WO2011081150A1 - 感光性組成物、隔壁、カラーフィルタおよび有機el素子 - Google Patents
感光性組成物、隔壁、カラーフィルタおよび有機el素子 Download PDFInfo
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- WO2011081150A1 WO2011081150A1 PCT/JP2010/073602 JP2010073602W WO2011081150A1 WO 2011081150 A1 WO2011081150 A1 WO 2011081150A1 JP 2010073602 W JP2010073602 W JP 2010073602W WO 2011081150 A1 WO2011081150 A1 WO 2011081150A1
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- photosensitive composition
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
-
- 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
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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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
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- 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
- the present invention relates to a photosensitive composition, a partition using the same, a color filter having the partition, and an organic EL device.
- partition walls between pixels of a color filter partition walls between pixels of an organic EL (Electro-Luminescence) display element, partition walls partitioning each TFT of an organic TFT (Thin Film Transistor) array, partition walls of an ITO electrode of a liquid crystal display element
- a photosensitive composition has attracted attention.
- a barrier rib pattern (which may also serve as a black matrix) is formed using photolithography, and then R (red), G (green), and B (blue) ink is applied to the openings between the partition walls to form pixels.
- 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.
- the upper surface of the partition wall needs to have a property of repelling ink, so-called liquid repellency.
- the opening between the partition walls needs to have a property of getting wet with ink, so-called lyophilic property.
- Patent Document 1 describes a partition wall composition (alkali development type photosensitive resist) containing a vinyl polymer having an ethylenically unsaturated double bond and a fluoroalkyl group.
- a partition wall composition alkali development type photosensitive resist
- the liquid repellency of the surface is so high that bubbles generated in the development process are adsorbed on the surface, hindering the development of the unexposed area and finally remaining as development defects I found out that there was a case.
- Patent Document 2 describes a negative photosensitive composition containing a fluorinated polymer in which a polyoxyalkylene chain is introduced to improve hydrophilicity in order to increase compatibility with a developer. .
- a polyoxyalkylene chain is introduced to improve hydrophilicity in order to increase compatibility with a developer.
- the compatibility of the developer is increased, so the liquid repellent part on the partition wall surface is easy. It has been found that there is a problem that the liquid repellency is deteriorated.
- Patent Document 3 describes a partition wall composition (alkali development type photosensitive resist) containing a vinyl polymer having a fluoroalkyl group in which an ethylenically unsaturated double bond is introduced at the end of a polyoxyalkylene chain.
- a partition wall composition alkali development type photosensitive resist
- a vinyl polymer having a fluoroalkyl group in which an ethylenically unsaturated double bond is introduced at the end of a polyoxyalkylene chain.
- Patent Document 4 describes a vinyl polymer having an ethylenically unsaturated double bond site, a fluoroalkyl group and an oxyalkylene group. However, these are aimed at improving the ink deposition property on the plate in the planographic printing field, and the exemplified compounds were not sufficiently effective for developing defects.
- the present invention has been made to solve the above-described problems of the prior art, can form a partition wall having a top surface that has no development defects, has good liquid repellency even after the development process, and is provided on the side surface of the partition wall. It is an object of the present invention to provide a photosensitive composition having good lyophilicity and capable of forming an opening that easily spreads ink. Moreover, an object of this invention is to provide the partition which has the favorable performance formed by hardening
- the present invention provides a photosensitive composition, a partition, a color filter, and an organic EL device having the following constitution.
- a photosensitive composition have the following meanings.
- X a hydrogen atom, a fluorine atom or a trifluoromethyl group
- R f a fluoroalkyl group having 1 to 20 carbon atoms which may have an etheric oxygen atom or a fluorine atom
- R 11 an alkylene group having 1 to 5 carbon atoms
- R 12 an alkyl group having 1 to 4 carbon atoms
- n An integer from 6 to 30.
- 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 [9].
- 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 [9]. element.
- the photosensitive composition of the present invention it is possible to form a partition wall that has no development defects during development, has an upper surface with good liquid repellency and a side surface with good lyophilicity, and an opening that easily spreads ink. It is. Moreover, according to this invention, the color filter and organic EL element which have the partition which has the favorable performance formed by hardening
- 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.
- Photosensitive composition of the present invention includes at least a side chain having a group represented by the following general formula (1), a side chain having a group represented by the following general formula (2), And a polymer (A) having a side chain having an ethylenic double bond, a photopolymerization initiator (B), and a photosensitive resin (C) having an acidic group and an ethylenic double bond.
- X is a hydrogen atom, a fluorine atom or a trifluoromethyl group
- R f is a fluoroalkyl group having 1 to 20 carbon atoms which may have an etheric oxygen atom, or It is a fluorine atom.
- R 11 is an alkylene group having 1 to 5 carbon atoms
- R 12 is an alkyl group having 1 to 4 carbon atoms
- n is an integer of 6 to 30.
- Polymer (A) Since the polymer (A) contained in the photosensitive composition of the present invention has a side chain having the group (1), a coating formed by applying the photosensitive composition of the present invention on a substrate. When the film is dried, it tends to move to the vicinity of the surface of the coating film. Moreover, since a polymer (A) has a side chain which has an ethylenic double bond, hardening progresses at the time of exposure and it is easy to be fix
- the partition formed by developing the coated film after exposure has no development defect and exhibits liquid repellency only on the upper surface of the partition. For this reason, when ink is applied to the opening surrounded by the partition wall using the ink jet method, it is possible to suppress the occurrence of color mixing between adjacent openings.
- the side wall of the partition wall and the opening have good lyophilicity, the ink wets and spreads at the opening and the occurrence of white spots can be suppressed.
- the mass average molecular weight (Mw) of the polymer (A) is preferably 1.2 ⁇ 10 4 to 15 ⁇ 10 4 , more preferably 3.0 ⁇ 10 4 to 12 ⁇ 10 4. 5 ⁇ 10 4 to 11 ⁇ 10 4 is particularly preferable.
- the number average molecular weight (Mn) of the polymer (A) is preferably 1.0 ⁇ 10 4 to 7.0 ⁇ 10 4, more preferably 2.5 ⁇ 10 4 to 6.0 ⁇ 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 mass average molecular weight of the polymer (A) is less than 1.2 ⁇ 10 4 , the lyophilicity of the opening between the partition walls may be insufficient, and the ink is applied when the ink is applied using an ink jet method. May not wet and spread sufficiently. If the mass average molecular weight exceeds 15 ⁇ 10 4 , alkali solubility and developability may be insufficient. Further, when the number average molecular weight of the polymer (A) is less than 1.0 ⁇ 10 4 , the lyophilic property of the opening between the partition walls may be insufficient, and when the ink is applied using an ink jet method There is a possibility that the ink does not spread sufficiently.
- the mass average molecular weight (Mw) is 3.0 ⁇ 10 4 to 12 ⁇ 10 4 , the liquid repellency is easily maintained regardless of the type and concentration of alkali and the condition of jet rinsing, and the manufacturing margin Is wide and preferable. Moreover, it is preferable also from the ease of manufacture of a polymer (A).
- the molecular weight distribution (mass average molecular weight / number average molecular weight) of the polymer (A) is preferably 8 or less, more preferably 4 or less. Within this range, developability is good.
- the lower limit of the molecular weight distribution is not particularly limited, but is preferably 1.5 or more from the viewpoint of easy synthesis and affinity with a developer.
- adjustment of the molecular weight of a polymer (A) is demonstrated in the manufacturing method of the below-mentioned polymer (A).
- the content of fluorine atoms in the polymer (A) is 5 to 35% by mass, and more preferably 10 to 30% by mass.
- the fluorine atom content is less than 5% by mass, the liquid repellency of the upper surface of the partition wall may be insufficient, and when it exceeds 35% by mass, the adhesion between the partition wall and the substrate may be lowered.
- content of the fluorine atom in a polymer (A) can be adjusted with the introduction amount of the side chain which has group (1) mainly demonstrated below to a polymer (A).
- 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.
- R f 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.
- 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.
- 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.
- 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.
- 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
- 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.
- a perfluoroalkyl group or a polyfluoroalkyl group having one hydrogen atom is preferable, and a perfluoroalkyl group is particularly preferable.
- the perfluoroalkyl group and the polyfluoroalkyl group include those having an etheric oxygen atom.
- the compound whose X is a hydrogen atom is preferable.
- the group (1) preferably has 4 to 6 carbon atoms.
- Specific examples of such a group (1) include — (CF 2 ) 3 CF 3 , — (CF 2 ) 4 CF 3 , — (CF 2 ) 5 CF 3 , —CF 2 O (CF 2 ) 2 OCF 3 , -CF 2 O (CF 2 ) 2 O (CF 2 ) 2 OCF 3 and the like.
- the number of introduced groups (1) in the side chain having the group (1) is 1.
- the group (1) may be the same or different. That is, the group (1) that the polymer (A) has in the side chain may be only one type or a combination of two or more types.
- the group (1) may be introduced into all side chains, but preferably the polymer (A) so as to have the above-mentioned fluorine atom content. The ratio of the side chain into which the group (1) is introduced relative to the whole is appropriately adjusted.
- the blending amount of the monomer having the group (1) with respect to the entire raw material monomer is adjusted.
- the side chain having the group (1) may be formed directly by a polymerization reaction or may be formed by chemical conversion after the polymerization reaction.
