WO2018052024A1 - Photosensitive resin composition, cured product and image display device - Google Patents

Photosensitive resin composition, cured product and image display device Download PDF

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Publication number
WO2018052024A1
WO2018052024A1 PCT/JP2017/033037 JP2017033037W WO2018052024A1 WO 2018052024 A1 WO2018052024 A1 WO 2018052024A1 JP 2017033037 W JP2017033037 W JP 2017033037W WO 2018052024 A1 WO2018052024 A1 WO 2018052024A1
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ring
group
mass
resin composition
photopolymerization initiator
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PCT/JP2017/033037
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French (fr)
Japanese (ja)
Inventor
植松　卓也
直人 関口
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三菱ケミカル株式会社
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Application filed by 三菱ケミカル株式会社 filed Critical 三菱ケミカル株式会社
Priority to JP2018511166A priority Critical patent/JP6341351B1/en
Priority to KR1020197007411A priority patent/KR102402726B1/en
Priority to CN201780056225.0A priority patent/CN109791357B/en
Publication of WO2018052024A1 publication Critical patent/WO2018052024A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D307/80—Radicals substituted by oxygen atoms

Definitions

  • the present invention relates to a photosensitive resin composition, a cured product, and an image display device.
  • the present invention relates to a photosensitive resin composition having high sensitivity and excellent fine-line adhesion, a cured product obtained by curing the photosensitive resin composition, and an image display device having the cured product.
  • the photosensitive resin composition of the present invention is particularly suitable for a photosensitive resin composition for a black matrix (Black Matrix, hereinafter sometimes abbreviated as “BM”) capable of forming highly sensitive and fine fine lines. Yes.
  • Black Matrix hereinafter sometimes abbreviated as “BM”
  • Color filters usually form a black matrix on the surface of a transparent substrate such as glass or plastic, followed by three or more different color pixels such as red, green, blue, etc. Formed in a pattern such as a shape or a mosaic.
  • the pattern size varies depending on the use of the color filter and each color, but is usually about 5 to 700 ⁇ m.
  • a pigment dispersion method is currently known as a typical method for producing a color filter.
  • a photosensitive resin composition containing a black pigment is applied on a transparent substrate and then dried, and after image exposure and development, it is cured by high-temperature treatment at 200 ° C. or higher. As a result, a BM is formed. This process is repeated for each color such as red, green, and blue to form a color filter.
  • the BM is generally arranged in a grid, stripe, or mosaic between pixels such as red, green, and blue, and serves to improve contrast by preventing color mixture between pixels or to prevent light leakage. . For this reason, the BM is required to have high light shielding properties.
  • the edge portions of the red, green, and blue pixels formed after the BM partially overlap with the BM, a step is formed at the overlapping portion under the influence of the BM film thickness. In this overlapping portion, the flatness of the pixels is impaired, and the liquid crystal cell gap becomes non-uniform or the alignment of the liquid crystal is disturbed, causing a reduction in display capability.
  • the ratio of the photopolymerization initiator that can be added is decreasing, and a highly sensitive initiator that can maintain the degree of crosslinking even when added in a small amount is demanded.
  • the output of the backlight is in the direction of lowering. Is being promoted.
  • downsizing such as tablets has become the mainstream in the liquid crystal display market, and the demand for high resolution is increasing for large televisions.
  • the line width of BM thin wires has been demanded from about 10 ⁇ m to about 6 to 8 ⁇ m at present.
  • the pattern line width of the exposure mask is less than 10 ⁇ m, the influence of diffraction of the light that has passed increases, and the amount of light that reaches the BM surface decreases accordingly. Therefore, a highly sensitive initiator is required.
  • the development time is generally set longer in order to eliminate residues, but this causes the dissolution (insertion) of the BM / substrate interface to proceed, and the line pattern is liable to peel off. .
  • the pattern line width is 10 ⁇ m or more, even if insertion of about 1 to 2 ⁇ m occurs (about 2 to 4 ⁇ m in total on both sides of the line), fine line adhesion can be maintained.
  • the BM / substrate adhesion area is small. Each time the line width is reduced and the line width is reduced by 1 ⁇ m, the decrease in the development adhesion is remarkably increased.
  • Patent Document 1 describes that an oxime ester compound having a nitrated carbazolyl structure is a highly sensitive photopolymerization initiator that efficiently absorbs and activates light having a long wavelength such as 405 nm and 365 nm.
  • Patent Document 2 describes that an oxime ester compound having a benzo-unsaturated 5-membered ring-carbonyl group has high sensitivity.
  • an object of the present invention is to provide a photosensitive resin composition having high sensitivity and excellent fine wire adhesion.
  • the present inventors have found that the above problems can be solved by including a specific combination of photopolymerization initiators in the photosensitive resin composition. That is, the gist of the present invention is as follows.
  • a photosensitive resin composition containing (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, and (d) a coloring material
  • the photopolymerization initiator (c) is a photopolymerization initiator (c1) represented by the following general formula (I), and a photopolymerization initiator having a maximum absorption wavelength of 334 nm or more in the wavelength range of 320 nm to 400 nm
  • a photosensitive resin composition comprising c2).
  • R 1 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • R 2 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • k represents 0 or 1;
  • R 3 to R 6 each independently represents an arbitrary monovalent substituent.
  • l, m and o each independently represents an integer of 0 to 3.
  • n represents 0 or 1.
  • R 7 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • R 8 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • p represents 0 or 1;
  • R 9 represents an arbitrary monovalent substituent.
  • q represents an integer of 0 to 3.
  • X represents —N (R 10 ) — or —C (R 11 ) (R 12 ) —.
  • R 10 to R 12 each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
  • R 11 and R 12 may be bonded to each other to form a ring.
  • FIG. 1 is a schematic cross-sectional view showing an example of an organic EL (Electro Luminescence) element provided with the color filter of the present invention.
  • organic EL Electro Luminescence
  • (meth) acryl means “acryl and / or methacryl”, and the same applies to “(meth) acrylate” and “(meth) acryloyl”.
  • all percentages and parts expressed by mass are the same as percentages and parts expressed by weight.
  • the “total solid content” means all components other than the solvent contained in the photosensitive resin composition or in the ink described later.
  • a weight average molecular weight refers to the weight average molecular weight (Mw) of polystyrene conversion by GPC (gel permeation chromatography).
  • the “amine value” means an amine value in terms of effective solid content, unless otherwise specified, and is a value represented by the weight of KOH equivalent to the base amount per 1 g of the solid content of the dispersant. It is. The measuring method will be described later.
  • the photosensitive resin composition of the present invention is a photosensitive resin composition containing (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, and (d) a coloring material.
  • the photopolymerization initiator (c) is a photopolymerization initiator (c1) represented by the following general formula (I), and a photopolymerization initiator having a maximum absorption wavelength of 334 nm or more in the wavelength range of 320 nm to 400 nm ( c2) is contained.
  • the “maximum absorption wavelength” of the photopolymerization initiator (c) means the maximum absorption wavelength in the wavelength range of 320 nm to 400 nm.
  • R 1 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • R 2 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • k represents 0 or 1;
  • R 3 to R 6 each independently represents an arbitrary monovalent substituent.
  • l, m and o each independently represents an integer of 0 to 3.
  • n represents 0 or 1.
  • the photosensitive resin composition of the present invention may further contain a dispersant and a thiol, and if necessary, an adhesion improver, a coatability improver, a development improver, an ultraviolet absorber, an antioxidant, Other compounding components such as pigment derivatives may be contained, and each compounding component is usually used in a state dissolved or dispersed in an organic solvent.
  • the photopolymerization initiator contains a photopolymerization initiator (c1) and a photopolymerization initiator (c2). First, (c) the photopolymerization initiator will be described.
  • the photopolymerization initiator (c) in the present invention contains a photopolymerization initiator (c1) represented by the following general formula (I) and a photopolymerization initiator (c2) having a maximum absorption wavelength of 334 nm or more. To do.
  • the photopolymerization initiator (c1) is a photopolymerization initiator represented by the following general formula (I).
  • R 1 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • R 2 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • k represents 0 or 1;
  • R 3 to R 6 each independently represents an arbitrary monovalent substituent.
  • l, m and o each independently represents an integer of 0 to 3.
  • n represents 0 or 1.
  • the photopolymerization initiator (c1) represented by the general formula (I) the adsorption of the photopolymerization initiator to the surface of the colorant particles is promoted, and the photopolymerization initiator at the time of exposure It is considered that the light absorptivity of the resin component is improved, the UV (Ultraviolet) light transmittance of the resin component is increased, the internal curability is improved, and the fine wire adhesion is improved.
  • R 1 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • the alkyl group in R 1 may be linear, branched, cyclic, or a combination thereof.
  • carbon number of an alkyl group is not specifically limited, Usually, it is 1 or more, Preferably it is 12 or less, More preferably, it is 6 or less, More preferably, it is 3 or less, Most preferably, it is 2 or less.
  • alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, cyclopentyl group, hexyl group and cyclohexyl group.
  • a methyl group, an ethyl group, a propyl group, or a butyl group is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is more preferable.
  • alkyl group may have examples include an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a halogen atom such as F, Cl, Br, and I, a hydroxyl group, and a nitro group.
  • a methoxy group or a hydroxyl group is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.
  • Examples of the aromatic ring group for R 1 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the carbon number is usually 4 or more, preferably 6 or more, 12 or less, more preferably 10 or less, and even more preferably 8 or less. Storage stability tends to be good when the number of carbon atoms of the aromatic ring group is equal to or higher than the lower limit value, and solvent solubility tends to be better when the aromatic ring group is equal to or lower than the upper limit value.
  • the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • the aromatic hydrocarbon ring group for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring having one free valence, Examples include acenaphthene ring, fluoranthene ring, fluorene ring and the like.
  • the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.
  • the aromatic heterocyclic group include one furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, and carbazole having one free valence.
  • Examples of the substituent that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I And a halogen atom such as a hydroxyl group, a nitro group, and the like. From the viewpoint of solvent solubility, a methoxy group or a hydroxyl group is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.
  • R 1 is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and even more preferably a methyl group.
  • R 2 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • the alkyl group in R 2 may be linear, branched, cyclic, or a combination thereof, but is preferably linear or branched from the viewpoint of solvent solubility, and more preferably branched. preferable.
  • the number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, further preferably 4 or more, particularly preferably 5 or more, and preferably 10 or less, more preferably 8 or less. More preferably, it is 7 or less, and particularly preferably 6 or less.
  • alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, cyclopentyl group, hexyl group and cyclohexyl group.
  • isopropyl, isobutyl, isopentyl, or cyclopentyl is preferable, isobutyl or isopentyl is more preferable, and isopentyl is more preferable.
  • substituent that the alkyl group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I
  • an alkoxy group having 1 to 3 carbon atoms is preferable.
  • it is preferably unsubstituted.
  • Examples of the aromatic ring group for R 2 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the carbon number is usually 4 or more, preferably 6 or more, 12 or less, more preferably 10 or less, and even more preferably 8 or less.
  • the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • the aromatic hydrocarbon ring group for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring having one free valence, Examples include acenaphthene ring, fluoranthene ring, fluorene ring and the like.
  • the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.
  • the aromatic heterocyclic group include one furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, and carbazole having one free valence.
  • Examples of the substituent that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I
  • an alkoxy group having 1 to 3 carbon atoms or a hydroxyl group is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.
  • R 2 is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and even more preferably an isopentyl group.
  • k represents 0 or 1. From the viewpoint of sensitivity, k is preferably 0, while from the viewpoint of solvent solubility, k is preferably 1.
  • R 3 to R 6 each independently represents an arbitrary monovalent substituent.
  • an alkyl group having 1 to 10 carbon atoms such as a methyl group or an ethyl group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group or an ethoxy group; F, Cl, Br, I or the like
  • R 3 , R 4 and R 6 when l, m and o are 2 or more, a plurality of R 3 , R 4 and R 6 may be bonded to form a ring.
  • the ring may be an aliphatic ring or an aromatic ring.
  • l, m and o each independently represents an integer of 0 to 3, and n represents 0 or 1. From the viewpoint of sensitivity, it is preferable that l, m and o are each independently 0 or 1, and more preferably 0. From the viewpoint of sensitivity, n is preferably 0.
  • the photopolymerization initiator represented by the general formula (I) is represented by the following general formula (I-1) from the viewpoint of an appropriate interaction with the coloring material in addition to the balance between solvent solubility and sensitivity. It is preferable that the photopolymerization initiator.
  • R 1 to R 6 and k to o have the same meanings as those in formula (I).
  • the maximum absorption wavelength of the photopolymerization initiator (c1) is not particularly limited, but is preferably 322 nm or more, more preferably 325 nm or more, further preferably 328 nm or more, still more preferably 329 nm or more, and 330 nm or more from the viewpoint of sensitivity. Particularly preferred, 337 nm or less is preferred, 336 nm or less is more preferred, 334 nm or less is more preferred, and 333 nm or less is even more preferred. Within the above range, there is a tendency that light between the 333 nm emission line emitted from the UV light source and the 365 nm emission line (i-line) can be effectively used.
  • the manufacturing method of the said photoinitiator (c1) is not specifically limited, For example, the method as described in international publication 2015/036910 is employable. Moreover, as a specific example of the said photoinitiator (c1), the following are mentioned, for example.
  • the photopolymerization initiator in the present invention contains a photopolymerization initiator (c2) having a maximum absorption wavelength of 334 nm or more in addition to the photopolymerization initiator (c1).
  • the photopolymerization initiator (c2) is a photopolymerization initiator having a maximum absorption wavelength of 334 nm or longer. In this way, in addition to the photopolymerization initiator (c1), the use of the photopolymerization initiator (c2) having a maximum absorption wavelength of 334 nm or more broadens the effective wavelength range of light and improves the sensitivity. It is done.
  • the maximum absorption wavelength of the photopolymerization initiator (c2) is not particularly limited as long as it is 334 nm or more, but from the viewpoint of sensitivity, it is preferably 335 nm or more, more preferably 336 nm or more, further preferably 338 nm or more, and more preferably 340 nm or more. More preferably, 345 nm or more is particularly preferable, 350 nm or more is most preferable, 390 nm or less is preferable, 380 nm or less is more preferable, 375 nm or less is further preferable, and 370 nm or less is particularly preferable.
  • the maximum absorption wavelength of the photopolymerization initiator (c2) is set to be equal to or greater than the lower limit value, the internal curing tends to be high, and when the maximum absorption wavelength is equal to or less than the upper limit value, the sensitivity tends to be high.
  • the difference in maximum absorption wavelength between the photopolymerization initiator (c2) and the photopolymerization initiator (c1) is preferably 5 nm or more, more preferably 10 nm or more, further preferably 20 nm or more, particularly preferably 30 nm or more, 60 nm or less is preferable, 50 nm or less is more preferable, 40 nm or less is more preferable, and a combination of the photopolymerization initiator (c1) and the photopolymerization initiator (c2) having an appropriate maximum absorption wavelength may be selected and used.
  • the difference between the maximum absorption wavelengths of the photopolymerization initiator (c1) and the photopolymerization initiator (c2) is greater than or equal to the lower limit value, there is a tendency that the light wavelength range that can be effectively used is widened and the sensitivity is increased, and the upper limit value or less. As a result, the sensitivity of UV light to i-line (365 nm) tends to increase.
  • the chemical structure of the photopolymerization initiator (c2) is not particularly limited, but is preferably an oxime ester photopolymerization initiator from the viewpoint of sensitivity, and in particular, a photopolymerization initiator having a fluorene skeleton or a carbazole skeleton. It is preferable. Note that having a fluorene skeleton or a carbazole skeleton means having a fluorene ring or a carbazole ring in the molecular structure, and these rings may be substituted. From the viewpoint of surface curability, the photopolymerization initiator (c2) is preferably a photopolymerization initiator represented by the following general formula (II).
  • R 7 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • R 8 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • p represents 0 or 1;
  • R 9 represents an arbitrary monovalent substituent.
  • q represents an integer of 0 to 3.
  • X represents —N (R 10 ) — or —C (R 11 ) (R 12 ) —.
  • R 10 to R 12 each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
  • R 11 and R 12 may be bonded to each other to form a ring.
  • R 7 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • the alkyl group for R 7 may be linear, branched, cyclic, or a combination thereof.
  • the number of carbon atoms of the alkyl group is not particularly limited, but is preferably 10 or less, more preferably 7 or less, further preferably 5 or less, particularly preferably 3 or less, most preferably 2 or less, and usually 1 or more. By setting the number of carbon atoms of the alkyl group to the upper limit value or less, the crosslinking density tends to increase.
  • alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, cyclopentyl group, hexyl group and cyclohexyl group.
  • a methyl group, an ethyl group, a propyl group, or a butyl group is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is more preferable.
  • alkyl group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I
  • an alkoxy group having 1 to 3 carbon atoms is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.
  • Examples of the aromatic ring group for R 7 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the carbon number is usually 4 or more, preferably 6 or more, 12 or less, more preferably 10 or less, and even more preferably 8 or less.
  • the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • the aromatic hydrocarbon ring group for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring having one free valence, Examples include acenaphthene ring, fluoranthene ring, fluorene ring and the like.
  • the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.
  • the aromatic heterocyclic group include one furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, and carbazole having one free valence.
  • Examples of the substituent that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I In view of solvent solubility, an alkoxy group having 1 to 3 carbon atoms or a hydroxyl group is preferable.
  • R 7 is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and further preferably a methyl group or an ethyl group.
  • a methyl group is preferable, and a methyl group is particularly preferable.
  • R 8 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • the alkyl group in R 8 may be linear, branched, cyclic, or a combination thereof, but is preferably linear or branched from the viewpoint of solvent solubility, and more preferably branched. preferable.
  • a group in which a linear alkyl group and a cyclic alkyl group are bonded is preferable.
  • the number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, still more preferably 5 or more, particularly preferably 6 or more, and most preferably 7 or more. Also, it is preferably 12 or less, more preferably 10 or less, still more preferably 9 or less, and particularly preferably 8 or less. There exists a tendency for solvent solubility to become favorable by making carbon number of an alkyl group more than the said lower limit, and there exists a tendency for it to become high sensitivity by making it into the said upper limit or less.
  • Examples of the substituent that the alkyl group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms.
  • Examples thereof include a carbonyl group, a halogen atom such as F, Cl, Br, and I, and a hydroxyl group.
  • an alkoxy group having 1 to 3 carbon atoms is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.
  • alkyl group examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, cyclopentyl, hexyl, cyclohexyl, cyclopentylmethyl, A cyclopentylethyl group, a cyclohexylmethyl group, a cyclohexylethyl group, etc. are mentioned.
  • an isopentyl group, a cyclohexylmethyl group, a cyclopentylethyl group, or a cyclohexylethyl group is preferable, a cyclopentylethyl group or a cyclohexylethyl group is more preferable, and a cyclohexylethyl group is more preferable.
  • Examples of the aromatic ring group for R 8 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the carbon number is usually 4 or more, preferably 6 or more, 12 or less, more preferably 10 or less, and even more preferably 8 or less.
  • the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • the aromatic hydrocarbon ring group for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring having one free valence, Examples include acenaphthene ring, fluoranthene ring, fluorene ring and the like.
  • the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.
  • the aromatic heterocyclic group include one furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, and carbazole having one free valence.
  • Examples of the substituent that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I In view of solvent solubility, an alkoxy group having 1 to 5 carbon atoms or a hydroxyl group is preferable.
  • the alkyl chain portion of the substituent may be linear or branched, and further has a substituent such as an alkoxy group having 1 to 3 carbon atoms, an alkylthio group having 1 to 3 carbon atoms, a halogen atom, a hydroxyl group, or a nitro group. You may do it.
  • R 8 is preferably an aromatic ring group which may have a substituent, and an aromatic hydrocarbon which may have a substituent.
  • a cyclic group is more preferable.
  • p represents 0 or 1. From the viewpoint of sensitivity, p is preferably 0, while from the viewpoint of solvent solubility, p is preferably 1.
  • R 9 represents an arbitrary monovalent substituent.
  • an alkyl group having 1 to 10 carbon atoms such as a methyl group or an ethyl group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group or an ethoxy group; F, Cl, Br, I or the like
  • Examples of the substituent that the benzoyl group or thethenoyl group may have include an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and the like. May be. Among these, from the viewpoint of increasing the absorption wavelength, a nitro group and a 2-thenoyl group are preferable, and a nitro group is more preferable.
  • R 9 when q is 2 or more, a plurality of R 9 may be bonded to each other to form a ring.
  • the ring may be an aliphatic ring or an aromatic ring.
  • q represents an integer of 0 to 3. From the viewpoint of radical generation efficiency, 0 or 1 is preferable, and 1 is more preferable.
  • X represents —N (R 10 ) — or —C (R 11 ) (R 12 ) —.
  • —N (R 10 ) — is preferable from the viewpoint of sensitivity.
  • R 10 to R 12 each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
  • the alkyl group in R 10 to R 12 may be linear, branched, cyclic, or a combination thereof, but is preferably linear or branched from the viewpoint of sensitivity. Is more preferable.
  • the number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, further preferably 4 or more, particularly preferably 5 or more, and preferably 10 or less, more preferably 8 or less. More preferably, it is 6 or less, and particularly preferably 4 or less.
  • solvent solubility to become favorable by making carbon number of an alkyl group more than the said lower limit, and there exists a tendency for it to become high sensitivity by making it into the said upper limit or less.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, and a 2-ethylhexyl group.
  • an ethyl group, a propyl group, an isopropyl group, or a butyl group is preferable, an ethyl group or a propyl group is more preferable, and an ethyl group is more preferable.
  • the substituent that the alkyl group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I
  • an alkoxy group having 1 to 3 carbon atoms is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.
  • Examples of the aromatic ring group in R 10 to R 12 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the carbon number is usually 4 or more, preferably 6 or more, 12 or less, more preferably 10 or less, and even more preferably 8 or less.
  • the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • the aromatic hydrocarbon ring group for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring having one free valence, Examples include acenaphthene ring, fluoranthene ring, fluorene ring and the like.
  • the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.
  • the aromatic heterocyclic group include one furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, and carbazole having one free valence.
  • Examples of the substituent that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I
  • an alkoxy group having 1 to 3 carbon atoms or a hydroxyl group is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.
  • R 11 and R 12 may be bonded to each other to form a ring, and the ring may be an aliphatic ring or an aromatic ring.
  • R 10 to R 12 are preferably each independently an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and R 10 is More preferably, it is a methyl group or an ethyl group, and R 11 and R 12 are more preferably a butyl group.
  • photopolymerization initiators (c2) include OXE-02 manufactured by BASF, TR-PBG-304, TR-PBG-314, TR-PBG-358 manufactured by Changzhou Strong Electronic New Materials Co., Ltd. Can be mentioned. Also, those described in Japanese Patent No. 4223071, those described in International Publication No. 2016/010036, and those described in Japanese Patent No. 5682094 can also be used.
  • nBu represents a normal butyl group.
  • the photopolymerization initiator may further contain other photopolymerization initiator other than the photopolymerization initiator (c1) and the photopolymerization initiator (c2).
  • other photopolymerization initiators include, for example, metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; JP-A 2000-56118 N-aryl- ⁇ -amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives and N-phenylglycine described in Japanese Patent Application Laid-Open No.
  • N-aryl- ⁇ -amino acid salts radical activators such as N-aryl- ⁇ -amino acid esters, ⁇ -aminoalkylphenone derivatives
  • radical activators such as N-aryl- ⁇ -amino acid esters, ⁇ -aminoalkylphenone derivatives
  • Japanese Unexamined Patent Publication No. 2000-80068 Japanese Unexamined Patent Publication No. 2006-36750
  • the oxime ester derivative etc. which are described in the gazette etc. are mentioned.
  • titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny) 1-yl), dicyclopentadienyltitanium di (2,6-difluorophen-1-yl), dicyclopentadienyltitanium di (2,4-difluorophen-1-yl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylsilane) Lopentadienyl) titanium bis (2,6-difluorophen-1-yl), di
  • Biimidazole derivatives include 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole. Dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4′-methoxy) Phenyl) -4,5-diphenylimidazole dimer and the like.
  • halomethylated oxadiazole derivatives examples include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [ ⁇ - (2′- Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [ ⁇ - (2 ′-(6 ′′ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2 -Trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.
  • halomethyl-s-triazine derivatives examples include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -S-triazine and the like.
  • ⁇ -aminoalkylphenone derivatives include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzo Eat, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- ( 4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. And the like
  • oxime ester derivatives include Japanese National Publication No. 2004-534797, Japanese Unexamined Patent Publication No. 2000-80068, Japanese Unexamined Patent Publication No. 2006-36750, Japanese Unexamined Patent Publication No. 2008-179611, Japanese Special Publication. Examples thereof include oxime ester compounds described in 2012-526185, Japanese Special Tables 2012-519191, and the like.
  • methyl 4-acetoxyimino-5- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -5-oxopentanoate is also used as the product name OXE-
  • Preferable examples include 01 (manufactured by BASF), TR-PBG-305 (manufactured by Changzhou Strong Company), NCI-930 (manufactured by ADEKA) and the like.
  • the said other photoinitiator may be used individually by 1 type, and may use 2 or more types together.
  • the photopolymerization initiator can be used in combination with a sensitizing dye according to the wavelength of the image exposure light source for the purpose of increasing the sensitivity.
  • these sensitizing dyes include xanthene dyes described in JP-A-4-221958, JP-A-4-219756, etc., JP-A-3-239703, JP-A-5-289335.
  • Examples thereof include dyes having a dialkylaminobenzene skeleton described in JP-A No. 288818.
  • amino group-containing sensitizing dyes preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone.
  • Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) Benzothiazole, 2- (p-diethi Ruaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, p-di
  • the content rate of a photoinitiator is 0.1 mass% or more normally with respect to the total solid of the photosensitive resin composition of this invention, Preferably it is 1 mass% or more, More preferably, it is 2 mass% or more. More preferably, it is 3% by mass or more, particularly preferably 4% by mass or more, and usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and still more. Preferably it is 8 mass% or less, Most preferably, it is 6 mass% or less.
  • the content rate of the photoinitiator (c1) in a photoinitiator is not specifically limited, 0.1 mass% or more is preferable, 1 mass% or more is more preferable, 10 mass% or more is more preferable, 20 More preferably, it is more preferably 30% by weight or more, most preferably 40% by weight or more, more preferably 99.9% by weight or less, more preferably 99% by weight or less, and even more preferably 90% by weight or less. 60 mass% or less is most preferable.
  • the content ratio of the photopolymerization initiator (c1) is not less than the above lower limit value, the internal curability tends to be good, and when it is not more than the above upper limit value, the curability of the pattern top portion is good. Tend to be.
  • the content rate of the photoinitiator (c2) in a photoinitiator is not specifically limited, 0.1 mass% or more is preferable, 1 mass% or more is more preferable, 10 mass% or more is further more preferable, 40 % By mass or more is most preferable, 99.9% by mass or less is preferable, 99% by mass or less is more preferable, 90% by mass or less is further preferable, 80% by mass or less is further more preferable, and 60% by mass or less is particularly preferable. .
  • the content ratio of the photopolymerization initiator (c2) is not less than the above lower limit value, the curability of the top portion of the pattern tends to be good, and when it is not more than the above upper limit value, the internal curability is good. Tend to be.
  • the photosensitive resin composition of this invention contains (a) alkali-soluble resin.
  • the alkali-soluble resin is particularly suitable as long as the solubility of the exposed part and the non-exposed part in the alkaline developer changes after the coating film obtained by applying and drying the photosensitive resin composition is exposed.
  • the alkali-soluble resin which has acidic functional groups such as a hydroxyl group, a carboxyl group, a phosphoric acid group, and a sulfonic acid group, is preferable, and the alkali-soluble resin which has a carboxyl group is more preferable.
  • alkali-soluble resin which has an ethylenically unsaturated group from a sclerosing
  • hardenable viewpoint is preferable, and alkali-soluble resin which has an ethylenically unsaturated group and a carboxyl group from a sclerosing
  • Specific examples include an epoxy (meth) acrylate resin having a carboxyl group and an acrylic copolymer resin, and more preferable examples are (A1-1), (A1-2), (A2- Examples include 1), (A2-2), (A2-3) and (A2-4), and these may be used alone or in combination of two or more.
  • epoxy (meth) acrylate resins (A1-1) and (A1-2) having a carboxyl group are particularly desirable.
  • the epoxy (meth) acrylate resin having a carboxyl group is a reaction product of an epoxy resin and an ⁇ , ⁇ -unsaturated monocarboxylic acid and / or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety. It is a resin obtained by further reacting a hydroxyl group generated by the reaction with a polybasic acid and / or an anhydride thereof. In addition, before reacting a polybasic acid and / or anhydride thereof with a hydroxyl group, after reacting a compound having two or more substituents capable of reacting with the hydroxyl group, the polybasic acid and / or anhydride thereof is reacted.
  • Resins obtained by reaction are also included in the epoxy (meth) acrylate resin. Furthermore, a resin obtained by reacting a carboxyl group of the resin obtained by the above reaction with a compound having a functional group capable of further reaction is also included in the epoxy (meth) acrylate resin.
  • the epoxy (meth) acrylate resin has substantially no epoxy group in terms of chemical structure, and is not limited to “(meth) acrylate”, but the epoxy resin is a raw material, and Since “(meth) acrylate” is a representative example, it is named in this manner according to common usage.
  • Examples of the epoxy (meth) acrylate resin having a carboxyl group include the following epoxy (meth) acrylate resin (A1-1) and / or epoxy (meth) acrylate resin (A1-2).
  • ⁇ Epoxy (meth) acrylate resin (A1-2)> An ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof. The alkali-soluble resin obtained by this.
