WO2011081149A1 - Photosensitive composition, partition wall, color filter and organic el element - Google Patents
Photosensitive composition, partition wall, color filter and organic el element Download PDFInfo
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- WO2011081149A1 WO2011081149A1 PCT/JP2010/073601 JP2010073601W WO2011081149A1 WO 2011081149 A1 WO2011081149 A1 WO 2011081149A1 JP 2010073601 W JP2010073601 W JP 2010073601W WO 2011081149 A1 WO2011081149 A1 WO 2011081149A1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
- G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
- H10K59/122—Pixel-defining structures or layers, e.g. banks
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/17—Passive-matrix OLED displays
- H10K59/173—Passive-matrix OLED displays comprising banks or shadow masks
Definitions
- an organic EL element after forming a partition pattern using photolithography, a solution such as a hole transport material and a light emitting material is applied to the opening between the partitions using an inkjet method, A pixel having a hole transport layer, a light emitting layer, and the like is formed.
- Patent Document 3 describes a technique relating to a partition made of an ink repellent material including a resin binder, an ink repellent agent having a compatible part with the resin binder, and a part having ink repellency.
- the number average molecular weight of the ink repellent in Patent Document 3 is 40,000 to 100,000, and examples include fluorine-containing block polymers having a number average molecular weight of 40,000 to 70,000. Yes.
- Polymer (A) is a fluoropolymer having a side chain having the group represented by the general formula (1) and having no side chain having an ethylenic double bond, and its mass average molecular weight.
- Mw (A)) is 4.2 ⁇ 10 4 ⁇ Mw (A) ⁇ 20 ⁇ 10 4 .
- a mass average molecular weight (Mw) and a number average molecular weight (Mn) mean the value which measured polystyrene as a standard substance by the gel permeation chromatography method.
- the partition matrix has these functional groups of the polymer (A) by post-baking treatment after exposure and development.
- the polymer (A) is sufficiently fixed to the partition wall by thermally crosslinking with the acidic group derived from the binder resin (C).
- the polymer (A) particularly at a portion where the polymer (A) on the upper surface of the partition wall is present at a high density. The two are heat-crosslinked to become more polymerized and are sufficiently fixed to the partition walls.
- a monomer which has the said group (1) used for manufacture of a polymer (A) it is preferable that it is a compound represented by following General formula (3). These may be used individually by 1 type, or may use 2 or more types together.
- CH 2 CR 4 —COO—Y—CFXR f (3)
- R 4 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, an etheric oxygen atom or a C 1-20 fluoro atom.
- monomers used for polymerization are appropriately selected from the monomers described above and copolymerized at an appropriate ratio.
- the preferable compounding ratio of the various monomers used when manufacturing a polymer (A) is as follows.
- the ratio of the monomer mass having the group (2) to the total mass of the monomer to be copolymerized is: It is preferable that the silicon (A) content in the polymer (A) is in the above preferred range, specifically 0.1 to 25% by mass, more preferably 0.5 to 20% by mass. Such a ratio depends on the type of the monomer having the group (2), but specifically, it is preferably 0.5 to 30% by mass, more preferably 2 to 20% by mass.
- the ratio of the monomer mass having the crosslinkable functional group to the total mass of the monomer to be copolymerized Is preferably 1 to 40% by mass, and more preferably 5 to 20% by mass.
- the ratio of the monomer having a crosslinkable functional group in all the monomers to be copolymerized is within this range, the polymer (A) can be immobilized on the partition wall without impairing the effects of the present invention. In addition, developability is improved.
- the adjustment of the mass average molecular weight of the polymer (A) can be performed by adjusting the conditions such as the polymerization temperature and time, the amount of the polymerization initiator, the addition amount of the chain transfer agent and the like.
- the polymer (A) thus produced is random copolymerization, but the block copolymer is prepared using a usual method such as changing the introduction timing of the raw material monomer into the copolymerization reaction system depending on the type of monomer. It is also possible to produce a polymer.
- the side chain having the above various groups in the polymer (A) used in the present invention in particular, the side chain having an acidic group or the side chain having a thermally crosslinkable functional group is also formed by chemical conversion after the polymerization reaction.
- a copolymer having a side chain having the group (1) and a side chain having a hydroxyl group is produced by the above polymerization, and a polybasic acid anhydride (such as maleic anhydride) is reacted with the hydroxyl group of the copolymer.
- a polymer (A) having a side chain having a carboxyl group as an acidic group can be produced.
- the polymer (A) ′ is a polymer essentially having a side chain having the group (2) instead of the side chain having the group (1) in the polymer (A).
- polymer (A) ' in addition to the side chain which has group (1), although the structure was described about the polymer (A) which has a side chain which has group (2), polymer (A) ' Can have the same configuration as that except that it does not have a side chain having the group (1).
- R 24 , R 26 and R 27 are preferably hydrogen atoms.
- the photosensitive resin (C1) is not particularly limited. Specifically, the resin (C1-1) having a side chain having an acidic group and a side chain having an ethylenic double bond, and an epoxy resin having ethylenic properties. Examples thereof include a resin (C1-2) into which a double bond and an acidic group are introduced. These may be used alone or in combination of two or more.
- Resin (C1-1) is, for example, a side chain having a reactive group obtained by copolymerizing a monomer having a reactive group such as a hydroxyl group, a carboxyl group, or an epoxy group with a monomer having an acidic group. And a copolymer having an acidic group-containing side chain, a functional group capable of bonding to the reactive group, and a compound having an ethylenic double bond dissolved in a solvent and reacted. it can.
- the monomer having a phosphate group as an acidic group is not particularly limited, and examples thereof include 2- (meth) acryloyloxyethane phosphoric acid.
- a commercially available product can be used as the resin (C1-2) in which an acidic group and an ethylenic double bond are introduced into an epoxy resin.
- all are trade names, such as KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, CCR-1163H, CCR-1166H, CCR-1159H, TCR-1025, TCR-1064H , TCR-1286H, ZAR-1535H, ZFR-1122H, ZFR-1124H, ZFR-1185H, ZFR-1492H, ZCR-1571H, ZCR-1569H, ZCR-1580H, ZCR-1581H, ZCR-1588H, ZCR-1629H (above And Nippon Kayaku Co., Ltd.), EX1010 (manufactured by Nagase ChemteX Corporation), and the like.
- the radical curable photosensitive composition according to the present invention preferably contains a crosslinking agent (D) having two or more ethylenic double bonds as an optional component for promoting radical curing.
- a crosslinking agent (D) having two or more ethylenic double bonds as an optional component for promoting radical curing.
- the radical curable photosensitive composition according to the present invention contains a dispersible material such as the black colorant (E), it is preferable to contain a polymer dispersant in order to improve the dispersibility.
- the polymer dispersant is not particularly limited, and is urethane type, polyimide type, alkyd type, epoxy type, polyester type, melamine type, phenol type, acrylic type, polyether type, vinyl chloride type, vinyl chloride vinyl acetate type.
- a polymer system, a polyamide system, a polycarbonate system and the like can be mentioned, and a urethane system or a polyester system is preferable.
- the polymer dispersant may have a structural unit derived from ethylene oxide and / or propylene oxide.
- the crosslinkable resin (C22) is preferably at least one selected from the group consisting of amino resins, epoxy compounds, and oxazoline compounds. These may be used alone or in combination of two or more.
- the solvent for diluting the photosensitive composition is not particularly limited. Specifically, alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol and ethylene glycol; ketones such as acetone, methyl isobutyl ketone and cyclohexanone; 2-methoxyethanol, 2-ethoxyethanol, 2- Cellsorbs such as butoxyethanol; carbitols such as 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol; methyl acetate, ethyl acetate, n- Butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol Methyl ether acetate, diethylene glycol monoethyl ether acetate,
- the coating method is not particularly limited, and examples thereof include spin coating, spraying, slit coating, roll coating, spin coating, and bar coating.
- the developer is not particularly limited, and examples thereof include aqueous alkali solutions such as inorganic alkalis, amines, alcohol amines, and quaternary ammonium salts.
- the development time that is, the time for contact with the developer is preferably 5 to 180 seconds.
- the developing method is not particularly limited, and examples thereof include a liquid filling method, a dipping method, and a shower method.
- the ink mainly contains a coloring component, a binder resin component, and a solvent, and may be either water-based ink or oil-based ink.
- a coloring component pigments and / or dyes excellent in heat resistance, light resistance and the like are preferable.
- the binder resin component a resin that is transparent and excellent in heat resistance is preferable, and examples thereof include an acrylic resin, a melamine resin, and a urethane resin.
- the water-based ink contains water as a solvent and, if necessary, a water-soluble organic solvent, and contains a water-soluble resin and / or a water-dispersible resin as a binder resin component.
- the oil-based ink contains an organic solvent as a solvent, and a resin soluble in the organic solvent as a binder resin component.
- a photo spacer may be formed on a partition wall, for example, a black matrix, if necessary.
- Photosensitive composition component photocuring initiator (B): photopolymerization initiator (B1)
- OXE02 OXE02 (manufactured by Ciba Specialty Chemicals, Etanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime) (the above general formula (5 ), R 21 and R 22 are methyl groups, R 23 is an ethyl group, R 24 , R 26 and R 27 are hydrogen atoms, and R 25 is a 2-methylbenzoyl group)
- EX1010 EX-1010 (manufactured by Nagase ChemteX Corporation, a solution of a resin in which an ethylenic double bond and an acidic group are introduced into the epoxy resin represented by the above general formula (7), solid content 70% by mass, mass average molecular weight : 3,0
- the column is maintained at 37 ° C., tetrahydrofuran is used as the eluent, the flow rate is 0.2 mL / min, and the 0.5 mass% tetrahydrofuran solution of the measurement sample is measured. 40 ⁇ L was injected.
- Liquid epoxy ME-562 (Nihon Pernox) (6.25 g), curing agent HV-562 (Nihon Pernox) (6.25 g), diethyl adipate (12.5 g) and diethyl malonate (25.0 g) ) was stirred and mixed using a stirrer for 1 hour to prepare an ink.
- the mass average molecular weight Mw (A) is Photosensitive material of the present invention containing each of the polymers (A-1) to (A-6) corresponding to the polymer (A) in the range of 4.2 ⁇ 10 4 ⁇ Mw (A) ⁇ 20 ⁇ 10 4
- the ink spreads in the openings between the partition walls, and no white spots were observed. This indicates that in the photosensitive compositions of Examples 1 to 6, the developability was good and the polymer (A) component did not move from the partition wall surface to the opening between the partition walls.
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Abstract
Description
特許文献2には、炭素数4~6のフルオロアルキル基を有するα位置換アクリレート、不飽和有機酸および、高軟化点モノマーを繰り返し単位とするフッ素系ポリマーを含有する撥液レジスト組成物が記載されている。特許文献2の実施例に記載されている含フッ素共重合体の質量平均分子量は最大で、10,100である。 In order to obtain the characteristics required for such a partition, it has been proposed to add an ink repellent component to the photosensitive composition for forming the partition. For example, Patent Document 1 describes an alkali developing photosensitive coloring composition containing a fluorine-containing block copolymer in which the A segment is a fluorine-containing segment and the B segment is a non-fluorine segment. The mass average molecular weights of the fluorine-containing block copolymers described in Examples of Patent Document 1 are 33,000, 36,000, 37,000, 38,000, 40,000, 42,000.