- the polymer (A) used for this invention has group (2) containing the polyoxyalkylene chain shown by the said General formula (2) in a side chain.
- the polyoxyalkylene chain refers to a moiety represented by — (R 11 —O) n —.
- This polyoxyalkylene chain is preferably a hydrophilic chain, and in particular 50 to 100% of the n oxyalkylene groups are preferably oxyethylene groups.
- a polyoxyalkylene chain having an oxyethylene group can exhibit good hydrophilicity.
- the ratio of the polymer unit containing the group represented by the general formula (2) is preferably 5 to 50% by mass, and preferably 10 to 40% by mass. Is more preferably 15 to 35% by mass.
- the ratio of the polymer unit containing the group represented by the general formula (2) in the polymer (A) is less than 5% by mass, adsorption of bubbles generated during development to the coating film surface is sufficiently suppressed. Therefore, many development defects may occur in the finally obtained partition walls and partition wall opening portions.
- the proportion of the above polymerized units exceeds 50% by mass, the liquid repellency may be lowered.
- the ratio of the polymer units containing the group represented by the general formula (2) is within this range, the portion where the group (2) (group having a polyoxyalkylene chain) per polymer (A) is present is uniform. The distribution is stable and the performance is stable.
- R 11 is preferably an alkylene group having 1 to 5 carbon atoms, and 50 to 100% of the number of R 11 present is preferably an ethylene group.
- R 11 other than the ethylene group is preferably an alkylene group having 3 to 5 carbon atoms, and particularly preferably a propylene group.
- the structure of the alkylene group having 3 to 5 carbon atoms may be a linear structure or a branched structure.
- n 11 R 11 is ethylene group, and particularly 100% is particularly preferably ethylene group. That is, the polyoxyalkylene chain is particularly preferably a polyoxyethylene chain.
- n — contains an oxyethylene group and an oxyalkylene group other than the oxyethylene group
- the group (2) is a block copolymer chain of the oxyethylene group and another oxyalkylene group. Is preferred.
- n which represents the number of repeating oxyalkylene groups represented by —R 11 —O—, is 6 to 30, preferably 8 to 25.
- n 6 or more, there is a hydrophilic effect, so that the wettability of the developer can be improved and the adsorption and stabilization of bubbles can be suppressed.
- n 30 or less, the group (2), that is, the portion where the polyoxyalkylene chain is present in the film surface has a uniform distribution.
- n in the group (2) is a value used as an average value between the polymerization units including the group (2) in the polymer (A).
- the terminal group R 12 bonded to the polyoxyalkylene chain: — (R 11 —O) n — is an alkyl group having 1 to 4 carbon atoms, preferably a methyl group. If the terminal group bonded to the polyoxyalkylene chain is a reactive site such as a hydroxyl group, it reacts simultaneously when other reactive groups are modified, reducing the effect of introducing the polyoxyalkylene chain. there is a possibility. Moreover, since the hydrophobicity will increase if the carbon number of the terminal group: R 12 is 5 or more, the effect of introducing a hydrophilic alkyloxylene chain will be reduced.
- Addition polymerizable groups such as a (meth) acryloyl group, an allyl group, a vinyl group, a vinyloxy group, are mentioned. .
- the content of the ethylenic double bond in the polymer (A) is preferably 1.0 to 5.0 mmol / g, and more preferably 1.2 to 2.5 mmol / g. Within this range, the immobilization of the polymer (A) to the partition walls and the developability will be good.
- the polymer (A) may further have a side chain having an acidic group as necessary.
- the polymer (A) which has not been cured at the time of exposure is easily removed from the upper surface of the partition wall at the time of development. Therefore, it can suppress that the polymer (A) which was not hardened
- the acidic group which a polymer (A) has in a side chain may be 1 type, or may be 2 or more types.
- the polymer (A) preferably has an acid value of 100 mgKOH / g or less, more preferably 10 to 50 mgKOH / g. Within this range, the polymer (A) that has not been fixed during exposure is easily removed from the upper surface of the partition wall during development.
- the acid value is the mass [mg] of potassium hydroxide necessary to neutralize 1 g of the sample, and the unit is described as mgKOH / g in this specification.
- the side chain having an acidic group may be formed directly by a polymerization reaction or may be formed by chemical conversion after the polymerization reaction.
- the polymer (A) includes a monomer having a group (1), a monomer having a group (2), a monomer having a reactive group, and an acidic group as necessary. It is bonded to a copolymer (a precursor of the polymer (A)) obtained by copolymerizing a monomer having a monomer and / or another monomer and a reactive group of the copolymer. It can be synthesized by reacting the resulting functional group with a compound having an ethylenic double bond.
- 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 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group or a trifluoromethyl group, and Y has a single bond or a fluorine atom having 1 to 6 carbon atoms.
- -CFXR f is a group corresponding to the group (1), that is, X is a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R f is an etheric group. (It is a fluoroalkyl group having 1 to 20 carbon atoms which may have an oxygen atom, or a fluorine atom.)
- the preferred embodiment of —CFXR f in the compound (3) is the same as described for the group (1).
- Y which is a divalent organic group having no fluorine atom having 1 to 6 carbon atoms, represents —R 5 —, —R 5 —NR 6.
- R 5 is an alkylene group having 1 to 6 carbon atoms
- R 6 is a hydrogen atom or 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. Etc.).
- R 5 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.
- R 7 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 ) — and the like.
- Y in the compound (3) is preferably an alkylene group having 2 to 4 carbon atoms from the viewpoint of availability.
- R 4 in the compound (3) a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, or a trifluoromethyl group is preferable, and a hydrogen atom or a methyl group is particularly preferable. That is, the compound (3) is particularly preferably (meth) acrylate.
- the compound represented by the general formula (3) is particularly preferably (meth) acrylate in which —CFXR f is a perfluoroalkyl group having 4 to 6 carbon atoms and Y is an alkylene group having 2 to 4 carbon atoms.
- Specific examples include 2- (perfluorohexyl) ethyl (meth) acrylate and 2- (perfluorobutyl) ethyl (meth) acrylate.
- the monomer having the group (2) used for the production of the polymer (A) is preferably a compound represented by the following general formula (4a) or (4b). These may be used individually by 1 type, or may use 2 or more types together.
- CH 2 CR 10 —COO— (W—O) q — (R 11 —O) n —R 12 (4a)
- CH 2 CR 10 —O— (W—O) q — (R 11 —O) n —R 12 (4b)
- R 10 is substituted with a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 7 to 20 carbon atoms.
- Q is 0 or 1.
- R 11 —O) n —R 12 is a group corresponding to the above group (2).
- — (W—O) q — represents a single bond when q is 0.
- — (W—O) q — is an organic group having an oxygen atom on the R 11 side.
- W is preferably a divalent hydrocarbon group having 2 to 10 carbon atoms, such as an alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 5 or 6 carbon atoms, or a cycloalkylene having 5 or 6 carbon atoms.
- a cycloalkylene group-containing alkylene group having 6 to 10 carbon atoms in total and having an alkylene group having 1 to 2 carbon atoms on both sides or one side of the group is preferable.
- q is regarded as 0 when W is the same alkylene group as R 11 .
- R 10 in the compounds (4a) and (4b) is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.
- the monomer which has a hydroxyl group, the acid anhydride which has an ethylenic double bond, and the monomer which has a carboxy group And monomers having an epoxy group may be used alone or in combination of two or more.
- the monomer which has a reactive group does not have group (1) substantially.
- Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl ( (Meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydroxymethyl (meth) acrylate Amide, N, N-bis (hydroxymethyl) (meth) acrylamide.
- C 6 H 10 is a cyclohexylene group
- C 4 H 8 is an n-butylene group
- C 3 H 6 is a propylene group.
- k is preferably an integer of 1 to 30
- m is preferably an integer of 0 to 30
- j is preferably an integer of 1 to 30
- m + j is preferably 1 to 30.
- Examples of the acid anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4,5,6-tetrahydrophthal And acid anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-ylsuccinic anhydride, and the like.
- Examples of the monomer having a carboxy group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof.
- Examples of the monomer having an epoxy group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.
- the monomer having an acidic group used as necessary for the production of the polymer (A) includes a monomer having a carboxy group, a monomer having a phenolic hydroxyl group, and a monomer having a sulfonic acid group. Etc. These may be used alone or in combination of two or more.
- a monomer having a carboxy group is used as a monomer having an acidic group and a monomer having a carboxy group is used as a monomer having a reactive group, the ethylenic double Any bond that is not introduced and remains as a carboxy group is regarded as a monomer.
- Examples of the monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, and one or more hydrogen atoms of these benzene rings, such as a methyl group, an ethyl group, and an n-butyl group. And an alkyl group, a methoxy group, an ethoxy group, an n-butoxy group or the like, a halogen atom, a haloalkyl group having one or more halogen atoms, a nitro group, a cyano group, a compound substituted with an amide group, etc. .
- Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, 2-hydroxy-3- (meth) allyloxypropane sulfonic acid, 2-methacrylic acid 2-sulfoethyl, Examples include 2-sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropane sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, and the like.