  • the epoxy resin used as a raw material includes a raw material compound before the resin is formed by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins. Moreover, the epoxy resin can use the compound obtained by making a phenolic compound and epihalohydrin react.
  • the phenolic compound is preferably a compound having a dihydric or higher phenolic hydroxyl group, and may be a monomer or a polymer.
  • Types of epoxy resins include cresol novolac type epoxy resins, phenol novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, trisphenol methane type epoxy resins, biphenyl novolac type epoxy resins, naphthalene novolac type epoxy resins, Epoxy resins, adamantyl group-containing epoxy resins, fluorene type epoxy resins, and the like, which are reaction products of a polyaddition reaction product of dicyclopentadiene and phenol or cresol and epihalohydrin, can be suitably used. Those having an aromatic ring can be suitably used.
  • epoxy resin examples include bisphenol A type epoxy resins (for example, “jER (registered trademark, the same applies hereinafter) 828”, “jER1001”, “jER1002”, “jER1004”, etc., manufactured by Mitsubishi Chemical Corporation), bisphenol A, and the like.
  • Type epoxy resin obtained by reaction of alcoholic hydroxyl group with epichlorohydrin for example, “NER-1302” (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resin (for example, Mitsubishi Chemical) “JER807”, “EP-4001”, “EP-4002”, “EP-4004”, etc., manufactured by the same company), epoxy resins obtained by the reaction of alcoholic hydroxyl groups of bisphenol F type epoxy resins with epichlorohydrin (eg Nippon Kayaku) “NER-7406” (epoxy 350, softening point 66 ° C.)), bisphenol S type epoxy resin, biphenyl glycidyl ether (eg “YX-4000” manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (eg “EPPN-” manufactured by Nippon Kayaku Co., Ltd.) 201 ",” EP-152 “,” EP-154 “manufactured by Mitsubishi Chemical Corporation,” DEN-438 "
  • Trisphenol methane type epoxy resin for example, “EPPN (registered trademark)” manufactured by Nippon Kayaku Co., Ltd.-5) 1 ”,“ EPPN-502 ”,“ EPPN-503 ”), cycloaliphatic epoxy resins (“ Celoxide (registered trademark; the same applies hereinafter) 2021P ”,“ Celoxide EHPE ”manufactured by Daicel), dicyclopentadiene and phenol
  • An epoxy resin obtained by glycidylation of a phenol resin by the reaction for example, “EXA-7200” manufactured by DIC, “NC-7300” manufactured by Nippon Kayaku Co., Ltd.
  • An epoxy resin or the like can be preferably used.
  • epoxy resins represented by the following general formula (a4) “XD-1000” manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (a1), and “XD-1000” manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (a2) NC-3000 ”,“ ESF-300 ”manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and the like are given as epoxy resins represented by the following general formula (a4).
  • b11 represents an average value and represents a number from 0 to 10.
  • R 11 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group.
  • the plurality of R 11 present in one molecule may be the being the same or different.
  • R 21 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group.
  • a plurality of R 21 present in one molecule may be the same as or different from each other.
  • X represents a linking group represented by the following general formula (a3-1) or (a3-2). However, one or more adamantane structures are included in the molecular structure.
  • b13 represents an integer of 2 or 3.
  • R 31 to R 34 and R 35 to R 37 are each independently an adamantyl group, a hydrogen atom, or a substituent which may have a substituent.
  • * mark in a formula represents the binding site in (a3).
  • p and q each independently represent an integer of 0 to 4
  • R 41 and R 42 each independently represent an alkyl group having 1 to 20 carbon atoms or a halogen atom.
  • R 43 and R 44 each independently represents an alkylene group having 1 to 5 carbon atoms.
  • x and y each independently represents an integer of 0 or more.
  • R 51 to R 54 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms
  • R 55 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms
  • each R 56 is independently an alkylene group having 1 to 5 carbon atoms. It is. k is an integer of 1 to 5, l is an integer of 0 to 13, and m is each independently an integer of 0 to 5.
  • Examples of the ⁇ , ⁇ -unsaturated monocarboxylic acid or the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, (meta ) Monocarboxylic acid such as ⁇ -position haloalkyl, alkoxyl, halogen, nitro, cyano substituent of acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- ( (Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- (Meth)
  • a monomer having one hydroxyl group at the end such as hydroxyalkyl (meth) acrylate, or a compound having one hydroxyl group at the end, such as pentaerythritol tri (meth) acrylate, (succinic anhydride), (Meth) acrylic acid ester having one or more ethylenically unsaturated groups and one carboxyl group at the end by adding an acid (anhydride) such as (anhydrous) phthalic acid or (anhydrous) maleic acid .
  • an acid (anhydride) such as (anhydrous) phthalic acid or (anhydrous) maleic acid .
  • (meth) acrylic acid dimer etc. are also mentioned.
  • (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity.
  • a method for adding an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin a known method can be used.
  • an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group can be reacted with an epoxy resin at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. it can.
  • esterification catalyst used here tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, dodecyltrimethylammonium chloride, and the like can be used. .
  • the epoxy resin, ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group, and esterification catalyst may be used alone or in combination of two types. You may use the above together.
  • the amount of ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of epoxy group of the epoxy resin. More preferably, it is in the range of 0.7 to 1.1 equivalents.
  • the amount of ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group is not less than the lower limit, the amount of unsaturated group introduced is sufficient, and the subsequent polybasic acid and Also, the reaction with the anhydride thereof is sufficient, and the remaining epoxy group tends to be suppressed.
  • the amount used is less than or equal to the above upper limit value, the ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group remains as an unreacted product and the curing characteristics deteriorate. There is a tendency that can be suppressed.
  • Polybasic acids and / or anhydrides thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methyl hexahydrophthal
  • examples thereof include one or more selected from acids, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.
  • maleic acid succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or anhydrides thereof.
  • Particularly preferred is tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.
  • a known method can be used for addition reaction of polybasic acid and / or anhydride thereof, and ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid having a carboxyl group to epoxy resin.
  • the target product can be obtained by continuing the reaction under the same conditions as in the ester addition reaction.
  • the addition amount of the polybasic acid and / or its anhydride component is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth) acrylate resin is in the range of 10 to 150 mgKOH / g, and further 20 The degree is preferably in the range of ⁇ 140 mgKOH / g.
  • the carboxyl group-containing epoxy (meth) acrylate resin is usually a polybasic acid and a reaction product of an epoxy resin and an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group. Or after mixing the anhydride, or a reaction product of an epoxy resin with an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group, Or it is obtained by heating after mixing the anhydride and polyhydric alcohol. In this case, the mixing order of the polybasic acid and / or its anhydride and the polyhydric alcohol is not particularly limited.
  • Any hydroxyl group present in the mixture of the reaction product of the epoxy resin with the ⁇ , ⁇ -unsaturated monocarboxylic acid or the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group and the polyhydric alcohol by heating.
  • the carboxyl group-containing epoxy (meth) acrylate resin may be used alone or as a mixture of two or more resins.
  • the amount of the polyhydric alcohol used is such that an epoxy resin component and an ⁇ , ⁇ -unsaturated monocarboxylic acid or ester moiety having a carboxyl group from the viewpoint of exhibiting an effect while suppressing thickening and gelation.
  • the amount is usually about 0.01 to 0.5 mass times, preferably about 0.02 to 0.2 mass times with respect to the reaction product with the unsaturated monocarboxylic acid ester component.
  • the acid value of the epoxy (meth) acrylate resins (A1-1) and (A1-2) thus obtained is usually 10 mgKOH / g or more, preferably 50 mgKOH / g or more, more preferably 70 mgKOH / g or more, Preferably it is 90 mgKOH / g or more, Preferably it is 200 mgKOH / g or less, More preferably, it is 150 mgKOH / g or less, More preferably, it is 120 mgKOH / g or less.
  • the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the epoxy (meth) acrylate resins (A1-1) and (A1-2) is preferably 1,000 or more. , 500 or more. Further, it is preferably 20,000 or less, more preferably 15,000 or less, further preferably 10,000 or less, still more preferably 8,000 or less, and 6,000 or less. It is particularly preferred that When the weight average molecular weight (Mw) is not less than the above lower limit value, the sensitivity, the coating film strength, and the alkali resistance tend to be good, and when it is not more than the above upper limit value, the developability and resolubility are good. There is a tendency to be able to.
  • acrylic copolymer resin examples include, for example, Japanese Patent Application Laid-Open No. 7-207211, Japanese Patent Application Laid-Open No. 8-259876, Japanese Patent Application Laid-Open No. 10-300922, Japanese Patent Application Laid-Open No. 11-140144, Japan Various types of documents described in Japanese Patent Laid-Open Nos. 11-174224, 2000-56118, 2003-233179, 2007-270147, etc. Although molecular compounds can be used, the following resins (A2-1) to (A2-4) are preferred, among which the (A2-1) resin is particularly preferred.
  • the photosensitive resin composition of the present invention is (A1-1), (A1-2), (A2-1), (A2-3) as an alkali-soluble resin containing an ethylenically unsaturated group. It is more preferable that at least one of these is included.
  • the photosensitive resin composition of the present invention is an epoxy (meth) acrylate resin as an alkali-soluble resin containing an ethylenically unsaturated group from the viewpoint of surface curability, and is at least one of (A1-1) and (A1-2). It is particularly preferable to include any of them.
  • the photosensitive resin composition of the present invention may be used in combination with other alkali-soluble resins.
  • limiting in other alkali-soluble resin What is necessary is just to select from resin normally used for the photosensitive resin composition for color filters. Examples thereof include alkali-soluble resins described in Japanese Patent Application Publication No. 2007-271727, Japanese Patent Application Publication No. 2007-316620, Japanese Patent Application Publication No. 2007-334290, and the like.
  • the content rate of alkali-soluble resin is normally 5 mass% or more with respect to the total solid of the photosensitive resin composition of this invention, Preferably it is 10 mass% or more, More preferably, it is 15 mass% or more, More preferably Is 20% by mass or more, and is usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, and further preferably 30% by mass or less.
  • the solubility of the unexposed area in the developer tends to be good. Excessive penetration of the liquid can be suppressed, and the sharpness and adhesion of the image tend to be good.
  • the photosensitive resin composition of the present invention is (a) an alkali-soluble resin as described above (A1-1), (A1-2), (A2-1), (A2-2). , (A2-3) and (A2-4) are preferred, and when other alkali-soluble resins are contained, the content ratio is 20 masses relative to the total of (a) alkali-soluble resins. % Or less, preferably 10% by mass or less.
  • the photosensitive resin composition of this invention contains the (b) photopolymerizable monomer from points, such as a sensitivity.
  • the photopolymerizable monomer (b) used in the present invention include compounds having at least one ethylenically unsaturated group in the molecule (hereinafter sometimes referred to as “ethylenic monomer”).
  • ethylenic monomer compounds having at least one ethylenically unsaturated group in the molecule
  • Specific examples include (meth) acrylic acid, (meth) acrylic acid alkyl ester, acrylonitrile, styrene, carboxylic acid having one ethylenically unsaturated bond, and ester of polyhydric or monohydric alcohol. .
  • a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule is particularly desirable.
  • the number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is usually 2 or more, preferably 3 or more, more preferably 4 or more, further preferably 5 or more, particularly preferably 6 or more, and usually 10 or less, preferably 8 or less.
  • the photosensitive resin composition tends to be highly sensitive, and when the number is less than the upper limit, curing shrinkage during polymerization tends to be reduced. is there.
  • polyfunctional ethylenic monomer examples include, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an aliphatic polyhydroxy compound, and an aromatic polyhydroxy compound.
  • esters obtained by an esterification reaction of a polyvalent hydroxy compound such as a hydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.
  • ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid examples include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc.
  • itaconic acid ester replaced by itaconate
  • ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid examples include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like. Etc.
  • the ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, but representative examples include acrylic acid, phthalic acid, and Examples include condensates of ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.
  • a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate ester are reacted.
  • the content of the photopolymerizable monomer is usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, and still more preferably 30% with respect to the total solid content of the photosensitive resin composition. It is 20 mass% or less, More preferably, it is 20 mass% or less, Most preferably, it is 10 mass% or less.
  • the lower limit of the content of the photopolymerizable monomer is usually 1% by mass or more, preferably 5% by mass or more. By being more than the said lower limit, it exists in the tendency for the photocuring by ultraviolet irradiation to improve, and for alkali developability to also become favorable.
  • the mass ratio of the content ratio of the (a) alkali-soluble resin to the content ratio of the (b) photopolymerizable monomer in the photosensitive resin composition of the present invention is usually 0.5 or more, preferably 1 or more, more preferably 2 or more. More preferably, it is 2.5 or more, usually 15 or less, preferably 10 or less, more preferably 8 or less, and further preferably 5 or less.
  • the photosensitive resin composition of the present invention contains a coloring material when used for forming a pixel of a color filter, a black matrix, a colored spacer, or the like.
  • a coloring material means what colors the photosensitive resin composition of this invention.
  • a dye or a pigment can be used, but a pigment is preferable from the viewpoint of heat resistance, light resistance and the like.
  • pigments of various colors such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used.
  • organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene
  • various inorganic pigments can be used. It is.
  • pigments that can be used in the present invention are shown by pigment numbers.
  • terms such as “CI Pigment Red 2” mentioned below mean a color index (CI).
  • red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170
  • C.I. I. Pigment Red 48 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.
  • blue pigments examples include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6.
  • green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58. Of these, C.I. I. Pigment Green 7, 36, 58.
  • ⁇ As yellow pigment C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183,
  • C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.
  • C.I. I. Pigment Orange 1 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79.
  • C.I. I. Pigment Violet 1 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50.
  • a black color material can be used as the (d) color material.
  • the black color material may be a black color material alone or a mixture of red, green, blue and the like. These color materials can be appropriately selected from inorganic or organic pigments and dyes. Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK 70: 100 (50240), Erioglaucine X (42080), No.
  • C.I. I Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.
  • black color material examples include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, perylene black, and lactam black.
  • carbon black when a black color material is used, carbon black is preferable from the viewpoints of light shielding rate and image characteristics. Examples of carbon black include the following carbon black.
  • titanium black As examples of other black pigments, titanium black, aniline black, iron oxide black pigments, and organic pigments of three colors of red, green, and blue can be mixed and used as black pigments. *
  • the pigment barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, or the like can also be used. These various pigments can be used in combination. For example, in order to adjust chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.
  • the average particle diameter of the pigment used in the present invention is not particularly limited as long as it can produce a desired color when it is used as a colored layer of a color filter, and varies depending on the type of pigment used. It is preferably in the range of ⁇ 100 nm, more preferably in the range of 10 to 70 nm. When the average particle diameter of the pigment is within the above range, the color characteristics of a liquid crystal display device produced using the photosensitive resin composition of the present invention tends to be high quality. Further, when the pigment is carbon black, the average particle size is preferably 60 nm or less, more preferably 50 nm or less, and preferably 20 nm or more.
  • the average particle diameter of the pigment can be obtained by a method of directly measuring the size of primary particles from an electron micrograph. Specifically, the minor axis diameter and major axis diameter of each primary particle are measured, and the average is taken as the particle diameter of the particle.
  • the volume (mass) of each particle is obtained by approximating a cuboid with the obtained particle size, and the volume average particle size is obtained and used as the average particle size.
  • the same result can be obtained regardless of whether the electron microscope is a transmission type (TEM) or a scanning type (SEM).
  • the photosensitive resin composition of the present invention preferably contains at least a pigment, but in addition, a dye may be used in combination as long as the effect of the present invention is not affected.
  • a dye may be used in combination as long as the effect of the present invention is not affected.
  • dyes that can be used in combination include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
  • azo dyes include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.
  • anthraquinone dyes examples include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
  • Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.
  • the content ratio of the coloring material can be selected in the range of usually 1 to 70% by mass with respect to the total solid content in the photosensitive resin composition. In this range, 20 mass% or more is more preferable, 30 mass% or more is more preferable, 40 mass% or more is especially preferable, and 60 mass% or less is more preferable.
  • the photosensitive resin composition of the present invention can be used for various applications as described above, but excellent image forming properties are particularly effective when used for forming a black matrix for a color filter. .
  • (d) Use the black color material such as carbon black or titanium black described above as the color material, or mix multiple types of color materials other than black and adjust to black. That's fine. Among these, it is particularly preferable to use carbon black from the viewpoints of dispersion stability and light shielding properties.
  • the present invention is particularly effective in the region where the pigment concentration of the black pigment increases. Particularly in recent years, it is necessary to increase the black pigment concentration in order to increase the degree of light shielding.
  • the content ratio of the black pigment in the region where the effect is large is 40% by mass or more, preferably 45% by mass or more, and preferably 50% by mass or more with respect to the total solid content of the photosensitive resin composition. Is more preferable.
  • the photosensitive resin composition when the content ratio of the black pigment is within the above range, a photosensitive resin composition having a high light shielding property (optical density, OD value) can be obtained.
  • the optical density when the black matrix having a thickness of 1 ⁇ m is formed using the photosensitive resin composition of the present invention is 4.0 or more.
  • the optical density is more preferably 4.2 or more.
  • ultraviolet rays are not easily transmitted to the deep part, and crosslinking due to photopolymerization is weak particularly in the part where the substrate and the fine line are in close contact, particularly when the photosensitive resin composition of the present invention is used.
  • the content ratio of is large, the effect of the present invention can be confirmed well.
  • the black pigment content 40 to 65% by mass is particularly effective. There is a tendency that it is possible to suppress the film thickness with respect to the color density from becoming too large by setting the content ratio of the black pigment to the lower limit value or more, and it is easy to ensure sufficient image formability by setting the content ratio to the upper limit value or less. Tend.
  • the content ratio of (d) the color material is usually 20 parts by mass or more, preferably 30 parts by mass or more, more preferably 40 parts by mass or more, per 100 parts by mass of the (a) alkali-soluble resin. More preferably 60 parts by mass or more, still more preferably 80 parts by mass or more, particularly preferably 120 parts by mass or more, most preferably 160 parts by mass or more, and usually 500 parts by mass or less, preferably 300 parts by mass or less, more Preferably it is 280 mass parts or less.
  • D By setting the content ratio of the color material to the lower limit value or more, there is a tendency to easily suppress a decrease in solubility in the developing solution in the unexposed area. There is a tendency to easily obtain a thickness.
  • ⁇ (E) Dispersant> it is important to finely disperse the color material and stabilize the dispersion state in order to ensure the stability of the quality. Therefore, it is preferable to include (e) a dispersant.
  • a dispersant a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; a primary, secondary, or tertiary amino group.
  • a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group
  • a quaternary ammonium base a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, pyrazine, or the like is particularly preferable.
  • polymer dispersants include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyl ethers.
  • examples thereof include a dispersant, a polyoxyethylene diester dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.
  • EFKA registered trademark, manufactured by EFKA Chemicals Beebuy (EFKA)
  • Disperbyk registered trademark, manufactured by BYK Chemie
  • Disparon registered trademark, Enomoto Kasei
  • SOLSPERSE registered trademark, manufactured by Lubrizol Corporation
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • Polyflow or Florene registered trademark, manufactured by Kyoeisha Chemical Co., Ltd.
  • Ajisper registered trademark, manufactured by Ajinomoto Fine Techno Co., Ltd.
  • the (e) dispersant contains a urethane polymer dispersant and / or an acrylic polymer dispersant having a basic functional group.
  • a urethane-based polymer dispersant is preferable in terms of adhesion.
  • a polymer dispersant having a basic functional group and having a polyester and / or polyether bond is preferred.
  • the weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1,000 or more, and usually 100,000 or less, preferably 50,000 or less, more preferably 30,000 or less. .
  • Mw weight average molecular weight
  • examples of urethane-based and acrylic polymer dispersants include DISPERBYK-160 to 167, 182 series (both are urethane-based), DISPERBYK-2000, 2001, etc. (both are acrylic-based) (all manufactured by BYK Chemie).
  • DISPERBYK-167, 182 and the like are particularly preferable urethane polymer dispersants having a basic functional group and having a polyester and / or polyether bond and having a weight average molecular weight of 30,000 or less.
  • a preferable chemical structure as a urethane-based polymer dispersant include, for example, the same as a polyisocyanate compound and a compound having one or two hydroxyl groups in the molecule and a number average molecular weight of 300 to 10,000.
  • examples thereof include a dispersion resin having a weight average molecular weight of 1,000 to 200,000, which is obtained by reacting an active hydrogen with a compound having a tertiary amino group in the molecule.
  • polyisocyanate compounds examples include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate.
  • polyisocyanate are trimers of organic diisocyanate, and most preferred are trimerene of tolylene diisocyanate and trimer of isophorone diisocyanate. These may be used alone or in combination of two or more.
  • the polyisocyanate may be converted into a part of an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.
  • trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like.
  • Examples of the compound having one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 10,000 include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, and one terminal hydroxyl group of these compounds has a carbon number. Examples thereof include those alkoxylated with 1 to 25 alkyl groups and mixtures of two or more thereof.
  • polyether glycol examples include polyether diol, polyether ester diol, and a mixture of two or more of these.
  • polyether diols are those obtained by homopolymerizing or copolymerizing alkylene oxides such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. The mixture of 2 or more types of these is mentioned.
  • Polyether ester diols include those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides or reacting polyester glycols with alkylene oxides, such as poly (poly And oxytetramethylene) adipate.
  • alkylene oxides such as poly (poly And oxytetramethylene) adipate.
  • the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.
  • Polyester glycol includes dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, , 6-hexanediol, 2-methyl-2,4 Pentanediol, 2,2,
  • Polycarbonate glycols include poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate, and polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, etc. Is mentioned. These may be used alone or in combination of two or more.
  • the number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, more preferably 1,000 to 4,000.
  • Active hydrogen that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom includes a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group.
  • a hydrogen atom of an amino group is preferred.
  • the tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.
  • Examples of such compounds having active hydrogen and tertiary amino group in the same molecule are N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4
  • examples of the nitrogen-containing heterocyclic ring include pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzo Nitrogen-containing hetero 6-membered rings such as triazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, etc., pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring A ring is mentioned.
  • nitrogen-containing heterocycles preferred are an imidazole ring or a triazole ring.
  • these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like.
  • specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like.
  • N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, and 3-amino-1,2,4-triazole preferable.
  • the preferred blending ratio of the raw materials for producing the urethane polymer dispersant is 10 compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by mass of the polyisocyanate compound. To 200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and 0.2 to 25 parts by mass of the compound having an active hydrogen and a tertiary amino group in the same molecule, preferably 0.3 ⁇ 24 parts by mass.
  • the production of the urethane-based polymer dispersant is performed according to a known method for producing a polyurethane resin.
  • a solvent for production usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used. These may be used alone or in combination of
  • a urethanization reaction catalyst is usually used.
  • the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and stannous octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. 1 type, or 2 or more types, such as a secondary amine type
  • the tertiary amine value of the dispersant is represented by the mass of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and can be measured by the following method. Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized and titrated with 0.1 mol / L HClO 4 (perchloric acid) acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.
  • Amine value [mgKOH / g] (561 ⁇ V) / (W ⁇ S) [However, W: Weighing amount of dispersant sample [g], V: Titration amount at the end of titration [mL], S: Solid content concentration [mass%] of the dispersant sample. ]
  • the introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g in terms of amine value after reaction. More preferably, it is in the range of 5 to 95 mgKOH / g.
  • the amine value is a value obtained by neutralizing and titrating a basic amino group with an acid, and representing the acid value in mg of KOH. When the amine value is not less than the lower limit value, the dispersibility tends to be good, and when the amine value is not more than the upper limit value, the developability tends to be good.
  • the weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000.
  • the weight average molecular weight (Mw) of the urethane polymer dispersant is particularly preferably 30,000 or less. When the weight average molecular weight (Mw) is at least the lower limit, the dispersibility and dispersion stability tend to be good. There is.
  • the content of the dispersant is usually 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less in the total solid content of the photosensitive resin composition. Especially preferably, it is 10 mass% or less, Usually 1 mass% or more, Preferably it is 3 mass% or more, More preferably, it is 5 mass% or more, More preferably, it is 7 mass% or more.
  • the content of the dispersant is usually 5 parts by mass or more, preferably 10 parts by mass or more, and usually 200 parts by mass or less, preferably 80 parts by mass or less, with respect to 100 parts by mass of the colorant (d).
  • the dispersant it is preferable to use a polymer dispersant and a pigment derivative (dispersion aid) in combination.
  • the content ratio of the pigment derivative is the total solid content of the photosensitive resin composition of the present invention.
  • it is usually 0.1% by mass or more, preferably 0.5% by mass or more, usually 10% by mass or less, preferably 5% by mass or less, more preferably 2% by mass or less.
  • the photosensitive resin composition of the present invention preferably contains a thiol for increasing sensitivity and improving adhesion to the substrate.
  • Types of thiols include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate , Butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, Ethylene glycol bis (3-mercaptobutyrate
  • the content ratio of the thiol compound is usually 0.1% by mass or more, preferably 0.3% by mass or more, and more preferably 0% with respect to the total solid content of the photosensitive resin composition of the present invention. 0.5 mass% or more, usually 10 mass% or less, preferably 5 mass% or less. There exists a tendency which can suppress a sensitivity fall by making the content rate of a thiol compound more than the said lower limit, and there exists a tendency which is easy to make a storage stability favorable by making it the said upper limit or less.
  • the photosensitive resin composition of the present invention usually comprises (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, (d) a coloring material, and various materials used as necessary. Is used in a state dissolved or dispersed in an organic solvent.
  • an organic solvent it is preferable to select an organic solvent having a boiling point (under a pressure of 101.25 [hPa], hereinafter the same for the boiling point) in the range of 100 to 300 ° C.
  • a solvent having a boiling point of 120 to 280 ° C. is more preferable.
  • Examples of such organic solvents include the following.
  • Ethylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol mono Chirueteru, glycol monoalkyl ethers such as tripropylene glycol methyl ether;
  • Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n
  • Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate; Alkyl acetates such as cyclohexanol acetate; Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether; Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl
  • Aromatic hydrocarbons such as benzene, toluene, xylene, cumene; Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, ⁇ -butyrolactone; Alkoxycarboxylic acids such as 3-methoxy
  • Halogenated hydrocarbons such as butyl chloride and amyl chloride; Ether ketones such as methoxymethylpentanone; Nitriles such as acetonitrile and benzonitrile.
  • Commercially available solvents corresponding to the above include mineral spirits, Barsol # 2, Apco # 18 solvent, Apco thinner, Soal Solvent No. 1 and no.
  • organic solvents may be used alone or in combination of two or more.
  • glycol alkyl ether acetates are preferred from the viewpoints of good balance of coatability, surface tension and the like, and relatively high solubility of the constituent components in the composition.
  • glycol alkyl ether acetates may be used alone or in combination with other organic solvents.
  • glycol monoalkyl ethers are particularly preferred.
  • propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition.
  • Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment tends to aggregate, and the storage stability tends to decrease such as the viscosity of the photosensitive resin composition obtained later increases.
  • the proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.
  • an organic solvent having a boiling point of 200 ° C. or higher hereinafter sometimes referred to as “high boiling point solvent”.
  • high boiling point solvent an organic solvent having a boiling point of 200 ° C. or higher
  • the photosensitive resin composition becomes difficult to dry, but there is an effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of a foreign matter defect due to precipitation or solidification of a color material or the like at the tip of the slit nozzle.
  • dipropylene glycol methyl ether acetate diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, 1,4-butanediol diacetate, 1, 3-butylene glycol diacetate, triacetin, and 1,6-hexanediol diacetate are preferred.
  • the content of the high boiling point solvent in the organic solvent is preferably 0% by mass to 50% by mass, more preferably 0.5% by mass to 40% by mass, and particularly preferably 1% by mass to 30% by mass.
  • the content of the organic solvent is not particularly limited, but from the viewpoint of ease of application and viscosity stability, the total solid content in the photosensitive resin composition is preferably 5% by mass or more, More preferably 8% by mass or more, further preferably 10% by mass or more, particularly preferably 12% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, particularly Preferably it is 20 mass% or less.
  • the photosensitive resin composition of the present invention can be appropriately mixed with an adhesion improver, a coatability improver, a pigment derivative, a development improver, an ultraviolet absorber, an antioxidant, and the like.
  • an adhesion improver may be included, and examples thereof include a silane coupling agent and a titanium coupling agent, and a silane coupling agent is particularly preferable.
  • silane coupling agents include KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, X12-1050 (manufactured by Shin-Etsu Silicone), Z- 6040, Z-6043, Z-6062 (manufactured by Toray Dow Corning) and the like.
  • 1 type may be used for a silane coupling agent and it may use 2 or more types together by arbitrary combinations and a ratio.
  • you may make the photosensitive resin composition of this invention contain adhesion improvers other than a silane coupling agent, For example, a phosphoric acid type adhesion improver, other adhesion improvers, etc. are mentioned.
  • (meth) acryloyloxy group-containing phosphates are preferable, and those represented by the following general formulas (g1), (g2), and (g3) are particularly preferable.
  • R 51 each independently represents a hydrogen atom or a methyl group
  • l and l ′ are each independently an integer of 1 to 10
  • m is each independently 1 2 or 3.
  • adhesion improvers include TEGO * Add Bond LTH (manufactured by Evonik). These phosphoric acid group-containing compounds and other adhesives may be used alone or in combination of two or more.
  • the content rate of the adhesion improving agent in the photosensitive resin composition is not particularly limited, it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, based on the total solid content. 5% by mass or more is more preferable, 1% by mass or more is particularly preferable, 25% by mass or less is preferable, 20% by mass or less is more preferable, and 10% by mass or less is more preferable.
  • the content is particularly preferably 8% by mass or less, and most preferably 6% by mass or less.
  • the photosensitive resin composition of the present invention may contain a surfactant as a coatability improver for improving coatability.