Patent Document 2 describes a liquid repellent resist composition containing an α-substituted acrylate having a C 4-6 fluoroalkyl group, an unsaturated organic acid, and a fluorine-based polymer having a high softening point monomer as a repeating unit. Has been. The mass average molecular weight of the fluorine-containing copolymer described in the Examples of Patent Document 2 is 10,100 at the maximum.
CH2=CH(Rx)COOY1RF …式1
(式中、Rxは、水素原子、メチル基またはトリフルオロメチル基、Y1は炭素数1~6の2価のフッ素原子を含まない有機基を示し、RFは、炭素数4~6のパーフルオロアルキル基を示す。)
特許文献4においては、上記含フッ素樹脂は、感光性成分の種類によって、エチレン性二重結合を有する基やカルボキシル基および/または水酸基を有することが好ましいとの記載がある。特許文献5の実施例に記載されている含フッ素樹脂においては、エチレン性二重結合を含まない含フッ素樹脂の質量平均分子量は最大で、8,100であり、エチレン性二重結合を有する含フッ素樹脂の質量平均分子量は最大で、11,600である。 Patent Document 4 discloses a fluorine-containing resin having a monomer unit formed from a monomer represented by the following formula 1, having a fluorine atom content of 7 to 35% by mass, and a wavelength of 100 to 600 nm. A resist composition containing a light sensitive photosensitive component is described.
CH 2 = CH (R x ) COOY 1 R F Formula 1
(In the formula, R x represents a hydrogen atom, a methyl group or a trifluoromethyl group, Y 1 represents an organic group containing 1 to 6 carbon atoms and does not contain a divalent fluorine atom, and R F represents 4 to 6 carbon atoms. Represents a perfluoroalkyl group.)
Patent Document 4 describes that the fluorine-containing resin preferably has a group having an ethylenic double bond, a carboxyl group and / or a hydroxyl group depending on the type of the photosensitive component. In the fluorine-containing resins described in Examples of Patent Document 5, the fluorine-containing resin not containing an ethylenic double bond has a maximum mass average molecular weight of 8,100, and has an ethylenic double bond. The mass average molecular weight of the fluororesin is 11,600 at the maximum.
また、撥インク成分として上記求められる性能を十分に備えたエチレン性二重結合を有する含フッ素樹脂においては、エチレン性二重結合を有する基を含フッ素樹脂に導入するために工程数が増える等製造面で不利な点があった。 However, in the conventional ink repellent component, when a fluorine-containing resin having an ethylenic double bond is used, the required performance of the obtained partition wall, that is, good ink repellency at the top of the partition wall, and erosion to the developer Performance such as resistance to the developer not developed, good wetting and spreading of the ink to the opening between the partition walls, etc. are sufficiently obtained, but when using a fluorine-containing resin having no ethylenic double bond, these performances The present condition is that the partition which fully satisfy | fills all is not obtained.
In addition, in the fluorine-containing resin having an ethylenic double bond sufficiently provided with the above-described performance as an ink repellent component, the number of steps is increased because a group having an ethylenic double bond is introduced into the fluorine-containing resin. There were disadvantages in manufacturing.
[1]下記一般式(1)で表される基を有する側鎖を有し、かつエチレン性二重結合を有する側鎖を有しない重合体(A)と、光硬化開始剤(B)と、バインダー樹脂(C)とを含む感光性組成物であって、
-CFXRf …(1)
(式中、Xは、水素原子、フッ素原子またはトリフルオロメチル基を表し、Rfは、エーテル性酸素原子を有していてもよい炭素数が1以上20以下のフルオロアルキル基またはフッ素原子を表す。)
前記重合体(A)の質量平均分子量(Mw(A))が、4.2×104<Mw(A)≦20×104であることを特徴とする感光性組成物。 The present invention provides a photosensitive composition, partition walls, a color filter, and an organic EL device having the following configuration.
[1] A polymer (A) having a side chain having a group represented by the following general formula (1) and not having a side chain having an ethylenic double bond, a photocuring initiator (B), A photosensitive composition comprising a binder resin (C),
-CFXR f (1)
(In the formula, X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R f represents a fluoroalkyl group or fluorine atom having 1 to 20 carbon atoms which may have an etheric oxygen atom. To express.)
The weight average molecular weight of the polymer (A) (Mw (A) ) is, 4.2 × 10 4 <Mw ( A) ≦ 20 × 10 photosensitive composition which is a 4.
[3]前記重合体(A)が、酸性基を有する[1]または[2]に記載の感光性組成物。
[4]前記重合体(A)におけるフッ素原子含有割合が、20~50質量%である[1]~[3]のいずれかに記載の感光性組成物。 [2] The photosensitive composition according to [1], wherein the number average molecular weight (Mn (A)) of the polymer (A) is 1.5 × 10 4 ≦ Mn (A) ≦ 6 × 10 4 .
[3] The photosensitive composition according to [1] or [2], wherein the polymer (A) has an acidic group.
[4] The photosensitive composition according to any one of [1] to [3], wherein the polymer (A) has a fluorine atom content of 20 to 50% by mass.
[6]前記重合体(A)が、エポキシ基、メルカプト基および水酸基からなる群から選ばれる1種以上をさらに有する[1]~[5]のいずれかに記載の感光性組成物。
[7]前記重合体(A)が、さらに下記一般式(2)で表される基を有する側鎖を有する[1]~[6]のいずれかに記載の感光性組成物。 [5] The photosensitive composition according to any one of [1] to [4], wherein the ratio of the polymer (A) in the total solid content of the photosensitive composition is 0.07 to 1% by mass.
[6] The photosensitive composition according to any one of [1] to [5], wherein the polymer (A) further has at least one selected from the group consisting of an epoxy group, a mercapto group, and a hydroxyl group.
[7] The photosensitive composition according to any one of [1] to [6], wherein the polymer (A) further has a side chain having a group represented by the following general formula (2).
[9]前記光硬化開始剤(B)が光重合開始剤であり、前記バインダー樹脂(C)が酸性基とエチレン性二重結合とを有する感光性樹脂である[1]~[8]のいずれかに記載の感光性組成物。 [8] Side chain having no side chain having the group represented by the general formula (1), having a side chain having the group represented by the general formula (2), and having an ethylenic double bond Polymer (A) ′ having a mass average molecular weight (Mw (A) ′) of 4.2 × 10 4 <Mw (A) ′ ≦ 20 × 10 4 The photosensitive composition according to any one of [1] to [7], further comprising:
[9] The photocuring initiator (B) is a photopolymerization initiator, and the binder resin (C) is a photosensitive resin having an acidic group and an ethylenic double bond. The photosensitive composition in any one.
[11]さらに、黒色着色剤(E)を含む[1]~[10]のいずれかに記載の感光性組成物。
[12]基板上を画素形成用の複数の区画に仕切るかたちに形成された隔壁であって、[1]~[11]のいずれかに記載の感光性組成物の塗膜硬化物からなることを特徴とする隔壁。 [10] The photosensitive composition according to [9], further comprising a crosslinking agent (D) having two or more ethylenic double bonds.
[11] The photosensitive composition according to any one of [1] to [10], further comprising a black colorant (E).
[12] A partition formed in a manner that partitions the substrate into a plurality of sections for pixel formation, and is made of a cured film of the photosensitive composition according to any one of [1] to [11] Septum characterized by.
[14]基板上に複数の画素と隣接する画素間に位置する隔壁とを有する有機EL素子であって、前記隔壁が[12]に記載の隔壁で形成されており、前記画素がインクジェット法により形成されたものであることを特徴とする有機EL素子。
なお、本明細書において、「光硬化開始剤」の用語は、光照射により活性種を発生して上記バインダー樹脂(C)の硬化反応を開始させる化合物、の総称として用いる。 [13] A color filter having a plurality of pixels and a partition located between adjacent pixels on the substrate, wherein the partition is formed by the partition described in [12], and the pixel is formed by an inkjet method A color filter characterized by being made.
[14] An organic EL element having a plurality of pixels and a partition located between adjacent pixels on the substrate, wherein the partition is formed by the partition described in [12], and the pixel is formed by an inkjet method. An organic EL element formed.
In the present specification, the term “photocuring initiator” is used as a general term for compounds that generate active species by light irradiation to initiate the curing reaction of the binder resin (C).
なお、本明細書において、特に説明のない限り、%は、質量%を表す。また、(メタ)アクリロイル基は、アクリロイル基とメタクリロイル基の両者を意味する総称として使用する。(メタ)アクリレートは、アクリレートとメタクリレートの両者を意味する総称として使用する。(メタ)アクリル酸は、アクリル酸とメタクリル酸の両者を意味する総称として使用する。(メタ)アクリルアミドは、アクリルアミドとメタクリルアミドの両者を意味する総称として使用する。(メタ)アリルは、アリルとメタリルの両者を意味する総称として使用する。一般式(1)で表される基を、基(1)ともいう。他の基も同様である。 Although the form for implementing this invention is demonstrated below, this invention is not limited to the following embodiment.
In the present specification, unless otherwise specified,% represents mass%. Further, the (meth) acryloyl group is used as a general term meaning both an acryloyl group and a methacryloyl group. (Meth) acrylate is used as a generic term for both acrylate and methacrylate. (Meth) acrylic acid is used as a generic term for both acrylic acid and methacrylic acid. (Meth) acrylamide is used as a general term for both acrylamide and methacrylamide. (Meth) allyl is used as a generic term for both allyl and methallyl. The group represented by the general formula (1) is also referred to as a group (1). The same applies to other groups.
本発明の感光性組成物は、下記一般式(1)で表される基を有する側鎖を有し、かつエチレン性二重結合を有する側鎖を有しない、質量平均分子量(Mw(A))が、4.2×104<Mw(A)≦20×104である重合体(A)と、光硬化開始剤(B)と、バインダー樹脂(C)とを含む感光性組成物である。
-CFXRf …(1)
(式中、Xは、水素原子、フッ素原子またはトリフルオロメチル基を表し、Rfは、エーテル性酸素原子を有していてもよい炭素数が1以上20以下のフルオロアルキル基またはフッ素原子を表す。) <1> Photosensitive composition The photosensitive composition of the present invention has a side chain having a group represented by the following general formula (1) and does not have a side chain having an ethylenic double bond, and is a mass. A polymer (A) having an average molecular weight (Mw (A)) of 4.2 × 10 4 <Mw (A) ≦ 20 × 10 4 , a photocuring initiator (B), a binder resin (C), It is a photosensitive composition containing this.
-CFXR f (1)
(In the formula, X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R f represents a fluoroalkyl group or fluorine atom having 1 to 20 carbon atoms which may have an etheric oxygen atom. To express.)