- Monomers other than those that can be optionally used for the production of the polymer (A) include hydrocarbon olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters. , (Meth) acrylic acid esters, (meth) acrylamides, aromatic vinyl compounds, chloroolefins, conjugated dienes, linear organopolysiloxane compounds modified at one end with a (meth) acryloyl group, etc. Considering the heat resistance of the partition walls, (meth) acrylic acid esters and (meth) acrylamides are preferable. Note that these compounds may have a functional group such as a carbonyl group or an alkoxy group.
- 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 mass of the monomer having the group (1) to the total mass of the monomer to be copolymerized is the ratio in the polymer (A) in which an ethylenic double bond is introduced via a reactive group described later. In terms of conversion, it is preferably 5 to 80% by mass, and more preferably 25 to 60% by mass. If this ratio is too low, the polymer (A) will not easily migrate to the vicinity of the upper surface of the partition formed using the photosensitive composition of the present invention, and the liquid repellency of the upper surface of the partition will be insufficient. There is. If this ratio is too high, the adhesion between the partition walls and the substrate may be reduced.
- the ratio of the mass of the monomer having the group (2) to the total mass of the monomer to be copolymerized is the ratio in the polymer (A) in which an ethylenic double bond is introduced via a reactive group described later. In terms of conversion, it is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 15 to 35% by mass. Within this range, the wettability of the developer can be improved and the adsorption and stabilization of bubbles can be suppressed. Further, the group (2), that is, the location where the polyoxyalkylene chain exists in the film surface has a uniform distribution.
- the ratio of the mass of the monomer having a reactive group to the total mass of the monomer to be copolymerized is converted to the ratio in the polymer (A) in which an ethylenic double bond is introduced through the reactive group described later.
- the content is preferably 5 to 50% by mass, more preferably 10 to 35% by mass.
- the ethylenic double bond introduced by the method described later via this reactive group is in a suitable amount in the polymer (A), specifically 1.0 to 5.0 mmol / g, more preferably in an amount of 1.2 to 2.5 mmol / g, and the immobilization of the polymer (A) on the partition walls and the developability are good.
- the ratio of the mass of the monomer having an acidic group to the total mass of the monomer to be copolymerized is determined by the polymer ( It is preferable that the acid value of A) be in the above-mentioned preferable range, specifically 100 mgKOH / g or less, more preferably 10 to 50 mgKOH / g. Such a ratio depends on the type of monomer having an acidic group, but is specifically preferably 2 to 20% by mass, more preferably 4 to 12% by mass. Within this range, the polymer (A) that has not been cured at the time of exposure tends to be washed away from the partition walls at the time of development.
- the ratio of the mass of the other monomers to the total mass of the monomers to be copolymerized is ethylene via a reactive group described later. It is preferably 50% by mass or less, more preferably 30% by mass or less, in terms of the ratio in the polymer (A) into which the ionic double bond is introduced. When the mass ratio exceeds 50% by mass, the alkali developability may be deteriorated.
- the copolymer comprises a monomer having a group (1), a monomer having a group (2), a monomer having a reactive group, and if necessary, a monomer having an acidic group and / or Or it can synthesize
- a chain transfer agent it is preferable to add a chain transfer agent as needed.
- Examples of the solvent used for the copolymerization include 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- Cellsorbs such as ethoxyethanol and 2-butoxyethanol; carbitols such as 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol and 2- (2-butoxyethoxy) ethanol; methyl acetate; Ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, glycerin Esters such as triacetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether.
- ketones
- polymerization initiator examples include known organic peroxides, inorganic peroxides, azo compounds and the like. Organic peroxides and inorganic peroxides can also be used as redox catalysts in combination with a reducing agent. These polymerization initiators may be used alone or in combination of two or more.
- organic peroxide examples include benzoyl peroxide, lauroyl peroxide, isobutyryl peroxide, t-butyl hydroperoxide, t-butyl- ⁇ -cumyl peroxide and the like.
- inorganic peroxides include ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, percarbonate and the like.
- Examples of the azo compound include 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2, 2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis (2 -Amidinopropane) dihydrochloride and the like.
- chain transfer agents examples include mercaptans such as n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolate, 2-ethylhexyl thioglycolate, and 2-mercaptoethanol; chloroform, carbon tetrachloride, tetraodor And alkyl halides such as carbon halides.
- mercaptans such as n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolate, 2-ethylhexyl thioglycolate, and 2-mercaptoethanol
- chloroform carbon tetrachloride
- tetraodor And alkyl halides such as carbon halides.
- the polymer (A) includes a copolymer that is a precursor of the polymer (A) thus obtained, a functional group that can be bonded to the reactive group of the copolymer, and an ethylenic duplex. It can be synthesized by reacting a compound having a bond. Examples of the combination of the functional group capable of binding to the reactive group and the compound having an ethylenic double bond with respect to the reactive group of the copolymer include the following combinations.
- A an acid anhydride having an ethylenic double bond with respect to the hydroxyl group;
- B a compound having an isocyanate group and an ethylenic double bond with respect to the hydroxyl group,
- C a compound having an acyl chloride group and an ethylenic double bond with respect to the hydroxyl group,
- D a compound having a hydroxyl group and an ethylenic double bond with respect to the acid anhydride,
- E a compound having an epoxy group and an ethylenic double bond with respect to the carboxy group,
- F A compound having a carboxy group and an ethylenic double bond with respect to the epoxy group.
- the acid anhydride having an ethylenic double bond in the above combination (a) those exemplified for the monomer having a reactive group described above can be used.
- the compound having an isocyanate group and an ethylenic double bond in the combination (b) include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate.
- Examples of the compound having an acyl chloride group and an ethylenic double bond in the combination (c) include (meth) acryloyl chloride.
- the compound having a hydroxyl group and an ethylenic double bond in the combination (d) those exemplified for the monomer having a hydroxyl group described above can be used.
- the compound having an epoxy group and an ethylenic double bond in the combination (e) those exemplified for the monomer having an epoxy group can be used.
- the compound having a carboxy group and an ethylenic double bond in the combination of (f) those exemplified for the monomer having a carboxy group can be used.
- a reactive group such as a hydroxyl group generated after the reaction and further react with an acid anhydride, if necessary.
- the side chain which has group (1), the side chain which has group (2), the side chain which has a reactive group, and the copolymer which has a side chain which has an acidic group as needed reaction When reacting a compound having a functional group capable of binding to a reactive group and an ethylenic double bond, a functional group capable of binding to the reactive group with respect to the reactive group of the copolymer;
- the functional group equivalent ratio of the compound having an ethylenic double bond is preferably 0.5 to 2.0, more preferably 0.8 to 1.5.
- the content of the ethylenic double bond in the polymer (A) is preferably within the above preferred range, specifically 1.0 to 5.0 mmol / g, more preferably 1.
- the amount can be 2 to 2.5 mmol / g.
- the equivalent ratio is less than 0.5, the content of the ethylenic double bond in the polymer (A) is not a suitable amount, and the polymer (A) is hardly fixed near the upper surface of the partition wall.
- the lyophilicity of the opening surrounded by the partition wall may be insufficient, and if it exceeds 2.0, the amount of unreacted compounds may increase and the appearance of the partition wall may be deteriorated.
- the polymer (A) is a co-polymer having a side chain having a group (1), a side chain having a group (2), a side chain having a reactive group, and a side chain having an acidic group, if necessary. And a compound having a functional group capable of bonding to the reactive group of the copolymer and an ethylenic double bond is dissolved in a solvent corresponding to the combination of (a) to (f) above. And can be synthesized by reacting under known reaction conditions according to each combination.
- the content of the polymer (A) in the total solid content of the photosensitive composition of the present invention is preferably 0.07 to 1% by mass, more preferably 0.1 to 0.5% by mass.
- the content of the polymer (A) is less than 0.07% by mass, the liquid repellency of the upper surface of the partition formed using the photosensitive composition of the present invention may be insufficient, When the content exceeds 1% by mass, the adhesion between the partition walls and the substrate may be lowered.
- Photopolymerization initiator (B) As a photoinitiator (B) which the photosensitive composition of this invention contains, the photoinitiator used for a normal radical curing type photosensitive composition can be especially used without a restriction
- ⁇ -diketones such as benzyl, diacetyl, methylphenylglyoxylate, and 9,10-phenanthrenequinone
- acyloins such as benzoin
- acylo such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether
- Inethers thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diisopropylthioxanthone, thioxanthone-4 Thioxanthones such as sulfonic acids; benzophenones such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis
- the photopolymerization initiator (B) used in the present invention is preferably a compound represented by the following general formula (5).
- R 21 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkyl group.
- R 22 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 8 carbon atoms, a phenyl group having 6 to 20 carbon atoms that is substituted or substituted with an alkyl group, an alkanoyl group having 2 to 20 carbon atoms, and a 7 to 20 carbon atom that is substituted or unsubstituted with an alkyl group a benzoyl group, a phenoxycarbonyl group alkoxycarbonyl group or an alkyl group substituted or unsubstituted 7 to 20 carbon atoms having a carbon number of 2 ⁇ 12, R 23 is an alkyl group having 1 to 12 carbon atoms There, R 24, R 25, R 26 and R 27 each independently represent a hydrogen atom, an alkyl group having 1 to 12
- R 21 is preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group having 6 to 12 carbon atoms substituted or unsubstituted with an alkyl group, such as a methyl group
- an alkyl group such as a methyl group
- Examples include an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a phenyl group.