  • a surfactant for example, anionic, cationic, nonionic and amphoteric surfactants can be used.
  • nonionic surfactants are preferably used because they are less likely to adversely affect various properties, and among them, fluorine-based or silicon-based surfactants are effective in terms of coatability.
  • surfactants examples include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), KP340. (Manufactured by Shin-Etsu Silicone), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC), SH7PA (manufactured by Dow Corning Toray), DS-401 (manufactured by Daikin) , L-77 (manufactured by Nihon Unicar) and FC4430 (manufactured by 3M Japan).
  • TSF4460 manufactured by Momentive Performance Materials
  • DFX-18 manufactured by Neos
  • BYK-300, BYK-325, BYK-330 manufactured by BYK Chemie
  • KP340 KP340.
  • 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and a ratio.
  • the content of the surfactant in the photosensitive resin composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on the total solid content. More preferably, it is 10% by mass or more, preferably 1.0% by mass or less, more preferably 0.7% by mass or less, and further preferably 0.5% by mass or less. The content is particularly preferably 0.3% by mass or less.
  • the photosensitive resin composition of the present invention may contain a pigment derivative for improving dispersibility and storage stability.
  • a pigment derivative for improving dispersibility and storage stability As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine Among them, derivatives such as phthalocyanines and quinophthalones are preferable.
  • substituents of pigment derivatives sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. can be directly in the pigment skeleton or alkyl groups, aryl groups, complex groups. Examples thereof include those bonded via a ring group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton.
  • the pigment derivative examples include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. These may be used alone or in combination of two or more.
  • the photosensitive resin composition of the present invention (hereinafter sometimes referred to as “resist”) is produced according to a conventional method.
  • the color material is preferably preliminarily dispersed using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like. Since (d) the color material is made into fine particles by the dispersion treatment, the resist coating characteristics are improved.
  • a black color material is used as a color material, it contributes to the improvement of a light-shielding capability.
  • the dispersion treatment is usually preferably carried out in a system in which (d) a color material, a solvent, and if necessary, (e) a dispersant and (a) a part or all of an alkali-soluble resin are used in combination.
  • a color material e.g., a color material
  • a solvent e.g., a solvent
  • a dispersant e.g., a dispersant and a part or all of an alkali-soluble resin
  • the mixture to be subjected to the dispersion treatment and the composition obtained by the treatment may be referred to as “ink” or “pigment dispersion”.
  • the mixture to be subjected to the dispersion treatment and the composition obtained by the treatment may be referred to as “ink” or “pigment dispersion”.
  • the mixture is obtained.
  • a highly reactive component may be modified due to heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.
  • the color material is dispersed with a sand grinder
  • glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used.
  • the temperature is usually from 0 ° C. to 100 ° C., and preferably from room temperature to 80 ° C.
  • the dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment apparatus.
  • the standard of dispersion is to control the gloss of the ink so that the 20-degree specular gloss of the resist (JIS Z8741) is in the range of 100 to 200.
  • the glossiness of the resist is not less than the above lower limit value, the dispersion treatment is sufficient, and there are few remaining rough pigment (coloring material) particles, and the developability, adhesion, resolution, etc. tend to be sufficient. There is.
  • the gloss value is less than or equal to the above upper limit value, there is a tendency that the pigment is crushed and a large number of ultrafine particles are produced, and on the contrary, the dispersion stability is impaired.
  • the ink obtained by the dispersion treatment and the other components contained in the resist are mixed to obtain a uniform solution.
  • fine dust is often mixed in the liquid, and thus the obtained resist is preferably filtered by a filter or the like.
  • a cured product can be obtained by curing the photosensitive resin composition of the present invention.
  • a cured product obtained by curing the photosensitive resin composition can be suitably used as a member constituting a color filter such as a pixel, a black matrix, or a colored spacer.
  • the support for forming the black matrix is not particularly limited as long as it has an appropriate strength.
  • a transparent substrate is mainly used, but the material is, for example, a polyester resin such as polyethylene terephthalate, a polyolefin resin such as polypropylene or polyethylene, a sheet made of a thermoplastic resin such as polycarbonate, polymethyl methacrylate or polysulfone, or an epoxy resin. And thermosetting resin sheets such as unsaturated polyester resins and poly (meth) acrylic resins, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance.
  • a transparent electrode such as ITO or IZO is formed on the surface of the substrate. Other than the transparent substrate, it can be formed on the TFT array.
  • the thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm.
  • the film thickness is usually 0.01 to 10 ⁇ m, preferably 0.05 to 5 ⁇ m.
  • the photosensitive resin composition of the present invention is applied on a transparent substrate and dried, and then a coating film is formed.
  • a black mask is formed by placing a photomask on the substrate and exposing the image through the photomask, developing, and thermosetting or photocuring as necessary.
  • the thickness of the coating film is usually preferably in the range of 0.2 to 10 ⁇ m, more preferably in the range of 0.5 to 6 ⁇ m, and still more preferably in the range of 1 to 4 ⁇ m, as the film thickness after drying. is there.
  • the thickness of the coating film is usually preferably in the range of 0.2 to 10 ⁇ m, more preferably in the range of 0.5 to 6 ⁇ m, and still more preferably in the range of 1 to 4 ⁇ m, as the film thickness after drying. is there.
  • the coating film after the photosensitive resin composition is applied to the substrate is preferably dried by a drying method using a hot plate, IR oven, or convection oven. Drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like.
  • the drying time is usually selected within the range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably 50 to 130 ° C., depending on the type of solvent component and the performance of the dryer used. It is selected in the range of 30 seconds to 3 minutes.
  • the drying process of this coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.
  • Exposure Image exposure is performed by overlaying a negative mask pattern on the coating film of the photosensitive resin composition and irradiating light of a wavelength from the ultraviolet region to the visible region through this mask pattern. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable coating film in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen.
  • the light source used for said image exposure is not specifically limited.
  • Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, and a lamp light source such as a carbon arc.
  • An optical filter can also be used when used by irradiating light of a specific wavelength.
  • the black matrix according to the present invention comprises an organic solvent or an aqueous solution containing a surfactant and an alkaline compound after the coating film made of the photosensitive resin composition is image-exposed with the above-mentioned light source.
  • An image can be formed on a substrate by development using a film.
  • This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.
  • Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate
  • Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine , Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc.
  • Organic alkaline compounds. These alkaline compounds may be a mixture of two or more.
  • surfactant examples include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids.
  • nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids.
  • anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters
  • amphoteric surfactants such as alkylbetaines and amino acids.
  • the organic solvent examples include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like.
  • the organic solvent may be used alone or in combination with an aqueous solution.
  • the development processing conditions are not particularly limited, and the development temperature is usually in the range of 10 to 50 ° C., particularly 15 to 45 ° C., particularly preferably 20 to 40 ° C.
  • the development methods are immersion development, spray development, brush Any of a developing method, an ultrasonic developing method and the like can be used.
  • thermosetting treatment The substrate after development is subjected to thermosetting treatment or photocuring treatment, preferably thermosetting treatment.
  • the thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C., preferably in the range of 150 to 250 ° C., and the time is in the range of 5 to 60 minutes.
  • the height of the black matrix formed as described above is usually 0.5 to 5 ⁇ m, preferably 0.8 to 4 ⁇ m.
  • the optical density (OD) per 1 ⁇ m thickness is 3.0 or more, preferably 3.5 or more, more preferably 3.8 or more, particularly preferably 4.0 or more, and most preferably 4.2 or more. .
  • a photosensitive resin composition containing a color material of one color of red, green, and blue is applied by the same process as (3-1) to (3-5) above, and dried. After that, a photomask is overlaid on the coating film, and a pixel image is formed through image exposure, development, and thermal curing or photocuring as necessary through this photomask to produce a colored layer.
  • a color filter image can be formed by performing this operation for each of the three color photosensitive resin compositions of red, green, and blue. The order of these is not limited to the above.
  • the photosensitive resin composition of the present invention can be used as a resist for colored spacers in addition to the black matrix.
  • a spacer is used in a TFT type LCD, the TFT may malfunction as a switching element due to light incident on the TFT, and a colored spacer is used to prevent this, for example, Japanese Patent Application Laid-Open No. 8-234212.
  • the publication discloses that the spacer is light-shielding.
  • the colored spacer can be formed in the same manner as the black matrix described above except that a mask for the colored spacer is used.
  • the color filter is used as part of components such as color displays and liquid crystal display devices by forming transparent electrodes such as ITO on the image in this state.
  • transparent electrodes such as ITO
  • a top coat layer such as polyamide or polyimide can be provided on the image as necessary.
  • the transparent electrode may not be formed.
  • the image display device of the present invention has a cured product obtained by curing the photosensitive resin composition of the present invention.
  • the image display device is not particularly limited as long as it is a device that displays an image or video, and examples thereof include a liquid crystal display device and an organic EL display described later.
  • the liquid crystal display device of the present invention has a cured product such as the above-described black matrix, color filter pixel, and colored spacer of the present invention, and is not particularly limited in terms of the order of formation and formation position of the color pixels and black matrix. Absent.
  • a liquid crystal display device usually forms an alignment film on a color filter, spreads spacers on the alignment film, and then bonds to the counter substrate to form a liquid crystal cell, injects liquid crystal into the formed liquid crystal cell, Complete by connecting to the counter electrode.
  • a resin film such as polyimide is suitable.
  • a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to be processed into a surface state in which the tilt of the liquid crystal can be adjusted.
  • spacer a spacer having a size corresponding to the gap (gap) with the counter substrate is used, and a spacer of 2 to 8 ⁇ m is usually preferable.
  • a photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by photolithography, and this can be used instead of the spacer.
  • the counter substrate an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.
  • the gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 ⁇ m.
  • portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin.
  • the sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
  • the liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. .
  • the degree of decompression in the liquid crystal cell is usually 1 ⁇ 10 ⁇ 2 to 1 ⁇ 10 ⁇ 7 Pa, preferably 1 ⁇ 10 ⁇ 3 to 1 ⁇ 10 ⁇ 6 Pa. Further, it is preferable to heat the liquid crystal cell during decompression, and the heating temperature is usually 30 to 100 ° C., more preferably 50 to 90 ° C.
  • the warming holding at the time of depressurization is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal.
  • the liquid crystal cell into which the liquid crystal is injected has a liquid crystal display device (panel) completed by sealing the liquid crystal injection port by curing the UV curable resin.
  • liquid crystal there are no particular restrictions on the type of liquid crystal, and it is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of lyotropic liquid crystal, thermotropic liquid crystal, and the like.
  • thermotropic liquid crystal nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, and the like are known, but any of them may be used.
  • Organic EL display The organic EL display of the present invention is produced using the color filter of the present invention.
  • an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. 1, first, a pattern (that is, the pixel 20 and the adjacent region) formed on the transparent support substrate 10 by the photosensitive resin composition.
  • a color filter in which a resin black matrix (not shown) provided between the pixels 20 to be formed is formed, and the organic light-emitting body 500 is formed on the color filter via the organic protective layer 30 and the inorganic oxide film 40.
  • the organic EL element 100 can be manufactured by stacking layers.
  • at least one of the pixel 20 and the resin black matrix is manufactured using the photosensitive resin composition of the present invention.
  • a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter.
  • a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used.
  • an organic EL display can be produced.
  • color filter of the present invention can be applied to both passive drive type organic EL displays and active drive type organic EL displays.
  • a carbon black ink was prepared by preparing a pigment, a dispersant, a dispersion aid (pigment derivative), and a solvent by the following composition and method. Specifically, first, the solid content of the pigment, the dispersant, and the dispersion aid and the solvent were prepared so as to have the following quantitative ratio.
  • Pigment RAVEN 1060U (manufactured by Birler, carbon black); 52.00 parts by mass Dispersant: DISPERBYK-167 (manufactured by Big Chemie, basic urethane dispersant); 7.30 parts by mass (solid content conversion) Dispersing aid (pigment derivative): S12000 (manufactured by Lubrizol, phthalocyanine pigment derivative having an acidic group); 1.03 parts by mass; Solvent: propylene glycol monomethyl ether acetate (PGMEA); 112.04 parts by mass
  • a dispersion treatment was carried out in the range of 25 to 45 ° C. for 6 hours using a paint shaker.
  • beads zirconia beads having a diameter of 0.5 mm were used and added at a ratio of 180 parts by mass of beads to 60 parts by mass of the dispersion. After the dispersion, the beads and the dispersion were separated by a filter to prepare a carbon black ink having a solid content of 35% by mass.
  • TMP trimethylolpropane
  • BPDA biphenyltetracarboxylic dianhydride
  • THPA tetrahydrophthalic anhydride
  • a photopolymerization initiator (1) having the above chemical structure synthesized by the method described in International Publication No. 2015/036910 was used.
  • the obtained photopolymerization initiator (1) is dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a 0.01% by mass solution, which is absorbed using a spectrophotometer U-3900H (manufactured by Hitachi High-Tech Science Co., Ltd.).
  • PGMEA propylene glycol monomethyl ether acetate
  • U-3900H manufactured by Hitachi High-Tech Science Co., Ltd.
  • a photopolymerization initiator (2) having the above chemical structure synthesized by the method described in International Publication No. 2008/078678 was used.
  • the maximum absorption wavelength was 368 nm.
  • the maximum absorption wavelength was 339 nm.
  • Photopolymerization initiator (4) As the photopolymerization initiator (4), TR-PBG-358 (compound having the following chemical structure) manufactured by Changzhou Strong Electronic New Materials Co., Ltd. was used.
  • the maximum absorption wavelength was 344 nm.
  • ⁇ Adhesion improver> As an adhesion improver, KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd., which is a silane coupling agent, and KAYAMER PM-21, manufactured by Nippon Kayaku Co., Ltd., which is a phosphate adhesion improver, were prepared.
  • Example 1> (Preparation of black resist 1) Using the carbon black ink prepared in ⁇ Preparation of carbon black ink>, each component was added so as to have the ratio shown in Table 1, and stirred and dissolved with a stirrer to prepare black resist 1. The total solid content in the black resist 1 is 15% by mass.
  • Example 2 (Preparation of black resist 2)
  • the total amount of the photopolymerization initiator is kept as it is, except that the mixing ratio (% by mass) of the photopolymerization initiators (1) and (2) is changed as shown in Table 2.
  • a black resist 2 having a solid concentration of 15% by mass was prepared in the same manner as the black resist 1.
  • Example 3 (Preparation of black resist 3)
  • the total amount of the photopolymerization initiator is kept as it is, except that the mixing ratio (% by mass) of the photopolymerization initiators (1) and (2) is changed as shown in Table 2.
  • a black resist 3 having a solid concentration of 15% by mass was prepared by the same method as that for black resist 1.
  • Example 4 (Preparation of black resist 6)
  • the total amount of the photopolymerization initiator is kept as it is, and the solid state is the same as that of the black resist 2 except that the photopolymerization initiator (2) is changed to the photopolymerization initiator (3).
  • a black resist 6 having a partial concentration of 15% by mass was prepared.
  • Example 5 (Preparation of black resist 7)
  • the total amount of the photopolymerization initiator was kept as it was, and the solid state was the same as that of the black resist 2 except that the photopolymerization initiator (2) was changed to the photopolymerization initiator (4).
  • a black resist 7 having a partial concentration of 15% by mass was prepared.
  • Pattern exposure through an exposure mask having an opening width of 1 to 10 ⁇ m (in 1 ⁇ m increments) and a linear opening of 15 ⁇ m at 35 mJ / cm 2 .
  • spray development (spray pressure: 0.1 MPa) at room temperature (23 ° C.) using an aqueous KOH solution prepared to 0.04% by mass with ultrapure water as an alkaline developer for 2.2 times the dissolution time.
  • spray cleaning spray pressure: 0.1 MPa
  • the dissolution time is the time from the development of the unexposed portion of the black resist film until the substrate surface begins to be visible, and the dissolution time of each black resist was in the range of 20 to 30 seconds.
  • the fine line adhesion was evaluated as 8 ⁇ m and classified as follows (here (For example, a pattern in which the width of the opening of the exposure mask corresponds to 7 ⁇ m is described as a 7 ⁇ m pattern.) If the evaluation is “ ⁇ ”, the fine line adhesion is good, and if “ ⁇ ”, it can be evaluated that the fine line adhesion is better, and “x” is evaluated as poor fine line adhesion.
  • A Fine lines of a pattern of 8 ⁇ m or more are in close contact (patterns of 7 ⁇ m or less are peeled).
  • X Fine lines with a pattern of 9 ⁇ m or more are in close contact (patterns of 8 ⁇ m or less are peeled).
  • the line width of a 15 ⁇ m line pattern was measured with an optical microscope, and the sensitivity determination was classified as follows (here, for example, a pattern corresponding to an exposure mask opening width of 15 ⁇ m is described as a 15 ⁇ m pattern) is doing.). If the evaluation is “ ⁇ ”, it can be evaluated that the sensitivity is good, and “X” is evaluated that the sensitivity is low.
  • X The line width of the pattern of 15 micrometers is less than 15 micrometers.
  • Comparative Example 1 the BM surface is strongly cured but the inside of the BM is insufficiently cured, so that it is considered that the thin line adhesion is poor although the line width is large.
  • Comparative Example 2 it is considered that the fine line adhesion is good for the thin line width because the hardening of the BM surface is loose but the hardening inside the BM is strong.
  • Examples 1 to 5 it is considered that the progress of the BM surface and internal curing in a well-balanced manner leads to both fine line adhesion and high sensitivity.
  • the line width becomes thick due to high sensitivity, but many advantages are desirable from the following viewpoints.
  • the amount of photopolymerization initiator can be reduced by the margin of sensitivity, and can be distributed to improve performance such as development resistance and substrate adhesion by replacing the reduced amount with alkali-soluble resin or photopolymerizable monomer. . ⁇
  • the exposure speed can be increased and the productivity is improved.
  • Comparative Example 1 is also a result of high sensitivity, since the curing inside the BM is insufficient, further reduction in the adhesion of fine wires is caused when the amount of the photopolymerization initiator is reduced or the exposure amount is reduced.
  • the phenyl sulfide photopolymerization initiator is excellent in UV absorption ability around 330 nm, but the benzofuran part of the condensed heterocyclic ring of the photopolymerization initiator (c1) represented by the general formula (I) is a coloring material,
  • the adsorption of the photopolymerization initiator (c1) to the surface of the colorant particles is promoted.
  • the light absorbed by the color material does not contribute to the polymerization and causes a significant decrease in exposure sensitivity.
  • the photopolymerization initiator covers the color material surface, so that the light absorption rate with respect to the photopolymerization initiator is improved. Further, the adsorption of the photopolymerization initiator to the coloring material relatively lowers the photopolymerization initiator concentration in the resin component, so that the light transmittance to the deep portion is improved. Thereby, it is considered that the internal curability of the resist film is improved and the fine wire adhesion is improved.
  • the photopolymerization initiator (c1) uses only a part of the low wavelength side of the UV wavelength range of the exposure light source, and sufficient sensitivity cannot be obtained, so the maximum absorption wavelength is in the long wavelength range.
  • the sensitivity particularly the surface sensitivity can be increased. Since there is a difference in the maximum absorption wavelength between the photopolymerization initiator (c1) and the photopolymerization initiator (c2), the influence on the internal curability due to the combined use can be suppressed. It is considered that the surface sensitivity and internal curing can be improved at the same time. From the above, it can be seen that by using the photosensitive resin composition of the present invention, it is possible to provide a photosensitive resin composition excellent in high sensitivity and fine wire adhesion performance.

Abstract

The present invention addresses the problem of providing a photosensitive resin composition which has high sensitivity and excellent thin wire adhesion. A photosensitive resin composition according to the present invention contains (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator and (d) a colorant; and the photopolymerization initiator (c) contains a photopolymerization initiator (c1) represented by general formula (I) and a photopolymerization initiator (c2) which has a maximum absorption wavelength of 334 nm or more within a wavelength range of from 320 nm to 400 nm. (In formula (I), R1-R6, k, l, m, n and o are as defined in the description.)

Description

感光性樹脂組成物、硬化物及び画像表示装置Photosensitive resin composition, cured product, and image display device
　本発明は、感光性樹脂組成物、硬化物及び画像表示装置に関する。特に、高感度かつ細線密着性に優れた感光性樹脂組成物、それを硬化させた硬化物、該硬化物を有する画像表示装置に関する。本発明の感光性樹脂組成物は、特に、高感度で高精細な細線を形成できるブラックマトリックス（Ｂｌａｃｋ　Ｍａｔｒｉｘ。以下「ＢＭ」と略称することがある。）用の感光性樹脂組成物に適している。 The present invention relates to a photosensitive resin composition, a cured product, and an image display device. In particular, the present invention relates to a photosensitive resin composition having high sensitivity and excellent fine-line adhesion, a cured product obtained by curing the photosensitive resin composition, and an image display device having the cured product. The photosensitive resin composition of the present invention is particularly suitable for a photosensitive resin composition for a black matrix (Black Matrix, hereinafter sometimes abbreviated as “BM”) capable of forming highly sensitive and fine fine lines. Yes.
　カラーフィルターは、通常、ガラス、プラスチック等の透明基板の表面に、黒色のブラックマトリックスを形成し、続いて、赤、緑、青等の３種以上の異なる色の画素を順次、格子状、ストライプ状またはモザイク状等のパターンで形成したものである。パターンサイズはカラーフィルターの用途並びにそれぞれの色により異なるが通常５～７００μｍ程度である。 Color filters usually form a black matrix on the surface of a transparent substrate such as glass or plastic, followed by three or more different color pixels such as red, green, blue, etc. Formed in a pattern such as a shape or a mosaic. The pattern size varies depending on the use of the color filter and each color, but is usually about 5 to 700 μm.
　カラーフィルターの代表的な製造方法として、現在、顔料分散法が知られている。顔料分散法によりカラーフィルターを製造する場合、まず黒色顔料を含有する感光性樹脂組成物を透明基板上に塗布した後に乾燥させ、更に画像露光、現像した後、２００℃以上の高温処理により硬化させることでＢＭを形成する。これを赤、緑、青等の各色ごとに繰り返すことでカラーフィルターを形成する。 A pigment dispersion method is currently known as a typical method for producing a color filter. When producing a color filter by the pigment dispersion method, first, a photosensitive resin composition containing a black pigment is applied on a transparent substrate and then dried, and after image exposure and development, it is cured by high-temperature treatment at 200 ° C. or higher. As a result, a BM is formed. This process is repeated for each color such as red, green, and blue to form a color filter.
　ＢＭは、赤、緑、青等の画素の間に格子状、ストライプ状またはモザイク状に配置するのが一般的であり、各画素間の混色抑制によるコントラスト向上あるいは光漏れを防止する役目がある。このため、ＢＭには高い遮光性が要求される。また、ＢＭ形成後に形成する赤、緑、青等の画素のエッジ部は、このＢＭと一部が重なるため、ＢＭの膜厚の影響を受けて、重なり部分で段差が形成される。この重なり部分では、画素の平坦性が損なわれ、液晶セルギャップの不均一化あるいは液晶の配向の乱れが発生して、表示能力低下の原因となる。そこで近年は特にＢＭの膜厚を薄膜化することが求められており、薄膜化した際でも十分な遮光性を発現するために、感光性樹脂組成物中における顔料含有割合はより高くなる方向にある。そのため、添加できる光重合開始剤の割合は減る方向であり、少量添加でも架橋度を維持できる高感度の開始剤が求められている。 The BM is generally arranged in a grid, stripe, or mosaic between pixels such as red, green, and blue, and serves to improve contrast by preventing color mixture between pixels or to prevent light leakage. . For this reason, the BM is required to have high light shielding properties. In addition, since the edge portions of the red, green, and blue pixels formed after the BM partially overlap with the BM, a step is formed at the overlapping portion under the influence of the BM film thickness. In this overlapping portion, the flatness of the pixels is impaired, and the liquid crystal cell gap becomes non-uniform or the alignment of the liquid crystal is disturbed, causing a reduction in display capability. Therefore, in recent years, it has been particularly demanded to reduce the film thickness of the BM, and in order to develop sufficient light-shielding properties even when the film is thinned, the pigment content in the photosensitive resin composition tends to be higher. is there. Therefore, the ratio of the photopolymerization initiator that can be added is decreasing, and a highly sensitive initiator that can maintain the degree of crosslinking even when added in a small amount is demanded.
　一方で、省エネルギー化やモバイルバッテリーの長寿命化のため、バックライトの出力は低くなる方向にあり、そのような条件下にあっても高輝度で画像表示できるよう、遮光部であるＢＭの細線化が進められている。また、近年では、液晶ディスプレイの市場において、タブレットなどのような小型化が主流となり、大型のテレビにおいては高解像度の要求が高くなってきている。これらの理由からも、ＢＭの高精細化の要望が高くなってきており、近年、ＢＭ細線の線幅は従来の１０μｍ前後から、現在では６～８μｍ前後が求められるようになってきている。露光マスクのパターン線幅が１０μｍ未満の領域にくると、通過した光の回折による影響が大きくなり、その分、ＢＭ表面に届く光量は減少してしまう。そのため、高感度の開始剤が求められている。また露光後の現像においては残渣を無くすために現像時間は長めに設定するのが一般的であるが、これによりＢＭ／基板界面の溶解（差込み）が進行し、ラインパターンの剥離が起こりやすくなる。パターン線幅が１０μｍ以上の場合は約１～２μｍの差込み（ライン両側の合計で約２～４μｍ）が生じても細線密着を維持できるが、１０μｍ未満の細線パターンではＢＭ／基板の密着面積が小さくなり、線幅を１μｍ狭めるごとの現像密着の低下幅が顕著に大きくなる。特にカラーフィルター製造装置等で使われるシャワー現像方式ではＢＭの物理的密着力も要求されるため、１０μｍ未満の細線パターン形成が困難であった。そのため、露光時の内部硬化性向上などの手段により細線密着性を高める必要がある。 On the other hand, in order to save energy and extend the life of the mobile battery, the output of the backlight is in the direction of lowering. Is being promoted. In recent years, downsizing such as tablets has become the mainstream in the liquid crystal display market, and the demand for high resolution is increasing for large televisions. For these reasons, there is a growing demand for higher definition of BM, and in recent years, the line width of BM thin wires has been demanded from about 10 μm to about 6 to 8 μm at present. When the pattern line width of the exposure mask is less than 10 μm, the influence of diffraction of the light that has passed increases, and the amount of light that reaches the BM surface decreases accordingly. Therefore, a highly sensitive initiator is required. Further, in development after exposure, the development time is generally set longer in order to eliminate residues, but this causes the dissolution (insertion) of the BM / substrate interface to proceed, and the line pattern is liable to peel off. . When the pattern line width is 10 μm or more, even if insertion of about 1 to 2 μm occurs (about 2 to 4 μm in total on both sides of the line), fine line adhesion can be maintained. However, with a fine line pattern of less than 10 μm, the BM / substrate adhesion area is small. Each time the line width is reduced and the line width is reduced by 1 μm, the decrease in the development adhesion is remarkably increased. In particular, in the shower developing method used in a color filter manufacturing apparatus or the like, it is difficult to form a fine line pattern of less than 10 μm because the physical adhesion of BM is also required. Therefore, it is necessary to improve the fine line adhesion by means such as improving the internal curability during exposure.
　こうした背景から、高感度、かつ１０μｍ未満の細線密着性に優れたＢＭ用の感光性樹脂組成物が求められている。 From such a background, there is a demand for a photosensitive resin composition for BM that has high sensitivity and excellent fine wire adhesion of less than 10 μm.
　特許文献１にはニトロ化したカルバゾリル構造を有するオキシムエステル化合物が、４０５ｎｍや３６５ｎｍ等の長波長の光を効率よく吸収し活性化される高感度の光重合開始剤であると記載されている。特許文献２にはベンゾ－不飽和５員環－カルボニル基を有するオキシムエステル化合物が、高感度であることが記載されている。 Patent Document 1 describes that an oxime ester compound having a nitrated carbazolyl structure is a highly sensitive photopolymerization initiator that efficiently absorbs and activates light having a long wavelength such as 405 nm and 365 nm. Patent Document 2 describes that an oxime ester compound having a benzo-unsaturated 5-membered ring-carbonyl group has high sensitivity.
国際公開第２００８／０７８６７８号International Publication No. 2008/078678 国際公開第２０１５／０３６９１０号International Publication No. 2015/036910
　本発明者らが、特許文献１に記載の光重合開始剤を用いてＢＭ評価を行ったところ、感度は高めとなるものの、シャワー現像方式での細線密着が不十分であることが見出された。また、特許文献２に記載の光重合開始剤を用いてＢＭ評価を行ったところ、細線密着は良好となるものの、線幅細りやパターントップの膜減りがあり、感度が十分ではないことが見出された。
　そこで本発明は、高感度かつ細線密着性に優れた感光性樹脂組成物を提供することを目的とする。 When the present inventors performed BM evaluation using the photopolymerization initiator described in Patent Document 1, it was found that the fine line adhesion in the shower developing method was insufficient, although the sensitivity was increased. It was. Moreover, when BM evaluation was performed using the photoinitiator described in Patent Document 2, it was found that although the fine line adhesion was good, there was thin line width and pattern top film reduction, and the sensitivity was not sufficient. It was issued.
Therefore, an object of the present invention is to provide a photosensitive resin composition having high sensitivity and excellent fine wire adhesion.
　本発明者らは前記課題を解決すべく鋭意検討した結果、感光性樹脂組成物において、特定の組み合わせの光重合開始剤を含有させることにより、前記課題を解決できることを見出した。即ち本発明の要旨は以下に存する。 As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by including a specific combination of photopolymerization initiators in the photosensitive resin composition. That is, the gist of the present invention is as follows.