ネガ型感光性組成物は、硬化の種類により、例えば、ラジカル硬化型、酸硬化型等の幾つかのタイプに分類され、その硬化の種類により、用いる光硬化開始剤(B)およびバインダー樹脂(C)の組合せが選択される。本発明の感光性組成物は、ネガ型感光性組成物であれば、いずれの硬化のタイプにも適用可能であるが、特にラジカル硬化型の感光性組成物に好適である。以下、本発明の感光性組成物の実施の形態について、ラジカル硬化型感光性組成物および酸硬化型感光性組成物を例として説明する。 The photosensitive composition of the present invention is a photosensitive composition comprising the polymer (A), a photocuring initiator (B), and a binder resin (C), and is a binder in a light irradiation portion upon exposure in photolithography or the like. It is a negative photosensitive composition in which the resin (C) is cured by the action of the photocuring initiator (B). In photolithography or the like, a portion that is not irradiated with light (an unexposed portion) is selectively removed during alkali development performed after exposure, and as a result, a partition wall made of a cured product of the photosensitive composition is formed. It is formed.
The negative photosensitive composition is classified into several types such as a radical curable type and an acid curable type depending on the type of curing, and depending on the type of curing, the photocuring initiator (B) and the binder resin ( A combination of C) is selected. The photosensitive composition of the present invention can be applied to any curing type as long as it is a negative photosensitive composition, but is particularly suitable for a radical curable photosensitive composition. Hereinafter, an embodiment of the photosensitive composition of the present invention will be described using a radical curable photosensitive composition and an acid curable photosensitive composition as examples.
本発明の感光性組成物がラジカル硬化型の場合、感光性組成物は、重合体(A)、光硬化開始剤(B)としての光重合開始剤(B1)、およびバインダー樹脂(C)としての酸性基およびエチレン性二重結合とを有する感光性樹脂(C1)を含有する。このようなラジカル硬化型感光性組成物は、フォトリソグラフィ等における露光に際して光照射部分では光重合開始剤(B1)の作用により感光性樹脂(C1)がラジカル重合し硬化が促進され塗膜硬化物を形成する。
本発明に係るラジカル硬化型感光性組成物が含有する各成分について以下に説明する。 (1) Radical curable photosensitive composition When the photosensitive composition of the present invention is a radical curable type, the photosensitive composition contains a polymer (A) and a photopolymerization initiator (B) as a photocuring initiator (B). B1) and a photosensitive resin (C1) having an acidic group and an ethylenic double bond as the binder resin (C). Such a radical curable photosensitive composition is a coating film cured product in which the photosensitive resin (C1) is radically polymerized by the action of the photopolymerization initiator (B1) in the light-irradiated portion during exposure in photolithography or the like, and curing is accelerated. Form.
Each component which the radical curable photosensitive composition concerning this invention contains is demonstrated below.
重合体(A)は、上記一般式(1)で表される基を有する側鎖を有し、かつエチレン性二重結合を有する側鎖を有しない含フッ素重合体であり、その質量平均分子量(Mw(A))は、4.2×104<Mw(A)≦20×104である。 (1-1) Polymer (A)
The polymer (A) is a fluoropolymer having a side chain having the group represented by the general formula (1) and having no side chain having an ethylenic double bond, and its mass average molecular weight. (Mw (A)) is 4.2 × 10 4 <Mw (A) ≦ 20 × 10 4 .
重合体(A)の質量平均分子量が4.2×104以下であると、隔壁間開口部の親液性が不十分であり、インクジェット法を用いてインクを塗布したときに開口部にインクが十分に濡れ拡がらない。また、質量平均分子量が20×104を超えると、アルカリ溶解性、現像性が不十分となる。 The mass average molecular weight (Mw (A)) of the polymer (A) used in the present invention is 4.2 × 10 4 <Mw (A) ≦ 20 × 10 4 . More preferably, 4.5 × 10 4 ≦ Mw (A) ≦ 12 × 10 4 , and particularly preferably 5.0 × 10 4 ≦ Mw (A) ≦ 10 × 10 4 .
When the mass average molecular weight of the polymer (A) is 4.2 × 10 4 or less, the lyophilicity of the opening between the partition walls is insufficient, and the ink is applied to the opening when the ink is applied using an ink jet method. Does not spread out sufficiently. On the other hand, when the mass average molecular weight exceeds 20 × 10 4 , alkali solubility and developability become insufficient.
なお、本明細書において、質量平均分子量(Mw)および数平均分子量(Mn)とは、ゲルパーミエーションクロマトグラフィー法により、ポリスチレンを標準物質として測定した値をいう。 The polymer (A) preferably further has a number average molecular weight (Mn (A)) of 1.5 × 10 4 ≦ Mn (A) ≦ 6.0 × 10 4 , and 1.8 × 10 4 ≦ more preferably Mn (a) ≦ 5.0 × 10 4, particularly preferably 2.0 × 10 4 ≦ Mn (a ) ≦ 4.0 × 10 4. When the number average molecular weight of the polymer (A) is less than 1.5 × 10 4 , the lyophilicity of the opening between the partition walls is insufficient, and the ink is applied to the opening when the ink is applied using an ink jet method. May not be sufficiently wet and spread, and if the number average molecular weight exceeds 6.0 × 10 4 , alkali solubility and developability may be insufficient.
In addition, in this specification, a mass average molecular weight (Mw) and a number average molecular weight (Mn) mean the value which measured polystyrene as a standard substance by the gel permeation chromatography method.
また、このフルオロアルキル基の構造としては、特に限定されず、直鎖構造、分岐構造、環構造、部分的に環を有する構造等が挙げられるが、直鎖構造が好ましい。さらに、Rfがエーテル性酸素原子を有するフルオロアルキル基である場合、エーテル性酸素原子は、フルオロアルキル基の炭素-炭素結合間に存在してもよいし、フルオロアルキル基の末端に存在していてもよい。
基(1)にけるRfとしては、上記エーテル性酸素原子を有していてもよい炭素数が1~20のフルオロアルキル基が好ましい。また、Xは、フッ素原子であることが特に好ましい。 The polymer (A) used for this invention has group (1) containing the fluorine atom shown by the said General formula (1) in a side chain. In the group (1), when R f is a fluoroalkyl group having 1 to 20 carbon atoms which may have an etheric oxygen atom, R f may have a halogen atom excluding a fluorine atom. Good. As such a halogen atom, a chlorine atom is preferable.
Further, the structure of the fluoroalkyl group is not particularly limited, and examples thereof include a linear structure, a branched structure, a ring structure, a structure having a partial ring, and the like, and a linear structure is preferable. Further, when R f is a fluoroalkyl group having an etheric oxygen atom, the etheric oxygen atom may be present between the carbon-carbon bonds of the fluoroalkyl group or at the end of the fluoroalkyl group. May be.
R f in the group (1) is preferably a fluoroalkyl group having 1 to 20 carbon atoms which may have the etheric oxygen atom. X is particularly preferably a fluorine atom.
Rfがエーテル性酸素原子を有していてもよい炭素数が1以上20以下のフルオロアルキル基の場合、Rfとしては、エーテル性酸素原子を有しないパーフルオロアルキル基とエーテル性酸素原子を有するパーフルオロアルキル基が好ましく、エーテル性酸素原子を有しないパーフルオロアルキル基がより好ましい。その炭素数は1~11が好ましく、3~5が特に好ましい。 In the above group (1), when R f is a fluoroalkyl group having 1 to 20 carbon atoms which may have an etheric oxygen atom, R f is particularly limited as long as it has such a configuration. Not. As R f , specifically, —CF 3 , —CF 2 CF 3 , —CF 2 CHF 2 , — (CF 2 ) 2 CF 3 , — (CF 2 ) 3 CF 3 , — (CF 2 ) 4 CF 3 , — (CF 2 ) 5 CF 3 , — (CF 2 ) 6 CF 3 , — (CF 2 ) 7 CF 3 , — (CF 2 ) 8 CF 3 , — (CF 2 ) 9 CF 3 , — ( CF 2 ) 11 CF 3 , — (CF 2 ) 15 CF 3 , —CF (CF 3 ) O (CF 2 ) 5 CF 3 , —CF 2 O (CF 2 CF 2 O) p CF 3 (p is 1 ), —CF (CF 3 ) O (CF 2 CF (CF 3 ) O) q C 6 F 13 (q is an integer of 1 to 4), —CF (CF 3 ) O (CF 2 CF (CF 3 ) O) r C 3 F 7 (r is an integer of 1 to 5).
If R f is carbon atoms, which may have an etheric oxygen atom is 1 to 20 fluoroalkyl group, the R f, a perfluoroalkyl group and an etheric oxygen atom having no etheric oxygen atom A perfluoroalkyl group having an etheric oxygen atom is more preferable. The number of carbon atoms is preferably 1 to 11 and particularly preferably 3 to 5.
本発明に用いる重合体(A)について、上記基(1)を有する側鎖を有する構成とし、さらに任意に、上記基(2)を有する側鎖、酸性基を有する側鎖、隔壁マトリックスが有する官能基と熱または光により架橋可能な官能基を有する側鎖等を有する構成とするためには、これらの基を有する側鎖を重合反応によって直接形成する、または、重合反応後の化学変換によって形成する方法が挙げられる。 (Production of polymer (A))
About the polymer (A) used for this invention, it is set as the structure which has the side chain which has the said group (1), Furthermore, the side chain which has the said group (2), the side chain which has an acidic group, and a partition matrix have In order to have a structure having a functional group and a side chain having a functional group that can be cross-linked by heat or light, the side chain having these groups is formed directly by a polymerization reaction, or by chemical conversion after the polymerization reaction. The method of forming is mentioned.
なお、共重合の種類としては、交互共重合、ブロック共重合、ランダム共重合等が挙げられ、それぞれ従来公知の方法で共重合を実行することができるが、本発明において、重合体(A)はランダム共重合により共重合して得られるランダム共重合体であることが好ましい。 In order to directly form the side chain having the group (1) that the polymer (A) has and the side chain having each of the groups that are optionally included by polymerization reaction, the monomer having the group (1) And, if necessary, a monomer having the group (2), a monomer having an acidic group, a monomer having a functional group that can be thermally cross-linked with the functional group of the partition matrix, and / or other The monomer may be copolymerized under appropriate conditions.
Examples of copolymerization include alternating copolymerization, block copolymerization, random copolymerization and the like, and the copolymerization can be carried out by a conventionally known method. In the present invention, the polymer (A) Is preferably a random copolymer obtained by copolymerization by random copolymerization.
CH2=CR4-COO-Y-CFXRf …(3) As a monomer which has the said group (1) used for manufacture of a polymer (A), it is preferable that it is a compound represented by following General formula (3). These may be used individually by 1 type, or may use 2 or more types together.
CH 2 = CR 4 —COO—Y—CFXR f (3)
これらのうちでも、化合物(3)におけるYとしては、入手の容易さから、炭素数が2~4のアルキレン基が好ましい。 Among the groups represented by Y in the above formula (3), Y, which is a divalent organic group having no fluorine atom having 1 to 6 carbon atoms, is —R 5 —, —R 5 —NR 6 —. SO 2 —, —R 5 —NR 6 —CO—, —CH 2 CH (OH) —R 7 — (R 5 is an alkylene group having 1 to 6 carbon atoms, and R 6 is a hydrogen atom or methyl R 7 is a single bond or an alkylene group having 1 to 4 carbon atoms, provided that when R 6 is a methyl group, R 5 bonded to NR 6 has 1 to 5 carbon atoms. ) And the like. Specific examples R 5, -CH 2 -, - CH 2 CH 2 -, - CH (CH 3) -, - CH 2 CH 2 CH 2 -, - C (CH 3) 2 -, - CH (CH 2 CH 3 ) —, —CH 2 CH 2 CH 2 CH 2 —, —CH (CH 2 CH 2 CH 3 ) —, —CH 2 (CH 2 ) 3 CH 2 —, —CH (CH 2 CH (CH 3 ) 2 )-and the like. Specific examples R 7, -CH 2 -, - CH 2 CH 2 -, - CH (CH 3) -, - CH 2 CH 2 CH 2 -, - C (CH 3) 2 -, - CH (CH 2 CH 3 ) —, —CH 2 CH 2 CH 2 CH 2 —, —CH (CH 2 CH 2 CH 3 ) — and the like.