- an alkyl group having 1 to 4 carbon atoms is preferable, an alkyl group having 1 or 2 carbon atoms is more preferable, and a methyl group is particularly preferable.
- R 22 is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxycarbonyl group having 2 to 5 carbon atoms, such as a methyl group, an ethyl group, or a propyl group.
- R 22 is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxycarbonyl group having 2 to 5 carbon atoms, such as a methyl group, an ethyl group, or a propyl group.
- an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is particularly preferable.
- examples of the alkyl group having 1 to 12 carbon atoms represented by R 23 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group.
- an alkyl group having 1 to 8 carbon atoms is preferable, an alkyl group having 2 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.
- R 24 , R 26 and R 27 are preferably hydrogen atoms.
- R 25 is a benzoyl group having 7 to 20 carbon atoms substituted or unsubstituted with an alkyl group or a carbon number having 7 to 20 carbon atoms substituted or unsubstituted with an alkyl group.
- a benzylcarbonyl group is preferable, and a 2-methylbenzoyl group, a benzylcarbonyl group, or a 1,3,5-trimethylbenzylcarbonyl group is particularly preferable.
- the compound represented by the general formula (5) (O-acyloxime compound) is not particularly limited, but in the general formula (5), R 21 is a phenyl group, R 22 is an octyl group, and R 23 is an ethyl group.
- R 24 , R 26 and R 27 are hydrogen atoms, R 25 is a benzoyl group;
- R 21 is a methyl group,
- R 22 is a butyl group, heptyl group or octyl group,
- R 23 is an ethyl group,
- R 24 , R 26 and R 27 are hydrogen atoms and
- R 25 is a benzoyl group;
- R 21 is a phenyl group, R 22 is an octyl group, R 23 is an ethyl group, R 24 , R 26 and R 27 are hydrogen atoms, and
- R 25 is compound 2-methylbenzoyl group;
- R 21 is a methyl group,
- R 22 is a methyl group or an octyl group,
- R 23 is ethyl,
- R 24, R 26 and R 27 are hydrogen atoms,
- R 5 is a 2-methylbenzoyl group compound;
- R 21 and R 22 is
- a commercial item can be used as a photoinitiator (B).
- Examples of commercially available products include OXE02 (trade name, manufactured by Ciba Specialty Chemicals, Etanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyl) Oxime): a compound in which, in 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) Is mentioned.
- the content of the photopolymerization initiator (B) in the total solid content of the photosensitive composition of the present invention is preferably 1 to 10% by mass, and more preferably 2 to 5% by mass. Within this range, curability is good, and a pattern or line width close to a mask pattern can be formed by exposure and development.
- Photosensitive resin (C) The photosensitive resin (C) contained in the photosensitive composition of the present invention is polymerized and cured by the radical generated by the photopolymerization initiator (B) to form a cured coating film, and the cured coating film. Is a photosensitive resin having an acidic group and an ethylenic double bond that enables alkali development. Since the photosensitive resin (C) has an acidic group and an ethylenic double bond in one molecule, the unexposed portion of the uncured photosensitive composition is selectively removed using an alkali developer. As a result, a partition wall can be formed. In addition, it is preferable that photosensitive resin (C) is compounds other than a polymer (A), and does not have group (1) substantially.
- a carboxy group, a phenolic hydroxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned, You may use 2 or more types together.
- the ethylenic double bond that the photosensitive resin (C) has is not particularly limited, and examples thereof include a double bond possessed by an addition polymerizable group such as a (meth) acryloyl group, an allyl group, a vinyl group, or a vinyloxy group. Two or more kinds may be used in combination. In addition, some or all of the hydrogen atoms of these addition polymerizable groups may be substituted with a hydrocarbon group, preferably a methyl group.
- the photosensitive resin (C) is not particularly limited, but is a resin (C-1) having a side chain having an acidic group and a side chain having an ethylenic double bond, and an epoxy resin having an ethylenic double bond and an acidic group. And a resin (C-2) into which a group is introduced. These may be used alone or in combination of two or more.
- Resin (C-1) can be synthesized in the same manner as polymer (A) except that a monomer having a monomer having group (1) is not used.
- the monomer having a phosphoric acid group is not particularly limited, and examples thereof include 2- (meth) acryloyloxyethane phosphoric acid.
- Resin (C-2) can be synthesized by reacting an epoxy resin with a compound having a carboxy group and an ethylenic double bond and then reacting with a polybasic carboxylic acid or an anhydride thereof. . Specifically, by reacting an epoxy resin with a compound having a carboxy group and an ethylenic double bond, the carboxyl group and the epoxy group of the epoxy resin react to introduce an ethylenic double bond. Next, a carboxy group can be introduced by reacting a polybasic carboxylic acid or its anhydride with a hydroxyl group of a resin into which an ethylenic double bond has been introduced.
- the epoxy resin is not particularly limited, but is bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenolmethane type epoxy resin, epoxy resin having naphthalene skeleton, Examples include an epoxy resin having a biphenyl skeleton represented by the formula (6), an epoxy resin represented by the following general formula (7), an epoxy resin represented by the following general formula (8), and the like.
- s is 1 to 50, preferably 2 to 10.
- R 31 , R 32 , R 33 and R 34 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and t is 0 to 10).
- each hydrogen atom of the benzene ring may be independently substituted with an alkyl group having 1 to 12 carbon atoms, a halogen atom, or an optionally substituted phenyl group. 0 to 10)
- C-2 Commercially available resins (C-2) in which an acidic group and an ethylenic double bond are introduced into an epoxy resin include 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 (Nippon Kayaku Co., Ltd.) and the like can be mentioned.
- the photosensitive resin (C) used in the present invention preferably has a mass average molecular weight of 1.5 ⁇ 10 3 to 20 ⁇ 10 3 , more preferably 2.0 ⁇ 10 3 to 15 ⁇ 10 3 .
- mass average molecular weight is less than 1.5 ⁇ 10 3 , curing during exposure may be insufficient, and when it exceeds 20 ⁇ 10 3 , developability may be deteriorated.
- the number of ethylenic double bonds that the photosensitive resin (C) has is preferably 3 or more, more preferably 6 or more in one molecule on average.
- the number of ethylenic double bonds is 3 or more, the difference in alkali solubility between the exposed portion and the unexposed portion is likely to be different, and a fine pattern can be formed with a smaller exposure amount.
- the photosensitive resin (C) preferably has an acid value of 10 to 300 mgKOH / g, more preferably 30 to 150 mgKOH / g. When the acid value is within this range, the developability of the photosensitive composition is good.
- the content of the photosensitive resin (C) in the total solid content of the photosensitive composition of the present invention is preferably 5 to 80% by mass, and more preferably 10 to 60% by mass. When the content of the photosensitive resin (C) is within this range, the developability of the photosensitive composition is good.
- the photosensitive composition of the present invention essentially comprises the polymer (A), the photopolymerization initiator (B), and a photosensitive resin (C) having an acidic group and an ethylenic double bond. Although it contains as a component, in the range which does not impair the effect of this invention, it is possible to contain the arbitrary components demonstrated below for the purpose of the improvement of various functions, etc. (Crosslinking agent (D))
- the photosensitive composition of this invention contains the crosslinking agent (D) which has 2 or more of ethylenic double bonds as needed. Thereby, the sclerosis
- the crosslinking agent (D) is not particularly limited, but a compound having 2 to 10 (meth) acryloyloxy groups is preferable. Specifically, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethoxylated isocyanuric acid triacrylate , Urethane acrylate and the like, and two or more of them may be
- crosslinking agent (D) examples 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, Shin-Nakamura) Chemical industry, ethoxylated isocyanuric acid triacrylate), NK ester A-9300-1CL (trade name, Shin-Nakamura Chemical Co., Ltd., ⁇ -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-dicarboximide) phenyl ⁇ methane), BANI-X (trade name) Manufactured by Maruzen Petrochemical Co., Ltd., N, N′
- urethane acrylate examples include KAYARAD UX series manufactured by Nippon Kayaku Co., Ltd., and specific product names include UX-3204, UX-6101, UX-0937, DPHA-40H, UXE-3501, UX-5000. UX-5002D-P20 and the like.
- the content of the crosslinking agent (D) in the total solid content of the photosensitive composition of the present invention is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass. When the content of the crosslinking agent (D) is within this range, the pattern shape of the photosensitive composition becomes good.
- a coloring agent (E) may be added to the photosensitive composition of this invention as needed.
- a black colorant (E) is used according to the required optical density of the partition walls. Can do.
- the black colorant (E) is not particularly limited, and examples thereof include carbon black, aniline black, anthraquinone black pigment, and perylene black pigment. Specifically, C.I. I. Pigment black 1, 6, 7, 12, 20, 31 etc. are mentioned.
- the black colorant (E) may be a mixture of organic pigments and inorganic pigments such as red pigments, blue pigments, and green pigments.
- carbon black is preferable in consideration of the light shielding property.
- Carbon black may be surface-treated with a resin or the like.
- carbon black in order to adjust the color tone of the black colorant (E), carbon black can be used in combination with a blue pigment or a purple pigment.
- the carbon black used as the colorant (E) preferably has a specific surface area of 50 to 200 m 2 / g by the BET method. If the specific surface area is too small, the shape of the partition wall may be deteriorated. If the specific surface area is too large, the dispersion aid is excessively adsorbed on the colorant (E), and a large amount of dispersion aid is added. May need to be done.