［１］　（ａ）アルカリ可溶性樹脂、（ｂ）光重合性モノマー、（ｃ）光重合開始剤及び（ｄ）色材を含有する感光性樹脂組成物であって、
　前記（ｃ）光重合開始剤が、下記一般式（Ｉ）で表される光重合開始剤（ｃ１）、及び、波長３２０ｎｍ～４００ｎｍの範囲における極大吸収波長が３３４ｎｍ以上である光重合開始剤（ｃ２）を含有することを特徴とする感光性樹脂組成物。 [1] A photosensitive resin composition containing (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, and (d) a coloring material,
The photopolymerization initiator (c) is a photopolymerization initiator (c1) represented by the following general formula (I), and a photopolymerization initiator having a maximum absorption wavelength of 334 nm or more in the wavelength range of 320 nm to 400 nm ( A photosensitive resin composition comprising c2).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
（式（Ｉ）中、Ｒ１は置換基を有していてもよいアルキル基又は置換基を有していてもよい芳香族環基を表す。
　Ｒ２は置換基を有していてもよいアルキル基又は置換基を有していてもよい芳香族環基を表す。
　ｋは０又は１を表す。
　Ｒ３～Ｒ６は各々独立に、任意の１価の置換基を表す。
　ｌ、ｍ及びｏは各々独立に、０～３の整数を表す。ｎは０又は１を表す。） (In formula (I), R 1 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R 2 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
k represents 0 or 1;
R 3 to R 6 each independently represents an arbitrary monovalent substituent.
l, m and o each independently represents an integer of 0 to 3. n represents 0 or 1. )
［２］　全固形分に対する前記（ｃ）光重合開始剤の含有割合が２質量％以上である、［１］に記載の感光性樹脂組成物。
［３］　前記（ｃ）光重合開始剤における、前記光重合開始剤（ｃ１）の含有割合が１質量％以上である、［１］又は［２］に記載の感光性樹脂組成物。
［４］　前記光重合開始剤（ｃ２）が、フルオレン骨格又はカルバゾール骨格を有する光重合開始剤である、［１］～［３］のいずれか１つに記載の感光性樹脂組成物。
［５］　前記光重合開始剤（ｃ２）が、下記一般式（ＩＩ）で表される光重合開始剤である、［４］に記載の感光性樹脂組成物。 [2] The photosensitive resin composition according to [1], wherein a content ratio of the (c) photopolymerization initiator with respect to the total solid content is 2% by mass or more.
[3] The photosensitive resin composition according to [1] or [2], wherein the content ratio of the photopolymerization initiator (c1) in the (c) photopolymerization initiator is 1% by mass or more.
[4] The photosensitive resin composition according to any one of [1] to [3], wherein the photopolymerization initiator (c2) is a photopolymerization initiator having a fluorene skeleton or a carbazole skeleton.
[5] The photosensitive resin composition according to [4], wherein the photopolymerization initiator (c2) is a photopolymerization initiator represented by the following general formula (II).
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
（式（ＩＩ）中、Ｒ７は置換基を有していてもよいアルキル基又は置換基を有していてもよい芳香族環基を表す。
　Ｒ８は置換基を有していてもよいアルキル基又は置換基を有していてもよい芳香族環基を表す。
　ｐは０又は１を表す。
　Ｒ９は任意の１価の置換基を表す。ｑは０～３の整数を表す。
　Ｘは－Ｎ（Ｒ１０）－又は－Ｃ（Ｒ１１）（Ｒ１２）－を表す。
　Ｒ１０～Ｒ１２は各々独立に、水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよい芳香族環基を表す。Ｒ１１とＲ１２は相互に結合して環を形成していてもよい。） (In Formula (II), R 7 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R 8 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
p represents 0 or 1;
R 9 represents an arbitrary monovalent substituent. q represents an integer of 0 to 3.
X represents —N (R 10 ) — or —C (R 11 ) (R 12 ) —.
R 10 to R 12 each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R 11 and R 12 may be bonded to each other to form a ring. )
［６］　前記（ｄ）色材がカーボンブラックである、［１］～［５］のいずれか１つに記載の感光性樹脂組成物。
［７］　全固形分に対する前記（ｄ）色材の含有割合が３０質量％以上である、［１］～［６］のいずれか１つに記載の感光性樹脂組成物。
［８］　前記（ａ）アルカリ可溶性樹脂が、カルボキシル基を有するエポキシ（メタ）アクリレート樹脂を含有する、［１］～［７］のいずれか１つに記載の感光性樹脂組成物。
［９］　［１］～［８］のいずれか１つに記載の感光性樹脂組成物を硬化させた硬化物。
［１０］　［９］に記載の硬化物を有する画像表示装置。 [6] The photosensitive resin composition according to any one of [1] to [5], wherein the color material (d) is carbon black.
[7] The photosensitive resin composition according to any one of [1] to [6], wherein the content of the color material (d) with respect to the total solid content is 30% by mass or more.
[8] The photosensitive resin composition according to any one of [1] to [7], wherein the (a) alkali-soluble resin contains an epoxy (meth) acrylate resin having a carboxyl group.
[9] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [8].
[10] An image display device having the cured product according to [9].
　本発明によれば、高感度かつ細線密着性に優れた感光性樹脂組成物を提供することができる。 According to the present invention, it is possible to provide a photosensitive resin composition having high sensitivity and excellent fine wire adhesion.
図１は、本発明のカラーフィルターを備えた有機ＥＬ（Electro Luminescence）素子の一例を示す断面概略図である。FIG. 1 is a schematic cross-sectional view showing an example of an organic EL (Electro Luminescence) element provided with the color filter of the present invention.
　以下、本発明の実施の形態を具体的に説明するが、本発明は、以下の実施の形態に限定されるものではなく、その要旨の範囲内で種々に変更して実施することができる。
　なお、本発明において、「（メタ）アクリル」とは「アクリル及び／又はメタクリル」を意味し、「（メタ）アクリレート」、「（メタ）アクリロイル」についても同様である。
　また、本発明において、質量で表される全ての百分率や部は、重量で表される百分率や部と同様である。 Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
In the present invention, “(meth) acryl” means “acryl and / or methacryl”, and the same applies to “(meth) acrylate” and “(meth) acryloyl”.
In the present invention, all percentages and parts expressed by mass are the same as percentages and parts expressed by weight.
　本発明において「全固形分」とは、感光性樹脂組成物中又は後述するインク中に含まれる、溶剤以外の全成分を意味するものとする。
　本発明において、重量平均分子量とは、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）によるポリスチレン換算の重量平均分子量（Ｍｗ）を指す。
　また、本発明において、「アミン価」とは、特に断りのない限り、有効固形分換算のアミン価を表し、分散剤の固形分１ｇあたりの塩基量と当量のＫＯＨの重量で表される値である。なお、測定方法については後述する。 In the present invention, the “total solid content” means all components other than the solvent contained in the photosensitive resin composition or in the ink described later.
In this invention, a weight average molecular weight refers to the weight average molecular weight (Mw) of polystyrene conversion by GPC (gel permeation chromatography).
Further, in the present invention, the “amine value” means an amine value in terms of effective solid content, unless otherwise specified, and is a value represented by the weight of KOH equivalent to the base amount per 1 g of the solid content of the dispersant. It is. The measuring method will be described later.
［感光性樹脂組成物］
　本発明の感光性樹脂組成物は、（ａ）アルカリ可溶性樹脂、（ｂ）光重合性モノマー、（ｃ）光重合開始剤及び（ｄ）色材を含有する感光性樹脂組成物であって、前記（ｃ）光重合開始剤が、下記一般式（Ｉ）で表される光重合開始剤（ｃ１）、及び、波長３２０ｎｍ～４００ｎｍの範囲における極大吸収波長が３３４ｎｍ以上である光重合開始剤（ｃ２）を含有することを特徴とする。なお、本発明において（ｃ）光重合開始剤の「極大吸収波長」とは、波長３２０ｎｍ～４００ｎｍの範囲における極大吸収波長を意味するものとする。 [Photosensitive resin composition]
The photosensitive resin composition of the present invention is a photosensitive resin composition containing (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, and (d) a coloring material. The photopolymerization initiator (c) is a photopolymerization initiator (c1) represented by the following general formula (I), and a photopolymerization initiator having a maximum absorption wavelength of 334 nm or more in the wavelength range of 320 nm to 400 nm ( c2) is contained. In the present invention, the “maximum absorption wavelength” of the photopolymerization initiator (c) means the maximum absorption wavelength in the wavelength range of 320 nm to 400 nm.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　式（Ｉ）中、Ｒ１は置換基を有していてもよいアルキル基又は置換基を有していてもよい芳香族環基を表す。
　Ｒ２は置換基を有していてもよいアルキル基又は置換基を有していてもよい芳香族環基を表す。
　ｋは０又は１を表す。
　Ｒ３～Ｒ６は各々独立に、任意の１価の置換基を表す。
　ｌ、ｍ及びｏは各々独立に、０～３の整数を表す。ｎは０又は１を表す。 In formula (I), R 1 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R 2 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
k represents 0 or 1;
R 3 to R 6 each independently represents an arbitrary monovalent substituent.
l, m and o each independently represents an integer of 0 to 3. n represents 0 or 1.
　本発明の感光性樹脂組成物は更に、分散剤、チオール類を含有していてもよく、必要に応じて、密着向上剤、塗布性向上剤、現像改良剤、紫外線吸収剤、酸化防止剤、顔料誘導体等のその他の配合成分を含んでいてもよく、通常、各配合成分が、有機溶剤に溶解又は分散した状態で使用される。
　本発明の特徴は、感光性樹脂組成物において（ｃ）光重合開始剤が、光重合開始剤（ｃ１）及び光重合開始剤（ｃ２）を含有することにある。まず、（ｃ）光重合開始剤について説明する。 The photosensitive resin composition of the present invention may further contain a dispersant and a thiol, and if necessary, an adhesion improver, a coatability improver, a development improver, an ultraviolet absorber, an antioxidant, Other compounding components such as pigment derivatives may be contained, and each compounding component is usually used in a state dissolved or dispersed in an organic solvent.
The feature of the present invention is that in the photosensitive resin composition (c) the photopolymerization initiator contains a photopolymerization initiator (c1) and a photopolymerization initiator (c2). First, (c) the photopolymerization initiator will be described.
＜（ｃ）光重合開始剤＞
　本発明における（ｃ）光重合開始剤は、後述の一般式（Ｉ）で表される光重合開始剤（ｃ１）、及び、極大吸収波長が３３４ｎｍ以上である光重合開始剤（ｃ２）を含有する。 <(C) Photopolymerization initiator>
The photopolymerization initiator (c) in the present invention contains a photopolymerization initiator (c1) represented by the following general formula (I) and a photopolymerization initiator (c2) having a maximum absorption wavelength of 334 nm or more. To do.
＜光重合開始剤（ｃ１）＞
　光重合開始剤（ｃ１）は、下記一般式（Ｉ）で表される光重合開始剤である。 <Photopolymerization initiator (c1)>
The photopolymerization initiator (c1) is a photopolymerization initiator represented by the following general formula (I).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　式（Ｉ）中、Ｒ１は置換基を有していてもよいアルキル基又は置換基を有していてもよい芳香族環基を表す。
　Ｒ２は置換基を有していてもよいアルキル基又は置換基を有していてもよい芳香族環基を表す。
　ｋは０又は１を表す。
　Ｒ３～Ｒ６は各々独立に、任意の１価の置換基を表す。
　ｌ、ｍ及びｏは各々独立に、０～３の整数を表す。ｎは０又は１を表す。 In formula (I), R 1 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R 2 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
k represents 0 or 1;
R 3 to R 6 each independently represents an arbitrary monovalent substituent.
l, m and o each independently represents an integer of 0 to 3. n represents 0 or 1.
　このように、前記一般式（Ｉ）で表される光重合開始剤（ｃ１）を含有することで、色材粒子表面への光重合開始剤の吸着が促進され、露光時の光重合開始剤の光吸収率が向上すると共に、樹脂成分のＵＶ（Ultraviolet）光透過性が上がって内部硬化性が向上し、細線密着性が良好になるものと考えられる。 Thus, by containing the photopolymerization initiator (c1) represented by the general formula (I), the adsorption of the photopolymerization initiator to the surface of the colorant particles is promoted, and the photopolymerization initiator at the time of exposure It is considered that the light absorptivity of the resin component is improved, the UV (Ultraviolet) light transmittance of the resin component is increased, the internal curability is improved, and the fine wire adhesion is improved.
（Ｒ１）
　前記式（Ｉ）において、Ｒ１は置換基を有していてもよいアルキル基又は置換基を有していてもよい芳香族環基を表す。
　Ｒ１におけるアルキル基は、直鎖状でも、分岐状でも、環状でも、それらが結合したものであってもよい。アルキル基の炭素数は特に限定されないが、通常１以上であり、また好ましくは１２以下、より好ましくは６以下、さらに好ましくは３以下、特に好ましくは２以下である。アルキル基の炭素数を前記上限値以下とすることで、架橋密度が高くなる傾向がある。
　アルキル基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基などが挙げられる。これらの中でも、感度の観点から、メチル基、エチル基、プロピル基、又はブチル基が好ましく、メチル基又はエチル基がより好ましく、メチル基がさらに好ましい。
　アルキル基が有していてもよい置換基としては、炭素数１～１０のアルコキシ基、炭素数１～１０のアルキルチオ基、Ｆ、Ｃｌ、Ｂｒ、Ｉなどのハロゲン原子、水酸基、ニトロ基などが挙げられ、溶剤溶解性の観点から、メトキシ基又は水酸基が好ましい。また、感度の観点からは、無置換であることが好ましい。 (R 1 )
In the formula (I), R 1 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
The alkyl group in R 1 may be linear, branched, cyclic, or a combination thereof. Although carbon number of an alkyl group is not specifically limited, Usually, it is 1 or more, Preferably it is 12 or less, More preferably, it is 6 or less, More preferably, it is 3 or less, Most preferably, it is 2 or less. By setting the number of carbon atoms of the alkyl group to the upper limit value or less, the crosslinking density tends to increase.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, cyclopentyl group, hexyl group and cyclohexyl group. Among these, from the viewpoint of sensitivity, a methyl group, an ethyl group, a propyl group, or a butyl group is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is more preferable.
Examples of the substituent that the alkyl group may have include an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a halogen atom such as F, Cl, Br, and I, a hydroxyl group, and a nitro group. From the viewpoint of solvent solubility, a methoxy group or a hydroxyl group is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.
　Ｒ１における芳香族環基としては、芳香族炭化水素環基及び芳香族複素環基が挙げられる。その炭素数は通常４以上であり、６以上が好ましく、また、１２以下が好ましく、１０以下がより好ましく、８以下がさらに好ましい。芳香族環基の炭素数を前記下限値以上とすることで保存安定性が良好となる傾向があり、また、前記上限値以下とすることで溶剤溶解性が良好となる傾向がある。 Examples of the aromatic ring group for R 1 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 6 or more, 12 or less, more preferably 10 or less, and even more preferably 8 or less. Storage stability tends to be good when the number of carbon atoms of the aromatic ring group is equal to or higher than the lower limit value, and solvent solubility tends to be better when the aromatic ring group is equal to or lower than the upper limit value.
　芳香族炭化水素環基における芳香族炭化水素環としては、単環であっても縮合環であってもよい。芳香族炭化水素環基としては、例えば、１個の遊離原子価を有する、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環などの基が挙げられる。
　また、芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。芳香族複素環基としては、例えば、１個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。
　これらの中でも溶剤溶解性の観点から、１個の遊離原子価を有するベンゼン環又はナフタレン環が好ましく、１個の遊離原子価を有するベンゼン環がより好ましい。 The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. As the aromatic hydrocarbon ring group, for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring having one free valence, Examples include acenaphthene ring, fluoranthene ring, fluorene ring and the like.
In addition, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the aromatic heterocyclic group include one furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, and carbazole having one free valence. Ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, Examples include pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
Among these, from the viewpoint of solvent solubility, a benzene ring or naphthalene ring having one free valence is preferable, and a benzene ring having one free valence is more preferable.
　芳香族環基が有していてもよい置換基としては、炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基、炭素数１～１０のアルキルチオ基、Ｆ、Ｃｌ、Ｂｒ、Ｉなどのハロゲン原子、水酸基、ニトロ基などが挙げられ、溶剤溶解性の観点から、メトキシ基又は水酸基が好ましい。また、感度の観点からは、無置換であることが好ましい。 Examples of the substituent that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I And a halogen atom such as a hydroxyl group, a nitro group, and the like. From the viewpoint of solvent solubility, a methoxy group or a hydroxyl group is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.
　これらの中でも硬化性の観点から、Ｒ１は置換基を有していてもよいアルキル基であることが好ましく、無置換のアルキル基であることがより好ましく、メチル基であることがさらに好ましい。 Among these, from the viewpoint of curability, R 1 is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and even more preferably a methyl group.
（Ｒ２）
　前記式（Ｉ）において、Ｒ２は置換基を有していてもよいアルキル基又は置換基を有していてもよい芳香族環基を表す。
　Ｒ２におけるアルキル基は、直鎖状でも、分岐状でも、環状でも、それらが結合したものであってもよいが、溶剤溶解性の観点から直鎖状又は分岐状が好ましく、分岐状がより好ましい。
　アルキル基の炭素数は特に限定されないが、通常１以上、好ましくは２以上、より好ましくは３以上、さらに好ましくは４以上、特に好ましくは５以上、また、好ましくは１０以下、より好ましくは８以下、さらに好ましくは７以下、特に好ましくは６以下である。アルキル基の炭素数を前記下限値以上とすることで溶剤溶解性が良好となる傾向があり、前記上限値以下とすることで高感度となる傾向がある。
　アルキル基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基などが挙げられる。これらの中でも、溶剤溶解性の観点から、イソプロピル基、イソブチル基、イソペンチル基、又はシクロペンチルが好ましく、イソブチル基又はイソペンチル基がより好ましく、イソペンチル基がさらに好ましい。
　アルキル基が有していてもよい置換基としては、炭素数６～１０の芳香族環基、炭素数１～１０のアルコキシ基、炭素数１～１０のアルキルチオ基、Ｆ、Ｃｌ、Ｂｒ、Ｉなどのハロゲン原子、水酸基などが挙げられ、溶剤溶解性の観点から、炭素数１～３のアルコキシ基が好ましい。また、感度の観点からは、無置換であることが好ましい。 (R 2 )
In the formula (I), R 2 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
The alkyl group in R 2 may be linear, branched, cyclic, or a combination thereof, but is preferably linear or branched from the viewpoint of solvent solubility, and more preferably branched. preferable.
The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, further preferably 4 or more, particularly preferably 5 or more, and preferably 10 or less, more preferably 8 or less. More preferably, it is 7 or less, and particularly preferably 6 or less. There exists a tendency for solvent solubility to become favorable by making carbon number of an alkyl group more than the said lower limit, and there exists a tendency for it to become high sensitivity by making it into the said upper limit or less.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, cyclopentyl group, hexyl group and cyclohexyl group. Among these, from the viewpoint of solvent solubility, isopropyl, isobutyl, isopentyl, or cyclopentyl is preferable, isobutyl or isopentyl is more preferable, and isopentyl is more preferable.
Examples of the substituent that the alkyl group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I In view of solvent solubility, an alkoxy group having 1 to 3 carbon atoms is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.
　Ｒ２における芳香族環基としては、芳香族炭化水素環基及び芳香族複素環基が挙げられる。その炭素数は通常４以上であり、６以上が好ましく、また、１２以下が好ましく、１０以下がより好ましく、８以下がさらに好ましい。芳香族環基の炭素数を前記下限値以上とすることで分子が安定となる傾向があり、また、前記上限値以下とすることで溶剤溶解性が良好となる傾向がある。 Examples of the aromatic ring group for R 2 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 6 or more, 12 or less, more preferably 10 or less, and even more preferably 8 or less. There exists a tendency for a molecule | numerator to become stable by making carbon number of an aromatic ring group more than the said lower limit, and there exists a tendency for solvent solubility to become favorable by making it into the said upper limit or less.
　芳香族炭化水素環基における芳香族炭化水素環としては、単環であっても縮合環であってもよい。芳香族炭化水素環基としては、例えば、１個の遊離原子価を有する、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環などの基が挙げられる。
　また、芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。芳香族複素環基としては、例えば、１個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。
　これらの中でも溶剤溶解性の観点から、１個の遊離原子価を有するベンゼン環又はナフタレン環が好ましく、１個の遊離原子価を有するベンゼン環がより好ましい。 The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. As the aromatic hydrocarbon ring group, for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring having one free valence, Examples include acenaphthene ring, fluoranthene ring, fluorene ring and the like.
In addition, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the aromatic heterocyclic group include one furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, and carbazole having one free valence. Ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, Examples include pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
Among these, from the viewpoint of solvent solubility, a benzene ring or naphthalene ring having one free valence is preferable, and a benzene ring having one free valence is more preferable.
　芳香族環基が有していてもよい置換基としては、炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基、炭素数１～１０のアルキルチオ基、Ｆ、Ｃｌ、Ｂｒ、Ｉなどのハロゲン原子、水酸基、ニトロ基などが挙げられ、溶剤溶解性の観点から、炭素数１～３のアルコキシ基又は水酸基が好ましい。また、感度の観点からは、無置換であることが好ましい。 Examples of the substituent that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I In view of solvent solubility, an alkoxy group having 1 to 3 carbon atoms or a hydroxyl group is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.
　これらの中でも感度の観点から、Ｒ２は置換基を有していてもよいアルキル基であることが好ましく、無置換のアルキル基であることがより好ましく、イソペンチル基であることがさらに好ましい。 Among these, from the viewpoint of sensitivity, R 2 is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and even more preferably an isopentyl group.
（ｋ）
　前記式（Ｉ）において、ｋは０又は１を表す。感度の観点からはｋが０であることが好ましく、一方で溶剤溶解性の観点からはｋが１であることが好ましい。 (K)
In the formula (I), k represents 0 or 1. From the viewpoint of sensitivity, k is preferably 0, while from the viewpoint of solvent solubility, k is preferably 1.
（Ｒ３～Ｒ６）
　前記式（Ｉ）において、Ｒ３～Ｒ６は各々独立に、任意の１価の置換基を表す。
　任意の１価の置換基としては、メチル基、エチル基等の炭素数１～１０のアルキル基；メトキシ基、エトキシ基などの炭素数１～１０のアルコキシ基；Ｆ、Ｃｌ、Ｂｒ、Ｉなどのハロゲン原子；炭素数１～１０のアシル基；炭素数１～１０のアルキルエステル基；炭素数１～１０のアルコキシカルボニル基；炭素数１～１０のハロゲン化アルキル基；炭素数４～１０の芳香族環基；アミノ基；炭素数１～１０のアミノアルキル基；水酸基；ニトロ基；ＣＮ基等が挙げられる。これらの中でも溶剤溶解性の観点から、メチル基、メトキシ基が好ましく、メチル基がより好ましい。
　Ｒ３、Ｒ４及びＲ６において、ｌ、ｍ及びｏが２以上の場合、複数のＲ３、Ｒ４及びＲ６同士が結合して環を形成していてもよい。環は脂肪族環であっても、芳香族環であってもよい。 (R 3 to R 6 )
In the formula (I), R 3 to R 6 each independently represents an arbitrary monovalent substituent.
As an arbitrary monovalent substituent, an alkyl group having 1 to 10 carbon atoms such as a methyl group or an ethyl group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group or an ethoxy group; F, Cl, Br, I or the like An acyl group having 1 to 10 carbon atoms; an alkyl ester group having 1 to 10 carbon atoms; an alkoxycarbonyl group having 1 to 10 carbon atoms; a halogenated alkyl group having 1 to 10 carbon atoms; Aromatic ring group; amino group; aminoalkyl group having 1 to 10 carbon atoms; hydroxyl group; nitro group; CN group. Among these, from the viewpoint of solvent solubility, a methyl group and a methoxy group are preferable, and a methyl group is more preferable.
In R 3 , R 4 and R 6 , when l, m and o are 2 or more, a plurality of R 3 , R 4 and R 6 may be bonded to form a ring. The ring may be an aliphatic ring or an aromatic ring.
（ｌ、ｍ、ｎ、ｏ）
　前記式（Ｉ）において、ｌ、ｍ及びｏは各々独立に、０～３の整数を表し、ｎは０又は１を表す。
　感度の観点から、ｌ、ｍ及びｏは各々独立に０又は１であることが好ましく、０であることがより好ましい。また、感度の観点から、ｎは０であることが好ましい。 (L, m, n, o)
In the formula (I), l, m and o each independently represents an integer of 0 to 3, and n represents 0 or 1.
From the viewpoint of sensitivity, it is preferable that l, m and o are each independently 0 or 1, and more preferably 0. From the viewpoint of sensitivity, n is preferably 0.
　前記一般式（Ｉ）で表される光重合開始剤は、溶剤溶解性と感度のバランスに加えて、色材との適度な相互作用の観点から、下記一般式（Ｉ－１）で表される光重合開始剤であることが好ましい。 The photopolymerization initiator represented by the general formula (I) is represented by the following general formula (I-1) from the viewpoint of an appropriate interaction with the coloring material in addition to the balance between solvent solubility and sensitivity. It is preferable that the photopolymerization initiator.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　式（Ｉ－１）中、Ｒ１～Ｒ６、ｋ～ｏは前記式（Ｉ）と同義である。 In formula (I-1), R 1 to R 6 and k to o have the same meanings as those in formula (I).
　前記光重合開始剤（ｃ１）の極大吸収波長は特に限定されないが、感度の観点から、３２２ｎｍ以上が好ましく、３２５ｎｍ以上がより好ましく、３２８ｎｍ以上がさらに好ましく、３２９ｎｍ以上がよりさらに好ましく、３３０ｎｍ以上が特に好ましく、また、３３７ｎｍ以下が好ましく、３３６ｎｍ以下がより好ましく、３３４ｎｍ以下がさらに好ましく、３３３ｎｍ以下がよりさらに好ましい。前記範囲内にすることでＵＶ光源が発する３３３ｎｍの輝線から３６５ｎｍの輝線（ｉ線）の間の光を有効利用できる傾向がある。 The maximum absorption wavelength of the photopolymerization initiator (c1) is not particularly limited, but is preferably 322 nm or more, more preferably 325 nm or more, further preferably 328 nm or more, still more preferably 329 nm or more, and 330 nm or more from the viewpoint of sensitivity. Particularly preferred, 337 nm or less is preferred, 336 nm or less is more preferred, 334 nm or less is more preferred, and 333 nm or less is even more preferred. Within the above range, there is a tendency that light between the 333 nm emission line emitted from the UV light source and the 365 nm emission line (i-line) can be effectively used.
　前記光重合開始剤（ｃ１）の製造方法は特に限定されないが、例えば、国際公開第２０１５／０３６９１０号に記載の方法を採用することができる。
　また、前記光重合開始剤（ｃ１）の具体例としては、例えば、以下のものが挙げられる。 Although the manufacturing method of the said photoinitiator (c1) is not specifically limited, For example, the method as described in international publication 2015/036910 is employable.
Moreover, as a specific example of the said photoinitiator (c1), the following are mentioned, for example.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　本発明における（ｃ）光重合開始剤は、前記光重合開始剤（ｃ１）の他に、極大吸収波長が３３４ｎｍ以上である光重合開始剤（ｃ２）を含有する。 (C) The photopolymerization initiator in the present invention contains a photopolymerization initiator (c2) having a maximum absorption wavelength of 334 nm or more in addition to the photopolymerization initiator (c1).
＜光重合開始剤（ｃ２）＞
　光重合開始剤（ｃ２）は、極大吸収波長が３３４ｎｍ以上である光重合開始剤である。
　このように、光重合開始剤（ｃ１）に加えて、極大吸収波長が３３４ｎｍ以上である光重合開始剤（ｃ２）を用いることで、有効利用できる光波長範囲が広がり、感度が良好になると考えられる。 <Photopolymerization initiator (c2)>
The photopolymerization initiator (c2) is a photopolymerization initiator having a maximum absorption wavelength of 334 nm or longer.
In this way, in addition to the photopolymerization initiator (c1), the use of the photopolymerization initiator (c2) having a maximum absorption wavelength of 334 nm or more broadens the effective wavelength range of light and improves the sensitivity. It is done.
　前記光重合開始剤（ｃ２）の極大吸収波長は、３３４ｎｍ以上であれば特に限定されないが、感度の観点から、３３５ｎｍ以上が好ましく、３３６ｎｍ以上がより好ましく、３３８ｎｍ以上がさらに好ましく、３４０ｎｍ以上がよりさらに好ましく、３４５ｎｍ以上が特に好ましく、３５０ｎｍ以上が最も好ましく、また、３９０ｎｍ以下が好ましく、３８０ｎｍ以下がより好ましく、３７５ｎｍ以下がさらに好ましく、３７０ｎｍ以下が特に好ましい。光重合開始剤（ｃ２）の極大吸収波長を前記下限値以上とすることで内部硬化が高くなる傾向があり、また、前記上限値以下とすることで高感度となる傾向がある。
　更に、光重合開始剤（ｃ２）と光重合開始剤（ｃ１）の極大吸収波長の差は、５ｎｍ以上が好ましく、１０ｎｍ以上がより好ましく、２０ｎｍ以上がさらに好ましく、３０ｎｍ以上が特に好ましく、また、６０ｎｍ以下が好ましく、５０ｎｍ以下がより好ましく、４０ｎｍ以下がさらに好ましく、適当な極大吸収波長を持つ光重合開始剤（ｃ１）と光重合開始剤（ｃ２）の組合せを選択して用いればよい。光重合開始剤（ｃ１）と光重合開始剤（ｃ２）の極大吸収波長の差を前記下限値以上とすることで有効利用できる光波長範囲が広がり高感度化する傾向があり、前記上限値以下とすることでＵＶ光のｉ線（３６５ｎｍ）に対する感度が高くなる傾向がある。 The maximum absorption wavelength of the photopolymerization initiator (c2) is not particularly limited as long as it is 334 nm or more, but from the viewpoint of sensitivity, it is preferably 335 nm or more, more preferably 336 nm or more, further preferably 338 nm or more, and more preferably 340 nm or more. More preferably, 345 nm or more is particularly preferable, 350 nm or more is most preferable, 390 nm or less is preferable, 380 nm or less is more preferable, 375 nm or less is further preferable, and 370 nm or less is particularly preferable. When the maximum absorption wavelength of the photopolymerization initiator (c2) is set to be equal to or greater than the lower limit value, the internal curing tends to be high, and when the maximum absorption wavelength is equal to or less than the upper limit value, the sensitivity tends to be high.
