溶解ないし分散させて調製される。
このような溶剤としては、例えば国際公開第2008/153000号などに記載の各種溶剤が挙げられる。
上記国際公開第2008/153000号に記載された溶剤のうち、塗布性、表面張力などのバランスがよく、組成物中の構成成分の溶解度が比較的高い点からは、グリコールアルキルエーテルアセテート類が好ましい。
なお沸点150℃以上の高沸点溶剤が、グリコールアルキルエーテルアセテート類であってもよく、またグリコールアルキルエーテル類であってもよく、この場合は、沸点150℃以上の高沸点溶剤を別途含有させなくてもかまわない。
本発明の着色感光性組成物には、上記の成分の他に、さらに重合加速剤、増感色素、界面活性剤、光酸発生剤、架橋剤、密着性向上剤、可塑剤、保存安定剤、表面保護剤、有機カルボン酸、有機カルボン酸無水物、現像改良剤、熱重合防止剤等を含んでいてもよい。
光酸発生剤とは、紫外線により酸を発生することができる化合物であり、露光を行った際に発生する酸の作用により、例えばメラミン化合物等架橋剤があることで架橋反応を進行させることとなる。係る光酸発生剤の中でも、溶剤に対する溶解性、特に着色感光性組成物に使われる溶剤に対する溶解性が大きいものが好ましいものであり、例えば、ジフェニルヨードニウム、ジトリルヨードニウム、フェニル(p-アニシル)ヨードニウム、ビス(m-ニトロフェニル)ヨードニウム、ビス(p-tert-ブチルフェニル)ヨードニウム、ビス(p-クロロフェニル)ヨードニウム、ビス(n-ドデシル)ヨードニウム、p-イソブチルフェニル(p-トリル)ヨードニウム、p-イソプロピルフェニル(p-トリル)ヨードニウムなどのジアリールヨードニウム、あるいはトリフェニルスルホニウムなどのトリアリールスルホニウムのクロリド、ブロミド、あるいはホウフッ化塩、へキサフルオロフォスフェート塩、ヘキサフルオロアルセネート塩、芳香族スルホン酸塩、テトラキス(ペンタフルオロフェニル)ボレート塩等や、ジフェニルフェナシルスルホニウム(n-ブチル)トリフェニルボレート等のスルホニウム有機ホウ素錯体類、あるいは、2-メチル-4,6-ビストリクロロメチルトリアジン、2-(4-メトキシフェニル)-4,6-ビストリクロロメチルトリアジンなどのトリアジン化合物等を挙げることができるがこの限りではない。
これらの光酸発生剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
本発明の着色感光性組成物には、さらに架橋剤を加えることができ、例えばメラミン又はグアナミン系の化合物を用いることができる。これら架橋剤としては、例えば、下記一般式(XI)で示されるメラミン又はグアナミン系の化合物を挙げることができる。
2,6-ビス(ヒドロキシメチル)-4-メチルフェノール、4-tert-ブチル-2,6-ビス(ヒドロキシメチル)フェノール、5-エチル-1,3-ビス(ヒドロキシメチル)ペルヒドロ-1,3,5-トリアジン-2-オン(通称N-エチルジメチロールトリアゾン)又はそのジメチルエーテル体、ジメチロールトリメチレン尿素又はそのジメチルエーテル体、3,5-ビス(ヒドロキシメチル)ペルヒドロ-1,3,5-オキサジアジン-4-オン(通称ジメチロールウロン)又はそのジメチルエーテル体、テトラメチロールグリオキザールジウレイン又はそのテトラメチルエーテル体。
本発明の着色感光性組成物には、細い線やドットを充分密着させるために、密着向上剤を含有させてもよい。
増感色素としては、例えば日本国特開平4-221958号、日本国特開平4-219756号公報に記載のキサンテン色素、日本国特開平3-239703号、日本国特開平5-289335号公報に記載の複素環を有するクマリン色素、日本国特開平3-239703号、日本国特開平5-289335号公報に記載の3-ケトクマリン化合物、日本国特開平6-19240号公報に記載のピロメテン色素、その他、日本国特開昭47-2528号、日本国特開昭54-155292号、日本国特公昭45-37377号、日本国特開昭48-84183号、日本国特開昭52-112681号、日本国特開昭58-15503号、日本国特開昭60-88005号、日本国特開昭59-56403号、日本国特開平2-69号、日本国特開昭57-168088号、日本国特開平5-107761号、日本国特開平5-210240号、日本国特開平4-288818号公報に記載のジアルキルアミノベンゼン骨格を有する色素等を挙げることができる。