- the carbon black used as the colorant (E) preferably has an oil absorption of dibutyl phthalate of 120 cc / 100 g or less, and more preferably less.
- the carbon black used as the colorant (E) preferably has an average primary particle size of 20 to 50 nm. If this average primary particle size is too small, it becomes difficult to disperse at a high concentration, it may be difficult to obtain a photosensitive composition with good stability over time, and if the average primary particle size is too large, It may cause deterioration of the shape of the partition wall.
- the carbon black preferably has an average secondary particle size of 80 to 200 nm. The particle size of carbon black can be measured using a transmission electron microscope.
- the content of the colorant (E) in the total solid content of the composition in the photosensitive composition of the present invention is appropriately selected depending on the function required of the colorant (E) within a range not impairing the effects of the present invention. .
- the black colorant (E) is blended in order to impart light-shielding properties such as a black matrix to the cured film formed from the photosensitive composition of the present invention
- the colorant (E) is contained.
- the amount is preferably 15 to 60% by mass, more preferably 20 to 50% by mass, and more preferably 25 to 40% by mass with respect to the total solid content of the composition, although it depends on the required light shielding properties and optical density. Particularly preferred.
- the optical density of the partition may be insufficient, and if the content is too large, the curability of the photosensitive composition is lowered and the appearance of the partition May decrease and liquid repellency may decrease.
- the photosensitive composition of the present invention preferably contains a polymer dispersant in order to improve the dispersibility of the colorant (E) such as the black colorant.
- 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. Examples thereof include a polymer system, a polyamide system, and a polycarbonate system. Among these, urethane type and polyester type are preferable.
- the polymer dispersant may have an oxyethylene group and / or an oxypropylene group.
- the polymer dispersant preferably has a basic group in consideration of the affinity for the colorant (E) such as the black colorant. Although it does not specifically limit as a basic group, A primary, secondary, or tertiary amino group is mentioned.
- Disparon DA-7301 manufactured by Enomoto Kasei Co., Ltd.
- BYK161, BYK162, BYK163, BYK182 above, manufactured by BYK-Chemie
- Solspurs 5000 Solspurs 17000 (above, manufactured by Geneca) Etc.
- the addition amount of the polymer dispersant is preferably 5 to 30% by mass and more preferably 10 to 25% by mass with respect to the colorant (E) such as the black colorant. If the amount added is too small, the effect of improving dispersibility may be insufficient, and if the amount added is too large, developability may be lowered.
- the photosensitive composition of the present invention may contain a phthalocyanine pigment derivative or a metal phthalocyanine sulfonamide compound as a dispersion aid.
- the dispersion aid is considered to have a function of improving dispersion stability by adsorbing to the colorant (E) such as the black colorant and the polymer dispersant.
- the photosensitive composition of 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.
- the fine particles are not particularly limited, and include inorganic fine particles such as silica, zirconia, magnesium fluoride, ITO and ATO; organic fine particles such as polyethylene and PMMA.
- inorganic fine particles are preferable in consideration of heat resistance, and silica and zirconia are preferable in consideration of availability and dispersion stability.
- the photosensitive composition contains a colorant (E) such as the black colorant and a polymer dispersant for improving the dispersibility thereof, the adsorption ability of the polymer dispersant is taken into consideration.
- the fine particles are preferably negatively charged.
- the fine particles do not absorb light irradiated at the time of exposure, i-line (365 nm), h-line (405 nm), which is the main emission wavelength of an ultra-high pressure mercury lamp, It is particularly preferable not to absorb g-line (436 nm).
- the fine particles preferably have an average particle size of 1 ⁇ m or less, more preferably 200 nm or less, because the surface smoothness of the partition walls is good.
- the content of fine particles in the total solid content of the photosensitive composition of the present invention is preferably 3 to 20% by mass, more preferably 5 to 15% by mass. If the content is too small, the shape of the partition wall may change during post-baking, and if the content is too large, the dispersion stability of the photosensitive composition may decrease.
- the photosensitive composition of this invention may contain the silane coupling agent as needed. Thereby, the adhesiveness of a partition and a board
- the silane coupling agent is not particularly limited. Specifically, tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyl Examples include trimethoxysilane, heptadecafluorooctylethyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, polyoxyalkylene having a triethoxysilyl group, and imidazolesilane. Good.
- the photosensitive composition of this invention may contain the phosphorus compound as needed. Thereby, the adhesiveness of a partition and a board
- the phosphoric acid compound is not particularly limited, and examples thereof include mono (meth) acryloyloxyethyl phosphate, di (meth) acryloyloxyethyl phosphate, and tris (meth) acryloyloxyethyl phosphate.
- the photosensitive composition of this invention may contain the thermosetting agent as needed. Thereby, the heat resistance of a partition and water permeability resistance can be improved.
- thermosetting agent Amino resin, a compound having two or more epoxy groups, a compound having two or more hydrazino groups, a polycarbodiimide compound, a compound having two or more oxazoline groups, two aziridine groups
- examples thereof include compounds having the above, polyvalent metals, compounds having two or more mercapto groups, polyisocyanate compounds, and the like.
- amino resins, compounds having two or more epoxy groups or compounds having two or more oxazoline groups are preferable.
- the photosensitive composition of the present invention contains, in addition to various components other than those described above, a curing accelerator, a thickener, a plasticizer, an antifoaming agent, a leveling agent, a repellency inhibitor, an ultraviolet absorber, and the like. May be included.
- the photosensitive composition of the present invention can be 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 usual method. .
- a coating film (wet film) is formed using a diluted solution obtained by diluting the photosensitive composition with a solvent, and then the solvent is volatilized and removed. It is preferable to form a coating film of the adhesive composition.
- 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 diluted solution obtained by diluting the photosensitive composition with a solvent is preferably prepared so that the concentration of the photosensitive composition, that is, the solid content concentration is 5 to 40% by mass, and is 10 to 25% by mass. It is more preferable to prepare.
- 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.
- 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.
- the substrate is preferably a heat resistant resin such as a glass plate and polyimide.
- the substrate is preferably transparent.
- the substrate is a substrate in which an organic film or an inorganic oxide film such as TFT, ITO, SiO 2 or the like is formed on a transparent substrate such as a glass substrate, or a laminated substrate in which these substrates are laminated. It may be.
- the coating method is not particularly limited, and examples thereof include spin coating, spraying, slit coating, roll coating, spin coating, and bar coating.
- 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.
- 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.
- a well-known super high pressure mercury lamp etc. can be used as a light source.
- Exposure is usually 5 ⁇ 1000mJ / cm 2 at i-line standard, preferably 10 ⁇ 400mJ / cm 2, more preferably 20 ⁇ 200mJ / cm 2, particularly preferably 50 ⁇ 100mJ / cm 2.
- the exposure amount is less than 5 mJ / cm 2 , the coating film may be insufficiently cured and the developability may be deteriorated.
- it exceeds 1000 mJ / cm 2 high resolution may not be obtained.
- the developer is not particularly limited, and examples thereof include aqueous alkali solutions such as inorganic alkalis, amines, alkanolamines, 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.
- water on the substrate can be removed by washing with running water and air-drying with compressed air or compressed nitrogen.
- post-exposure may be performed on the developed partition wall.
- 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.
- the light source a known ultra-high pressure mercury lamp, high-pressure mercury lamp, or the like can be used. These light sources emit light having a wavelength of 600 nm or less that contributes to hardening of the partition walls, and emit less light having a wavelength of 200 nm or less that causes oxidative decomposition of the partition walls. Furthermore, it is preferable that the quartz tube glass used for the light source has a function of an optical filter that cuts light having a wavelength of 200 nm or less.
- Exposure is usually at 50 mJ / cm 2 or more, preferably 200 mJ / cm 2 or more, more preferably 1000 mJ / cm 2 or more, 2000 mJ / cm 2 or more is particularly preferable.
- a low-pressure mercury lamp may be used as the light source.
- the exposure amount is preferably 500 mJ / cm 2 or less, and 300 mJ / cm 2 or less. Is more preferable.
- 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.
- a hot plate, an oven or the like can be used as the heating device.
- the partition wall of the present invention is formed by curing the photosensitive composition of the present invention through the photolithography process as described above. If necessary, the partition wall of the present invention can constitute a black matrix exhibiting black color by blending a black colorant (E) into the photosensitive composition used for its production. In this case, a black matrix will be formed by forming a partition using a photosensitive composition.
- the partition wall of the present invention preferably has a width (average value) of 100 ⁇ m or less, more preferably 20 ⁇ m or less. Further, the distance between adjacent partition walls, that is, the width (average value) of the openings is preferably 300 ⁇ m or less, and more preferably 100 ⁇ m or less. Further, the height (average value) of the partition walls is preferably 0.05 to 50 ⁇ m, more preferably 0.2 to 10 ⁇ m.
- the liquid repellency (ink repellency) of the partition walls made of a cured film of the photosensitive composition includes water repellency and oil repellency, and water and PGMEA (propylene glycol monomethyl ether acetate: as a solvent for the ink, respectively) It can be evaluated by the contact angle of a commonly used organic solvent).