Furthermore, the difference in maximum absorption wavelength between the photopolymerization initiator (c2) and the photopolymerization initiator (c1) is preferably 5 nm or more, more preferably 10 nm or more, further preferably 20 nm or more, particularly preferably 30 nm or more, 60 nm or less is preferable, 50 nm or less is more preferable, 40 nm or less is more preferable, and a combination of the photopolymerization initiator (c1) and the photopolymerization initiator (c2) having an appropriate maximum absorption wavelength may be selected and used. By making the difference between the maximum absorption wavelengths of the photopolymerization initiator (c1) and the photopolymerization initiator (c2) greater than or equal to the lower limit value, there is a tendency that the light wavelength range that can be effectively used is widened and the sensitivity is increased, and the upper limit value or less. As a result, the sensitivity of UV light to i-line (365 nm) tends to increase.
　前記光重合開始剤（ｃ２）の化学構造は特に限定されないが、感度の観点から、オキシムエステル系光重合開始剤であることが好ましく、特に、フルオレン骨格又はカルバゾール骨格を有する光重合開始剤であることが好ましい。なお、フルオレン骨格又はカルバゾール骨格を有するとは、分子構造中にフルオレン環又はカルバゾール環を有することを意味し、それらの環は置換されていてもよい。
　また、表面硬化性の観点から、光重合開始剤（ｃ２）は下記一般式（ＩＩ）で表される光重合開始剤であることが好ましい。 The chemical structure of the photopolymerization initiator (c2) is not particularly limited, but is preferably an oxime ester photopolymerization initiator from the viewpoint of sensitivity, and in particular, a photopolymerization initiator having a fluorene skeleton or a carbazole skeleton. It is preferable. Note that having a fluorene skeleton or a carbazole skeleton means having a fluorene ring or a carbazole ring in the molecular structure, and these rings may be substituted.
From the viewpoint of surface curability, the photopolymerization initiator (c2) is preferably a photopolymerization initiator represented by the following general formula (II).
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　式（ＩＩ）中、Ｒ７は置換基を有していてもよいアルキル基又は置換基を有していてもよい芳香族環基を表す。
　Ｒ８は置換基を有していてもよいアルキル基又は置換基を有していてもよい芳香族環基を表す。
　ｐは０又は１を表す。
　Ｒ９は任意の１価の置換基を表す。ｑは０～３の整数を表す。
　Ｘは－Ｎ（Ｒ１０）－又は－Ｃ（Ｒ１１）（Ｒ１２）－を表す。
　Ｒ１０～Ｒ１２は各々独立に、水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよい芳香族環基を表す。Ｒ１１とＲ１２は相互に結合して環を形成していてもよい。 In formula (II), R 7 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R 8 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
p represents 0 or 1;
R 9 represents an arbitrary monovalent substituent. q represents an integer of 0 to 3.
X represents —N (R 10 ) — or —C (R 11 ) (R 12 ) —.
R 10 to R 12 each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R 11 and R 12 may be bonded to each other to form a ring.
（Ｒ７）
　前記式（ＩＩ）において、Ｒ７は置換基を有していてもよいアルキル基又は置換基を有していてもよい芳香族環基を表す。
　Ｒ７におけるアルキル基は、直鎖状でも、分岐状でも、環状でも、それらが結合したものであってもよい。アルキル基の炭素数は特に限定されないが、好ましくは１０以下、より好ましくは７以下、さらに好ましくは５以下、特に好ましくは３以下、最も好ましくは２以下であり、通常１以上である。アルキル基の炭素数を前記上限値以下とすることで、架橋密度が高くなる傾向がある。
　アルキル基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基などが挙げられる。これらの中でも、感度の観点から、メチル基、エチル基、プロピル基、又はブチル基が好ましく、メチル基又はエチル基がより好ましく、メチル基がさらに好ましい。
　アルキル基が有していてもよい置換基としては、炭素数６～１０の芳香族環基、炭素数１～１０のアルコキシ基、炭素数１～１０のアルキルチオ基、Ｆ、Ｃｌ、Ｂｒ、Ｉなどのハロゲン原子、水酸基などが挙げられ、溶剤溶解性の観点から、炭素数１～３のアルコキシ基が好ましい。また、感度の観点からは、無置換であることが好ましい。 (R 7 )
In the formula (II), R 7 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
The alkyl group for R 7 may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 10 or less, more preferably 7 or less, further preferably 5 or less, particularly preferably 3 or less, most preferably 2 or less, and usually 1 or more. By setting the number of carbon atoms of the alkyl group to the upper limit value or less, the crosslinking density tends to increase.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, cyclopentyl group, hexyl group and cyclohexyl group. Among these, from the viewpoint of sensitivity, a methyl group, an ethyl group, a propyl group, or a butyl group is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is more preferable.
Examples of the substituent that the alkyl group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I In view of solvent solubility, an alkoxy group having 1 to 3 carbon atoms is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.
　Ｒ７における芳香族環基としては、芳香族炭化水素環基及び芳香族複素環基が挙げられる。その炭素数は通常４以上であり、６以上が好ましく、また、１２以下が好ましく、１０以下がより好ましく、８以下がさらに好ましい。芳香族環基の炭素数を前記下限値以上とすることで分子が安定となる傾向があり、また、前記上限値以下とすることで溶剤溶解性が良好となる傾向がある。 Examples of the aromatic ring group for R 7 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 6 or more, 12 or less, more preferably 10 or less, and even more preferably 8 or less. There exists a tendency for a molecule | numerator to become stable by making carbon number of an aromatic ring group more than the said lower limit, and there exists a tendency for solvent solubility to become favorable by making it into the said upper limit or less.
　芳香族炭化水素環基における芳香族炭化水素環としては、単環であっても縮合環であってもよい。芳香族炭化水素環基としては、例えば、１個の遊離原子価を有する、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環などの基が挙げられる。
　また、芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。芳香族複素環基としては、例えば、１個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。
　これらの中でも溶剤溶解性の観点から、１個の遊離原子価を有するベンゼン環又はナフタレン環が好ましく、１個の遊離原子価を有するベンゼン環がより好ましい。 The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. As the aromatic hydrocarbon ring group, for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring having one free valence, Examples include acenaphthene ring, fluoranthene ring, fluorene ring and the like.
In addition, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the aromatic heterocyclic group include one furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, and carbazole having one free valence. Ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, Examples include pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
Among these, from the viewpoint of solvent solubility, a benzene ring or naphthalene ring having one free valence is preferable, and a benzene ring having one free valence is more preferable.
　芳香族環基が有していてもよい置換基としては、炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基、炭素数１～１０のアルキルチオ基、Ｆ、Ｃｌ、Ｂｒ、Ｉなどのハロゲン原子、水酸基、ニトロ基などが挙げられ、溶剤溶解性の観点から、炭素数１～３のアルコキシ基又は水酸基が好ましい。 Examples of the substituent that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I In view of solvent solubility, an alkoxy group having 1 to 3 carbon atoms or a hydroxyl group is preferable.
　これらの中でも感度の観点から、Ｒ７は置換基を有していてもよいアルキル基であることが好ましく、無置換のアルキル基であることがより好ましく、メチル基又はエチル基であることがさらに好ましく、メチル基であることが特に好ましい。 Among these, from the viewpoint of sensitivity, R 7 is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and further preferably a methyl group or an ethyl group. A methyl group is preferable, and a methyl group is particularly preferable.
（Ｒ８）
　前記式（ＩＩ）において、Ｒ８は置換基を有していてもよいアルキル基又は置換基を有していてもよい芳香族環基を表す。
　Ｒ８におけるアルキル基は、直鎖状でも、分岐状でも、環状でも、それらが結合したものであってもよいが、溶剤溶解性の観点から直鎖状又は分岐状が好ましく、分岐状がより好ましい。一方で、感度の観点からは直鎖状アルキル基と環状アルキル基とを結合した基が好ましい。 (R 8)
In the formula (II), R 8 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
The alkyl group in R 8 may be linear, branched, cyclic, or a combination thereof, but is preferably linear or branched from the viewpoint of solvent solubility, and more preferably branched. preferable. On the other hand, from the viewpoint of sensitivity, a group in which a linear alkyl group and a cyclic alkyl group are bonded is preferable.
　アルキル基の炭素数は特に限定されないが、通常１以上、好ましくは２以上、より好ましくは３以上、さらに好ましくは４以上、よりさらに好ましくは５以上、特に好ましくは６以上、最も好ましくは７以上、また、好ましくは１２以下、より好ましくは１０以下、さらに好ましくは９以下、特に好ましくは８以下である。アルキル基の炭素数を前記下限値以上とすることで溶剤溶解性が良好となる傾向があり、前記上限値以下とすることで高感度となる傾向がある。 The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, still more preferably 5 or more, particularly preferably 6 or more, and most preferably 7 or more. Also, it is preferably 12 or less, more preferably 10 or less, still more preferably 9 or less, and particularly preferably 8 or less. There exists a tendency for solvent solubility to become favorable by making carbon number of an alkyl group more than the said lower limit, and there exists a tendency for it to become high sensitivity by making it into the said upper limit or less.
　アルキル基が有していてもよい置換基としては、炭素数６～１０の芳香族環基、炭素数１～１０のアルコキシ基、炭素数１～１０のアルキルチオ基、炭素数１～１０のアルコキシカルボニル基、Ｆ、Ｃｌ、Ｂｒ、Ｉなどのハロゲン原子、水酸基などが挙げられ、溶剤溶解性の観点から、炭素数１～３のアルコキシ基が好ましい。また、感度の観点からは、無置換であることが好ましい。 Examples of the substituent that the alkyl group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. Examples thereof include a carbonyl group, a halogen atom such as F, Cl, Br, and I, and a hydroxyl group. From the viewpoint of solvent solubility, an alkoxy group having 1 to 3 carbon atoms is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.
　アルキル基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、シクロペンチルメチル基、シクロペンチルエチル基、シクロヘキシルメチル基、シクロヘキシルエチル基などが挙げられる。これらの中でも、溶剤溶解性の観点から、イソペンチル基、シクロヘキシルメチル基、シクロペンチルエチル基、又はシクロヘキシルエチル基が好ましく、シクロペンチルエチル基又はシクロヘキシルエチル基がより好ましく、シクロヘキシルエチル基がさらに好ましい。 Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, cyclopentyl, hexyl, cyclohexyl, cyclopentylmethyl, A cyclopentylethyl group, a cyclohexylmethyl group, a cyclohexylethyl group, etc. are mentioned. Among these, from the viewpoint of solvent solubility, an isopentyl group, a cyclohexylmethyl group, a cyclopentylethyl group, or a cyclohexylethyl group is preferable, a cyclopentylethyl group or a cyclohexylethyl group is more preferable, and a cyclohexylethyl group is more preferable.
　Ｒ８における芳香族環基としては、芳香族炭化水素環基及び芳香族複素環基が挙げられる。その炭素数は通常４以上であり、６以上が好ましく、また、１２以下が好ましく、１０以下がより好ましく、８以下がさらに好ましい。芳香族環基の炭素数を前記下限値以上とすることで分子が安定となる傾向があり、また、前記上限値以下とすることで溶剤溶解性が良好となる傾向がある。 Examples of the aromatic ring group for R 8 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 6 or more, 12 or less, more preferably 10 or less, and even more preferably 8 or less. There exists a tendency for a molecule | numerator to become stable by making carbon number of an aromatic ring group more than the said lower limit, and there exists a tendency for solvent solubility to become favorable by making it into the said upper limit or less.
　芳香族炭化水素環基における芳香族炭化水素環としては、単環であっても縮合環であってもよい。芳香族炭化水素環基としては、例えば、１個の遊離原子価を有する、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環などの基が挙げられる。
　また、芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。芳香族複素環基としては、例えば、１個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。
　これらの中でも溶剤溶解性の観点から、１個の遊離原子価を有するベンゼン環又はナフタレン環が好ましく、１個の遊離原子価を有するベンゼン環がより好ましい。 The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. As the aromatic hydrocarbon ring group, for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring having one free valence, Examples include acenaphthene ring, fluoranthene ring, fluorene ring and the like.
In addition, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the aromatic heterocyclic group include one furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, and carbazole having one free valence. Ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, Examples include pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
Among these, from the viewpoint of solvent solubility, a benzene ring or naphthalene ring having one free valence is preferable, and a benzene ring having one free valence is more preferable.
　芳香族環基が有していてもよい置換基としては、炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基、炭素数１～１０のアルキルチオ基、Ｆ、Ｃｌ、Ｂｒ、Ｉなどのハロゲン原子、水酸基、ニトロ基などが挙げられ、溶剤溶解性の観点から、炭素数１～５のアルコキシ基又は水酸基が好ましい。置換基のアルキル鎖部分は、直鎖状でも分岐状でもよく、更に、炭素数１～３のアルコキシ基、炭素数１～３のアルキルチオ基、ハロゲン原子、水酸基、ニトロ基などの置換基を有していてもよい。 Examples of the substituent that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I In view of solvent solubility, an alkoxy group having 1 to 5 carbon atoms or a hydroxyl group is preferable. The alkyl chain portion of the substituent may be linear or branched, and further has a substituent such as an alkoxy group having 1 to 3 carbon atoms, an alkylthio group having 1 to 3 carbon atoms, a halogen atom, a hydroxyl group, or a nitro group. You may do it.
　これらの中でも光吸収波長の長波長化などの観点から、Ｒ８は置換基を有していてもよい芳香族環基であることが好ましく、置換基を有していてもよい芳香族炭化水素環基であることがより好ましい。 Among these, from the viewpoint of increasing the light absorption wavelength, R 8 is preferably an aromatic ring group which may have a substituent, and an aromatic hydrocarbon which may have a substituent. A cyclic group is more preferable.
（ｐ）
　前記式（ＩＩ）において、ｐは０又は１を表す。感度の観点からはｐが０であることが好ましく、一方で溶剤溶解性の観点からはｐが１であることが好ましい。 (P)
In the formula (II), p represents 0 or 1. From the viewpoint of sensitivity, p is preferably 0, while from the viewpoint of solvent solubility, p is preferably 1.
（Ｒ９）
　前記式（ＩＩ）において、Ｒ９は任意の１価の置換基を表す。
　任意の１価の置換基としては、メチル基、エチル基等の炭素数１～１０のアルキル基；メトキシ基、エトキシ基などの炭素数１～１０のアルコキシ基；Ｆ、Ｃｌ、Ｂｒ、Ｉなどのハロゲン原子；炭素数１～１０のアシル基；炭素数１～１０のアルキルエステル基；炭素数１～１０のアルコキシカルボニル基；炭素数１～１０のハロゲン化アルキル基；炭素数４～１０の芳香族環基；アミノ基；炭素数１～１０のアミノアルキル基；水酸基；ニトロ基；ＣＮ基；置換基を有していてもよいベンゾイル基；置換基を有していてもよいテノイル基等が挙げられる。ベンゾイル基、または、テノイル基が有していてもよい置換基としては、炭素数１～３のアルキル基、炭素数１～３のアルコキシ基等が挙げられ、０～３個の範囲で有してもよい。これらの中でも吸収波長の長波長化の観点から、ニトロ基、２－テノイル基が好ましく、ニトロ基がより好ましい。
　Ｒ９において、ｑが２以上の場合、複数のＲ９同士が結合して環を形成していてもよい。環は脂肪族環であっても、芳香族環であってもよい。 (R 9 )
In the formula (II), R 9 represents an arbitrary monovalent substituent.
As an arbitrary monovalent substituent, an alkyl group having 1 to 10 carbon atoms such as a methyl group or an ethyl group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group or an ethoxy group; F, Cl, Br, I or the like An acyl group having 1 to 10 carbon atoms; an alkyl ester group having 1 to 10 carbon atoms; an alkoxycarbonyl group having 1 to 10 carbon atoms; a halogenated alkyl group having 1 to 10 carbon atoms; Aromatic ring group; amino group; aminoalkyl group having 1 to 10 carbon atoms; hydroxyl group; nitro group; CN group; benzoyl group which may have a substituent; tenoyl group which may have a substituent Is mentioned. Examples of the substituent that the benzoyl group or thethenoyl group may have include an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and the like. May be. Among these, from the viewpoint of increasing the absorption wavelength, a nitro group and a 2-thenoyl group are preferable, and a nitro group is more preferable.
In R 9 , when q is 2 or more, a plurality of R 9 may be bonded to each other to form a ring. The ring may be an aliphatic ring or an aromatic ring.
（ｑ）
　前記式（ＩＩ）において、ｑは０～３の整数を表す。ラジカル生成効率の観点から、０又は１であることが好ましく、１であることがより好ましい。 (Q)
In the formula (II), q represents an integer of 0 to 3. From the viewpoint of radical generation efficiency, 0 or 1 is preferable, and 1 is more preferable.
（Ｘ）
　前記式（ＩＩ）において、Ｘは－Ｎ（Ｒ１０）－又は－Ｃ（Ｒ１１）（Ｒ１２）－を表す。これらの中でも、感度の観点からは－Ｎ（Ｒ１０）－が好ましい。 (X)
In the formula (II), X represents —N (R 10 ) — or —C (R 11 ) (R 12 ) —. Among these, —N (R 10 ) — is preferable from the viewpoint of sensitivity.
（Ｒ１０～Ｒ１２）
　前記式（ＩＩ）において、Ｒ１０～Ｒ１２は各々独立に、水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよい芳香族環基を表す。 (R 10 to R 12 )
In the formula (II), R 10 to R 12 each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
　Ｒ１０～Ｒ１２におけるアルキル基は、直鎖状でも、分岐状でも、環状でも、それらが結合したものであってもよいが、感度の観点から直鎖状又は分岐状が好ましく、直鎖状がより好ましい。
　アルキル基の炭素数は特に限定されないが、通常１以上、好ましくは２以上、より好ましくは３以上、さらに好ましくは４以上、特に好ましくは５以上、また、好ましくは１０以下、より好ましくは８以下、さらに好ましくは６以下、特に好ましくは４以下である。アルキル基の炭素数を前記下限値以上とすることで溶剤溶解性が良好となる傾向があり、前記上限値以下とすることで高感度となる傾向がある。
　アルキル基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、２－エチルヘキシル基などが挙げられる。これらの中でも、感度と溶剤溶解性のバランスの観点から、エチル基、プロピル基、イソプロピル基、又はブチル基が好ましく、エチル基又はプロピル基がより好ましく、エチル基がさらに好ましい。
　アルキル基が有していてもよい置換基としては、炭素数６～１０の芳香族環基、炭素数１～１０のアルコキシ基、炭素数１～１０のアルキルチオ基、Ｆ、Ｃｌ、Ｂｒ、Ｉなどのハロゲン原子、水酸基などが挙げられ、溶剤溶解性の観点から、炭素数１～３のアルコキシ基が好ましい。また、感度の観点からは、無置換であることが好ましい。 The alkyl group in R 10 to R 12 may be linear, branched, cyclic, or a combination thereof, but is preferably linear or branched from the viewpoint of sensitivity. Is more preferable.
The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, further preferably 4 or more, particularly preferably 5 or more, and preferably 10 or less, more preferably 8 or less. More preferably, it is 6 or less, and particularly preferably 4 or less. There exists a tendency for solvent solubility to become favorable by making carbon number of an alkyl group more than the said lower limit, and there exists a tendency for it to become high sensitivity by making it into the said upper limit or less.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, and a 2-ethylhexyl group. Etc. Among these, from the viewpoint of balance between sensitivity and solvent solubility, an ethyl group, a propyl group, an isopropyl group, or a butyl group is preferable, an ethyl group or a propyl group is more preferable, and an ethyl group is more preferable.
Examples of the substituent that the alkyl group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I In view of solvent solubility, an alkoxy group having 1 to 3 carbon atoms is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.
　Ｒ１０～Ｒ１２における芳香族環基としては、芳香族炭化水素環基及び芳香族複素環基が挙げられる。その炭素数は通常４以上であり、６以上が好ましく、また、１２以下が好ましく、１０以下がより好ましく、８以下がさらに好ましい。芳香族環基の炭素数を前記下限値以上とすることで分子が安定となる傾向があり、また、前記上限値以下とすることで溶剤溶解性が良好となる傾向がある。 Examples of the aromatic ring group in R 10 to R 12 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 6 or more, 12 or less, more preferably 10 or less, and even more preferably 8 or less. There exists a tendency for a molecule | numerator to become stable by making carbon number of an aromatic ring group more than the said lower limit, and there exists a tendency for solvent solubility to become favorable by making it into the said upper limit or less.
　芳香族炭化水素環基における芳香族炭化水素環としては、単環であっても縮合環であってもよい。芳香族炭化水素環基としては、例えば、１個の遊離原子価を有する、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環などの基が挙げられる。
　また、芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。芳香族複素環基としては、例えば、１個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。これらの中でも溶剤溶解性の観点から、１個の遊離原子価を有するベンゼン環又はナフタレン環が好ましく、１個の遊離原子価を有するベンゼン環がより好ましい。 The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. As the aromatic hydrocarbon ring group, for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring having one free valence, Examples include acenaphthene ring, fluoranthene ring, fluorene ring and the like.
In addition, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the aromatic heterocyclic group include one furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, and carbazole having one free valence. Ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, Examples include pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring. Among these, from the viewpoint of solvent solubility, a benzene ring or naphthalene ring having one free valence is preferable, and a benzene ring having one free valence is more preferable.
　芳香族環基が有していてもよい置換基としては、炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基、炭素数１～１０のアルキルチオ基、Ｆ、Ｃｌ、Ｂｒ、Ｉなどのハロゲン原子、水酸基、ニトロ基などが挙げられ、溶剤溶解性の観点から、炭素数１～３のアルコキシ基又は水酸基が好ましい。また、感度の観点からは、無置換であることが好ましい。 Examples of the substituent that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I In view of solvent solubility, an alkoxy group having 1 to 3 carbon atoms or a hydroxyl group is preferable. Further, from the viewpoint of sensitivity, it is preferably unsubstituted.
　また、Ｒ１１とＲ１２は相互に結合して環を形成していてもよく、該環は脂肪族環でもよく芳香族環でもよい。 R 11 and R 12 may be bonded to each other to form a ring, and the ring may be an aliphatic ring or an aromatic ring.
　これらの中でも感度の観点から、Ｒ１０～Ｒ１２は各々独立に、置換基を有していてもよいアルキル基であることが好ましく、無置換のアルキル基であることがより好ましく、Ｒ１０はメチル基又はエチル基であることが、Ｒ１１及びＲ１２はブチル基であることがさらに好ましい。 Among these, from the viewpoint of sensitivity, R 10 to R 12 are preferably each independently an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and R 10 is More preferably, it is a methyl group or an ethyl group, and R 11 and R 12 are more preferably a butyl group.
　また、光重合開始剤（ｃ２）の市販品としては、ＢＡＳＦ社製のＯＸＥ－０２、常州強力電子新材料社製のＴＲ－ＰＢＧ－３０４、ＴＲ－ＰＢＧ－３１４、ＴＲ－ＰＢＧ－３５８などが挙げられる。また、日本国特許第４２２３０７１号公報に記載のもの、国際公開第２０１６／０１００３６号に記載のもの、日本国特許第５６８２０９４号公報に記載のものを用いることもできる。 Commercially available photopolymerization initiators (c2) include OXE-02 manufactured by BASF, TR-PBG-304, TR-PBG-314, TR-PBG-358 manufactured by Changzhou Strong Electronic New Materials Co., Ltd. Can be mentioned. Also, those described in Japanese Patent No. 4223071, those described in International Publication No. 2016/010036, and those described in Japanese Patent No. 5682094 can also be used.
　光重合開始剤（ｃ２）の具体例としては、例えば、以下のものが挙げられる。なお、式中、ｎＢｕはノルマルブチル基を表す。 Specific examples of the photopolymerization initiator (c2) include the following. In the formula, nBu represents a normal butyl group.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　（ｃ）光重合開始剤は、前記光重合開始剤（ｃ１）及び前記光重合開始剤（ｃ２）以外の、その他の光重合開始剤をさらに含んでいてもよい。
　その他の光重合開始剤としては、例えば、日本国特開昭５９－１５２３９６号公報、日本国特開昭６１－１５１１９７号各公報に記載のチタノセン化合物を含むメタロセン化合物；日本国特開２０００－５６１１８号公報に記載のヘキサアリールビイミダゾール誘導体；日本国特開平１０－３９５０３号公報記載のハロメチル化オキサジアゾール誘導体、ハロメチル－ｓ－トリアジン誘導体、Ｎ－フェニルグリシン等のＮ－アリール－α－アミノ酸類、Ｎ－アリール－α－アミノ酸塩類、Ｎ－アリール－α－アミノ酸エステル類等のラジカル活性剤、α－アミノアルキルフェノン誘導体；日本国特開２０００－８００６８号公報、日本国特開２００６－３６７５０号公報等に記載されているオキシムエステル誘導体等が挙げられる。 (C) The photopolymerization initiator may further contain other photopolymerization initiator other than the photopolymerization initiator (c1) and the photopolymerization initiator (c2).
Examples of other photopolymerization initiators include, for example, metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; JP-A 2000-56118 N-aryl-α-amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives and N-phenylglycine described in Japanese Patent Application Laid-Open No. 10-39503 , N-aryl-α-amino acid salts, radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; Japanese Unexamined Patent Publication No. 2000-80068, Japanese Unexamined Patent Publication No. 2006-36750 The oxime ester derivative etc. which are described in the gazette etc. are mentioned.
　具体的には、例えば、チタノセン誘導体類としては、ジシクロペンタジエニルチタニウムジクロライド、ジシクロペンタジエニルチタニウムビスフェニル、ジシクロペンタジエニルチタニウムビス（２，３，４，５，６－ペンタフルオロフェニ－１－イル）、ジシクロペンタジエニルチタニウムビス（２，３，５，６－テトラフルオロフェニ－１－イル）、ジシクロペンタジエニルチタニウムビス（２，４，６－トリフルオロフェニ－１－イル）、ジシクロペンタジエニルチタニウムジ（２，６－ジフルオロフェニ－１－イル）、ジシクロペンタジエニルチタニウムジ（２，４－ジフルオロフェニ－１－イル）、ジ（メチルシクロペンタジエニル）チタニウムビス（２，３，４，５，６－ペンタフルオロフェニ－１－イル）、ジ（メチルシクロペンタジエニル）チタニウムビス（２，６－ジフルオロフェニ－１－イル）、ジシクロペンタジエニルチタニウム〔２，６－ジ－フルオロ－３－（ピロ－１－イル）－フェニ－１－イル〕等が挙げられる。 Specifically, for example, titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny) 1-yl), dicyclopentadienyltitanium di (2,6-difluorophen-1-yl), dicyclopentadienyltitanium di (2,4-difluorophen-1-yl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylsilane) Lopentadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadienyltitanium [2,6-difluoro-3- (pyro-1-yl) -phen-1-yl] and the like Can be mentioned.
　また、ビイミダゾール誘導体類としては、２－（２’－クロロフェニル）－４，５－ジフェニルイミダゾール２量体、２－（２’－クロロフェニル）－４，５－ビス（３’－メトキシフェニル）イミダゾール２量体、２－（２’－フルオロフェニル）－４，５－ジフェニルイミダゾール２量体、２－（２’－メトキシフエニル）－４，５－ジフェニルイミダゾール２量体、（４’－メトキシフエニル）－４，５－ジフェニルイミダゾール２量体等が挙げられる。 Biimidazole derivatives include 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole. Dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4′-methoxy) Phenyl) -4,5-diphenylimidazole dimer and the like.
　また、ハロメチル化オキサジアゾール誘導体類としては、２－トリクロロメチル－５－（２’－ベンゾフリル）－１，３，４－オキサジアゾール、２－トリクロロメチル－５－〔β－（２’－ベンゾフリル）ビニル〕－１，３，４－オキサジアゾール、２－トリクロロメチル－５－〔β－（２’－（６”－ベンゾフリル）ビニル）〕－１，３，４－オキサジアゾール、２－トリクロロメチル－５－フリル－１，３，４－オキサジアゾール等が挙げられる。 Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′- Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2 -Trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.
　また、ハロメチル－ｓ－トリアジン誘導体類としては、２－（４－メトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－メトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－エトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－エトキシカルボニルナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン等が挙げられる。 Examples of halomethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -S-triazine and the like.
　また、α－アミノアルキルフェノン誘導体類としては、２－メチル－１－〔４－（メチルチオ）フェニル〕－２－モルフォリノプロパン－１－オン、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）－ブタノン－１、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、４－ジメチルアミノエチルベンゾエ－ト、４－ジメチルアミノイソアミルベンゾエ－ト、４－ジエチルアミノアセトフェノン、４－ジメチルアミノプロピオフェノン、２－エチルヘキシル－１，４－ジメチルアミノベンゾエート、２，５－ビス（４－ジエチルアミノベンザル）シクロヘキサノン、７－ジエチルアミノ－３－（４－ジエチルアミノベンゾイル）クマリン、４－（ジエチルアミノ）カルコン等が挙げられる。 Further, α-aminoalkylphenone derivatives include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzo Eat, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- ( 4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. And the like.