Among these, Y in the compound (3) is preferably an alkylene group having 2 to 4 carbon atoms from the viewpoint of availability.
上記Zが示す基のうちでも、化合物(4)が有するZとしては、炭素数が1~6の2価の炭化水素基が好ましく、具体的には、-CH2-、-CH2CH2-、-CH(CH3)-、-CH2CH2CH2-、-C(CH3)2-、-CH(CH2CH3)-、-CH2CH2CH2CH2-、-CH(CH2CH2CH3)-、-CH2(CH2)3CH2-、-CH(CH2CH(CH3)2)-等が挙げられる。Zとしては、炭素数2~4の直鎖状アルキレン基が特に好ましい。 Preferred embodiments of R 1 , R 2 , R 3 and n in the compound (4) are the same as those described for the group (2).
Of the groups represented by Z, the compound (4) has a divalent hydrocarbon group having 1 to 6 carbon atoms, specifically, —CH 2 —, —CH 2 CH 2 -, -CH (CH 3 )-, -CH 2 CH 2 CH 2- , -C (CH 3 ) 2- , -CH (CH 2 CH 3 )-, -CH 2 CH 2 CH 2 CH 2 -,- CH (CH 2 CH 2 CH 3 ) —, —CH 2 (CH 2 ) 3 CH 2 —, —CH (CH 2 CH (CH 3 ) 2 ) — and the like can be mentioned. Z is particularly preferably a linear alkylene group having 2 to 4 carbon atoms.
このようにして製造される重合体(A)はランダム共重合であるが、共重合反応系へ原料単量体の導入時期を単量体の種類により変える等の通常の方法を用いてブロック共重合体を製造することも可能である。 The polymer (A) used in the present invention has a side chain having the group (1) as an essential component, and optionally, a side chain having the group (2), a side chain having an acidic group, and a crosslinking. A copolymer having a side chain or the like having a functional functional group, the monomer having the group (1), the monomer having the group (2), and the monomer having an acidic group, if necessary The monomer can be synthesized by dissolving a monomer having a crosslinkable functional group and / or another monomer in a solvent, heating, and adding a polymerization initiator to carry out copolymerization. In addition, when making it copolymerize, it is preferable to add a chain transfer agent as needed. Moreover, you may add a monomer, a polymerization initiator, a solvent, and a chain transfer agent continuously. Here, the adjustment of the mass average molecular weight of the polymer (A) can be performed by adjusting the conditions such as the polymerization temperature and time, the amount of the polymerization initiator, the addition amount of the chain transfer agent and the like.
The polymer (A) thus produced is random copolymerization, but the block copolymer is prepared using a usual method such as changing the introduction timing of the raw material monomer into the copolymerization reaction system depending on the type of monomer. It is also possible to produce a polymer.
重合体(A)’は、言い換えれば、重合体(A)において基(1)を有する側鎖に替えて基(2)を有する側鎖を必須に有する重合体である。また、上記重合体(A)において、基(1)を有する側鎖に加えて、基(2)を有する側鎖を有する重合体(A)について構成を記載したが、重合体(A)’は、基(1)を有する側鎖を有しないことを除いて、その構成と同様の構成とすることができる。 Moreover, in the radical curable photosensitive composition which concerns on this invention, it is possible to contain the component which can provide a liquid-repellent effect | action to a partition other than the said polymer (A). Specifically, as such a component, it does not have a side chain having the group (1), has a side chain having a group represented by the general formula (2), and has an ethylenic double bond. Polymer (A) ′ having no side chain and having a mass average molecular weight (Mw (A) ′) of 4.2 × 10 4 <Mw (A) ′ ≦ 20 × 10 4 ( A) '.
In other words, the polymer (A) ′ is a polymer essentially having a side chain having the group (2) instead of the side chain having the group (1) in the polymer (A). Moreover, in the said polymer (A), in addition to the side chain which has group (1), although the structure was described about the polymer (A) which has a side chain which has group (2), polymer (A) ' Can have the same configuration as that except that it does not have a side chain having the group (1).
本発明の感光性組成物がラジカル硬化型の場合、光硬化開始剤(B)としては、光の照射によりラジカルを発生する光重合開始剤(B1)が用いられる。 (1-2) Photocuring initiator (B) (Photopolymerization initiator (B1))
When the photosensitive composition of the present invention is a radical curable type, a photopolymerization initiator (B1) that generates radicals upon irradiation with light is used as the photocuring initiator (B).
本発明の感光性組成物がラジカル硬化型の場合、バインダー樹脂(C)としては、上記光重合開始剤(B1)が発生したラジカルにより重合する、酸性基およびエチレン性二重結合を有する感光性樹脂(C1)が用いられる。
感光性樹脂(C1)は、1分子内に上記光重合に関与するエチレン性二重結合を有し、さらに酸性基を有するため、アルカリ現像液を用いて、硬化されていない感光性組成物の未露光部を選択的に除去することができ、その結果、隔壁を形成することができる。なお、感光性樹脂(C1)は、基(1)および基(2)を実質的に有しないことが好ましい。 (1-3) Binder resin (C) (Photosensitive resin (C1))
When the photosensitive composition of the present invention is a radical curable type, the binder resin (C) is a photosensitive resin having an acidic group and an ethylenic double bond that is polymerized by the radical generated by the photopolymerization initiator (B1). Resin (C1) is used.
Since the photosensitive resin (C1) has an ethylenic double bond involved in the photopolymerization in one molecule and further has an acidic group, the photosensitive resin (C1) is an uncured photosensitive composition using an alkaline developer. Unexposed portions can be selectively removed, and as a result, barrier ribs can be formed. In addition, it is preferable that photosensitive resin (C1) does not have group (1) and group (2) substantially.
本発明に係るラジカル硬化型感光性組成物は、上記重合体(A)、光硬化開始剤(B)としての光重合開始剤(B1)、およびバインダー樹脂(C)としての酸性基およびエチレン性二重結合とを有する感光性樹脂(C1)を必須成分として含有するが、本発明の効果を損なわない範囲において、各種機能の向上等を目的として以下に説明する任意成分を含有することが可能である。
(エチレン性二重結合を2個以上有する架橋剤(D))
本発明に係るラジカル硬化型感光性組成物は、ラジカル硬化を促進する任意成分として、エチレン性二重結合を2個以上有する架橋剤(D)を含むことが好ましい。これにより、露光時における上記感光性樹脂(C1)の硬化性が向上し、隔壁を形成する際の露光量を低減することができる。なお、上記架橋剤(D)は、酸性基を実質的に有しないことが好ましい。 (1-3) Optional Components The radical curable photosensitive composition according to the present invention comprises the polymer (A), a photopolymerization initiator (B1) as a photocuring initiator (B), and a binder resin (C). As an essential component, the photosensitive resin (C1) having an acidic group and an ethylenic double bond as an optional component is described below for the purpose of improving various functions and the like as long as the effects of the present invention are not impaired. It is possible to contain components.
(Crosslinking agent (D) having two or more ethylenic double bonds)
The radical curable photosensitive composition according to the present invention preferably contains a crosslinking agent (D) having two or more ethylenic double bonds as an optional component for promoting radical curing. Thereby, the sclerosis | hardenability of the said photosensitive resin (C1) at the time of exposure improves, and the exposure amount at the time of forming a partition can be reduced. In addition, it is preferable that the said crosslinking agent (D) does not have an acidic group substantially.
また、ウレタンアクリレートとしては、日本化薬社製のKAYARAD UXシリーズが挙げられ、具体的商品名としては、UX-3204、UX-6101、UX-0937、DPHA-40H、UX-5000、UX-5002D-P20などが挙げられる。A-9300、BANI-MおよびBANI-Xは塗膜に硬さを付与し、熱垂れを抑制する観点から好ましい。A-9300-1CLは塗膜に柔軟性を付与する観点から好ましい。ウレタンアクリレートは、適度な現像時間が実現可能となり、現像性が良好になるので好ましい。 In the present invention, a commercially available product can be used as the crosslinking agent (D) having two or more ethylenic double bonds. Examples of such commercially available products include KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), NK ester A-9300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) , Ethoxylated isocyanuric acid triacrylate), NK ester A-9300-1CL (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate), BANI-M (trade name) Manufactured by Maruzen Petrochemical Co., Ltd., bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane), BANI-X (trade name, Maruzen Petrochemical) N, N′-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene- , 3-dicarboximide)), and the like.
Examples of urethane acrylate include KAYARAD UX series manufactured by Nippon Kayaku Co., Ltd., and specific product names include UX-3204, UX-6101, UX-0937, DPHA-40H, UX-5000, UX-5002D. -P20 and the like. A-9300, BANI-M and BANI-X are preferable from the viewpoint of imparting hardness to the coating film and suppressing thermal sagging. A-9300-1CL is preferable from the viewpoint of imparting flexibility to the coating film. Urethane acrylate is preferable because an appropriate development time can be realized and developability is improved.
本発明に係るラジカル硬化型感光性組成物は、この硬化物がブラックマトリックスのように遮光性を求められる用途に用いられる場合には、求められる隔壁の光学濃度に応じて黒色着色剤(E)を含有することが好ましい。 (Black colorant (E))
The radical curable photosensitive composition according to the present invention has a black colorant (E) according to the required optical density of the partition wall when the cured product is used in applications requiring light shielding properties such as a black matrix. It is preferable to contain.
本発明に係るラジカル硬化型感光性組成物が、上記黒色着色剤(E)等の分散性材料を含有する場合、その分散性を向上させるために、高分子分散剤を含有することが好ましい。高分子分散剤としては、特に限定されず、ウレタン系、ポリイミド系、アルキッド系、エポキシ系、ポリエステル系、メラミン系、フェノール系、アクリル系、ポリエーテル系、塩化ビニル系、塩化ビニル酢酸ビニル系共重合体系、ポリアミド系、ポリカーボネート系等が挙げられるが、ウレタン系、またはポリエステル系が好ましい。また、高分子分散剤は、エチレンオキサイドおよび/またはプロピレンオキサイド由来の構成単位を有していてもよい。 (Polymer dispersant / dispersion aid)
When the radical curable photosensitive composition according to the present invention contains a dispersible material such as the black colorant (E), it is preferable to contain a polymer dispersant in order to improve the dispersibility. The polymer dispersant is not particularly limited, and is urethane type, polyimide type, alkyd type, epoxy type, polyester type, melamine type, phenol type, acrylic type, polyether type, vinyl chloride type, vinyl chloride vinyl acetate type. A polymer system, a polyamide system, a polycarbonate system and the like can be mentioned, and a urethane system or a polyester system is preferable. The polymer dispersant may have a structural unit derived from ethylene oxide and / or propylene oxide.