界面活性剤としてはアニオン系、カチオン系、非イオン系、両性界面活性剤等各種のものの1種又は2種以上を用いることができるが、諸特性に悪影響を及ぼす可能性が低い点で、非イオン系界面活性剤を用いるのが好ましい。また、フッ素系やシリコン系のものは、塗布性の面で効果的である。
本発明の着色感光性組成物は、現像性の向上や地汚れ改善の目的で有機カルボン酸及び有機カルボン酸無水物のうち少なくとも一方を含んでいてもよい。
脂肪族カルボン酸としては、具体的には、ギ酸、酢酸、プロピオン酸、酪酸、吉草酸、ピバル酸、カプロン酸、ジエチル酢酸、エナント酸、カプリル酸、グリコール酸、アクリル酸、メタクリル酸などのモノカルボン酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ブラシル酸、メチルマロン酸、エチルマロン酸、ジメチルマロン酸、メチルコハク酸、テトラメチルコハク酸、シクロヘキサンジカルボン酸、シクロヘキセンジカルボン酸、イタコン酸、シトラコン酸、マレイン酸、フマル酸などのジカルボン酸、トリカルバリル酸、アコニット酸、カンホロン酸などのトリカルボン酸などが挙げられる。
また、芳香族カルボン酸としては、具体的には、安息香酸、トルイル酸、クミン酸、へメリト酸、メシチレン酸、フタル酸、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、トリメシン酸、メロファン酸、ピロメリット酸、フェニル酢酸、ヒドロアトロパ酸、ヒドロケイ皮酸、マンデル酸、フェニルコハク酸、アトロパ酸、ケイ皮酸、ケイ皮酸メチル、ケイ皮酸ベンジル、シンナミリデン酢酸、クマル酸、ウンベル酸などのフェニル基に直接カルボキシル基が結合したカルボン酸、及びフェニル基から炭素結合を介してカルボキシル基が結合したカルボン酸等が挙げられる。
熱重合防止剤としては、例えば、ハイドロキノン、p-メトキシフェノール、ピロガロール、カテコール、2,6-t-ブチル-p-クレゾール、β-ナフトール等の1種又は2種以上が用いられる。
可塑剤としては、例えば、ジオクチルフタレート、ジドデシルフタレート、トリエチレングリコールジカプリレート、ジメチルグリコールフタレート、トリクレジルホスフェート、ジオクチルアジペート、ジブチルセバケート、トリアセチルグリセリン等の1種又は2種以上が用いられる。
本発明の着色感光性組成物は常法に従って調製される。以下に、例を挙げて具体的に説明するが、本発明における着色感光性組成物の調製方法は、当該方法に限定される訳ではない。
顔料、溶剤及び分散剤、必要に応じて分散助剤を各々所定量秤量し、分散処理工程において、顔料を分散させて液状の顔料分散液とする。この分散処理工程では、ペイントコンディショナー(ペイントシェイカー)、サンドグラインダー、ボールミル、ロールミル、ストーンミル、ジェットミル、ホモジナイザーなどを使用することができる。この分散処理を行うことによって顔料が微粒子化されるため、このようにして調製された顔料分散液を用いた着色感光性組成物は塗布特性、及び形状や直線性などのパターニング特性が向上する。
この場合、JIS Z8741(1997)における20度鏡面光沢度が100~200の範囲となるように顔料分散液の光沢を制御するのが分散の目安である。顔料分散液の光沢が低い場合には分散処理が十分でなく荒い顔料粒子が残っていることが多く、現像性、密着性、解像性等の点で不十分となる場合がある。また、光沢値が上記範囲を超えるまで分散処理すると超微粒子が多数生じるために却って分散安定性が損なわれることになりやすい。
この場合、バインダー樹脂の添加量は、顔料分散液中の顔料に対して、通常5~100重量%、好ましくは10~60重量%とすることが好ましい。バインダー樹脂の添加量を上記下限値以上とすることにより、より高い分散安定性やパターニング特性を有することができ、また上記上限値以下とすることにより、高い顔料濃度を確保でき、より高い遮光性が得られるため好ましい。