　オキシムエステル誘導体としては、日本国特表２００４－５３４７９７号公報、日本国特開２０００－８００６８号公報、日本国特開２００６－３６７５０号公報、日本国特開２００８－１７９６１１号公報、日本国特表２０１２－５２６１８５号公報、日本国特表２０１２－５１９１９１号公報等に記載されているオキシムエステル化合物が挙げられる。中でも感度の観点から４－アセトキシイミノ－５－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－５－オキソペンタン酸メチルが、また製品名として、ＯＸＥ－０１（ＢＡＳＦ社製）、ＴＲ－ＰＢＧ－３０５（常州強力社製）、ＮＣＩ－９３０（ＡＤＥＫＡ社製）等を好ましいものとして挙げることができる。
　上記その他の光重合開始剤は１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of oxime ester derivatives include Japanese National Publication No. 2004-534797, Japanese Unexamined Patent Publication No. 2000-80068, Japanese Unexamined Patent Publication No. 2006-36750, Japanese Unexamined Patent Publication No. 2008-179611, Japanese Special Publication. Examples thereof include oxime ester compounds described in 2012-526185, Japanese Special Tables 2012-519191, and the like. Among these, from the viewpoint of sensitivity, methyl 4-acetoxyimino-5- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -5-oxopentanoate is also used as the product name OXE- Preferable examples include 01 (manufactured by BASF), TR-PBG-305 (manufactured by Changzhou Strong Company), NCI-930 (manufactured by ADEKA) and the like.
The said other photoinitiator may be used individually by 1 type, and may use 2 or more types together.
＜増感色素＞
　光重合開始剤には、必要に応じて、感応感度を高める目的で、画像露光光源の波長に応じた増感色素を併用させることができる。これら増感色素としては、日本国特開平４－２２１９５８号公報、日本国特開平４－２１９７５６号公報等に記載のキサンテン色素、日本国特開平３－２３９７０３号公報、日本国特開平５－２８９３３５号公報等に記載の複素環を有するクマリン色素、日本国特開平３－２３９７０３号公報、日本国特開平５－２８９３３５号公報等に記載の３－ケトクマリン化合物、日本国特開平６－１９２４０号公報に記載のピロメテン色素、その他、日本国特開昭４７－２５２８号公報、日本国特開昭５４－１５５２９２号公報、日本国特公昭４５－３７３７７号公報、日本国特開昭４８－８４１８３号公報、日本国特開昭５２－１１２６８１号公報、日本国特開昭５８－１５５０３号公報、日本国特開昭６０－８８００５号公報、日本国特開昭５９－５６４０３号公報、日本国特開平２－６９号公報、日本国特開昭５７－１６８０８８号公報、日本国特開平５－１０７７６１号公報、日本国特開平５－２１０２４０号公報、日本国特開平４－２８８８１８号公報等に記載のジアルキルアミノベンゼン骨格を有する色素等を挙げることができる。 <Sensitizing dye>
If necessary, the photopolymerization initiator can be used in combination with a sensitizing dye according to the wavelength of the image exposure light source for the purpose of increasing the sensitivity. Examples of these sensitizing dyes include xanthene dyes described in JP-A-4-221958, JP-A-4-219756, etc., JP-A-3-239703, JP-A-5-289335. Coumarin dyes having a heterocyclic ring described in JP-A No. 5-239335, 3-ketocoumarin compounds described in JP-A No. 3-239703, JP-A No. 5-289335, etc., JP-A No. 6-19240 In addition to the pyromethene dyes described in JP-A No. 47-2528, JP-A No. 54-155292, JP-B No. 45-37377, JP-A No. 48-84183. JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59 No. 56403, Japanese Unexamined Patent Publication No. 2-69, Japanese Unexamined Patent Publication No. 57-168088, Japanese Unexamined Patent Publication No. 5-107761, Japanese Unexamined Patent Publication No. 5-210240, Japanese Unexamined Patent Publication No. 4-4. Examples thereof include dyes having a dialkylaminobenzene skeleton described in JP-A No. 288818.
　これらの増感色素のうち好ましいものは、アミノ基含有増感色素であり、更に好ましいものは、アミノ基及びフェニル基を同一分子内に有する化合物である。特に、好ましいものは、例えば、４，４’－ジメチルアミノベンゾフェノン、４，４’－ジエチルアミノベンゾフェノン、２－アミノベンゾフェノン、４－アミノベンゾフェノン、４，４’－ジアミノベンゾフェノン、３，３’－ジアミノベンゾフェノン、３，４－ジアミノベンゾフェノン等のベンゾフェノン系化合物；２－（ｐ－ジメチルアミノフェニル）ベンゾオキサゾール、２－（ｐ－ジエチルアミノフェニル）ベンゾオキサゾール、２－（ｐ－ジメチルアミノフェニル）ベンゾ［４，５］ベンゾオキサゾール、２－（ｐ－ジメチルアミノフェニル）ベンゾ［６，７］ベンゾオキサゾール、２，５－ビス（ｐ－ジエチルアミノフェニル）１，３，４－オキサゾール、２－（ｐ－ジメチルアミノフェニル）ベンゾチアゾール、２－（ｐ－ジエチルアミノフェニル）ベンゾチアゾール、２－（ｐ－ジメチルアミノフェニル）ベンズイミダゾール、２－（ｐ－ジエチルアミノフェニル）ベンズイミダゾール、２，５－ビス（ｐ－ジエチルアミノフェニル）１，３，４－チアジアゾール、（ｐ－ジメチルアミノフェニル）ピリジン、（ｐ－ジエチルアミノフェニル）ピリジン、（ｐ－ジメチルアミノフェニル）キノリン、（ｐ－ジエチルアミノフェニル）キノリン、（ｐ－ジメチルアミノフェニル）ピリミジン、（ｐ－ジエチルアミノフェニル）ピリミジン等のｐ－ジアルキルアミノフェニル基含有化合物等である。
　このうち最も好ましいものは、４，４’－ジアルキルアミノベンゾフェノンである。
　増感色素もまた１種を単独で用いてもよく、２種以上を併用してもよい。 Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone. Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) Benzothiazole, 2- (p-diethi Ruaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, etc. And p-dialkylaminophenyl group-containing compounds.
Of these, 4,4′-dialkylaminobenzophenone is most preferred.
A sensitizing dye may also be used individually by 1 type, and may use 2 or more types together.
　（ｃ）光重合開始剤の含有割合は、本発明の感光性樹脂組成物の全固形分に対して、通常０．１質量％以上、好ましくは１質量％以上、より好ましくは２質量％以上、さらに好ましくは３質量％以上、特に好ましくは４質量％以上であり、通常３０質量％以下、好ましくは２０質量％以下、より好ましくは１５質量％以下、さらに好ましくは１０質量％以下、よりさらに好ましくは８質量％以下、特に好ましくは６質量％以下である。（ｃ）光重合開始剤の含有割合を前記下限値以上とすることで酸素阻害の影響を抑制できる傾向があり、また、前記上限値以下とすることで基板密着性が良好となる傾向がある。 (C) The content rate of a photoinitiator is 0.1 mass% or more normally with respect to the total solid of the photosensitive resin composition of this invention, Preferably it is 1 mass% or more, More preferably, it is 2 mass% or more. More preferably, it is 3% by mass or more, particularly preferably 4% by mass or more, and usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and still more. Preferably it is 8 mass% or less, Most preferably, it is 6 mass% or less. (C) By making the content rate of a photoinitiator more than the said lower limit, there exists a tendency which can suppress the influence of oxygen inhibition, and there exists a tendency for board | substrate adhesiveness to become favorable by making it the said upper limit or less. .
　（ｃ）光重合開始剤における光重合開始剤（ｃ１）の含有割合は特に限定されないが、０．１質量％以上が好ましく、１質量％以上がより好ましく、１０質量％以上がさらに好ましく、２０質量％以上がよりさらに好ましく、３０質量％以上が特に好ましく、４０質量％以上が最も好ましく、また、９９．９質量％以下が好ましく、９９質量％以下がより好ましく、９０質量％以下がさらに好ましく、６０質量％以下が最も好ましい。光重合開始剤（ｃ１）の含有割合を前記下限値以上とすることで内部硬化性が良好となる傾向があり、また、前記上限値以下とすることでパターンのトップ部分の硬化性が良好となる傾向がある。 (C) Although the content rate of the photoinitiator (c1) in a photoinitiator is not specifically limited, 0.1 mass% or more is preferable, 1 mass% or more is more preferable, 10 mass% or more is more preferable, 20 More preferably, it is more preferably 30% by weight or more, most preferably 40% by weight or more, more preferably 99.9% by weight or less, more preferably 99% by weight or less, and even more preferably 90% by weight or less. 60 mass% or less is most preferable. When the content ratio of the photopolymerization initiator (c1) is not less than the above lower limit value, the internal curability tends to be good, and when it is not more than the above upper limit value, the curability of the pattern top portion is good. Tend to be.
　（ｃ）光重合開始剤における光重合開始剤（ｃ２）の含有割合は特に限定されないが、０．１質量％以上が好ましく、１質量％以上がより好ましく、１０質量％以上がさらに好ましく、４０質量％以上が最も好ましく、また、９９．９質量％以下が好ましく、９９質量％以下がより好ましく、９０質量％以下がさらに好ましく、８０質量％以下がよりさらに好ましく、６０質量％以下が特に好ましい。光重合開始剤（ｃ２）の含有割合を前記下限値以上とすることでパターンのトップ部分の硬化性が良好となる傾向があり、また、前記上限値以下とすることで内部硬化性が良好となる傾向がある。 (C) Although the content rate of the photoinitiator (c2) in a photoinitiator is not specifically limited, 0.1 mass% or more is preferable, 1 mass% or more is more preferable, 10 mass% or more is further more preferable, 40 % By mass or more is most preferable, 99.9% by mass or less is preferable, 99% by mass or less is more preferable, 90% by mass or less is further preferable, 80% by mass or less is further more preferable, and 60% by mass or less is particularly preferable. . When the content ratio of the photopolymerization initiator (c2) is not less than the above lower limit value, the curability of the top portion of the pattern tends to be good, and when it is not more than the above upper limit value, the internal curability is good. Tend to be.
＜（ａ）アルカリ可溶性樹脂＞
　本発明の感光性樹脂組成物は（ａ）アルカリ可溶性樹脂を含む。（ａ）アルカリ可溶性樹脂は、感光性樹脂組成物を塗布、乾燥して得られる塗膜を露光後、露光部と非露光部のアルカリ現像液に対する溶解性が変化するようなものであれば特に限定されないが、水酸基、カルボキシル基、リン酸基、スルホン酸基などの酸性の官能基を有するアルカリ可溶性樹脂が好ましく、カルボキシル基を有するアルカリ可溶性樹脂がより好ましい。また、硬化性の観点からエチレン性不飽和基を有するものが好ましく、硬化性と現像性の観点からエチレン性不飽和基とカルボキシル基を有するアルカリ可溶性樹脂がより好ましい。具体的には、カルボキシル基を有するエポキシ（メタ）アクリレート樹脂やアクリル共重合樹脂が挙げられ、好ましいものとしてより具体的には、後述の（Ａ１－１）、（Ａ１－２）、（Ａ２－１）、（Ａ２－２）、（Ａ２－３）及び（Ａ２－４）として記載のものが挙げられ、これらは１種を用いても２種以上を用いてもよい。上記の中でも、カルボキシル基を有するエポキシ（メタ）アクリレート樹脂（Ａ１－１）、（Ａ１－２）が特に望ましい。 <(A) Alkali-soluble resin>
The photosensitive resin composition of this invention contains (a) alkali-soluble resin. (A) The alkali-soluble resin is particularly suitable as long as the solubility of the exposed part and the non-exposed part in the alkaline developer changes after the coating film obtained by applying and drying the photosensitive resin composition is exposed. Although not limited, the alkali-soluble resin which has acidic functional groups, such as a hydroxyl group, a carboxyl group, a phosphoric acid group, and a sulfonic acid group, is preferable, and the alkali-soluble resin which has a carboxyl group is more preferable. Moreover, what has an ethylenically unsaturated group from a sclerosing | hardenable viewpoint is preferable, and alkali-soluble resin which has an ethylenically unsaturated group and a carboxyl group from a sclerosing | hardenable and developable viewpoint is more preferable. Specific examples include an epoxy (meth) acrylate resin having a carboxyl group and an acrylic copolymer resin, and more preferable examples are (A1-1), (A1-2), (A2- Examples include 1), (A2-2), (A2-3) and (A2-4), and these may be used alone or in combination of two or more. Among the above, epoxy (meth) acrylate resins (A1-1) and (A1-2) having a carboxyl group are particularly desirable.
　カルボキシル基を有するエポキシ（メタ）アクリレート樹脂は、エポキシ樹脂とα，β－不飽和モノカルボン酸及び／又はエステル部分にカルボキシル基を有するα，β－不飽和モノカルボン酸エステルとの反応物の、反応で生成した水酸基に更に多塩基酸、及び／又はその無水物を反応させて得られる樹脂である。また、多塩基酸及び／又はその無水物を水酸基と反応させる前に、該水酸基と反応し得る置換基を２個以上有する化合物を反応させた後、多塩基酸、及び／又はその無水物を反応させて得られる樹脂も、エポキシ（メタ）アクリレート樹脂に含まれる。さらに上記反応で得られた樹脂のカルボキシル基に、更に反応し得る官能基を有する化合物を反応させて得られる樹脂も、エポキシ（メタ）アクリレート樹脂に含まれる。
　このように、エポキシ（メタ）アクリレート樹脂は化学構造上、実質的にエポキシ基を有さず、かつ「（メタ）アクリレート」に限定されるものではないが、エポキシ樹脂が原料であり、かつ、「（メタ）アクリレート」が代表例であるので慣用に従いこのように命名されている。 The epoxy (meth) acrylate resin having a carboxyl group is a reaction product of an epoxy resin and an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety. It is a resin obtained by further reacting a hydroxyl group generated by the reaction with a polybasic acid and / or an anhydride thereof. In addition, before reacting a polybasic acid and / or anhydride thereof with a hydroxyl group, after reacting a compound having two or more substituents capable of reacting with the hydroxyl group, the polybasic acid and / or anhydride thereof is reacted. Resins obtained by reaction are also included in the epoxy (meth) acrylate resin. Furthermore, a resin obtained by reacting a carboxyl group of the resin obtained by the above reaction with a compound having a functional group capable of further reaction is also included in the epoxy (meth) acrylate resin.
Thus, the epoxy (meth) acrylate resin has substantially no epoxy group in terms of chemical structure, and is not limited to “(meth) acrylate”, but the epoxy resin is a raw material, and Since “(meth) acrylate” is a representative example, it is named in this manner according to common usage.
　カルボキシル基を有するエポキシ（メタ）アクリレート樹脂としては、例えば、以下のエポキシ（メタ）アクリレート樹脂（Ａ１－１）及び／又はエポキシ（メタ）アクリレート樹脂（Ａ１－２）が挙げられる。 Examples of the epoxy (meth) acrylate resin having a carboxyl group include the following epoxy (meth) acrylate resin (A1-1) and / or epoxy (meth) acrylate resin (A1-2).
　＜エポキシ（メタ）アクリレート樹脂（Ａ１－１）＞
　エポキシ樹脂にα，β－不飽和モノカルボン酸又はカルボキシル基を有するα，β－不飽和モノカルボン酸エステルを付加させ、さらに、多塩基酸及び／又はその無水物を反応させることによって得られたアルカリ可溶性樹脂。
　＜エポキシ（メタ）アクリレート樹脂（Ａ１－２）＞
　エポキシ樹脂にα，β－不飽和モノカルボン酸又はカルボキシル基を有するα，β－不飽和モノカルボン酸エステルを付加させ、さらに、多価アルコール、及び多塩基酸及び／又はその無水物と反応させることによって得られたアルカリ可溶性樹脂。 <Epoxy (meth) acrylate resin (A1-1)>
It was obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and / or an anhydride thereof. Alkali-soluble resin.
<Epoxy (meth) acrylate resin (A1-2)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof. The alkali-soluble resin obtained by this.
＜エポキシ（メタ）アクリレート樹脂（Ａ１－１）＞
　原料となるエポキシ樹脂とは、熱硬化により樹脂を形成する以前の原料化合物をも含めて言うこととし、そのエポキシ樹脂としては、公知のエポキシ樹脂の中から適宜選択して用いることができる。また、エポキシ樹脂は、フェノール性化合物とエピハロヒドリンとを反応させて得られる化合物を用いることができる。フェノール性化合物としては、２価以上のフェノール性水酸基を有する化合物が好ましく、単量体でも重合体でもよい。
　エポキシ樹脂の種類としては、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、トリスフェノールメタン型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、ナフタレンノボラック型エポキシ樹脂、ジシクロペンタジエンとフェノールまたはクレゾールとの重付加反応物とエピハロヒドリンとの反応生成物であるエポキシ樹脂、アダマンチル基含有エポキシ樹脂、フルオレン型エポキシ樹脂等を好適に用いることができ、このように主鎖に芳香族環を有するものを好適に用いることができる。
　エポキシ樹脂の具体例としては、ビスフェノールＡ型エポキシ樹脂（例えば、三菱ケミカル社製の「ｊＥＲ（登録商標。以下同じ。）８２８」、「ｊＥＲ１００１」、「ｊＥＲ１００２」、「ｊＥＲ１００４」等）、ビスフェノールＡ型エポキシ樹脂のアルコール性水酸基とエピクロルヒドリンの反応により得られるエポキシ（例えば、日本化薬社製の「ＮＥＲ－１３０２」（エポキシ当量３２３，軟化点７６℃））、ビスフェノールＦ型樹脂（例えば、三菱ケミカル社製の「ｊＥＲ８０７」、「ＥＰ－４００１」、「ＥＰ－４００２」、「ＥＰ－４００４」等）、ビスフェノールＦ型エポキシ樹脂のアルコール性水酸基とエピクロルヒドリンの反応により得られるエポキシ樹脂（例えば、日本化薬社製の「ＮＥＲ－７４０６」（エポキシ当量３５０，軟化点６６℃））、ビスフェノールＳ型エポキシ樹脂、ビフェニルグリシジルエーテル（例えば、三菱ケミカル社製の「ＹＸ－４０００」）、フェノールノボラック型エポキシ樹脂（例えば、日本化薬社製の「ＥＰＰＮ－２０１」、三菱ケミカル社製の「ＥＰ－１５２」、「ＥＰ－１５４」、ダウケミカル社製の「ＤＥＮ－４３８」）、（ｏ，ｍ，ｐ－）クレゾールノボラック型エポキシ樹脂（例えば、日本化薬社製の「ＥＯＣＮ（登録商標。以下同じ。）－１０２Ｓ」、「ＥＯＣＮ－１０２０」、「ＥＯＣＮ－１０４Ｓ」）、トリグリシジルイソシアヌレート（例えば、日産化学社製の「ＴＥＰＩＣ（登録商標）」）、トリスフェノールメタン型エポキシ樹脂（例えば、日本化薬社製の「ＥＰＰＮ（登録商標。以下同じ。）－５０１」、「ＥＰＰＮ－５０２」、「ＥＰＰＮ－５０３」）、脂環式エポキシ樹脂（ダイセル社製の「セロキサイド（登録商標。以下同じ。）２０２１Ｐ」、「セロキサイドＥＨＰＥ」）、ジシクロペンタジエンとフェノールの反応によるフェノール樹脂をグリシジル化したエポキシ樹脂（例えば、ＤＩＣ社製の「ＥＸＡ－７２００」、日本化薬社製の「ＮＣ－７３００」）、下記一般式（ａ１）～（ａ５）で表されるエポキシ樹脂、等を好適に用いることができる。具体的には、下記一般式（ａ１）で表されるエポキシ樹脂として日本化薬社製の「ＸＤ－１０００」、下記一般式（ａ２）で表されるエポキシ樹脂として日本化薬社製の「ＮＣ－３０００」、下記一般式（ａ４）で表されるエポキシ樹脂として新日鐵住金化学社製の「ＥＳＦ－３００」等が挙げられる。 <Epoxy (meth) acrylate resin (A1-1)>
The epoxy resin used as a raw material includes a raw material compound before the resin is formed by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins. Moreover, the epoxy resin can use the compound obtained by making a phenolic compound and epihalohydrin react. The phenolic compound is preferably a compound having a dihydric or higher phenolic hydroxyl group, and may be a monomer or a polymer.
Types of epoxy resins include cresol novolac type epoxy resins, phenol novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, trisphenol methane type epoxy resins, biphenyl novolac type epoxy resins, naphthalene novolac type epoxy resins, Epoxy resins, adamantyl group-containing epoxy resins, fluorene type epoxy resins, and the like, which are reaction products of a polyaddition reaction product of dicyclopentadiene and phenol or cresol and epihalohydrin, can be suitably used. Those having an aromatic ring can be suitably used.
Specific examples of the epoxy resin include bisphenol A type epoxy resins (for example, “jER (registered trademark, the same applies hereinafter) 828”, “jER1001”, “jER1002”, “jER1004”, etc., manufactured by Mitsubishi Chemical Corporation), bisphenol A, and the like. Type epoxy resin obtained by reaction of alcoholic hydroxyl group with epichlorohydrin (for example, “NER-1302” (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resin (for example, Mitsubishi Chemical) “JER807”, “EP-4001”, “EP-4002”, “EP-4004”, etc., manufactured by the same company), epoxy resins obtained by the reaction of alcoholic hydroxyl groups of bisphenol F type epoxy resins with epichlorohydrin (eg Nippon Kayaku) “NER-7406” (epoxy 350, softening point 66 ° C.)), bisphenol S type epoxy resin, biphenyl glycidyl ether (eg “YX-4000” manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (eg “EPPN-” manufactured by Nippon Kayaku Co., Ltd.) 201 "," EP-152 "," EP-154 "manufactured by Mitsubishi Chemical Corporation," DEN-438 "manufactured by Dow Chemical Company), (o, m, p-) cresol novolac type epoxy resin "EOCN (registered trademark)-102S", "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd. ), Trisphenol methane type epoxy resin (for example, “EPPN (registered trademark)” manufactured by Nippon Kayaku Co., Ltd.-5) 1 ”,“ EPPN-502 ”,“ EPPN-503 ”), cycloaliphatic epoxy resins (“ Celoxide (registered trademark; the same applies hereinafter) 2021P ”,“ Celoxide EHPE ”manufactured by Daicel), dicyclopentadiene and phenol An epoxy resin obtained by glycidylation of a phenol resin by the reaction (for example, “EXA-7200” manufactured by DIC, “NC-7300” manufactured by Nippon Kayaku Co., Ltd.), represented by the following general formulas (a1) to (a5) An epoxy resin or the like can be preferably used. Specifically, “XD-1000” manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (a1), and “XD-1000” manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (a2) NC-3000 ”,“ ESF-300 ”manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and the like are given as epoxy resins represented by the following general formula (a4).
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　上記一般式（ａ１）において、ｂ１１は平均値を示し０～１０の数を示す。Ｒ１１は水素原子、ハロゲン原子、炭素数１～８のアルキル基、炭素数３～１０のシクロアルキル基、フェニル基、ナフチル基、又はビフェニル基を表す。なお、１分子中に存在する複数のＲ１１は互いに同一であっても異なっていてもよい。 In the general formula (a1), b11 represents an average value and represents a number from 0 to 10. R 11 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. The plurality of R 11 present in one molecule may be the being the same or different.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　上記一般式（ａ２）において、ｂ１２は平均値を示し０～１０の数を示す。Ｒ２１は水素原子、ハロゲン原子、炭素数１～８のアルキル基、炭素数３～１０のシクロアルキル基、フェニル基、ナフチル基、又はビフェニル基を表す。なお、１分子中に存在する複数のＲ２１は互いに同一であっても異なっていてもよい。 In the general formula (a2), b12 represents an average value and represents a number from 0 to 10. R 21 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. A plurality of R 21 present in one molecule may be the same as or different from each other.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　上記一般式（ａ３）において、Ｘは下記一般式（ａ３－１）又は（ａ３－２）で表される連結基を示す。但し、分子構造中に１つ以上のアダマンタン構造を含む。ｂ１３は２又は３の整数を示す。 In the general formula (a3), X represents a linking group represented by the following general formula (a3-1) or (a3-2). However, one or more adamantane structures are included in the molecular structure. b13 represents an integer of 2 or 3.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　上記一般式（ａ３－１）及び（ａ３－２）において、Ｒ３１～Ｒ３４及びＲ３５～Ｒ３７は、各々独立に、置換基を有していてもよいアダマンチル基、水素原子、置換基を有していてもよい炭素数１～１２のアルキル基、又は置換基を有していてもよいフェニル基を示す。また、式中の＊印は（ａ３）中の結合部位を表す。 In the general formulas (a3-1) and (a3-2), R 31 to R 34 and R 35 to R 37 are each independently an adamantyl group, a hydrogen atom, or a substituent which may have a substituent. And an alkyl group having 1 to 12 carbon atoms which may have a phenyl group which may have a substituent. Moreover, * mark in a formula represents the binding site in (a3).
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　上記一般式（ａ４）において、ｐ及びｑはそれぞれ独立に０～４の整数を表し、Ｒ４１及びＲ４２は各々独立に炭素数１～２０のアルキル基又はハロゲン原子を表す。Ｒ４３及びＲ４４は各々独立に炭素数１～５のアルキレン基を表す。ｘ及びｙはそれぞれ独立して０以上の整数を表す。 In the general formula (a4), p and q each independently represent an integer of 0 to 4, and R 41 and R 42 each independently represent an alkyl group having 1 to 20 carbon atoms or a halogen atom. R 43 and R 44 each independently represents an alkylene group having 1 to 5 carbon atoms. x and y each independently represents an integer of 0 or more.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　上記一般式（ａ５）において、Ｒ５１～Ｒ５４は各々独立に、水素原子、炭素数１～２０のアルキル基、炭素原子６～２０のアリール基、又は、炭素原子７～２０のアラルキル基、であり、Ｒ５５は炭素数１～２０のアルキル基、炭素数６～２０のアリール基、又は炭素数７～２０のアラルキル基であり、Ｒ５６は各々独立に炭素数１～５のアルキレン基である。ｋは１～５の整数であり、ｌは０～１３の整数であり、ｍは各々独立に０～５の整数である。
　これらの中で、一般式（ａ１）～（ａ５）のいずれかで表されるエポキシ樹脂を用いるのが好ましい。 In the general formula (a5), R 51 to R 54 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, R 55 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and each R 56 is independently an alkylene group having 1 to 5 carbon atoms. It is. k is an integer of 1 to 5, l is an integer of 0 to 13, and m is each independently an integer of 0 to 5.
Among these, it is preferable to use an epoxy resin represented by any one of the general formulas (a1) to (a5).
　α，β－不飽和モノカルボン酸又はカルボキシル基を有するα，β－不飽和モノカルボン酸エステルとしては、（メタ）アクリル酸、クロトン酸、ｏ－、ｍ－、ｐ－ビニル安息香酸、（メタ）アクリル酸のα位ハロアルキル、アルコキシル、ハロゲン、ニトロ、シアノ置換体などのモノカルボン酸、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルアジピン酸、２－（メタ）アクリロイロキシエチルフタル酸、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイロキシエチルマレイン酸、２－（メタ）アクリロイロキシプロピルコハク酸、２－（メタ）アクリロイロキシプロピルアジピン酸、２－（メタ）アクリロイロキシプロピルテトラヒドロフタル酸、２－（メタ）アクリロイロキシプロピルフタル酸、２－（メタ）アクリロイロキシプロピルマレイン酸、２－（メタ）アクリロイロキシブチルコハク酸、２－（メタ）アクリロイロキシブチルアジピン酸、２－（メタ）アクリロイロキシブチルヒドロフタル酸、２－（メタ）アクリロイロキシブチルフタル酸、２－（メタ）アクリロイロキシブチルマレイン酸、
　（メタ）アクリル酸エステルとしては、（メタ）アクリル酸にε－カプロラクトン、β－プロピオラクトン、γ－ブチロラクトン、δ－バレロラクトン等のラクトン類を付加させ末端に１個の水酸基を有する単量体や、
　或いはヒドロキシアルキル（メタ）アクリレートのような末端に１個の水酸基を有する単量体や、ペンタエリスリトールトリ（メタ）アクリレートのような末端に１個の水酸基を有する化合物に、（無水）コハク酸、（無水）フタル酸、（無水）マレイン酸などの酸（無水物）を付加させ、１個以上のエチレン不飽和基と末端に１個のカルボキシル基を有する（メタ）アクリル酸エステルなどが挙げられる。また、（メタ）アクリル酸ダイマーなども挙げられる。 Examples of the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, (meta ) Monocarboxylic acid such as α-position haloalkyl, alkoxyl, halogen, nitro, cyano substituent of acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- ( (Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- ( (Meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyl tetrahydrophthalic acid, 2- (meth) a Acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutylsuccinic acid, 2- (meth) acryloyloxybutyladipic acid, 2- (meth) acryloyl Loxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid,
The (meth) acrylic acid ester is a single monomer having one hydroxyl group at the terminal by adding a lactone such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone to (meth) acrylic acid. Body,
Alternatively, a monomer having one hydroxyl group at the end, such as hydroxyalkyl (meth) acrylate, or a compound having one hydroxyl group at the end, such as pentaerythritol tri (meth) acrylate, (succinic anhydride), (Meth) acrylic acid ester having one or more ethylenically unsaturated groups and one carboxyl group at the end by adding an acid (anhydride) such as (anhydrous) phthalic acid or (anhydrous) maleic acid . Moreover, (meth) acrylic acid dimer etc. are also mentioned.