本発明に係るラジカル硬化型感光性組成物は、必要に応じて、微粒子を含んでいてもよい。これにより、後述するポストベーク時に隔壁の形状が変化することを抑制することができる。 (Fine particles)
The radical curable photosensitive composition according to the present invention may contain fine particles as necessary. Thereby, it can suppress that the shape of a partition changes at the time of the post-baking mentioned later.
本発明に係るラジカル硬化型感光性組成物は、必要に応じて、シランカップリング剤を含んでいてもよい。これにより、隔壁と基板との密着性を向上させることができる。 (Silane coupling agent)
The radical curable photosensitive composition according to the present invention may contain a silane coupling agent as required. Thereby, the adhesiveness of a partition and a board | substrate can be improved.
本発明に係るラジカル硬化型感光性組成物は、必要に応じて、熱硬化剤を含んでいてもよい。これにより、隔壁の耐熱性、耐透水性を向上させることができる。また、上記重合体(A)が熱架橋性官能基を有する場合には、重合体(A)と熱硬化剤が化学結合し、それにより重合体(A)を隔壁に固定化する効果も得られる。 (Thermosetting agent)
The radical curable photosensitive composition according to the present invention may contain a thermosetting agent, if necessary. Thereby, the heat resistance of a partition and water permeability resistance can be improved. Further, when the polymer (A) has a thermally crosslinkable functional group, the polymer (A) and the thermosetting agent are chemically bonded, thereby obtaining an effect of fixing the polymer (A) to the partition wall. It is done.
本発明に係るラジカル硬化型感光性組成物は、必要に応じて、リン酸化合物を含んでいてもよい。これにより、基板との密着性を向上させることができるので好ましい。リン酸化合物しては、モノ(メタ)アクリロイルオキシエチルフォスフェート、ジ(メタ)アクリロイルオキシエチルフォスフェート、トリス(メタ)アクリロイルオキシエチルフォスフェートなどが挙げられる。 (Phosphate compound)
The radical curable photosensitive composition according to the present invention may contain a phosphate compound as necessary. This is preferable because adhesion to the substrate can be improved. Examples of the phosphoric acid compound include mono (meth) acryloyloxyethyl phosphate, di (meth) acryloyloxyethyl phosphate, tris (meth) acryloyloxyethyl phosphate, and the like.
また、本発明に係るラジカル硬化型感光性組成物は、上記以外の各種成分に加えて必要に応じて、硬化促進剤、増粘剤、可塑剤、消泡剤、レベリング剤、ハジキ防止剤、紫外線吸収剤等を含んでいてもよい。
本発明に係るラジカル硬化型感光性組成物は、上記説明した各種必須成分と、必要に応じて添加される任意成分を、上記配合量に合わせて、通常の方法で均一に混合することにより調製することができる。 (Other optional ingredients)
Moreover, the radical curable photosensitive composition according to the present invention includes a curing accelerator, a thickener, a plasticizer, an antifoaming agent, a leveling agent, a repellency inhibitor, as necessary, in addition to various components other than those described above. An ultraviolet absorber or the like may be included.
The radical curable photosensitive composition according to the present invention is prepared by uniformly mixing the above-described various essential components and optional components added as necessary according to the above-mentioned blending amount by a normal method. can do.
本発明の感光性組成物が酸硬化型の場合、感光性組成物は、重合体(A)、光硬化開始剤(B)としての光酸発生剤(B2)、およびバインダー樹脂(C)としてのカルボキシル基および/またはフェノール性水酸基を有するアルカリ可溶性樹脂(C21)と、カルボキシル基および/またはフェノール性水酸基と反応し得る基を2個以上有する化合物である架橋性樹脂(C22)を含有する。このような酸硬化型の感光性組成物は、フォトリソグラフィ等における露光に際して光照射部分では光酸発生剤(B2)から酸が発生し、カルボキシル基および/またはフェノール性水酸基を有するアルカリ可溶性樹脂(C21)と、カルボキシル基および/またはフェノール性水酸基と反応し得る基を2個以上有する化合物である架橋性樹脂(C22)とが架橋反応することにより塗膜硬化物を形成する。 (2) Acid curable photosensitive composition When the photosensitive composition of the present invention is an acid curable type, the photosensitive composition comprises a polymer (A) and a photoacid generator (B) as a photocuring initiator (B). B2) and an alkali-soluble resin (C21) having a carboxyl group and / or a phenolic hydroxyl group as the binder resin (C), and a compound having two or more groups capable of reacting with the carboxyl group and / or the phenolic hydroxyl group Contains a crosslinkable resin (C22). In such an acid-curable photosensitive composition, an acid is generated from the photoacid generator (B2) in the light irradiation portion during exposure in photolithography or the like, and an alkali-soluble resin having a carboxyl group and / or a phenolic hydroxyl group ( C21) and a crosslinkable resin (C22) which is a compound having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group undergo a crosslinking reaction to form a cured coating film.
(2-1)重合体(A)
本発明に係る酸硬化型感光性組成物が含有する重合体(A)は、本発明の感光性組成物における特徴的な成分であり、その好ましい態様も含めて、上記ラジカル硬化型感光性組成物において説明した重合体(A)が、酸硬化型感光性組成物において適用可能である。また、重合体(A)の感光性組成物における含有量も上記同様とすることができる。さらに、上記重合体(A)以外に隔壁に撥液作用を付与できる成分として上で説明した重合体(A)’をラジカル硬化型感光性組成物の場合と同様に用いることが可能である。 Each component contained in the acid-curable photosensitive composition according to the present invention will be described below.
(2-1) Polymer (A)
The polymer (A) contained in the acid-curable photosensitive composition according to the present invention is a characteristic component in the photosensitive composition of the present invention, and includes the above-described radical curable photosensitive composition including preferred embodiments thereof. The polymer (A) described in the article can be applied to the acid-curable photosensitive composition. The content of the polymer (A) in the photosensitive composition can also be the same as described above. Furthermore, in addition to the polymer (A), the polymer (A) ′ described above as a component capable of imparting a liquid repellency to the partition walls can be used in the same manner as in the case of the radical curable photosensitive composition.
本発明の感光性組成物が酸硬化型の場合、光硬化開始剤(B)としては、光により酸を発生する化合物である光酸発生剤(B2)が用いられる。光酸発生剤(B2)としては、例えば、ジアリールヨードニウム塩、トリアリールスルホニウム塩、トリアジン系化合物、スルホニル化合物、スルホン酸エステル類等が挙げられる。 (2-2) Photocuring initiator (B) (photoacid generator (B2))
When the photosensitive composition of the present invention is an acid curable type, a photoacid generator (B2) that is a compound that generates an acid by light is used as the photocuring initiator (B). Examples of the photoacid generator (B2) include diaryliodonium salts, triarylsulfonium salts, triazine compounds, sulfonyl compounds, sulfonic acid esters, and the like.
本発明の感光性組成物が酸硬化型の場合、バインダー樹脂(C)としては、上記光酸発生剤(B2)が発生した酸の作用により架橋重合する、カルボキシル基および/またはフェノール性水酸基を有するアルカリ可溶性樹脂(C21)と、カルボキシル基および/またはフェノール性水酸基と反応し得る基を2個以上有する化合物である架橋性樹脂(C22)の組合せが挙げられる。 (2-2) Binder resin (C) (alkali-soluble resin (C21) / crosslinkable resin (C22))
When the photosensitive composition of the present invention is an acid curable type, the binder resin (C) includes a carboxyl group and / or a phenolic hydroxyl group that undergoes cross-linking polymerization by the action of the acid generated by the photoacid generator (B2). And a combination of the alkali-soluble resin (C21) having a crosslinkable resin (C22) which is a compound having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group.
アルカリ可溶性樹脂(C21)は、カルボキシル基および/またはフェノール性水酸基を有する。カルボキシル基および/またはフェノール性水酸基を有することによりアルカリ性溶液に可溶であり、また、カルボキシル基および/またはフェノール性水酸基と反応し得る基を2個以上有する化合物である架橋性樹脂(C22)と架橋し塗膜硬化物を形成し得る。アルカリ可溶性樹脂(C21)は、感光性組成物のフォトリソグラフィ等において使用する現像液を構成するアルカリ性溶液に対して可溶の樹脂であれば何等制限なく使用することが可能であり、例えば、カルボキシル基とエチレン性二重結合を有する単量体および/またはフェノール性水酸基とエチレン性二重結合を有する単量体を必須として重合させて得られる樹脂(C21-1)、フェノール樹脂等が挙げられる。これらの樹脂は、基(1)および基(2)を実質的に有しないことが好ましい。 (Alkali-soluble resin (C21))
The alkali-soluble resin (C21) has a carboxyl group and / or a phenolic hydroxyl group. A crosslinkable resin (C22) which is a compound which is soluble in an alkaline solution by having a carboxyl group and / or a phenolic hydroxyl group, and which has two or more groups capable of reacting with the carboxyl group and / or the phenolic hydroxyl group; It can be crosslinked to form a cured film. The alkali-soluble resin (C21) can be used without any limitation as long as it is a resin that is soluble in an alkaline solution constituting a developer used in photolithography of the photosensitive composition. And a resin (C21-1) obtained by polymerizing a monomer having a group and an ethylenic double bond and / or a monomer having a phenolic hydroxyl group and an ethylenic double bond as essential, and a phenol resin. . These resins preferably have substantially no groups (1) and (2).
架橋性樹脂(C22)は、カルボキシル基および/またはフェノール性水酸基と反応し得る基を2個以上有する化合物である。カルボキシル基および/またはフェノール性水酸基と反応し得る基を2個以上有することにより、カルボキシル基および/またはフェノール性水酸基を有するアルカリ可溶性樹脂(C21)と架橋し塗膜硬化物を形成し得る。また、上記重合体(A)がカルボキシル基および/または水酸基を有する場合には重合体(A)とも架橋し塗膜硬化物を形成し得る。架橋性樹脂(C22)は、基(1)および基(2)を実質的に有しない化合物であることが好ましい。 (Crosslinkable resin (C22))
The crosslinkable resin (C22) is a compound having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group. By having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group, it can be crosslinked with an alkali-soluble resin (C21) having a carboxyl group and / or a phenolic hydroxyl group to form a cured coating film. Moreover, when the said polymer (A) has a carboxyl group and / or a hydroxyl group, it can also bridge | crosslink with a polymer (A) and a coating-film cured | curing material can be formed. The crosslinkable resin (C22) is preferably a compound substantially free of the group (1) and the group (2).