- the upper surface of the partition wall of the present invention preferably has a water contact angle of 90 ° to 150 °, more preferably 95 ° to 120 °. Further, the upper surface of the partition wall preferably has a PGMEA contact angle of 35 ° to 55 °, more preferably 40 ° to 50 °.
- 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. It is characterized by.
- the partition walls are preferably a black matrix having an optical density of about 2 to 7.
- a partition for example, a black matrix, is formed on a substrate, and then ink is applied to the opening of the partition using, for example, an ink jet method to form a pixel. Can be manufactured.
- the inkjet method is not particularly limited, but is a method in which charged ink is continuously ejected and controlled by a magnetic field, a method in which ink is intermittently ejected using a piezoelectric element, and ink is heated and foamed. The method etc. which inject intermittently are mentioned.
- the arrangement of the pixels is not particularly limited, and examples thereof include known arrangements such as a stripe type, a mosaic type, a triangle type, and a four-pixel arrangement type.
- 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.
- an ink to a partition for example, an opening of a black matrix
- using an inkjet method drying, heat curing, ultraviolet curing, or the like can be performed as necessary.
- a protective film can be formed as necessary. Thereby, the surface smoothness of the color filter can be improved, and the elution from the partition walls (black matrix) and pixels can be blocked from reaching the liquid crystal layer adjacent to the protective film.
- a method for removing the liquid repellency on the upper surface of the partition wall (black matrix) is not particularly limited, and examples thereof include plasma ashing treatment and optical ashing treatment.
- a photo spacer may be formed on a partition wall, for example, a black matrix, if necessary.
- Organic EL Element 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. It is characterized by that.
- 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.
- a partition wall for example, a black matrix is formed on the substrate, and then, for example, an inkjet method is used to form holes in the openings of the partition wall (black matrix) as ink.
- a hole transport layer and a light emitting layer are formed by sequentially applying and drying a solution of a transport material and a solution of a light emitting material.
- 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.
- a part means a mass part.
- PME-400 Bremer PME-400 (manufactured by NOF Corporation: ⁇ -methyl- ⁇ -methacryloyloxypoly (oxyethylene): CH 2 ⁇ C (CH 3 ) COO (CH 2 CH 2 O) k CH 3 : K of k indicates an average value between molecules, and the value of k is about 9.)
- PE-350 Bremer PE-350 (manufactured by NOF Corporation: ⁇ -hydro- ⁇ -methacryloyloxypoly (oxyethylene): CH 2 ⁇ C (CH 3 ) COO (CH 2 CH 2 O) k H :: K represents an average value between molecules, and the value
- Photosensitive composition component OXE02 OXE02 (manufactured by Ciba Specialty Chemicals, Etanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyl) Oxime) (in the 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) 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 4710) DPHA: KAYARAD DPHA (Nippon Kayaku Co., Ltd., mixture
- the polymer (A-1) has a number average molecular weight of 34,900, a weight average molecular weight of 69,300, an F atom content of 21.1% by mass, and an ethylenic double bond content of 1.26 ⁇ 10. -3 mol / g, acid value was 26.8 mgKOH / g.
- the number average molecular weight and the mass average molecular weight were measured by gel permeation chromatography using polystyrene as a standard substance.
- gel permeation chromatography HPLC-8220GPC (manufactured by Tosoh Corporation) was used.
- column a column in which three shodex LF-604 were connected was used.
- An RI detector was used as the detector.
- EasiCal PS1 manufactured by Polymer Laboratories
- the column is maintained at 37 ° C., tetrahydrofuran is used as the eluent, the flow rate is 0.2 mL / min, and a 0.5% tetrahydrofuran solution of the measurement sample is used. 40 ⁇ L was injected.
- the acid value is a theoretical value calculated from the blending ratio of monomers as raw materials.
- Example 1 Polymer (A-1) (0.06 parts), OXE02 (1.3 parts) as photopolymerization initiator (B), ZCR1569H (12.9 parts) as a dispersion of photosensitive resin (C), DPHA as a crosslinking agent (D) (3.9 parts) CB (38.6 parts) as a dispersion of black colorant (E), silica (15.0 parts) as a silica dispersion, and PGMEA as a solvent (28.24 parts) was 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 0.20% by mass.
- a diluted solution of the photosensitive composition is applied on a glass substrate, and then dried on a hot plate at 100 ° C. for 2 minutes to form a coating film of the photosensitive composition having a thickness of 2.0 ⁇ m. did.
- the coating film was irradiated with light having an exposure amount of 100 mJ / cm 2 on the basis of i-line (365 nm) through a mask to be exposed.
- the mask has a lattice pattern with a light shielding portion of 150 ⁇ m ⁇ 400 ⁇ m and a light transmitting portion of 20 ⁇ m, and the volume of the formed opening is 40 pL.
- the area of the pattern was 10 cm 2.
- the developer used was a 10-fold diluted aqueous solution of an inorganic alkali type developer semi-clean DL-A4 (trade name, manufactured by Yokohama Oils and Fats Industries Co., Ltd.), and the nozzle had an irradiation angle on the substrate reduced to 8 degrees or less.
- bubbles were generated by applying a pressure of 0.15 MPa to the substrate to generate bubbles, and spin development was performed. Thereafter, the unexposed portion was washed away with water and dried to obtain a glass substrate sample (1) of Example 1 in which partition walls were formed.
- Example 1 A glass substrate sample (2) of Example 1 in which a cured product of the coating film of the photosensitive composition after development was formed was obtained.
- Examples 2 to 5, Comparative Examples 1 to 5 The polymers (A-2) to (A-5) obtained in the above synthesis examples and the comparative example polymers (A) were prepared in the same manner as in Example 1 except that the composition of each component was changed as shown in Table 3.
- a glass substrate sample (3) on which a cured product of the film was formed was obtained.
- the number of development defects per area of less than 30 is ⁇
- the number of development defects is 30 or more and less than 50
- the number of development defects is 50 or more is ⁇
- This evaluation method is a method for intentionally generating a large amount of bubbles, and in this evaluation, if it is less than 30, it means that there is almost no development defect in the actual production line.
- the water repellency was evaluated by measuring the contact angle of water on the surface of the cured film of the glass substrate (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 water repellency of the cured film.
- a water contact angle of 95 ° or more was evaluated as “ ⁇ ”
- a water contact angle of 90 ° or more and less than 95 ° was evaluated as “ ⁇ ”
- a water contact angle of less than 90 ° was determined as “X”.
- Oil repellency was evaluated by measuring the contact angle of PGMEA on the surface of the cured film of the glass substrate (3).
- the definition of the contact angle is the same as that of water repellency, and the larger the contact angle, the better the oil repellency of the cured film.
- the PGMEA contact angle of 40 ° or more and 50 ° or less was evaluated as “ ⁇ ”, that of 35 ° or more and less than 40 ° as “ ⁇ ”, and that of less than 35 ° as “x”.
- 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.
- Comparative Example 3 with a short polyoxyalkylene chain, many development defects were generated and there was no effect.
- Comparative Example 4 having a long polyoxyalkylene chain development defects increased as compared with the case of the polyoxyalkylene chain having a length in the range used in Examples 1 to 5.
- Comparative Example 5 although the liquid repellency was good, there was a double bond at the end of the polyoxyalkylene chain and it was fixed by photocuring, so it had no effect on development defects.
- the photosensitive composition of the present invention has sufficient liquid repellency, has no development defects, and can form a partition having a top surface with good liquid repellency and a side surface with good lyophilicity even after the development process. In addition, it is possible to form an opening that allows ink to easily spread.
- 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.
- 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.