　これらの内、感度の点から、特に好ましいものは（メタ）アクリル酸である。
　エポキシ樹脂にα，β－不飽和モノカルボン酸又はカルボキシル基を有するα，β－不飽和モノカルボン酸エステルを付加させる方法としては、公知の手法を用いることができる。例えば、エステル化触媒の存在下、５０～１５０℃の温度で、α，β－不飽和モノカルボン酸又はカルボキシル基を有するα，β－不飽和モノカルボン酸エステルとエポキシ樹脂とを反応させることができる。ここで用いるエステル化触媒としては、トリエチルアミン、トリメチルアミン、ベンジルジメチルアミン、ベンジルジエチルアミン等の三級アミン、テトラメチルアンモニウムクロライド、テトラエチルアンモニウムクロライド、ドデシルトリメチルアンモニウムクロライド等の四級アンモニウム塩等を用いることができる。 Of these, (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity.
As a method for adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, a known method can be used. For example, an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group can be reacted with an epoxy resin at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. it can. As the esterification catalyst used here, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, dodecyltrimethylammonium chloride, and the like can be used. .
　なお、エポキシ樹脂、α，β－不飽和モノカルボン酸又はカルボキシル基を有するα，β－不飽和モノカルボン酸エステル、及びエステル化触媒は、いずれも１種を単独で用いてもよく、２種以上を併用してもよい。
　α，β－不飽和モノカルボン酸又はカルボキシル基を有するα，β－不飽和モノカルボン酸エステルの使用量は、エポキシ樹脂のエポキシ基１当量に対し０．５～１．２当量の範囲が好ましく、さらに好ましくは０．７～１．１当量の範囲である。
　α，β－不飽和モノカルボン酸又はカルボキシル基を有するα，β－不飽和モノカルボン酸エステルの使用量が前記下限値以上であると不飽和基の導入量が十分となり、引き続く多塩基酸及び／又はその無水物との反応も十分となり、また、エポキシ基の残存も抑制できる傾向がある。一方、該使用量が前記上限値以下であるとα，β－不飽和モノカルボン酸又はカルボキシル基を有するα，β－不飽和モノカルボン酸エステルが未反応物として残存して硬化特性が悪化するのを抑制できる傾向がある。 The epoxy resin, α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and esterification catalyst may be used alone or in combination of two types. You may use the above together.
The amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of epoxy group of the epoxy resin. More preferably, it is in the range of 0.7 to 1.1 equivalents.
When the amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is not less than the lower limit, the amount of unsaturated group introduced is sufficient, and the subsequent polybasic acid and Also, the reaction with the anhydride thereof is sufficient, and the remaining epoxy group tends to be suppressed. On the other hand, if the amount used is less than or equal to the above upper limit value, the α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group remains as an unreacted product and the curing characteristics deteriorate. There is a tendency that can be suppressed.
　多塩基酸及び／又はその無水物としては、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ベンゾフェノンテトラカルボン酸、メチルヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸、クロレンド酸、メチルテトラヒドロフタル酸、ビフェニルテトラカルボン酸、及びこれらの無水物等から選ばれた、１種又は２種以上が挙げられる。 Polybasic acids and / or anhydrides thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methyl hexahydrophthal Examples thereof include one or more selected from acids, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.
　好ましくは、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ビフェニルテトラカルボン酸、又はこれらの無水物である。特に好ましくは、テトラヒドロフタル酸、ビフェニルテトラカルボン酸、無水テトラヒドロフタル酸、又はビフェニルテトラカルボン酸二無水物である。 Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or anhydrides thereof. Particularly preferred is tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.
　多塩基酸及び／又はその無水物の付加反応に関しても公知の手法を用いることができ、エポキシ樹脂へのα，β－不飽和モノカルボン酸又はカルボキシル基を有するα，β－不飽和モノカルボン酸エステルの付加反応と同様な条件下で、継続反応させて目的物を得ることができる。多塩基酸及び／又はその無水物成分の付加量は、生成するカルボキシル基含有エポキシ（メタ）アクリレート樹脂の酸価が１０～１５０ｍｇＫＯＨ／ｇの範囲となるような程度であることが好ましく、さらに２０～１４０ｍｇＫＯＨ／ｇの範囲となるような程度であることが好ましい。カルボキシル基含有エポキシ（メタ）アクリレート樹脂の酸価を前記下限値以上とすることでアルカリ現像性が良好となる傾向があり、前記上限値以下とすることで硬化性が良好となる傾向がある。 A known method can be used for addition reaction of polybasic acid and / or anhydride thereof, and α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid having a carboxyl group to epoxy resin. The target product can be obtained by continuing the reaction under the same conditions as in the ester addition reaction. The addition amount of the polybasic acid and / or its anhydride component is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth) acrylate resin is in the range of 10 to 150 mgKOH / g, and further 20 The degree is preferably in the range of ~ 140 mgKOH / g. There exists a tendency for alkali developability to become favorable by making the acid value of carboxyl group-containing epoxy (meth) acrylate resin more than the said lower limit, and there exists a tendency for sclerosis | hardenability to become favorable by making it below the said upper limit.
＜（Ａ１－１）樹脂の合成と（Ａ１－１）樹脂に多価アルコールを添加し分岐構造を導入した（Ａ１－２）樹脂の合成＞
　上記（Ａ１－１）樹脂の多塩基酸及び／又はその無水物の付加反応合成時に、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトールなどの多価アルコールを添加し、多分岐構造を導入したものとしてもよい。
　カルボキシル基含有エポキシ（メタ）アクリレート樹脂は、通常、エポキシ樹脂とα，β－不飽和モノカルボン酸又はカルボキシル基を有するα，β－不飽和モノカルボン酸エステルとの反応物に、多塩基酸及び／又はその無水物を混合した後、もしくは、エポキシ樹脂とα，β－不飽和モノカルボン酸又はカルボキシル基を有するα，β－不飽和モノカルボン酸エステルとの反応物に、多塩基酸及び／又はその無水物及び多価アルコールを混合した後に、加温することにより得られる。この場合、多塩基酸及び／又はその無水物と多価アルコールの混合順序に、特に制限はない。加温により、エポキシ樹脂とα，β－不飽和モノカルボン酸又はカルボキシル基を有するα，β－不飽和モノカルボン酸エステルとの反応物と多価アルコールとの混合物中に存在するいずれかの水酸基に対して多塩基酸及び／又はその無水物が付加反応する。 <Synthesis of (A1-1) Resin and (A1-1) Synthesis of (A1-2) Resin Introduced with Branched Structure by Adding Polyhydric Alcohol to Resin>
(A1-1) Polyhydric alcohol such as trimethylolpropane, pentaerythritol, dipentaerythritol, etc. was added at the time of addition reaction synthesis of polybasic acid and / or anhydride thereof of (A1-1) resin, and a multi-branched structure was introduced. Also good.
The carboxyl group-containing epoxy (meth) acrylate resin is usually a polybasic acid and a reaction product of an epoxy resin and an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group. Or after mixing the anhydride, or a reaction product of an epoxy resin with an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group, Or it is obtained by heating after mixing the anhydride and polyhydric alcohol. In this case, the mixing order of the polybasic acid and / or its anhydride and the polyhydric alcohol is not particularly limited. Any hydroxyl group present in the mixture of the reaction product of the epoxy resin with the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group and the polyhydric alcohol by heating. To the polybasic acid and / or its anhydride.
　カルボキシル基含有エポキシ（メタ）アクリレート樹脂は、１種を単独で用いても、２種以上の樹脂を混合して用いてもよい。
　多価アルコールの使用量は、増粘やゲル化を抑制しつつ効果を発現するとの観点から、エポキシ樹脂成分とα，β－不飽和モノカルボン酸又はエステル部分にカルボキシル基を有するα，β－不飽和モノカルボン酸エステル成分との反応物に対して、通常０．０１～０．５質量倍程度、好ましくは０．０２～０．２質量倍程度である。 The carboxyl group-containing epoxy (meth) acrylate resin may be used alone or as a mixture of two or more resins.
The amount of the polyhydric alcohol used is such that an epoxy resin component and an α, β-unsaturated monocarboxylic acid or ester moiety having a carboxyl group from the viewpoint of exhibiting an effect while suppressing thickening and gelation. The amount is usually about 0.01 to 0.5 mass times, preferably about 0.02 to 0.2 mass times with respect to the reaction product with the unsaturated monocarboxylic acid ester component.
　このようにして得られるエポキシ（メタ）アクリレート樹脂（Ａ１－１）、（Ａ１－２）の酸価は、通常１０ｍｇＫＯＨ／ｇ以上、好ましくは５０ｍｇＫＯＨ／ｇ以上、より好ましくは７０ｍｇＫＯＨ／ｇ以上、さらに好ましくは９０ｍｇＫＯＨ／ｇ以上であり、また好ましくは２００ｍｇＫＯＨ／ｇ以下、より好ましくは１５０ｍｇＫＯＨ／ｇ以下、さらに好ましくは１２０ｍｇＫＯＨ／ｇ以下である。前記樹脂の酸価を前記下限値以上とすることで現像性が良好となる傾向があり、前記上限値以下とすることでアルカリ耐性を良好にすることができる傾向がある。 The acid value of the epoxy (meth) acrylate resins (A1-1) and (A1-2) thus obtained is usually 10 mgKOH / g or more, preferably 50 mgKOH / g or more, more preferably 70 mgKOH / g or more, Preferably it is 90 mgKOH / g or more, Preferably it is 200 mgKOH / g or less, More preferably, it is 150 mgKOH / g or less, More preferably, it is 120 mgKOH / g or less. There exists a tendency for developability to become favorable by making the acid value of the said resin more than the said lower limit, and there exists a tendency for alkali tolerance to be made favorable by making it the said upper limit or less.
　エポキシ（メタ）アクリレート樹脂（Ａ１－１）、（Ａ１－２）のゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定によるポリスチレン換算の重量平均分子量（Ｍｗ）は、１，０００以上であることが好ましく、１，５００以上であることがより好ましい。また、２０，０００以下であることが好ましく、１５，０００以下であることがより好ましく、１０，０００以下であることがさらに好ましく、８，０００以下であることがよりさらに好ましく、６，０００以下であることが特に好ましい。重量平均分子量（Ｍｗ）を前記下限値以上とすることで感度、塗膜強度、アルカリ耐性が良好となる傾向があり、前記上限値以下とすることで現像性や再溶解性を良好なものとすることができる傾向がある。 The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the epoxy (meth) acrylate resins (A1-1) and (A1-2) is preferably 1,000 or more. , 500 or more. Further, it is preferably 20,000 or less, more preferably 15,000 or less, further preferably 10,000 or less, still more preferably 8,000 or less, and 6,000 or less. It is particularly preferred that When the weight average molecular weight (Mw) is not less than the above lower limit value, the sensitivity, the coating film strength, and the alkali resistance tend to be good, and when it is not more than the above upper limit value, the developability and resolubility are good. There is a tendency to be able to.
＜アクリル共重合樹脂（Ａ２－１）、（Ａ２－２）、（Ａ２－３）、（Ａ２－４）＞
　アクリル共重合樹脂としては、例えば、日本国特開平７－２０７２１１号公報、日本国特開平８－２５９８７６号公報、日本国特開平１０－３００９２２号公報、日本国特開平１１－１４０１４４号公報、日本国特開平１１－１７４２２４号公報、日本国特開２０００－５６１１８号公報、日本国特開２００３－２３３１７９号公報、日本国特開２００７－２７０１４７号公報などの各公報等に記載された様々な高分子化合物を使用することができるが、好ましくは、以下の（Ａ２－１）～（Ａ２－４）の樹脂等が挙げられ、中でも、（Ａ２－１）樹脂が特に好ましい。 <Acrylic copolymer resin (A2-1), (A2-2), (A2-3), (A2-4)>
Examples of the acrylic copolymer resin include, for example, Japanese Patent Application Laid-Open No. 7-207211, Japanese Patent Application Laid-Open No. 8-259876, Japanese Patent Application Laid-Open No. 10-300922, Japanese Patent Application Laid-Open No. 11-140144, Japan Various types of documents described in Japanese Patent Laid-Open Nos. 11-174224, 2000-56118, 2003-233179, 2007-270147, etc. Although molecular compounds can be used, the following resins (A2-1) to (A2-4) are preferred, among which the (A2-1) resin is particularly preferred.
　（Ａ２－１）：エポキシ基含有（メタ）アクリレートと、他のラジカル重合性単量体との共重合体に対し、当該共重合体が有するエポキシ基の少なくとも一部に不飽和一塩基酸を付加させてなる樹脂、或いは当該付加反応により生じた水酸基の少なくとも一部に多塩基酸無水物を付加させて得られる樹脂
　（Ａ２－２）：主鎖にカルボキシル基を含有する直鎖状アルカリ可溶性樹脂
　（Ａ２－３）：前記（Ａ２－２）樹脂のカルボキシル基部分に、エポキシ基含有不飽和化合物を付加させた樹脂
　（Ａ２－４）：（メタ）アクリル系樹脂 (A2-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. Resin obtained by addition, or resin obtained by adding polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction (A2-2): linear alkali-soluble containing a carboxyl group in the main chain Resin (A2-3): Resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the (A2-2) resin (A2-4): (Meth) acrylic resin
　本発明の感光性樹脂組成物は、感度の観点から、エチレン性不飽和基を含有するアルカリ可溶性樹脂として（Ａ１－１）、（Ａ１－２）、（Ａ２－１）、（Ａ２－３）の少なくとも何れかを含むのがさらに好ましい。本発明の感光性樹脂組成物は、表面硬化性の観点から、エチレン性不飽和基を含有するアルカリ可溶性樹脂としてエポキシ（メタ）アクリレート樹脂である（Ａ１－１）、（Ａ１－２）の少なくとも何れかを含むのが特に好ましい。 From the viewpoint of sensitivity, the photosensitive resin composition of the present invention is (A1-1), (A1-2), (A2-1), (A2-3) as an alkali-soluble resin containing an ethylenically unsaturated group. It is more preferable that at least one of these is included. The photosensitive resin composition of the present invention is an epoxy (meth) acrylate resin as an alkali-soluble resin containing an ethylenically unsaturated group from the viewpoint of surface curability, and is at least one of (A1-1) and (A1-2). It is particularly preferable to include any of them.
　本発明の感光性樹脂組成物は、その他のアルカリ可溶性樹脂を併用してもよい。
　その他のアルカリ可溶性樹脂に制限は無く、カラーフィルター用感光性樹脂組成物に通常使用される樹脂から選択すればよい。例えば、日本国特開２００７－２７１７２７号公報、日本国特開２００７－３１６６２０号公報、日本国特開２００７－３３４２９０号公報などに記載のアルカリ可溶性樹脂などが挙げられる。 The photosensitive resin composition of the present invention may be used in combination with other alkali-soluble resins.
There is no restriction | limiting in other alkali-soluble resin, What is necessary is just to select from resin normally used for the photosensitive resin composition for color filters. Examples thereof include alkali-soluble resins described in Japanese Patent Application Publication No. 2007-271727, Japanese Patent Application Publication No. 2007-316620, Japanese Patent Application Publication No. 2007-334290, and the like.
　（ａ）アルカリ可溶性樹脂の含有割合は、本発明の感光性樹脂組成物の全固形分に対して、通常５質量％以上、好ましくは１０質量％以上、より好ましくは１５質量％以上、さらに好ましくは２０質量％以上であり、通常９０質量％以下、好ましくは７０質量％以下、より好ましくは５０質量％以下、さらに好ましくは３０質量％以下である。（ａ）アルカリ可溶性樹脂の含有割合を前記下限値以上とすることで未露光部の現像液に対する溶解性が良好となる傾向があり、また、前記上限値以下とすることで露光部への現像液の過剰な浸透を抑制することができ、画像のシャープ製や密着性が良好となる傾向がある。
　尚、上述のように、本発明の感光性樹脂組成物は、（ａ）アルカリ可溶性樹脂として、前述の（Ａ１－１）、（Ａ１－２）、（Ａ２－１）、（Ａ２－２）、（Ａ２－３）及び（Ａ２－４）の少なくとも１種を含むのが好ましく、その他のアルカリ可溶性樹脂を含む場合、その含有割合は、（ａ）アルカリ可溶性樹脂の合計に対して、２０質量％以下、好ましくは１０質量％以下である。 (A) The content rate of alkali-soluble resin is normally 5 mass% or more with respect to the total solid of the photosensitive resin composition of this invention, Preferably it is 10 mass% or more, More preferably, it is 15 mass% or more, More preferably Is 20% by mass or more, and is usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, and further preferably 30% by mass or less. (A) By setting the content ratio of the alkali-soluble resin to be equal to or higher than the lower limit value, the solubility of the unexposed area in the developer tends to be good. Excessive penetration of the liquid can be suppressed, and the sharpness and adhesion of the image tend to be good.
As described above, the photosensitive resin composition of the present invention is (a) an alkali-soluble resin as described above (A1-1), (A1-2), (A2-1), (A2-2). , (A2-3) and (A2-4) are preferred, and when other alkali-soluble resins are contained, the content ratio is 20 masses relative to the total of (a) alkali-soluble resins. % Or less, preferably 10% by mass or less.
＜（ｂ）光重合性モノマー＞
　本発明の感光性樹脂組成物は、感度等の点から（ｂ）光重合性モノマーを含有する。
　本発明に用いられる（ｂ）光重合性モノマーとしては、分子内にエチレン性不飽和基を少なくとも１個有する化合物（以下、「エチレン性単量体」と称することがある）を挙げることができる。具体的には、例えば（メタ）アクリル酸、（メタ）アクリル酸アルキルエステル、アクリロニトリル、スチレン、及びエチレン性不飽和結合を１個有するカルボン酸と、多価又は１価アルコールのエステル等が挙げられる。 <(B) Photopolymerizable monomer>
The photosensitive resin composition of this invention contains the (b) photopolymerizable monomer from points, such as a sensitivity.
Examples of the photopolymerizable monomer (b) used in the present invention include compounds having at least one ethylenically unsaturated group in the molecule (hereinafter sometimes referred to as “ethylenic monomer”). . Specific examples include (meth) acrylic acid, (meth) acrylic acid alkyl ester, acrylonitrile, styrene, carboxylic acid having one ethylenically unsaturated bond, and ester of polyhydric or monohydric alcohol. .
　本発明においては、特に、１分子中にエチレン性不飽和基を２以上有する多官能エチレン性単量体を使用することが望ましい。多官能エチレン性単量体におけるエチレン性不飽和基の数は通常２以上、好ましくは３以上、より好ましくは４以上、さらに好ましくは５以上、特に好ましくは６以上、また通常１０以下、好ましくは８以下である。エチレン性不飽和基の数を前記下限値以上とすることで感光性樹脂組成物が高感度となる傾向があり、また、前記上限値以下とすることで重合時の硬化収縮が小さくなる傾向がある。
　多官能エチレン性単量体の例としては、例えば脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル；芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル；脂肪族ポリヒドロキシ化合物、芳香族ポリヒドロキシ化合物等の多価ヒドロキシ化合物と、不飽和カルボン酸及び多塩基性カルボン酸とのエステル化反応により得られるエステルなどが挙げられる。 In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. The number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is usually 2 or more, preferably 3 or more, more preferably 4 or more, further preferably 5 or more, particularly preferably 6 or more, and usually 10 or less, preferably 8 or less. When the number of ethylenically unsaturated groups is at least the lower limit, the photosensitive resin composition tends to be highly sensitive, and when the number is less than the upper limit, curing shrinkage during polymerization tends to be reduced. is there.
Examples of the polyfunctional ethylenic monomer include, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an aliphatic polyhydroxy compound, and an aromatic polyhydroxy compound. Examples thereof include esters obtained by an esterification reaction of a polyvalent hydroxy compound such as a hydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.
　前記脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルとしては、エチレングリコールジアクリレート、トリエチレングリコールジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールエタントリアクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、グリセロールアクリレート等の脂肪族ポリヒドロキシ化合物のアクリル酸エステル、これら例示化合物のアクリレートをメタクリレートに代えたメタクリル酸エステル、同様にイタコネートに代えたイタコン酸エステル、クロネートに代えたクロトン酸エステルもしくはマレエートに代えたマレイン酸エステル等が挙げられる。 Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. In the same way, itaconic acid ester replaced by itaconate, Maleic acid esters in which instead of the crotonic acid ester or maleate was changed to bets and the like.
　芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルとしては、ハイドロキノンジアクリレート、ハイドロキノンジメタクリレート、レゾルシンジアクリレート、レゾルシンジメタクリレート、ピロガロールトリアクリレート等の芳香族ポリヒドロキシ化合物のアクリル酸エステル及びメタクリル酸エステル等が挙げられる。
　多塩基性カルボン酸及び不飽和カルボン酸と、多価ヒドロキシ化合物のエステル化反応により得られるエステルとしては必ずしも単一物ではないが、代表的な具体例を挙げれば、アクリル酸、フタル酸、及びエチレングリコールの縮合物、アクリル酸、マレイン酸、及びジエチレングリコールの縮合物、メタクリル酸、テレフタル酸及びペンタエリスリトールの縮合物、アクリル酸、アジピン酸、ブタンジオール及びグリセリンの縮合物等が挙げられる。 Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like. Etc.
The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, but representative examples include acrylic acid, phthalic acid, and Examples include condensates of ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.
　その他、本発明に用いられる多官能エチレン性単量体の例としては、ポリイソシアネート化合物と水酸基含有（メタ）アクリル酸エステル又はポリイソシアネート化合物とポリオール及び水酸基含有（メタ）アクリル酸エステルを反応させて得られるようなウレタン（メタ）アクリレート類；多価エポキシ化合物とヒドロキシ（メタ）アクリレート又は（メタ）アクリル酸との付加反応物のようなエポキシアクリレート類；エチレンビスアクリルアミド等のアクリルアミド類；フタル酸ジアリル等のアリルエステル類；ジビニルフタレート等のビニル基含有化合物等が有用である。
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。 In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate ester are reacted. Urethane (meth) acrylates as obtained; epoxy acrylates such as addition reaction product of polyvalent epoxy compound and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate Allyl esters such as: vinyl group-containing compounds such as divinyl phthalate are useful.
These may be used alone or in combination of two or more.
　（ｂ）光重合性モノマーの含有割合は、感光性樹脂組成物の全固形分に対して、通常９０質量％以下、好ましくは７０質量％以下、より好ましくは５０質量％以下、さらに好ましくは３０質量％以下、よりさらに好ましくは２０質量％以下、特に好ましくは１０質量％以下である。光重合性モノマーの含有量が上記上限値以下であることで、露光部への現像液の浸透性が適度となり良好な画像を得ることができる傾向にある。（ｂ）光重合性モノマーの含有量の下限値は、通常１質量％以上、好ましくは５質量％以上である。上記下限値以上であることで、紫外線照射による光硬化を向上させるとともにアルカリ現像性も良好となる傾向にある。 (B) The content of the photopolymerizable monomer is usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, and still more preferably 30% with respect to the total solid content of the photosensitive resin composition. It is 20 mass% or less, More preferably, it is 20 mass% or less, Most preferably, it is 10 mass% or less. When the content of the photopolymerizable monomer is not more than the above upper limit value, the permeability of the developer into the exposed area becomes appropriate, and a good image tends to be obtained. (B) The lower limit of the content of the photopolymerizable monomer is usually 1% by mass or more, preferably 5% by mass or more. By being more than the said lower limit, it exists in the tendency for the photocuring by ultraviolet irradiation to improve, and for alkali developability to also become favorable.
　本発明の感光性樹脂組成物における（ｂ）光重合性モノマーの含有割合に対する（ａ）アルカリ可溶性樹脂の含有割合の質量比は、通常０．５以上、好ましくは１以上、より好ましくは２以上、さらに好ましくは２．５以上、また通常１５以下、好ましくは１０以下、より好ましくは８以下、さらに好ましくは５以下である。前記下限値以上とすることで、硬化時の硬化収縮が小さくなる傾向があり、また、前記上限値以下とすることで、硬化膜の硬度が高くなる傾向がある。 The mass ratio of the content ratio of the (a) alkali-soluble resin to the content ratio of the (b) photopolymerizable monomer in the photosensitive resin composition of the present invention is usually 0.5 or more, preferably 1 or more, more preferably 2 or more. More preferably, it is 2.5 or more, usually 15 or less, preferably 10 or less, more preferably 8 or less, and further preferably 5 or less. By setting it to the lower limit value or more, curing shrinkage at the time of curing tends to be small, and by setting it to the upper limit value or less, the hardness of the cured film tends to be high.
＜（ｄ）色材＞
　本発明の感光性樹脂組成物は、カラーフィルターの画素、ブラックマトリックス、着色スペーサーの形成等に用いられる場合には、色材を含有する。色材は、本発明の感光性樹脂組成物を着色するものをいう。色材としては、染料や顔料が使用できるが、耐熱性、耐光性等の点から顔料が好ましい。 <(D) Color material>
The photosensitive resin composition of the present invention contains a coloring material when used for forming a pixel of a color filter, a black matrix, a colored spacer, or the like. A coloring material means what colors the photosensitive resin composition of this invention. As the coloring material, a dye or a pigment can be used, but a pigment is preferable from the viewpoint of heat resistance, light resistance and the like.
　顔料としては青色顔料、緑色顔料、赤色顔料、黄色顔料、紫色顔料、オレンジ顔料、ブラウン顔料、黒色顔料等各種の色の顔料を使用することができる。また、その構造としてはアゾ系、フタロシアニン系、キナクリドン系、ベンズイミダゾロン系、イソインドリノン系、ジオキサジン系、インダンスレン系、ペリレン系等の有機顔料の他に種々の無機顔料等も利用可能である。 As the pigment, pigments of various colors such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments can be used. It is.
　以下に、本発明に使用できる顔料の具体例をピグメントナンバーで示す。なお、以下に挙げる「Ｃ．Ｉ．ピグメントレッド２」等の用語は、カラーインデックス（Ｃ．Ｉ．）を意味する。
　赤色顔料としては、Ｃ．Ｉ．ピグメントレッド１、２、３、４、５、６、７、８、９、１２、１４、１５、１６、１７、２１、２２、２３、３１、３２、３７、３８、４１、４７、４８、４８：１、４８：２、４８：３、４８：４、４９、４９：１、４９：２、５０：１、５２：１、５２：２、５３、５３：１、５３：２、５３：３、５７、５７：１、５７：２、５８：４、６０、６３、６３：１、６３：２、６４、６４：１、６８、６９、８１、８１：１、８１：２、８１：３、８１：４、８３、８８、９０：１、１０１、１０１：１、１０４、１０８、１０８：１、１０９、１１２、１１３、１１４、１２２、１２３、１４４、１４６、１４７、１４９、１５１、１６６、１６８、１６９、１７０、１７２、１７３、１７４、１７５、１７６、１７７、１７８、１７９、１８１、１８４、１８５、１８７、１８８、１９０、１９３、１９４、２００、２０２、２０６、２０７、２０８、２０９、２１０、２１４、２１６、２２０、２２１、２２４、２３０、２３１、２３２、２３３、２３５、２３６、２３７、２３８、２３９、２４２、２４３、２４５、２４７、２４９、２５０、２５１、２５３、２５４、２５５、２５６、２５７、２５８、２５９、２６０、２６２、２６３、２６４、２６５、２６６、２６７、２６８、２６９、２７０、２７１、２７２、２７３、２７４、２７５、２７６を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントレッド４８：１、１２２、１６８、１７７、２０２、２０６、２０７、２０９、２２４、２４２、２５４、更に好ましくはＣ．Ｉ．ピグメントレッド１７７、２０９、２２４、２５４を挙げることができる。 Hereinafter, specific examples of pigments that can be used in the present invention are shown by pigment numbers. Note that terms such as “CI Pigment Red 2” mentioned below mean a color index (CI).
Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.
　青色顔料としては、Ｃ．Ｉ．ピグメントブルー１、１：２、９、１４、１５、１５：１、１５：２、１５：３、１５：４、１５：６、１６、１７、１９、２５、２７、２８、２９、３３、３５、３６、５６、５６：１、６０、６１、６１：１、６２、６３、６６、６７、６８、７１、７２、７３、７４、７５、７６、７８、７９を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントブルー１５、１５：１、１５：２、１５：３、１５：４、１５：６、更に好ましくはＣ．Ｉ．ピグメントブルー１５：６を挙げることができる。
　緑色顔料としては、Ｃ．Ｉ．ピグメントグリーン１、２、４、７、８、１０、１３、１４、１５、１７、１８、１９、２６、３６、４５、４８、５０、５１、５４、５５、５８を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントグリーン７、３６、５８を挙げることができる。 Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6.
Examples of green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58. Of these, C.I. I. Pigment Green 7, 36, 58.
　黄色顔料としては、Ｃ．Ｉ．ピグメントイエロー１、１：１、２、３、４、５、６、９、１０、１２、１３、１４、１６、１７、２４、３１、３２、３４、３５、３５：１、３６、３６：１、３７、３７：１、４０、４１、４２、４３、４８、５３、５５、６１、６２、６２：１、６３、６５、７３、７４、７５、８１、８３、８７、９３、９４、９５、９７、１００、１０１、１０４、１０５、１０８、１０９、１１０、１１１、１１６、１１７、１１９、１２０、１２６、１２７、１２７：１、１２８、１２９、１３３、１３４、１３６、１３８、１３９、１４２、１４７、１４８、１５０、１５１、１５３、１５４、１５５、１５７、１５８、１５９、１６０、１６１、１６２、１６３、１６４、１６５、１６６、１６７、１６８、１６９、１７０、１７２、１７３、１７４、１７５、１７６、１８０、１８１、１８２、１８３、１８４、１８５、１８８、１８９、１９０、１９１、１９１：１、１９２、１９３、１９４、１９５、１９６、１９７、１９８、１９９、２００、２０２、２０３、２０４、２０５、２０６、２０７、２０８を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントイエロー８３、１１７、１２９、１３８、１３９、１５０、１５４、１５５、１８０、１８５、更に好ましくはＣ．Ｉ．ピグメントイエロー８３、１３８、１３９、１５０、１８０を挙げることができる。 ¡As yellow pigment, C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.