本発明に係る酸硬化型感光性組成物は、上記重合体(A)、光硬化開始剤(B)としての光酸発生剤(B2)、およびバインダー樹脂(C)としてのカルボキシル基および/またはフェノール性水酸基を有するアルカリ可溶性樹脂(C21)と、カルボキシル基および/またはフェノール性水酸基と反応し得る基を2個以上有する化合物である架橋性樹脂(C22)を含有する。さらに、本発明の効果を損なわない範囲において、各種機能の向上等を目的として各種任意成分を含有することが可能である。
このような任意成分としては、上記ラジカル硬化型感光性組成物で説明した任意成分のうちの、エチレン性二重結合を2個以上有する架橋剤(D)以外の全ての成分を、ラジカル硬化型感光性組成物の場合と同様に、酸硬化型感光性組成物に用いることが可能である。 (2-3) Optional Components The acid curable photosensitive composition according to the present invention includes the polymer (A), a photoacid generator (B2) as a photocuring initiator (B), and a binder resin (C). And an alkali-soluble resin (C21) having a carboxyl group and / or a phenolic hydroxyl group and a crosslinkable resin (C22) which is a compound having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group. . Furthermore, various optional components can be contained for the purpose of improving various functions and the like within a range not impairing the effects of the present invention.
Examples of such optional components include all components other than the crosslinking agent (D) having two or more ethylenic double bonds among the optional components described in the radical curable photosensitive composition. As in the case of the photosensitive composition, it can be used for an acid-curable photosensitive composition.
上記説明したラジカル硬化型感光性組成物や酸硬化型感光性組成物等の本発明の感光性組成物を用いて隔壁を形成する際には、感光性組成物を溶媒で希釈した希釈液を用いて塗膜(湿潤膜)を形成した後に、溶媒を揮発除去し、感光性組成物の塗膜を形成することが好ましい。 [Dilution solvent]
When forming a partition using the photosensitive composition of the present invention such as the above-described radical curable photosensitive composition or acid curable photosensitive composition, a diluted solution obtained by diluting the photosensitive composition with a solvent is used. It is preferable to form a coating film of the photosensitive composition by volatilizing and removing the solvent after using it to form a coating film (wet film).
本発明の隔壁は、上記本発明の感光性組成物の塗膜硬化物により、基板上を画素形成用の複数の区画に仕切るかたちに形成された隔壁であって、カラーフィルタや有機EL素子のブラックマトリックス等に適用することができる。 <2> Partition Wall The partition wall of the present invention is a partition wall formed by partitioning the substrate into a plurality of pixel forming sections by using the cured film of the photosensitive composition of the present invention. It can be applied to a black matrix of an organic EL element.
まず、本発明の感光性組成物の希釈液を基板に塗布する。基板としては、特に限定されず、各種ガラス板;SiC基板、シリコン等の無機基板;ITO等の無機酸化物基板;ポリエステル(ポリエチレンテレフタレート等)、ポリオレフィン(ポリエチレン、ポリプロピレン等)、ポリカーボネート、ポリメチルメタクリレート、ポリスルホン、ポリイミド、ポリ(メタ)アクリル樹脂等の熱可塑性樹脂シート;エポキシ樹脂、不飽和ポリエステル等の熱硬化性樹脂の硬化シート等が挙げられる。耐熱性を考慮すると、基板としては、ガラス板とポリイミド等の耐熱性樹脂が好ましい。また、基板の隔壁が形成されていない側の面からの露光が可能であることから、基板は、透明であることが好ましい。さらに、基板は、ガラス基板等の透明基板上に、有機膜またはTFT(Thin Film Transistor:薄膜トランジスタ)、ITO、SiO2等の無機酸化物膜が形成された基板またはパターニングされた基板、シリコンナイトライドやポリイミドなどの絶縁膜を形成させた基板、これらの基板が積層されている積層基板であってもよい。 (Coating process)
First, a diluted solution of the photosensitive composition of the present invention is applied to a substrate. The substrate is not particularly limited, and various glass plates; SiC substrate, inorganic substrate such as silicon; inorganic oxide substrate such as ITO; polyester (polyethylene terephthalate, etc.), polyolefin (polyethylene, polypropylene, etc.), polycarbonate, polymethyl methacrylate And thermoplastic resin sheets such as polysulfone, polyimide, and poly (meth) acrylic resin; and cured sheets of thermosetting resin such as epoxy resin and unsaturated polyester. Considering heat resistance, the substrate is preferably a heat resistant resin such as a glass plate and polyimide. Moreover, since the exposure from the surface where the partition wall of the substrate is not formed is possible, the substrate is preferably transparent. Furthermore, the substrate is a substrate in which an inorganic film such as an organic film or TFT (Thin Film Transistor), ITO, SiO 2 is formed on a transparent substrate such as a glass substrate, or a patterned substrate, silicon nitride Or a substrate on which an insulating film such as polyimide is formed, or a laminated substrate in which these substrates are laminated.
次に、基板に形成された塗膜を乾燥する。これにより、溶媒が揮発するため、粘着性のない感光性組成物の塗膜が得られる。乾燥方法としては、特に限定されず、真空乾燥、加熱乾燥が挙げられる。塗膜の外観のムラを発生させず、効率よく乾燥させるために、真空乾燥と加熱乾燥を併用することが好ましい。乾燥条件は、感光性組成物に含まれる成分の種類、組成等により異なるが、真空乾燥は、10~500Pa(絶対圧)で10~300秒間であることが好ましく、加熱乾燥は、50~120℃で10~2000秒間であることが好ましい。 (Drying process)
Next, the coating film formed on the substrate is dried. Thereby, since a solvent volatilizes, the coating film of the photosensitive composition without stickiness is obtained. It does not specifically limit as a drying method, Vacuum drying and heat drying are mentioned. In order to efficiently dry the coating film without causing uneven appearance, it is preferable to use vacuum drying and heat drying in combination. The drying conditions vary depending on the type and composition of the components contained in the photosensitive composition, but the vacuum drying is preferably 10 to 500 Pa (absolute pressure) for 10 to 300 seconds, and the heat drying is 50 to 120. It is preferable that the temperature is 10 to 2000 seconds at ° C.
次に、所定パターンのマスクを介して、塗膜を露光する。露光時に照射される光としては、特に限定されず、可視光、紫外線、遠紫外線、KrFエキシマレーザー、ArFエキシマレーザー、F2エキシマレーザー、Kr2エキシマレーザー、KrArエキシマレーザー、Ar2エキシマレーザー等のエキシマレーザー、X線、電子線等が挙げられる。波長が100~600nmの光が好ましく、波長が300~500nmの光がより好ましく、i線(365nm)、h線(405nm)、g線(436nm)が特に好ましい。なお、光源としては、公知の超高圧水銀灯等を用いることができる。 (Exposure process)
Next, the coating film is exposed through a mask having a predetermined pattern. The light irradiated at the time of exposure is not particularly limited, and visible light, ultraviolet light, far ultraviolet light, KrF excimer laser, ArF excimer laser, F 2 excimer laser, Kr 2 excimer laser, KrAr excimer laser, Ar 2 excimer laser, etc. Excimer laser, X-ray, electron beam and the like can be mentioned. Light having a wavelength of 100 to 600 nm is preferable, light having a wavelength of 300 to 500 nm is more preferable, and i-line (365 nm), h-line (405 nm), and g-line (436 nm) are particularly preferable. In addition, a well-known super high pressure mercury lamp etc. can be used as a light source.
次に、現像液を用いて、塗膜の未露光部を除去し、現像する。現像液としては、特に限定されないが、無機アルカリ類、アミン類、アルコールアミン類、第4級アンモニウム塩等のアルカリの水溶液が挙げられる。現像時間、すなわち、現像液に接触させる時間は、5~180秒間であることが好ましい。現像方法としては、特に限定されないが、液盛り法、ディッピング法、シャワー法等が挙げられる。 (Development process)
Next, using a developing solution, the unexposed part of the coating film is removed and developed. The developer is not particularly limited, and examples thereof include aqueous alkali solutions such as inorganic alkalis, amines, alcohol amines, and quaternary ammonium salts. The development time, that is, the time for contact with the developer is preferably 5 to 180 seconds. The developing method is not particularly limited, and examples thereof include a liquid filling method, a dipping method, and a shower method.
次に、現像された隔壁に対してポスト露光を行ってもよい。このとき、隔壁が形成されている側の面および隔壁が形成されていない側の面のいずれから露光してもよいし、両面から露光してもよい。露光時に照射される光は、紫外線であることが好ましい。 (Post exposure process)
Next, post-exposure may be performed on the developed partition wall. At this time, the exposure may be performed from either the surface on which the partition is formed or the surface on which the partition is not formed, or may be performed from both surfaces. The light irradiated during exposure is preferably ultraviolet light.
現像後(ポスト露光を行う際は、ポスト露光後)に、隔壁を加熱することが好ましい。加熱条件は、150~250℃で5~90分間であることが好ましく、加熱温度は、180℃以上がより好ましい。加熱温度が低すぎると、耐薬品性が不十分となることがあり、隔壁にインクを塗布した場合に、隔壁が膨潤したり、インクが滲んだりすることがある。一方、加熱温度が高すぎると、隔壁が熱分解することがある。 (Post bake process)
It is preferable to heat the partition after development (when post-exposure is performed, after post-exposure). The heating condition is preferably 150 to 250 ° C. for 5 to 90 minutes, and the heating temperature is more preferably 180 ° C. or higher. If the heating temperature is too low, chemical resistance may be insufficient, and when ink is applied to the partition walls, the partition walls may swell or the ink may ooze. On the other hand, if the heating temperature is too high, the partition walls may be thermally decomposed.
本発明のカラーフィルタは、基板上に複数の画素と隣接する画素間に位置する隔壁とを有するカラーフィルタであって、前記隔壁が上記本発明の隔壁で形成されており、前記画素がインクジェット法により形成されたものであることを特徴とする。なお、本発明のカラーフィルタにおいて、隔壁は光学濃度が2~7程度のブラックマトリックスであることが好ましい。
本発明のカラーフィルタは、前述のように、基板上に、隔壁、例えば、ブラックマトリックスを形成した後、インクジェット法を用いて、隔壁の開口部にインクを塗布して画素を形成することにより製造することができる。 <3> Color filter The color filter of the present invention is a color filter having a plurality of pixels and a partition located between adjacent pixels on the substrate, and the partition is formed of the partition of the present invention. The pixel is formed by an inkjet method. In the color filter of the present invention, the partition walls are preferably a black matrix having an optical density of about 2 to 7.
As described above, the color filter of the present invention is manufactured by forming a partition, for example, a black matrix on a substrate, and then forming a pixel by applying ink to the opening of the partition using an inkjet method. can do.
本発明の有機EL素子は、基板上に複数の画素と隣接する画素間に位置する隔壁とを有する有機EL素子であって、前記隔壁が上記本発明の隔壁で形成されており、前記画素がインクジェット法により形成されたものであることを特徴とする。
本発明の有機EL素子は、以下のようにして、製造することができる。まず、スパッタ法等を用いて、ガラス基板等の透明基板にITO等の透明電極を形成し、必要に応じて、透明電極を所望のパターンにエッチングする。次に、カラーフィルタの場合と同様にして、基板上に、隔壁、例えば、ブラックマトリックスを形成した後、インクジェット法を用いて、隔壁(ブラックマトリックス)の開口部に、インクとして、正孔輸送材料の溶液および発光材料の溶液を順次塗布、乾燥して、正孔輸送層および発光層を形成する。さらに、蒸着法等を用いて、アルミニウム等の電極を形成して画素を形成することにより、有機EL素子が得られる。 <4> Organic EL Element The organic EL element of the present invention is an organic EL element having a plurality of pixels and a partition located between adjacent pixels on a substrate, and the partition is formed of the partition of the present invention. The pixel is formed by an inkjet method.