ここで、「全固形分」とは、溶剤以外の顔料分散液の全成分を指す。
本発明の着色感光性組成物は、上記工程により得られた顔料分散液に、着色感光性組成物が含有する他の成分を添加し、混合して均一な溶液とすることにより調製される。なお、着色感光性組成物として配合する全成分を同時に混合した液での分散処理は、分散時に生じる発熱のため高反応性の成分が変性するおそれがある。また、製造工程においては微細なゴミが液中に混じることが多いため、得られた着色感光性組成物溶液はフィルター等により濾過処理するのが望ましい。
本発明の着色感光性組成物は、公知のカラーフィルター用着色感光性組成物と同様の用途に使用されるが、以下、ブラックフォトスペーサーとして使用される場合について、本発明の着色感光性組成物を用いたブラックフォトスペーサーの形成方法の具体例に従って説明する。
本発明の着色感光性組成物は、通常、溶剤に溶解或いは分散された状態で、基板上へ供給される。その供給方法としては、従来公知の方法、例えば、スピナー法、ワイヤーバー法、フローコート法、ダイコート法、ロールコート法、スプレーコート法などによって行うことができる。また、インクジェット法や印刷法などにより、パターン状に供給されてもよい。中でも、ダイコート法によれば、塗布液の使用量が大幅に削減され、かつ、スピンコート法によった際に付着するミストなどの影響が全くない、異物発生が抑制されるなど、総合的な観点から好ましい。
基板上に着色感光性組成物溶液を供給した後の乾燥は、ホットプレート、IRオーブン、コンベクションオーブンを使用した乾燥方法によるのが好ましい。また、温度を高めず、減圧チャンバー内で乾燥を行う、減圧乾燥法を組み合わせてもよい。
露光は、着色感光性組成物の塗布膜上に、ネガのマスクパターンを重ね、このマスクパターンを介し、紫外線又は可視光線の光源を照射して行う。露光マスクを用いて露光を行う場合には、露光マスクを着色感光性組成物の塗布膜に近接させる方法や、露光マスクを着色感光性組成物の塗布膜から離れた位置に配置し、該露光マスクを介した露光光を投影する方法によってもよい。また、マスクパターンを用いないレーザー光による走査露光方式によってもよい。この際、必要に応じ、酸素による光重合性層の感度の低下を防ぐため、脱酸素雰囲気下で行ったり、光重合性層上にポリビニルアルコール層などの酸素遮断層を形成した後に露光を行ったりしてもよい。
中間透過開口部は、例えば、微小な多角形の遮光ユニットを有するマトリックス状遮光パターンによって作成する方法等が知られている。また吸収体として、クロム系、モリブデン系、タングステン系、シリコン系などの材料の膜によって、光透過率を制御し作成する方法等が知られている。
また、近接露光方式の場合には、露光対象とマスクパターンとの距離としては、通常10μm以上、好ましくは50μm以上、より好ましくは75μm以上であり、通常500μm以下、好ましくは400μm以下、より好ましくは300μm以下である。
上記の露光を行った後、アルカリ性化合物の水溶液、又は有機溶剤を用いる現像によって、基板上に画像パターンを形成することができる。この水溶液には、さらに界面活性剤、有機溶剤、緩衝剤、錯化剤、染料又は顔料を含ませることができる。
現像の後の基板には、必要により上記の露光方法と同様な方法により追露光を行ってもよく、また熱硬化処理を行ってもよい。この際の熱硬化処理条件は、温度は100℃~280℃の範囲、好ましくは150℃~250℃の範囲で選ばれ、時間は5分間~60分間の範囲で選ばれる。
本発明のカラーフィルターは、上述のような本発明のブラックフォトスペーサーを備えるものであり、例えば透明基板としてのガラス基板上に、ブラックマトリクスと、赤色、緑色、青色の画素着色層と、オーバーコート層とが積層されて、ブラックフォトスペーサーを形成した後配向膜を形成して製造される。
日本化薬(株)製「ZCR-1569H」(MW=3000~4000、酸価=約100mg-KOH/g)