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Abstract
Description
-CFXRf …(1)
下記一般式(2)で表される基を有する側鎖、
-(R11-O)n-R12 …(2)
およびエチレン性二重結合を有する側鎖、を有する重合体(A)、光重合開始剤(B)、および酸性基とエチレン性二重結合とを有する感光性樹脂(C)を含むことを特徴とする感光性組成物。
ただし、式中の記号は以下の意味を示す。
X:水素原子、フッ素原子またはトリフルオロメチル基、
Rf: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、
R11:炭素数1~5のアルキレン基、
R12:炭素数1~4のアルキル基、
n:6~30の整数。
[3]前記重合体(A)におけるフッ素原子の含有量が、5質量%以上35質量%以下である[1]または[2]に記載の感光性組成物。
[4]前記重合体(A)における前記一般式(2)で表される基を含む重合単位の割合が、5質量%以上50質量%以下である[1]~[3]のいずれかに記載の感光性組成物。
[5]前記重合体(A)が酸性基を有する側鎖をさらに有する[1]~[4]のいずれかに記載の感光性組成物。
[7]着色剤(E)をさらに含む[1]~[6]のいずれかに記載の感光性組成物。
[8]前記感光性組成物の全固形分に対する重合体(A)の含有量が、0.07質量%以上1質量%以下である[1]~[7]のいずれかに記載の感光性組成物。
[10]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[9]に記載の隔壁で形成されていることを特徴とするカラーフィルタ。
[11]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[9]に記載の隔壁で形成されていることを特徴とする有機EL素子。
なお、本明細書において、特に説明のない場合、%は、質量%を表す。(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。
本発明の感光性組成物は、少なくとも、下記一般式(1)で表される基を有する側鎖、下記一般式(2)で表される基を有する側鎖、およびエチレン性二重結合を有する側鎖、を有する重合体(A)、光重合開始剤(B)、および酸性基とエチレン性二重結合とを有する感光性樹脂(C)を含むことを特徴とする。
-CFXRf …(1)
(式(1)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であり、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である。)
下記一般式(2)で表される基を有する側鎖、
-(R11-O)n-R12 …(2)
(式(2)中、R11は、炭素数1~5のアルキレン基であり、R12は、炭素数1~4のアルキル基であり、nは6~30の整数である。)
本発明の感光性組成物が含有する重合体(A)は、上記基(1)を有する側鎖を有するため、基板上に、本発明の感光性組成物を塗布することにより形成される塗膜を乾燥する際に、塗膜の表面近傍に移行しやすい。また、重合体(A)は、エチレン性二重結合を有する側鎖を有するため、露光時に硬化が進行し、塗膜の表面近傍に固定化されやすい。また、上記基(2)を有する側鎖を有するため、現像時に発生する気泡の塗膜表面への吸着を抑制し、気泡の吸着起因と考えられる現像欠陥を防止することができる。したがって、露光後の塗膜を現像することにより形成される隔壁は、現像欠陥がなく、かつ隔壁上面にのみ撥液性を発現する。このため、インクジェット法を用いて、隔壁で囲まれた開口部にインクを塗布する際に、隣接する開口部間における混色の発生を抑制することができる。また、これにより隔壁側面および開口部は良好な親液性が確保されることから、開口部でのインクの濡れ拡がり性がよく白抜けの発生も抑制することができる。
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。
なお、重合体(A)の分子量の調整については、後述の重合体(A)の製造方法において説明する。
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)における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。
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。
なお、本発明で用いる重合体(A)における上記一般式(2)で表される基を含む重合単位の割合は、5~50質量%であることが好ましく、10~40質量%であることがより好ましく、15~35質量%であることが特に好ましい。重合体(A)における上記一般式(2)で表される基を含む重合単位の割合が、5質量%未満であると、現像時に発生する気泡の塗膜表面への吸着を十分に抑制することができず、最終的に得られる隔壁や隔壁開口部に多くの現像欠陥が発生することがある。また、上記重合単位の割合が50質量%を超えると、撥液性が低下するおそれがある。上記一般式(2)で表される基を含む重合単位の割合がこの範囲であると、重合体(A)あたりの基(2)(ポリオキシアルキレン鎖を有する基)が存在する箇所が均一な分布になり、性能が安定する。
-(R11-O)n-がオキシエチレン基とオキシエチレン基以外のオキシアルキレン基とを含む場合、基(2)はオキシエチレン基と他のオキシアルキレン基とのブロック共重合鎖であることが好ましい。
ここで、基(2)におけるnは、重合体(A)における基(2)を含む重合単位間の平均値として用いる値である。
重合体(A)中のエチレン性二重結合の含有量は、1.0~5.0mmol/gであることが好ましく、1.2~2.5mmol/gがより好ましい。この範囲であると、重合体(A)の隔壁への固定化および現像性が良好となる。
本発明において、重合体(A)は、基(1)を有する単量体と、基(2)を有する単量体と、反応性基を有する単量体と、必要に応じて、酸性基を有する単量体および/またはその他の単量体を共重合することにより得られる共重合体(重合体(A)の前駆体)と、この共重合体が有する反応性基に対して結合し得る官能基とエチレン性二重結合とを有する化合物とを反応させることにより合成することができる。
CH2=CR4-COO-Y-CFXRf …(3)
(式中、R4は、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メチル基またはトリフルオロメチル基であり、Yは、単結合または炭素数が1~6のフッ素原子を有さない2価の有機基である。-CFXRfは上記基(1)に相当する基である。すなわち、Xは、水素原子、フッ素原子またはトリフルオロメチル基である。Rfは、エーテル性酸素原子を有していてもよい炭素数が1~20のフルオロアルキル基、またはフッ素原子である。)
なお、上記化合物(3)における-CFXRfの好ましい態様は、上記基(1)に関して説明したのと同様である。
また、化合物(3)におけるR4としては、水素原子、フッ素原子、塩素原子、メチル基、またはトリフルオロメチル基が好ましく、水素原子またはメチル基が特に好ましい。すなわち、化合物(3)は(メタ)アクリレートであることが特に好ましい。
CH2=CR10-COO-(W-O)q-(R11-O)n-R12 …(4a)
CH2=CR10-O-(W-O)q-(R11-O)n-R12 …(4b)
(式(4a)および(4b)中、R10は、水素原子、塩素原子、臭素原子、ヨウ素原子、シアノ基、炭素数1~20のアルキル基、炭素数7~20のアリール基で置換されたアルキル基、炭素数6~20のアリール基、または炭素数3~20のシクロアルキル基、である。Wは、炭素数が1~10のフッ素原子を有さない2価の有機基である。qは0または1である。(R11-O)n-R12は上記基(2)に相当する基である。)
化合物(4a)および(4b)における-(W-O)q-は、qが0の場合は単結合を表す。qが1の場合、-(W-O)q-はR11側に酸素原子を有する有機基である。qが1の場合、Wは炭素数2~10の2価の炭化水素基が好ましく、炭素数2~6のアルキレン基、炭素数5または6のシクロアルキレン基、炭素数5または6のシクロアルキレン基の両側または片側に炭素数1~2のアルキレン基を有する合計炭素数6~10のシクロアルキレン基含有アルキレン基であることが好ましい。ただし、WがR11と同一のアルキレン基である場合はqが0とみなす。
また、化合物(4a)および(4b)におけるR10としては、水素原子、フッ素原子、塩素原子、メチル基、またはトリフルオロメチル基が好ましく、水素原子またはメチル基が特に好ましい。
kは1~30の整数であることが好ましく、mは0~30の整数であることが好ましく、jは1~30の整数であることが好ましく、m+jは1~30であることが好ましい。
上記共重合体が有する反応性基に対する、当該反応性基と結合し得る官能基とエチレン性二重結合とを有する化合物との組合せとして、例えば以下の組み合わせが挙げられる。
(a)水酸基に対し、エチレン性二重結合を有する酸無水物、
(b)水酸基に対し、イソシアネート基とエチレン性二重結合を有する化合物、
(c)水酸基に対し、塩化アシル基とエチレン性二重結合を有する化合物、
(d)酸無水物に対し、水酸基とエチレン性二重結合を有する化合物、
(e)カルボキシ基に対し、エポキシ基とエチレン性二重結合を有する化合物、
(f)エポキシ基に対し、カルボキシ基とエチレン性二重結合を有する化合物。
本発明の感光性組成物が含有する光重合開始剤(B)としては、通常のラジカル硬化型感光性組成物に用いる光重合開始剤を特に制限なく用いることができる。
光重合開始剤(B)としては、光の照射によりラジカルを発生する化合物であれば、特に限定されない。具体的には、ベンジル、ジアセチル、メチルフェニルグリオキシレート、9,10-フェナンスレンキノン等のα-ジケトン類;ベンゾイン等のアシロイン類;ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等のアシロインエーテル類;チオキサントン、2-クロロチオキサントン、2-メチルチオキサントン、2,4-ジメチルチオキサントン、イソプロピルチオキサントン、2,4-ジエチルチオキサントン、2,4-ジクロロチオキサントン、2,4-ジイソプロピルチオキサントン、チオキサントン-4-スルホン酸等のチオキサントン類;ベンゾフェノン、4,4'-ビス(ジメチルアミノ)ベンゾフェノン、4,4'-ビス(ジエチルアミノ)ベンゾフェノン等のベンゾフェノン類;アセトフェノン、2-(4-トルエンスルホニルオキシ)-2-フェニルアセトフェノン、p-ジメチルアミノアセトフェノン、2,2'-ジメトキシ-2-フェニルアセトフェノン、p-メトキシアセトフェノン、2-メチル-[4-(メチルチオ)フェニル]-2-モルフォリノ-1-プロパノン、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタン-1-オン等のアセトフェノン類;アントラキノン、2-エチルアントラキノン、カンファーキノン、1,4-ナフトキノン等のキノン類;2-ジメチルアミノ安息香酸エチル、4-ジメチルアミノ安息香酸エチル、4-ジメチルアミノ安息香酸(n-ブトキシ)エチル、4-ジメチルアミノ安息香酸イソアミル、4-ジメチルアミノ安息香酸2-エチルヘキシル等のアミノ安息香酸類;フェナシルクロライド、トリハロメチルフェニルスルホン等のハロゲン化合物;アシルホスフィンオキシド類;ジ-t-ブチルパーオキサイド等の過酸化物;1,2-オクタンジオン、1-[4-(フェニルチオ)-,2-(O-ベンゾイルオキシム)]、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)等のオキシムエステル類等が挙げられ、2種以上を併用してもよい。
本発明の感光性組成物が含有する感光性樹脂(C)は、上記光重合開始剤(B)が発生したラジカルにより重合・硬化して、塗膜硬化物を形成し、その塗膜硬化物がアルカリ現像可能となるような、酸性基およびエチレン性二重結合を有する感光性樹脂である。
感光性樹脂(C)は、1分子内に酸性基およびエチレン性二重結合を有するため、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(C)は、重合体(A)以外の化合物であり、基(1)を実質的に有さないことが好ましい。
本発明の感光性組成物は、上記重合体(A)、光重合開始剤(B)、および、酸性基とエチレン性二重結合とを有する感光性樹脂(C)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。
(架橋剤(D))
本発明の感光性組成物は、必要に応じて、エチレン性二重結合を2個以上有する架橋剤(D)を含む。これにより、感光性組成物の硬化性が向上し、隔壁を形成する際の露光量を低減することができる。
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、UXE-3501、UX-5000、UX-5002D-P20などが挙げられる。
また、本発明の感光性組成物には、必要に応じて着色剤(E)を添加してもよい。例えば、本発明の感光性組成物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の着色剤(E)を用いることができる。黒色の着色剤(E)としては、特に限定されないが、カーボンブラック、アニリンブラック、アントラキノン系黒色顔料、ペリレン系黒色顔料等が挙げられる。具体的には、C.I.ピグメントブラック1、6、7、12、20、31等が挙げられる。また、黒色の着色剤(E)は、赤色顔料、青色顔料、緑色顔料等の有機顔料や無機顔料の混合物であってもよい。中でも、遮光性の大きさを考慮すると、カーボンブラックが好ましい。なお、カーボンブラックは、樹脂等で表面処理されていてもよい。また、黒色の着色剤(E)の色調を調整するために、カーボンブラックを、青色顔料や紫色顔料と併用することができる。