The organic EL device of the present invention can be produced as follows. First, using a sputtering method or the like, a transparent electrode such as ITO is formed on a transparent substrate such as a glass substrate, and the transparent electrode is etched into a desired pattern as necessary. Next, in the same manner as in the case of the color filter, a partition, for example, a black matrix is formed on the substrate, and then a hole transport material is used as an ink in the opening of the partition (black matrix) using an ink jet method. The solution of the above and the solution of the light emitting material are sequentially applied and dried to form a hole transport layer and a light emitting layer. Furthermore, an organic EL element is obtained by forming an electrode, such as aluminum, using a vapor deposition method or the like to form a pixel.
以下の各例において用いた化合物の略号を以下に示す。 Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In addition, a part means a mass part.
The abbreviations of the compounds used in the following examples are shown below.
(単量体)
C6FMA:CH2=C(CH3)COOCH2CH2(CF2)6F
X-24-8201:ジメチルシリコーン鎖含有メタクリレートX-24-8201(信越化学工業社製)(一般式(4)において、R8がメチル基、Zがトリメチレン基、R1、R2、R3がそれぞれメチル基、nが分子間の平均値として24である化合物)
MAA:メタクリル酸
2-HEMA:2-ヒドロキシエチルメタクリレート
GMA:グリシジルメタクリレート
MMA:メタクリル酸メチル
(重合開始剤)
V-65:V-65(和光純薬社製、2,2'-アゾビス(2,4-ジメチルバレロニトリル))
(連鎖移動剤)
n-DM:n-ドデシルメルカプタン
(溶媒)
MEK:2-ブタノン [1] Compound (monomer) used for production of polymer (A) and polymer (R)
C6FMA: CH 2 = C (CH 3) COOCH 2 CH 2 (CF 2) 6 F
X-24-8201: Dimethyl silicone chain-containing methacrylate X-24-8201 (manufactured by Shin-Etsu Chemical Co., Ltd.) (in the general formula (4), R 8 is a methyl group, Z is a trimethylene group, R 1 , R 2 , R 3 Are compounds in which each is a methyl group and n is 24 as an average value between molecules)
MAA: methacrylic acid 2-HEMA: 2-hydroxyethyl methacrylate GMA: glycidyl methacrylate MMA: methyl methacrylate (polymerization initiator)
V-65: V-65 (Wako Pure Chemical Industries, 2,2'-azobis (2,4-dimethylvaleronitrile))
(Chain transfer agent)
n-DM: n-dodecyl mercaptan (solvent)
MEK: 2-butanone
(光硬化開始剤(B):光重合開始剤(B1))
OXE02:OXE02(チバスペシャルティケミカルズ社製、エタノン 1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾイル-3-イル]-1-(O-アセチルオキシム)(上記一般式(5)において、R21およびR22がメチル基、R23がエチル基、R24、R26およびR27が水素原子、R25が2-メチルベンゾイル基である化合物)
(バインダー樹脂(C):感光性樹脂(C1))
EX1010:EX-1010(ナガセケムテックス社製、上記一般式(7)で表されるエポキシ樹脂にエチレン性二重結合と酸性基とを導入した樹脂の溶液、固形分70質量%、質量平均分子量:3,020)
ZCR1569H:ZCR-1569H(日本化薬社製、一般式(6)で表されるビフェニル骨格を有するエポキシ樹脂にエチレン性二重結合と酸性基とを導入した樹脂の溶液;固形分70質量%、質量平均分子量:4,710)
(架橋剤(D))
DPHA:KAYARAD DPHA(日本化薬社製、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物)
A9300:NKエステル A-9300(新中村化学工業社製、エトキシ化イソシアヌル酸トリアクリレート)
(溶媒)
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
(黒色着色剤(E)、微粒子)
CB:カーボンブラック分散液(平均二次粒径120nm、分散媒:PGMEA、カーボンブラック20質量%、アミン価が18mgKOH/gのポリウレタン系高分子分散剤5質量%)
シリカ:シリカ分散液(平均粒径20nm、分散媒PGMEA、固形分30質量%) [2] Photosensitive composition component (photocuring initiator (B): photopolymerization initiator (B1))
OXE02: OXE02 (manufactured by Ciba Specialty Chemicals, Etanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime) (the above general formula (5 ), R 21 and R 22 are methyl groups, R 23 is an ethyl group, R 24 , R 26 and R 27 are hydrogen atoms, and R 25 is a 2-methylbenzoyl group)
(Binder resin (C): photosensitive resin (C1))
EX1010: EX-1010 (manufactured by Nagase ChemteX Corporation, a solution of a resin in which an ethylenic double bond and an acidic group are introduced into the epoxy resin represented by the above general formula (7), solid content 70% by mass, mass average molecular weight : 3,020)
ZCR1569H: ZCR-1569H (manufactured by Nippon Kayaku Co., Ltd., a solution of a resin in which an ethylenic double bond and an acidic group are introduced into an epoxy resin having a biphenyl skeleton represented by the general formula (6); solid content: 70% by mass; (Mass average molecular weight: 4,710)
(Crosslinking agent (D))
DPHA: KAYARAD DPHA (Nippon Kayaku Co., Ltd., mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
A9300: NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated isocyanuric acid triacrylate)
(solvent)
PGMEA: Propylene glycol monomethyl ether acetate (black colorant (E), fine particles)
CB: carbon black dispersion (average secondary particle size 120 nm, dispersion medium: PGMEA, carbon black 20% by mass, polyurethane polymer dispersant 5% by mass with amine value of 18 mgKOH / g)
Silica: Silica dispersion (average particle size 20 nm, dispersion medium PGMEA, solid content 30% by mass)
撹拌機を備えた内容積1Lのオートクレーブに、MEK(420.0g)、C6FMA(86.4g)、MAA(18.0g)、GMA(21.6g)、MMA(54.0g)および重合開始剤V-65(0.8g)を仕込み、窒素雰囲気下で撹拌しながら、50℃で24時間重合させ、粗共重合体を合成した。得られた粗共重合体の溶液にヘキサンを加えて再沈精製した後、真空乾燥し、重合体(A)に相当する重合体(A-1)(162.7g)を得た。重合体(A-1)は、数平均分子量が49,325、質量平均分子量が125,152であった。 [Synthesis Example 1 of Polymer (A)]
To an autoclave with an internal volume of 1 L equipped with a stirrer, MEK (420.0 g), C6FMA (86.4 g), MAA (18.0 g), GMA (21.6 g), MMA (54.0 g) and a polymerization initiator V-65 (0.8 g) was charged and polymerized at 50 ° C. for 24 hours with stirring under a nitrogen atmosphere to synthesize a crude copolymer. Hexane was added to the obtained crude copolymer solution for purification by reprecipitation, followed by vacuum drying to obtain polymer (A-1) (162.7 g) corresponding to polymer (A). The polymer (A-1) had a number average molecular weight of 49,325 and a mass average molecular weight of 125,152.
上記重合体(A-1)の合成において、原料の配合を表1のように変更した他は同様の反応により、重合体(A)に相当する重合体(A-2)~(A-5)を得た。 [Synthesis Examples 2 to 5 of Polymer (A)]
In the synthesis of the polymer (A-1), polymers (A-2) to (A-5) corresponding to the polymer (A) were obtained by the same reaction except that the composition of the raw materials was changed as shown in Table 1. )
上記重合体(A-1)の合成において、原料の配合を表1のように変更した他は同様の反応により、本発明における重合体(A)に適合しない重合体(R-1)~(R-3)を得た。 [Comparative Synthesis Examples 1 to 3]: Synthesis of Comparative Example Polymer (R) Not Compatible with Polymer (A) In the synthesis of the polymer (A-1), the composition of raw materials was changed as shown in Table 1. In the same manner, polymers (R-1) to (R-3) that were not compatible with the polymer (A) in the present invention were obtained.
数平均分子量(Mn)および質量平均分子量(Mw)は、ゲルパーミエーションクロマトグラフィー法により、ポリスチレンを標準物質として測定した。ゲルパーミエーションクロマトグラフィーとしては、HPLC-8220GPC(東ソー社製)を使用した。カラムとしては、shodex LF-604を3本接続したものを使用した。検出器としては、RI検出器を使用した。標準物質としては、EasiCal PS1(Polymer Laboratories社製)を使用した。さらに、数平均分子量および質量平均分子量を測定する際は、カラムを37℃で保持し、溶離液としてはテトラヒドロフランを用い、流速を0.2mL/分とし、測定サンプルの0.5質量%テトラヒドロフラン溶液40μLを注入した。 <Molecular weight>
The number average molecular weight (Mn) and the mass average molecular weight (Mw) were measured by gel permeation chromatography using polystyrene as a standard substance. As the gel permeation chromatography, HPLC-8220GPC (manufactured by Tosoh Corporation) was used. As the column, a column in which three shodex LF-604 were connected was used. An RI detector was used as the detector. As a standard substance, EasiCal PS1 (manufactured by Polymer Laboratories) was used. Further, when measuring the number average molecular weight and the mass average molecular weight, the column is maintained at 37 ° C., tetrahydrofuran is used as the eluent, the flow rate is 0.2 mL / min, and the 0.5 mass% tetrahydrofuran solution of the measurement sample is measured. 40 μL was injected.
重合体中のフッ素原子の含有量は、重合反応の仕込み値から算出した。
<ケイ素原子含有量>
重合体中のケイ素原子の含有量は、重合反応の仕込み値から算出した。 <Fluorine atom content>
The fluorine atom content in the polymer was calculated from the charged value of the polymerization reaction.
<Silicon atom content>
The content of silicon atoms in the polymer was calculated from the charged value of the polymerization reaction.
酸価は、原料である単量体の配合割合から算出した理論値である。 <Acid value>
The acid value is a theoretical value calculated from the blending ratio of monomers as raw materials.
上記で得られた各重合体を、0.1%のNaCO3水溶液(pH11、温度23℃)に添加し、撹拌条件:50rpmで溶解した重合体の割合(質量%)を求め、重合体のアルカリ水溶液に対する溶解性の指標とした。 <Developer solubility>
Each polymer obtained above was added to a 0.1% aqueous NaCO 3 solution (pH 11, temperature 23 ° C.), and the stirring condition: the ratio (mass%) of the polymer dissolved at 50 rpm was determined. It was used as an index of solubility in an alkaline aqueous solution.
上記合成例で得られた重合体(A-1)(0.09部)、黒色着色剤(E)の分散液としてのCB(31.5部)、光重合開始剤(B1)としてのOXE02(0.75部)、感光性樹脂(C1)の分散液としてのEX1010(6.3部)、架橋剤(D)としてのDPHA(1.9部)および溶媒としてのPGMEA(34.8部)、シクロヘキサノン(24.7部)を混合して、感光性組成物の希釈液を得た。感光性組成物の希釈液の全固形分中の重合体(A-1)の含有量は、0.60質量%であった。 [Example 1]
Polymer (A-1) (0.09 parts) obtained in the above synthesis example, CB (31.5 parts) as a dispersion of black colorant (E), OXE02 as photopolymerization initiator (B1) (0.75 part), EX1010 (6.3 parts) as a dispersion of the photosensitive resin (C1), DPHA (1.9 parts) as a crosslinking agent (D) and PGMEA (34.8 parts) as a solvent ) And cyclohexanone (24.7 parts) were mixed to obtain a diluted solution of the photosensitive composition. The content of the polymer (A-1) in the total solid content of the diluted liquid of the photosensitive composition was 0.60% by mass.