なお、このバインダー樹脂-1は、本発明における「アルカリ可溶性樹脂(A)」に相当する。
日本化薬(株)製「ZCR-1642H」(MW=5000~6500、酸価=約100mg-KOH/g)
なお、このバインダー樹脂-2は、本発明における「アルカリ可溶性樹脂(A)」に相当する。
下記構造(11)のエポキシ化合物とアクリル酸との反応物を、トリメチロールプロパン(TMP)及びビフェニルテトラカルボン酸2無水物(BPDA)と反応させて得られた樹脂(MW=3500~4500、酸価=約110mg-KOH/g)
<合成例1:バインダー樹脂-3の合成>
上記構造(11)のエポキシ化合物(エポキシ当量264)50g、アクリル酸13.65g、メトキシブチルアセテート60.5g、トリフェニルホスフィン0.936g、及びパラメトキシフェノール0.032gを、温度計、攪拌機、冷却管を取り付けたフラスコに入れ、攪拌しながら90℃で酸価が5mgKOH/g以下になるまで反応させる。反応には12時間を要し、エポキシアクリレート溶液を得る。
樹脂溶液が透明になったところでメトキシブチルアセテートで希釈し、固形分50重量%となるよう調製し、バインダー樹脂-3を得る。
ビックケミー社製「DisperBYK-2000」
<分散助剤>
ループリゾール社製「S12000」
<界面活性剤>
大日本インキ化学社製「メガファック F-475」
<溶剤-1>
PGMEA:プロピレングリコールモノメチルエーテルアセテート
<溶剤-2>
MB:3-メトキシブタノール
下記化合物。
DPHA:日本化薬(株)製ジペンタエリスリトールヘキサアクリレート
表1に記載の顔料、分散剤、分散助剤、バインダー樹脂、及び溶剤を、表1に記載の重量比で混合した。ここに、分散容器の容積の80%のジリコニアビーズ(平均粒径0.3mm)を混合した後、ピコミル分散容器に充填し、表1に示す必要なリテンション時間(RT)にて分散させて、各顔料分散液を調製した。
上記の通り調製された顔料分散液と表2に示す他の各成分とを、表2に示す割合で配合、撹拌して着色感光性組成物を調製した。
<高さの異なる硬化物の一括形成方法>
ガラス基板(AGC社製「AN100」)上にスピナーを用いて各着色感光性組成物を塗布した。次いで、110℃にて70秒間、ホットプレート上で加熱乾燥して塗布膜を形成した。
得られた塗布膜に対し、直径5~50μmの各種直径の円形パターンの完全透過開口部及び直径5~50μmの各種直径の円形パターンの中間透過開口部、さらにはベタ部を有する露光マスクを用いて露光処理を施した。中間透過開口部は、Cr酸化物の薄膜で波長365nmにおける光透過率を10±2%としたものである。露光ギャップ(マスクと塗布面間の距離)は、250μmであった。光射光としては、波長365nmでの強度が32mW/cm2である紫外線を用い、露光量は40~90mJ/cm2の6水準とした。また、紫外線照射は空気下で行った。
これらの操作により、不要部分を除去したパターンを得た。当該パターンの形成された基板をオーブン中、230℃で20分間加熱してパターンを硬化させ、略円柱状のスペーサーパターンを得た。
直径15μmの円形パターンの完全透過開口部及び直径35μmの円形パターンの中間透過開口部の高さの差異(段差ΔH)を算出し、露光量40~90mJ/cm2における最大値を求めると共に、ΔHの値を以下の基準で評価した。
(段差ΔHの評価基準)
0.5μm以上 :○
0.3μm以上0.5μm未満:△
0.3μm未満 :×
高さの差異(ΔH)が最大となる露光量にて、5~50μmの円形パターンの完全透過開口部と、同じく5~50μmの中間透過開口部において、それぞれパターンが解像性良く残っている最小の開口直径(μm)を最小密着として表2に示した。この値は小さい程基板密着性に優れる。尚、解像性良く残っているとは、同一サイズのパターンを24個形成して、その全てのパターンが正常に形成されていることをいう。
ベタ部の光学濃度(OD)を透過濃度計(グレタグマクベス社製「D 200-II」)にて測定した。さらに測定箇所の膜厚も測定し、単位膜厚あたりの光学濃度(単位OD)を算出し、以下の基準で評価した。なお、OD値は遮光能力を示す数値であり数値が大きい程高遮光性であることを示す。