本発明の感光性組成物は、上記黒色着色剤等の着色剤(E)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。その中でも、ウレタン系、ポリエステル系が好ましい。また、高分子分散剤は、オキシエチレン基および/またはオキシプロピレン基を有していてもよい。
本発明の感光性組成物は、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。
本発明の感光性組成物は、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。
本発明の感光性組成物は、必要に応じて、リン化合物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。
本発明の感光性組成物は、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。
本発明の感光性組成物は、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。
本発明の感光性組成物は、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。
(希釈用溶媒)
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。
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。
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、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、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。
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、粘着性の無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。
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。
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、アルカノールアミン類、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、即ち、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。
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。
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。
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い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、例えば、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。
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、例えば、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。
[1]重合体(A)および重合体(R)の製造に用いた化合物
C6FMA:CH2=C(CH3)COOCH2CH2(CF2)6F
MAA:メタクリル酸
MMA:メタクリル酸メチル
2-HEMA:2-ヒドロキシエチルメタクリレート
PME-200:ブレンマーPME-200(日本油脂社製:α-メチル-ω-メタクリロイルオキシポリ(オキシエチレン):CH2=C(CH3)COO(CH2CH2O)kCH3:式中のkは分子間の平均値を示し、kの値は4である。)
PME-400:ブレンマーPME-400(日本油脂社製:α-メチル-ω-メタクリロイルオキシポリ(オキシエチレン):CH2=C(CH3)COO(CH2CH2O)kCH3:式中のkは分子間の平均値を示し、kの値は約9である。)
PME-4000:ブレンマーPME-4000(日本油脂社製:α-メチル-ω-メタクリロイルオキシポリ(オキシエチレン):CH2=C(CH3)COO(CH2CH2O)kCH3:式中のkは分子間の平均値を示し、kの値は90である。)
PE-350:ブレンマーPE-350(日本油脂社製:α-ヒドロ-ω-メタクリロイルオキシポリ(オキシエチレン):CH2=C(CH3)COO(CH2CH2O)kH::式中のkは分子間の平均値を示し、kの値は8である。)
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))
AOI:カレンズAOI(昭和電工社製、2-アクリロイルオキシエチルイソシアネート)
DBTDL:ジブチル錫ジラウレート
TBQ:t-ブチル-p-ベンゾキノン
MEK:2-ブタノン
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)(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)
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4710)
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)
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
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%)
[重合体(A-1)の合成]
撹拌機を備えた内容積1Lのオートクレーブに、MEK(420.0g)、C6FMA(81.0g)、2-HEMA(36.0g)、PME-400(54.0g)、MAA(9.0g)および重合開始剤V-65(1.1g)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、共重合体1の溶液を得た。共重合体1は、数平均分子量が34,200、質量平均分子量が63,900であった。
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、共重合体2~5を合成した。得られた共重合体2~5を用いて表2の原料配合により、上記同様にして重合体(A)に相当する重合体(A-2)~(A-5)を得た。
[重合体(R-1)、(R-3)~(R-5)の合成]
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、共重合体6、8~10合成した。得られた共重合体6、8~10を用いて表2の原料配合により、上記同様にして、本発明における重合体(A)に適合しない重合体(R-1)、(R-3)~(R-5)を得た。
撹拌機を備えた内容積1Lのオートクレーブに、MEK(420.0g)、C6FMA(99.0g)、2-HEMA(18.0g)、PME-400(27.0g)、MAA(18.0g)、MMA(18.0g)および重合開始剤V-65(1.1g)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、共重合体7の溶液を得た。
得られた溶液にヘキサンを加えて再沈精製した後、真空乾燥し、本発明における重合体(A)に適合しない重合体(R-2)(170.0g)を得た。重合体(R-2)は、数平均分子量が26,600、質量平均分子量が57,600、F原子含有量が31.4質量%、酸価が65.2mgKOH/gであった。
数平均分子量および質量平均分子量は、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%テトラヒドロフラン溶液40μLを注入した。
重合体中のフッ素原子の含有量は、1,4-ジトリフルオロメチルベンゼンを標準物質として、19F NMR測定により算出した。
重合体中のエチレン性二重結合の含有量は、1,4-ジトリフルオロメチルベンゼンを標準物質として、1H NMR測定により算出した。
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。
重合体(A-1)(0.06部)、光重合開始剤(B)としてのOXE02(1.3部)、感光性樹脂(C)の分散液としてのZCR1569H(12.9部)、架橋剤(D)としてのDPHA(3.9部)黒色着色剤(E)の分散液としてのCB(38.6部)、シリカ分散液としてのシリカ(15.0部)および溶媒としてのPGMEA(28.24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、0.20質量%であった。
各成分の配合を表3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-5)、比較例重合体(R-1)~(R-5)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2~5、比較例1~5のガラス基板サンプル(1)、および、現像後の感光性組成物の塗膜の硬化物が形成されたガラス基板サンプル(2)、ガラス基板サンプル(2)と同様の工程を行い、最後に熱処理を行った感光性組成物の塗膜の硬化物が形成されたガラス基板サンプル(3)を得た。
実施例1~5および比較例1~5のガラス基板サンプル(1)、(2)および(3)を用いて、現像性、撥水撥油性、開口部内のインクの濡れ拡がり性を以下に示す方法で評価した。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4に示す。
表中、◎は最良、○は良、△は可、×は不可を示す。本発明は、全ての評価が◎または○であるものが良い。
ガラス基板(1)において、面積あたりの現像欠陥数が30個未満のものを○、現像欠陥数が30個以上50個未満のものを△、現像欠陥数が50個以上のものを×として、判定した。なおこの評価方法は故意に気泡を大量に発生させる方法であり、この評価において30個未満であると実際の製造ラインにおいて、ほぼ現像欠陥が無いことを意味する。
ガラス基板(2)の塗膜硬化物の表面の水の接触角を測定することにより、撥水性を評価した。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、塗膜硬化物の撥水性が優れることを意味する。
ガラス基板(3)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、撥油性を評価した。接触角の定義は、撥水性と同様であり、接触角が大きい程、塗膜硬化物の撥油性が優れることを意味する。
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。
なお、2009年12月28日に出願された日本特許出願2009-298960号の明細書、特許請求の範囲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。
Claims (11)
- 少なくとも、
下記一般式(1)で表される基を有する側鎖、
-CFXRf …(1)
下記一般式(2)で表される基を有する側鎖、
-(R11-O)n-R12 …(2)
およびエチレン性二重結合を有する側鎖、を有する重合体(A)、光重合開始剤(B)、および酸性基とエチレン性二重結合とを有する感光性樹脂(C)を含むことを特徴とする感光性組成物。
ただし、式中の記号は以下の意味を示す。
X:水素原子、フッ素原子またはトリフルオロメチル基。
Rf: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。
R11:炭素数1~5のアルキレン基。
R12:炭素数1~4のアルキル基。
n:6~30の整数。 - 前記重合体(A)の質量平均分子量が、1.2×104以上15×104以下である請求項1に記載の感光性組成物。
- 前記重合体(A)におけるフッ素原子の含有量が、5質量%以上35質量%以下である請求項1または2に記載の感光性組成物。
- 前記重合体(A)における前記一般式(2)で表される基を含む重合単位の割合が、5質量%以上50質量%以下である請求項1~3のいずれか1項に記載の感光性組成物。
- 前記重合体(A)が酸性基を有する側鎖をさらに有する請求項1~4のいずれか1項に記載の感光性組成物。
- エチレン性二重結合を2個以上有する架橋剤(D)をさらに含む請求項1~5のいずれか1項に記載の感光性組成物。
- 着色剤(E)をさらに含む請求項1~6のいずれか1項に記載の感光性組成物。
- 前記感光性組成物の全固形分に対する重合体(A)の含有量が、0.07質量%以上1質量%以下である請求項1~7のいずれか1項に記載の感光性組成物。
- 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1~8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。
- 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9に記載の隔壁で形成されていることを特徴とするカラーフィルタ。
- 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9に記載の隔壁で形成されていることを特徴とする有機EL素子。
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