各成分の配合を表2に示すように変更した以外は、実施例1と同様にして、上記合成例で得られた重合体(A-2)~(A-6)をそれぞれ含有する感光性組成物の塗膜硬化物からなる隔壁が形成された実施例2~6のガラス基板サンプル(1)、および、該感光性組成物の塗膜の硬化物が形成された実施例2~6のガラス基板サンプル(2)を得た。 [Examples 2 to 6]
Photosensitivity containing each of the polymers (A-2) to (A-6) obtained in the above synthesis examples in the same manner as in Example 1 except that the composition of each component was changed as shown in Table 2. Glass substrate samples (1) of Examples 2 to 6 in which partition walls made of a cured film of the composition were formed, and Examples 2 to 6 of which a cured product of the coating film of the photosensitive composition was formed A glass substrate sample (2) was obtained.
各成分の配合を表2に示すように変更した以外は、実施例1と同様にして、上記比較合成例で得られた重合体(R-1)~(R-3)をそれぞれ含有する感光性組成物の塗膜硬化物からなる隔壁が形成された比較例1~3のガラス基板サンプル(1)、および、該感光性組成物の塗膜の硬化物が形成された比較例1~3のガラス基板サンプル(2)を得た。 [Comparative Examples 1 to 3]
Photosensitive materials each containing the polymers (R-1) to (R-3) obtained in the above comparative synthesis examples in the same manner as in Example 1 except that the composition of each component was changed as shown in Table 2. Glass substrate samples (1) of Comparative Examples 1 to 3 in which partition walls made of a cured film of the photosensitive composition were formed, and Comparative Examples 1 to 3 in which a cured product of the coating film of the photosensitive composition was formed A glass substrate sample (2) was obtained.
以下に説明する方法で、上記各実施例および比較例で作製したガラス基板サンプル(2)を用いて、撥液性を、また上記各実施例および比較例で作製したガラス基板サンプル(1)を用いて、隔壁間開口部内のインクの濡れ拡がり性を評価した。評価結果を、感光性組成物の全固形成分における各成分の含有質量%とともに表3に示す。 [Evaluation method and evaluation results]
Using the glass substrate samples (2) prepared in each of the above examples and comparative examples, the liquid repellency was determined by the method described below, and the glass substrate samples (1) prepared in the above examples and comparative examples were used. It was used to evaluate the wetting and spreading properties of the ink in the opening between the partition walls. An evaluation result is shown in Table 3 with the content mass% of each component in the total solid component of the photosensitive composition.
ガラス基板サンプル(2)の塗膜硬化物の表面のPGMEAの接触角を測定することにより、撥液性を評価した。接触角とは、固体と液体が接触する点における液体表面に対する接線と固体表面がなす角であり、液体を含む側の角度で定義する。このため、接触角が大きい程、塗膜硬化物の撥液性が優れることを意味する。 <Liquid repellency>
The liquid repellency was evaluated by measuring the contact angle of PGMEA on the surface of the cured film of the glass substrate sample (2). The contact angle is an angle formed by a solid surface and a tangent to the liquid surface at a point where the solid and the liquid come into contact, and is defined as an angle on the side including the liquid. For this reason, the larger the contact angle, the better the liquid repellency of the cured film.
液状エポキシME-562(日本ペルノックス社製)(6.25g)、硬化剤HV-562(日本ペルノックス社製)(6.25g)、アジピン酸ジエチル(12.5g)およびマロン酸ジエチル(25.0g)を、スターラーを用いて1時間攪拌混合し、インクを調製した。 <Wetting and spreading of ink in the opening between the partition walls>
Liquid epoxy ME-562 (Nihon Pernox) (6.25 g), curing agent HV-562 (Nihon Pernox) (6.25 g), diethyl adipate (12.5 g) and diethyl malonate (25.0 g) ) Was stirred and mixed using a stirrer for 1 hour to prepare an ink.
○は良、×は不可を表す。 In the obtained photograph, the inside of the opening between the partition walls was covered with ink, and the case where there was no part where ink was repelled was judged as ◯, and the case where there was part where ink was repelled was judged as x.
○ indicates good and × indicates impossibility.
なお、2009年12月28日に出願された日本特許出願2009-298959号の明細書、特許請求の範囲、図面及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 The photosensitive composition of the present invention is an ink repellent component that does not have an ethylenic double bond, but has good ink repellency at the upper part of the partition wall, resistance to developer that is not eroded by the developer, and good resistance to the opening between the partition walls. It is the photosensitive composition containing the ink repellent component which can provide the wet spreading property of an ink to the partition obtained. Such a photosensitive composition of the present invention is suitably used for forming barrier ribs, for example, for manufacturing color filters using an inkjet recording technique and for manufacturing organic EL display elements. Furthermore, it is suitably used as a material for forming a permanent film such as a partition for partitioning each TFT of an organic TFT (Thin Film Transistor) array, a partition for an ITO electrode of a liquid crystal display element, a partition for a circuit wiring board.
It should be noted that the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2009-298959 filed on December 28, 2009 are cited here as disclosure of the specification of the present invention. Incorporated.
Claims (14)
- 下記一般式(1)で表される基を有する側鎖を有し、かつエチレン性二重結合を有する側鎖を有しない重合体(A)と、光硬化開始剤(B)と、バインダー樹脂(C)とを含む感光性組成物であって、
-CFXRf …(1)
(式中、Xは、水素原子、フッ素原子またはトリフルオロメチル基を表し、Rfは、エーテル性酸素原子を有していてもよい炭素数が1以上20以下のフルオロアルキル基またはフッ素原子を表す。)
前記重合体(A)の質量平均分子量(Mw(A))が、4.2×104<Mw(A)≦20×104であることを特徴とする感光性組成物。 Polymer (A) having a side chain having a group represented by the following general formula (1) and not having a side chain having an ethylenic double bond, a photocuring initiator (B), and a binder resin A photosensitive composition comprising (C),
-CFXR f (1)
(In the formula, X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R f represents a fluoroalkyl group or fluorine atom having 1 to 20 carbon atoms which may have an etheric oxygen atom. To express.)
The weight average molecular weight of the polymer (A) (Mw (A) ) is, 4.2 × 10 4 <Mw ( A) ≦ 20 × 10 photosensitive composition which is a 4. - 前記重合体(A)の数平均分子量(Mn(A))が、1.5×104≦Mn(A)≦6×104である請求項1に記載の感光性組成物。 The photosensitive composition according to claim 1, wherein the number average molecular weight (Mn (A)) of the polymer (A) is 1.5 × 10 4 ≦ Mn (A) ≦ 6 × 10 4 .
- 前記重合体(A)が、酸性基を有する請求項1または2に記載の感光性組成物。 The photosensitive composition according to claim 1 or 2, wherein the polymer (A) has an acidic group.
- 前記重合体(A)におけるフッ素原子含有割合が、20~50質量%である請求項1~3のいずれか1項に記載の感光性組成物。 The photosensitive composition according to any one of claims 1 to 3, wherein a fluorine atom content ratio in the polymer (A) is 20 to 50 mass%.
- 前記感光性組成物の全固形分における前記重合体(A)の割合が、0.07~1質量%である請求項1~4のいずれか1項に記載の感光性組成物。 The photosensitive composition according to any one of claims 1 to 4, wherein the ratio of the polymer (A) in the total solid content of the photosensitive composition is 0.07 to 1% by mass.
- 前記重合体(A)が、エポキシ基、メルカプト基および水酸基からなる群から選ばれる1種以上をさらに有する請求項1~5のいずれか1項に記載の感光性組成物。 The photosensitive composition according to any one of claims 1 to 5, wherein the polymer (A) further comprises one or more selected from the group consisting of an epoxy group, a mercapto group, and a hydroxyl group.
- 前記重合体(A)が、さらに下記一般式(2)で表される基を有する側鎖を有する請求項1~6のいずれか1項に記載の感光性組成物。
- 前記一般式(1)で表される基を有する側鎖を有しない、下記一般式(2)で表される基を有する側鎖を有する、かつエチレン性二重結合を有する側鎖を有しない重合体(A)’であって、質量平均分子量(Mw(A)’)が、4.2×104<Mw(A)’≦20×104である重合体(A)’を、さらに含有する請求項1~7のいずれか1項に記載の感光性組成物。
- 前記光硬化開始剤(B)が光重合開始剤であり、前記バインダー樹脂(C)が酸性基とエチレン性二重結合とを有する感光性樹脂である請求項1~8のいずれか1項に記載の感光性組成物。 9. The photo-initiator (B) is a photo-polymerization initiator, and the binder resin (C) is a photosensitive resin having an acidic group and an ethylenic double bond. The photosensitive composition as described.
- さらに、エチレン性二重結合を2個以上有する架橋剤(D)を含む請求項9に記載の感光性組成物。 Furthermore, the photosensitive composition of Claim 9 containing the crosslinking agent (D) which has 2 or more of ethylenic double bonds.
- さらに、黒色着色剤(E)を含む請求項1~10のいずれか1項に記載の感光性組成物。 The photosensitive composition according to any one of claims 1 to 10, further comprising a black colorant (E).
- 基板上を画素形成用の複数の区画に仕切るかたちに形成された隔壁であって、請求項1~11のいずれか1項に記載の感光性組成物の塗膜硬化物からなることを特徴とする隔壁。 A partition formed in the form of partitioning a substrate into a plurality of sections for pixel formation, wherein the partition is made of a cured coating film of the photosensitive composition according to any one of claims 1 to 11. Partition wall.
- 基板上に複数の画素と隣接する画素間に位置する隔壁とを有するカラーフィルタであって、前記隔壁が請求項12に記載の隔壁で形成されており、前記画素がインクジェット法により形成されたものであることを特徴とするカラーフィルタ。 A color filter having a plurality of pixels and a partition located between adjacent pixels on a substrate, wherein the partition is formed by the partition according to claim 12, and the pixel is formed by an inkjet method The color filter characterized by being.
- 基板上に複数の画素と隣接する画素間に位置する隔壁とを有する有機EL素子であって、前記隔壁が請求項12に記載の隔壁で形成されており、前記画素がインクジェット法により形成されたものであることを特徴とする有機EL素子。 An organic EL element having a plurality of pixels and a partition located between adjacent pixels on a substrate, wherein the partition is formed by the partition according to claim 12, and the pixel is formed by an inkjet method. An organic EL element characterized by being a thing.
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CN103730207B (en) * | 2013-11-26 | 2016-08-17 | 沃太能源南通有限公司 | A kind of preparation method of monocrystaline silicon solar cell aluminium paste |
CN109065762A (en) * | 2018-08-01 | 2018-12-21 | 武汉华星光电半导体显示技术有限公司 | The production method and OLED device of OLED device |
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