(単位ODの評価基準)
0.8以上 :○
0.8未満 :×
<液晶セルの作製>
5cm角の片全面にITO膜を形成した電極基板A(イーエッチシー製、評価用ガラスITOベタ)と、2.5cm角の同ガラス基板の片面中央部に、2mm幅の取り出し電極がつながった1cm角のITO膜を形成した電極基板B(イーエッチシー製、評価用ガラスSZ-B111MIN(B))を用意した。
その後、電極基板Bの外周上に、ディスペンサーを用いて、直径5μmのシリカビーズを含有するエポキシ樹脂系シール剤を塗布した後、電極基板Bの表側(シール剤側)に評価用電極基板Aの塗布面を圧着したまま貼り付けて、空セルが完成した。熱風循環炉内で180℃で2時間加熱した。
こうして得られた空セルに、液晶(メルクジャパン社製MLC-6608)を注入し、周辺部をUV硬化型シール剤によって封止し、電圧保持率測定用液晶セルを完成した。
上記液晶セルを、アニール処理(熱風循環炉内で105℃、2.5時間加熱)した後、評価用電極基板A、Bに、電圧5V、0.6Hz、フレーム時間1667msecの条件で電圧印加し、電圧保持率を(株)東陽テクニカ製「VHR-6254型」にて測定した。
Claims (6)
- 顔料、バインダー樹脂、光重合性モノマー、及び光重合開始剤を含む着色感光性組成物であって、前記顔料が、下記(A)に示す顔料及び(B)に示す顔料を含む着色感光性組成物。
(A)C.I.ピグメントオレンジ43、C.I.ピグメントオレンジ64、及びC.I.ピグメントオレンジ72からなる群より選ばれる1つ
(B)C.I.ピグメントブルー60 - 前記顔料が、C.I.ピグメントオレンジ64及びC.I.ピグメントブルー60を含む請求項1に記載の着色感光性組成物。
- 前記顔料が、C.I.ピグメントレッド254、C.I.ピグメントバイオレット23、及びC.I.ピグメントバイオレット29からなる群より選ばれる1つをさらに含む請求項1又は2に記載の着色感光性組成物。
- 前記顔料が、下記(1)に示す顔料又は(2)に示す顔料を含む請求項1に記載の着色感光性組成物。
(1) C.I.ピグメントオレンジ64、C.I.ピグメントブルー60、及びC.I.ピグメントレッド254
(2) C.I.ピグメントオレンジ64、C.I.ピグメントブルー60、及びC.I.ピグメントバイオレット29 - 請求項1乃至4のいずれか1項に記載の着色感光性組成物を用いて形成されたブラックフォトスペーサー。
- 請求項5に記載のブラックフォトスペーサーを含むカラーフィルター。
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KR102078989B1 (ko) | 2020-02-19 |
JP2018009194A (ja) | 2018-01-18 |
JP6229210B2 (ja) | 2017-11-15 |
JPWO2013115268A1 (ja) | 2015-05-11 |
TWI585529B (zh) | 2017-06-01 |
CN110244513A (zh) | 2019-09-17 |
JP6036708B2 (ja) | 2016-11-30 |
JP2017033023A (ja) | 2017-02-09 |
CN104081280A (zh) | 2014-10-01 |
KR101985564B1 (ko) | 2019-06-03 |
TW201337460A (zh) | 2013-09-16 |
CN110244513B (zh) | 2022-10-14 |
CN104081280B (zh) | 2019-05-31 |
JP6409936B2 (ja) | 2018-10-24 |
KR20190058671A (ko) | 2019-05-29 |
KR20140121824A (ko) | 2014-10-16 |
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