　オレンジ顔料としては、Ｃ．Ｉ．ピグメントオレンジ１、２、５、１３、１６、１７、１９、２０、２１、２２、２３、２４、３４、３６、３８、３９、４３、４６、４８、４９、６１、６２、６４、６５、６７、６８、６９、７０、７１、７２、７３、７４、７５、７７、７８、７９を挙げることができる。この中でも、好ましくは、Ｃ．Ｉ．ピグメントオレンジ３８、７１を挙げることができる。 】 As orange pigment, C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Of these, C.I. I. And CI pigment oranges 38 and 71.
　紫色顔料としては、Ｃ．Ｉ．ピグメントバイオレット１、１：１、２、２：２、３、３：１、３：３、５、５：１、１４、１５、１６、１９、２３、２５、２７、２９、３１、３２、３７、３９、４２、４４、４７、４９、５０を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントバイオレット１９、２３、更に好ましくはＣ．Ｉ．ピグメントバイオレット２３を挙げることができる。 As purple pigment, C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19, 23, more preferably C.I. I. And CI Pigment Violet 23.
　また、本発明の感光性樹脂組成物が、カラーフィルターの樹脂ブラックマトリックス用感光性樹脂組成物である場合、（ｄ）色材としては、黒色の色材を用いることができる。黒色色材は、黒色色材単独としてもよく、赤、緑、青等の混合としてもよい。また、これら色材は無機又は有機の顔料、染料の中から適宜選択することができる。
　黒色色材を調製するために混合使用可能な色材としては、ビクトリアピュアブルー（４２５９５）、オーラミンＯ（４１０００）、カチロンブリリアントフラビン（ベーシック１３）、ローダミン６ＧＣＰ（４５１６０）、ローダミンＢ（４５１７０）、サフラニンＯＫ７０：１００（５０２４０）、エリオグラウシンＸ（４２０８０）、Ｎｏ．１２０／リオノールイエロー（２１０９０）、リオノールイエローＧＲＯ（２１０９０）、シムラーファーストイエロー８ＧＦ（２１１０５）、ベンジジンイエロー４Ｔ－５６４Ｄ（２１０９５）、シムラーファーストレッド４０１５（１２３５５）、リオノールレッド７Ｂ４４０１（１５８５０）、ファーストゲンブルーＴＧＲ－Ｌ（７４１６０）、リオノールブルーＳＭ（２６１５０）、リオノールブルーＥＳ（ピグメントブルー１５：６）、リオノーゲンレッドＧＤ（ピグメントレッド１６８）、リオノールグリーン２ＹＳ（ピグメントグリーン３６）等が挙げられる（なお、上記の（　）内の数字は、カラーインデックス（Ｃ．Ｉ．）を意味する。）。 When the photosensitive resin composition of the present invention is a photosensitive resin composition for a resin black matrix of a color filter, a black color material can be used as the (d) color material. The black color material may be a black color material alone or a mixture of red, green, blue and the like. These color materials can be appropriately selected from inorganic or organic pigments and dyes.
Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK 70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (The numbers in parentheses above indicate the color index (CI)).
　また、更に他の混合使用可能な顔料についてＣ．Ｉ．ナンバーにて示すと、例えば、Ｃ．Ｉ．黄色顔料２０、２４、８６、９３、１０９、１１０、１１７、１２５、１３７、１３８、１４７、１４８、１５３、１５４、１６６、Ｃ．Ｉ．オレンジ顔料３６、４３、５１、５５、５９、６１、Ｃ．Ｉ．赤色顔料９、９７、１２２、１２３、１４９、１６８、１７７、１８０、１９２、２１５、２１６、２１７、２２０、２２３、２２４、２２６、２２７、２２８、２４０、Ｃ．Ｉ．バイオレット顔料１９、２３、２９、３０、３７、４０、５０、Ｃ．Ｉ．青色顔料１５、１５：１、１５：４、２２、６０、６４、Ｃ．Ｉ．緑色顔料７、Ｃ．Ｉ．ブラウン顔料２３、２５、２６等を挙げることができる。 In addition, other pigments that can be used in combination are C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.
　また、単独使用可能な黒色色材としては、カーボンブラック、アセチレンブラック、ランプブラック、ボーンブラック、黒鉛、鉄黒、アニリンブラック、シアニンブラック、チタンブラック、ペリレンブラック、ラクタムブラック等が挙げられる。
　これらの（ｄ）色材の中で黒色の色材を用いる場合には、遮光率、画像特性の観点からカーボンブラックが好ましい。カーボンブラックの例としては、以下のようなカーボンブラックが挙げられる。 Examples of the black color material that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, perylene black, and lactam black.
Among these (d) color materials, when a black color material is used, carbon black is preferable from the viewpoints of light shielding rate and image characteristics. Examples of carbon black include the following carbon black.
　三菱ケミカル社製：ＭＡ７、ＭＡ７７、ＭＡ８、ＭＡ１１、ＭＡ１００、ＭＡ１００Ｒ、ＭＡ２２０、ＭＡ２３０、ＭＡ６００、＃５、＃１０、＃２０、＃２５、＃３０、＃３２、＃３３、＃４０、＃４４、＃４５、＃４７、＃５０、＃５２、＃５５、＃６５０、＃７５０、＃８５０、＃９５０、＃９６０、＃９７０、＃９８０、＃９９０、＃１０００、＃２２００、＃２３００、＃２３５０、＃２４００、＃２６００、＃３０５０、＃３１５０、＃３２５０、＃３６００、＃３７５０、＃３９５０、＃４０００、＃４０１０、ＯＩＬ７Ｂ、ＯＩＬ９Ｂ、ＯＩＬ１１Ｂ、ＯＩＬ３０Ｂ、ＯＩＬ３１Ｂ
　デグサ社製：Ｐｒｉｎｔｅｘ（登録商標。以下同じ。）３、Ｐｒｉｎｔｅｘ３ＯＰ、Ｐｒｉｎｔｅｘ３０、Ｐｒｉｎｔｅｘ３０ＯＰ、Ｐｒｉｎｔｅｘ４０、Ｐｒｉｎｔｅｘ４５、Ｐｒｉｎｔｅｘ５５、Ｐｒｉｎｔｅｘ６０、Ｐｒｉｎｔｅｘ７５、Ｐｒｉｎｔｅｘ８０、Ｐｒｉｎｔｅｘ８５、Ｐｒｉｎｔｅｘ９０、Ｐｒｉｎｔｅｘ　Ａ、Ｐｒｉｎｔｅｘ　Ｌ、Ｐｒｉｎｔｅｘ　Ｇ、Ｐｒｉｎｔｅｘ　Ｐ、Ｐｒｉｎｔｅｘ　Ｕ、Ｐｒｉｎｔｅｘ　Ｖ、ＰｒｉｎｔｅｘＧ、ＳｐｅｃｉａｌＢｌａｃｋ５５０、ＳｐｅｃｉａｌＢｌａｃｋ３５０、ＳｐｅｃｉａｌＢｌａｃｋ２５０、ＳｐｅｃｉａｌＢｌａｃｋ１００、ＳｐｅｃｉａｌＢｌａｃｋ６、ＳｐｅｃｉａｌＢｌａｃｋ５、ＳｐｅｃｉａｌＢｌａｃｋ４、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ１、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ２、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ２Ｖ、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ１８、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ１８、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ２００、Ｃｏｌｏｒ　Ｂｌａｃｋ　Ｓ１６０、Ｃｏｌｏｒ　Ｂｌａｃｋ　Ｓ１７０
　キャボット社製：Ｍｏｎａｒｃｈ（登録商標。以下同じ。）１２０、Ｍｏｎａｒｃｈ２８０、Ｍｏｎａｒｃｈ４６０、Ｍｏｎａｒｃｈ８００、Ｍｏｎａｒｃｈ８８０、Ｍｏｎａｒｃｈ９００、Ｍｏｎａｒｃｈ１０００、Ｍｏｎａｒｃｈ１１００、Ｍｏｎａｒｃｈ１３００、Ｍｏｎａｒｃｈ１４００、Ｍｏｎａｒｃｈ４６３０、ＲＥＧＡＬ（登録商標。以下同じ。）９９、ＲＥＧＡＬ９９Ｒ、ＲＥＧＡＬ４１５、ＲＥＧＡＬ４１５Ｒ、ＲＥＧＡＬ２５０、ＲＥＧＡＬ２５０Ｒ、ＲＥＧＡＬ３３０、ＲＥＧＡＬ４００Ｒ、ＲＥＧＡＬ５５Ｒ０、ＲＥＧＡＬ６６０Ｒ、ＢＬＡＣＫ　ＰＥＡＲＬＳ４８０、ＰＥＡＲＬＳ１３０、ＶＵＬＣＡＮ（登録商標）　ＸＣ７２Ｒ、ＥＬＦＴＥＸ（登録商標）－８
　ビルラー社製：ＲＡＶＥＮ１１、ＲＡＶＥＮ１４、ＲＡＶＥＮ１５、ＲＡＶＥＮ１６、ＲＡＶＥＮ２２ＲＡＶＥＮ３０、ＲＡＶＥＮ３５、ＲＡＶＥＮ４０、ＲＡＶＥＮ４１０、ＲＡＶＥＮ４２０、ＲＡＶＥＮ４５０、ＲＡＶＥＮ５００、ＲＡＶＥＮ７８０、ＲＡＶＥＮ８５０、ＲＡＶＥＮ８９０Ｈ、ＲＡＶＥＮ１０００、ＲＡＶＥＮ１０２０、ＲＡＶＥＮ１０４０、ＲＡＶＥＮ１０６０Ｕ、ＲＡＶＥＮ１０８０Ｕ、ＲＡＶＥＮ１１７０、ＲＡＶＥＮ１１９０Ｕ、ＲＡＶＥＮ１２５０、ＲＡＶＥＮ１５００、ＲＡＶＥＮ２０００、ＲＡＶＥＮ２５００Ｕ、ＲＡＶＥＮ３５００、ＲＡＶＥＮ５０００、ＲＡＶＥＮ５２５０、ＲＡＶＥＮ５７５０、ＲＡＶＥＮ７０００ Mitsubishi Chemical Corporation: MA7, MA77, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350 , # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B
Made by Degussa: Printex (registered trademark, the same applies hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, PrintP85, PrintP85, PrintP85 U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBl4, ck FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170
Manufactured by Cabot Corporation: Monarch (registered trademark; the same shall apply hereinafter) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (99, REGAL 99) REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark) XC72R, ELFTEX (registered trademark) -8
Made by Birler: Raven11, Raven14, Raven15, Raven16, Raven22 Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven850, Raven890H, Raven1000, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10 RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000
　他の黒色顔料の例としては、チタンブラック、アニリンブラック、酸化鉄系黒色顔料、及び、赤色、緑色、青色の三色の有機顔料を混合して黒色顔料として用いることができる。　 As examples of other black pigments, titanium black, aniline black, iron oxide black pigments, and organic pigments of three colors of red, green, and blue can be mixed and used as black pigments. *
　また、顔料として、硫酸バリウム、硫酸鉛、酸化チタン、黄色鉛、ベンガラ、酸化クロム等を用いることもできる。これら各種の顔料は、複数種を併用することもできる。例えば、色度の調整のために、緑色顔料と黄色顔料とを併用したり、青色顔料と紫色顔料とを併用することができる。 Further, as the pigment, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, or the like can also be used. These various pigments can be used in combination. For example, in order to adjust chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.
　本発明に用いられる顔料の平均粒径としては、カラーフィルターの着色層とした場合に、所望の発色が可能なものであればよく、特に限定されず、用いる顔料の種類によっても異なるが、１０～１００ｎｍの範囲内であることが好ましく、１０～７０ｎｍの範囲内であることがより好ましい。該顔料の平均粒径が上記範囲であることにより、本発明の感光性樹脂組成物を用いて製造された液晶表示装置の色特性を高品質なものとすることができる傾向がある。
　また、顔料がカーボンブラックの場合の平均粒径は、６０ｎｍ以下が好ましく、５０ｎｍ以下がさらに好ましく、また、２０ｎｍ以上が好ましい。平均粒径を前記上限値以下とすることで、散乱が小さくなり、遮光性やコントラストなどの色特性の低下を抑制できる傾向がある。また、平均粒径を前記下限値以上とすることで、分散剤の量が過度に多くならずに済み、分散性が良好となる傾向がある。
　なお、上記顔料の平均粒径は、電子顕微鏡写真から一次粒子の大きさを直接計測する方法で求めることができる。具体的には、個々の一次粒子の短軸径と長軸径を計測し、その平均をその粒子の粒径とする。次に、１００個以上の粒子について、それぞれの粒子の体積（質量）を、求めた粒径の直方体と近似して求め、体積平均粒径を求めそれを平均粒径とする。なお、電子顕微鏡は透過型（ＴＥＭ）または走査型（ＳＥＭ）のいずれを用いても同じ結果を得ることができる。 The average particle diameter of the pigment used in the present invention is not particularly limited as long as it can produce a desired color when it is used as a colored layer of a color filter, and varies depending on the type of pigment used. It is preferably in the range of ˜100 nm, more preferably in the range of 10 to 70 nm. When the average particle diameter of the pigment is within the above range, the color characteristics of a liquid crystal display device produced using the photosensitive resin composition of the present invention tends to be high quality.
Further, when the pigment is carbon black, the average particle size is preferably 60 nm or less, more preferably 50 nm or less, and preferably 20 nm or more. By setting the average particle size to be equal to or smaller than the above upper limit value, scattering tends to be reduced, and a decrease in color characteristics such as light shielding properties and contrast tends to be suppressed. Further, by setting the average particle size to be equal to or greater than the lower limit, the amount of the dispersant does not need to be excessively increased, and the dispersibility tends to be good.
In addition, the average particle diameter of the pigment can be obtained by a method of directly measuring the size of primary particles from an electron micrograph. Specifically, the minor axis diameter and major axis diameter of each primary particle are measured, and the average is taken as the particle diameter of the particle. Next, for 100 or more particles, the volume (mass) of each particle is obtained by approximating a cuboid with the obtained particle size, and the volume average particle size is obtained and used as the average particle size. The same result can be obtained regardless of whether the electron microscope is a transmission type (TEM) or a scanning type (SEM).
　また、本発明の感光性樹脂組成物は、少なくとも顔料を含むことが好ましいが、その他に、本発明の効果に影響を及ぼさない範囲で染料を併用してもよい。併用できる染料としては、アゾ系染料、アントラキノン系染料、フタロシアニン系染料、キノンイミン系染料、キノリン系染料、ニトロ系染料、カルボニル系染料、メチン系染料等が挙げられる。 The photosensitive resin composition of the present invention preferably contains at least a pigment, but in addition, a dye may be used in combination as long as the effect of the present invention is not affected. Examples of dyes that can be used in combination include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
　アゾ系染料としては、例えば、Ｃ．Ｉ．アシッドイエロー１１、Ｃ．Ｉ．アシッドオレンジ７、Ｃ．Ｉ．アシッドレッド３７、Ｃ．Ｉ．アシッドレッド１８０、Ｃ．Ｉ．アシッドブルー２９、Ｃ．Ｉ．ダイレクトレッド２８、Ｃ．Ｉ．ダイレクトレッド８３、Ｃ．Ｉ．ダイレクトイエロー１２、Ｃ．Ｉ．ダイレクトオレンジ２６、Ｃ．Ｉ．ダイレクトグリーン２８、Ｃ．Ｉ．ダイレクトグリーン５９、Ｃ．Ｉ．リアクティブイエロー２、Ｃ．Ｉ．リアクティブレッド１７、Ｃ．Ｉ．リアクティブレッド１２０、Ｃ．Ｉ．リアクティブブラック５、Ｃ．Ｉ．ディスパースオレンジ５、Ｃ．Ｉ．ディスパースレッド５８、Ｃ．Ｉ．ディスパースブルー１６５、Ｃ．Ｉ．ベーシックブルー４１、Ｃ．Ｉ．ベーシックレッド１８、Ｃ．Ｉ．モルダントレッド７、Ｃ．Ｉ．モルダントイエロー５、Ｃ．Ｉ．モルダントブラック７等が挙げられる。 Examples of azo dyes include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.
　アントラキノン系染料としては、例えば、Ｃ．Ｉ．バットブルー４、Ｃ．Ｉ．アシッドブルー４０、Ｃ．Ｉ．アシッドグリーン２５、Ｃ．Ｉ．リアクティブブルー１９、Ｃ．Ｉ．リアクティブブルー４９、Ｃ．Ｉ．ディスパースレッド６０、Ｃ．Ｉ．ディスパースブルー５６、Ｃ．Ｉ．ディスパースブルー６０等が挙げられる。
　この他、フタロシアニン系染料として、例えば、Ｃ．Ｉ．パッドブルー５等が、キノンイミン系染料として、例えば、Ｃ．Ｉ．ベーシックブルー３、Ｃ．Ｉ．ベーシックブルー９等が、キノリン系染料として、例えば、Ｃ．Ｉ．ソルベントイエロー３３、Ｃ．Ｉ．アシッドイエロー３、Ｃ．Ｉ．ディスパースイエロー６４等が、ニトロ系染料として、例えば、Ｃ．Ｉ．アシッドイエロー１、Ｃ．Ｉ．アシッドオレンジ３、Ｃ．Ｉ．ディスパースイエロー４２等が挙げられる。 Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.
　（ｄ）色材の含有割合は、感光性樹脂組成物中の全固形分量に対して通常１～７０質量％の範囲で選ぶことができる。この範囲の中では、２０質量％以上がより好ましく、３０質量％以上がさらに好ましく、４０質量％以上が特に好ましく、また、６０質量％以下がより好ましい。 (D) The content ratio of the coloring material can be selected in the range of usually 1 to 70% by mass with respect to the total solid content in the photosensitive resin composition. In this range, 20 mass% or more is more preferable, 30 mass% or more is more preferable, 40 mass% or more is especially preferable, and 60 mass% or less is more preferable.
　本発明の感光性樹脂組成物は、前述したように種々な用途に使用することができるが、優れた画像形成性は、カラーフィルター用ブラックマトリックスの形成に使用した場合に、特に効果的である。ブラックマトリックス形成に使用する場合には（ｄ）色材として、前述したカーボンブラックやチタンブラック等の黒色色材を使用するか、黒色以外の色材を複数種類混合し黒色に調整して使用すればよい。その中でも分散安定性及び遮光性の観点から、カーボンブラックを使用することが、特に好ましい。 The photosensitive resin composition of the present invention can be used for various applications as described above, but excellent image forming properties are particularly effective when used for forming a black matrix for a color filter. . When using for black matrix formation, (d) Use the black color material such as carbon black or titanium black described above as the color material, or mix multiple types of color materials other than black and adjust to black. That's fine. Among these, it is particularly preferable to use carbon black from the viewpoints of dispersion stability and light shielding properties.
　本発明は特に黒色顔料の顔料濃度が大きくなる領域で効果が大きい。特に近年は遮光度を上げるために黒色顔料濃度を多くする必要がある。このように効果が大きくなる領域における黒色顔料の含有割合は感光性樹脂組成物の全固形分に対し４０質量％以上であり、４５質量％以上であることが好ましく、５０質量％以上であることがより好ましい。 The present invention is particularly effective in the region where the pigment concentration of the black pigment increases. Particularly in recent years, it is necessary to increase the black pigment concentration in order to increase the degree of light shielding. Thus, the content ratio of the black pigment in the region where the effect is large is 40% by mass or more, preferably 45% by mass or more, and preferably 50% by mass or more with respect to the total solid content of the photosensitive resin composition. Is more preferable.
　感光性樹脂組成物において、黒色顔料の含有割合が上記範囲内であることにより、遮光性（光学密度、ＯＤ値）の高い感光性樹脂組成物を得ることができる。具体的には、黒色顔料の含有量を４５質量％以上とすることにより、本発明の感光性樹脂組成物を用いて厚さ１μｍのブラックマトリックスを形成した場合における光学濃度を４．０以上の値とすることができる。光学濃度はより好ましくは４．２以上である。遮光性が高い領域では紫外線が深部に透過しにくく、光重合による架橋が特に基板と細線の密着する部分で弱くなるが、本発明の感光性樹脂組成物を用いた場合は、特にその黒色顔料の含有割合が大きい場合に、本発明の効果をよく確認できる。黒色顔料の含有割合としては４０～６５質量％が特に効果的である。黒色顔料の含有割合を前記下限値以上とすることで色濃度に対する膜厚が大きくなりすぎるのを抑制できる傾向があり、また、前記上限値以下とすることで十分な画像形成性を確保しやすい傾向がある。 In the photosensitive resin composition, when the content ratio of the black pigment is within the above range, a photosensitive resin composition having a high light shielding property (optical density, OD value) can be obtained. Specifically, by setting the black pigment content to 45% by mass or more, the optical density when the black matrix having a thickness of 1 μm is formed using the photosensitive resin composition of the present invention is 4.0 or more. Can be a value. The optical density is more preferably 4.2 or more. In the region where the light shielding property is high, ultraviolet rays are not easily transmitted to the deep part, and crosslinking due to photopolymerization is weak particularly in the part where the substrate and the fine line are in close contact, particularly when the photosensitive resin composition of the present invention is used. When the content ratio of is large, the effect of the present invention can be confirmed well. As the black pigment content, 40 to 65% by mass is particularly effective. There is a tendency that it is possible to suppress the film thickness with respect to the color density from becoming too large by setting the content ratio of the black pigment to the lower limit value or more, and it is easy to ensure sufficient image formability by setting the content ratio to the upper limit value or less. Tend.
　なお感光性樹脂組成物において、（ｄ）色材の含有割合は、（ａ）アルカリ可溶性樹脂１００質量部あたり、通常２０質量部以上、好ましくは３０質量部以上、より好ましくは４０質量部以上、さらに好ましくは６０質量部以上、よりさらに好ましくは８０質量部以上、特に好ましくは１２０質量部以上、最も好ましくは１６０質量部以上であり、また通常５００質量部以下、好ましくは３００質量部以下、より好ましくは２８０質量部以下である。（ｄ）色材の含有割合を前記下限値以上とすることで未露光部の現像液に対する溶解性の低下を抑制しやすい傾向があり、また、前記上限値以下とすることで所望の画像膜厚が得やすい傾向がある。 In the photosensitive resin composition, the content ratio of (d) the color material is usually 20 parts by mass or more, preferably 30 parts by mass or more, more preferably 40 parts by mass or more, per 100 parts by mass of the (a) alkali-soluble resin. More preferably 60 parts by mass or more, still more preferably 80 parts by mass or more, particularly preferably 120 parts by mass or more, most preferably 160 parts by mass or more, and usually 500 parts by mass or less, preferably 300 parts by mass or less, more Preferably it is 280 mass parts or less. (D) By setting the content ratio of the color material to the lower limit value or more, there is a tendency to easily suppress a decrease in solubility in the developing solution in the unexposed area. There is a tendency to easily obtain a thickness.
＜（ｅ）分散剤＞
　本発明においては、色材を微細に分散させ、且つその分散状態を安定化させることが品質の安定性確保には重要なため、（ｅ）分散剤を含むことが好ましい。
　分散剤としては、官能基を有する高分子分散剤が好ましく、更には、分散安定性の面からカルボキシル基；リン酸基；スルホン酸基；又はこれらの塩基；一級、二級又は三級アミノ基；四級アンモニウム塩基；ピリジン、ピリミジン、ピラジン等の含窒素ヘテロ環由来の基、等の官能基を有する高分子分散剤が好ましい。中でも特に、一級、二級又は三級アミノ基；四級アンモニウム塩基；ピリジン、ピリミジン、ピラジン等の含窒素ヘテロ環由来の基、等の塩基性官能基を有する高分子分散剤が特に好ましい。これら塩基性官能基を有する高分子分散剤を使用することにより、分散性を良好にでき、高い遮光性を達成できる傾向がある。 <(E) Dispersant>
In the present invention, it is important to finely disperse the color material and stabilize the dispersion state in order to ensure the stability of the quality. Therefore, it is preferable to include (e) a dispersant.
As the dispersant, a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; a primary, secondary, or tertiary amino group. A quaternary ammonium base; a polymer dispersant having a functional group such as a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine and pyrazine, is preferable. Among these, a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, pyrazine, or the like is particularly preferable. By using the polymer dispersant having these basic functional groups, there is a tendency that the dispersibility can be improved and a high light-shielding property can be achieved.
　また高分子分散剤としては、例えばウレタン系分散剤、アクリル系分散剤、ポリエチレンイミン系分散剤、ポリアリルアミン系分散剤、アミノ基を持つモノマーとマクロモノマーからなる分散剤、ポリオキシエチレンアルキルエーテル系分散剤、ポリオキシエチレンジエステル系分散剤、ポリエーテルリン酸系分散剤、ポリエステルリン酸系分散剤、ソルビタン脂肪族エステル系分散剤、脂肪族変性ポリエステル系分散剤等を挙げることができる。 Examples of polymer dispersants include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyl ethers. Examples thereof include a dispersant, a polyoxyethylene diester dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.
　このような分散剤の具体例としては、商品名で、ＥＦＫＡ（登録商標。エフカーケミカルズビーブイ（ＥＦＫＡ）社製。）、Ｄｉｓｐｅｒｂｙｋ（登録商標。ビックケミー社製。）、ディスパロン（登録商標。楠本化成社製。）、ＳＯＬＳＰＥＲＳＥ（登録商標。ルーブリゾール社製。）、ＫＰ（信越化学工業社製）、ポリフロー又はフローレン（登録商標。共栄社化学社製。）、アジスパー（登録商標。味の素ファインテクノ社製。）等を挙げることができる。
　これらの高分子分散剤は１種を単独で使用してもよく、又は２種以上を併用してもよい。 Specific examples of such a dispersant are trade names of EFKA (registered trademark, manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (registered trademark, manufactured by BYK Chemie), and Disparon (registered trademark, Enomoto Kasei). , SOLSPERSE (registered trademark, manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow or Florene (registered trademark, manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark, manufactured by Ajinomoto Fine Techno Co., Ltd.) Etc.).
These polymer dispersants may be used alone or in combination of two or more.
　これらの内、密着性及び直線性の面から、（ｅ）分散剤は塩基性官能基を有するウレタン系高分子分散剤及び／又はアクリル系高分子分散剤を含むことが、特に好ましい。特にはウレタン系高分子分散剤が密着性の面で好ましい。また分散性、保存性の面から、塩基性官能基を有し、ポリエステル及び／又はポリエーテル結合を有する高分子分散剤が好ましい。 Among these, from the viewpoint of adhesion and linearity, it is particularly preferable that the (e) dispersant contains a urethane polymer dispersant and / or an acrylic polymer dispersant having a basic functional group. In particular, a urethane-based polymer dispersant is preferable in terms of adhesion. From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and having a polyester and / or polyether bond is preferred.
　高分子分散剤の重量平均分子量（Ｍｗ）は通常７００以上、好ましくは１，０００以上であり、また通常１００，０００以下、好ましくは５０，０００以下であり、より好ましくは３０，０００以下である。重量平均分子量（Ｍｗ）を前記上限値以下とすることで、顔料濃度が高い時でもアルカリ現像性が良好となる傾向がある。
　ウレタン系及びアクリル系高分子分散剤としては、例えばＤＩＳＰＥＲＢＹＫ－１６０～１６７、１８２シリーズ（いずれもウレタン系）、ＤＩＳＰＥＲＢＹＫ－２０００，２００１等（いずれもアクリル系）（以上すべてビックケミー社製）が挙げられる。上記の塩基性官能基を有し、ポリエステル及び／又はポリエーテル結合を有するウレタン系高分子分散剤で重量平均分子量３０，０００以下の特に好ましいものとしてＤＩＳＰＥＲＢＹＫ－１６７、１８２などが挙げられる。 The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1,000 or more, and usually 100,000 or less, preferably 50,000 or less, more preferably 30,000 or less. . By setting the weight average molecular weight (Mw) to the upper limit or less, the alkali developability tends to be good even when the pigment concentration is high.
Examples of urethane-based and acrylic polymer dispersants include DISPERBYK-160 to 167, 182 series (both are urethane-based), DISPERBYK-2000, 2001, etc. (both are acrylic-based) (all manufactured by BYK Chemie). . DISPERBYK-167, 182 and the like are particularly preferable urethane polymer dispersants having a basic functional group and having a polyester and / or polyether bond and having a weight average molecular weight of 30,000 or less.
＜ウレタン系高分子分散剤＞
　ウレタン系高分子分散剤として好ましい化学構造を具体的に例示するならば、例えば、ポリイソシアネート化合物と、分子内に水酸基を１個又は２個有する数平均分子量３００～１０，０００の化合物と、同一分子内に活性水素と三級アミノ基を有する化合物とを反応させることによって得られる、重量平均分子量１，０００～２００，０００の分散樹脂等が挙げられる。 <Urethane polymer dispersant>
Specific examples of a preferable chemical structure as a urethane-based polymer dispersant include, for example, the same as a polyisocyanate compound and a compound having one or two hydroxyl groups in the molecule and a number average molecular weight of 300 to 10,000. Examples thereof include a dispersion resin having a weight average molecular weight of 1,000 to 200,000, which is obtained by reacting an active hydrogen with a compound having a tertiary amino group in the molecule.
　上記のポリイソシアネート化合物の例としては、パラフェニレンジイソシアネート、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、４，４′－ジフェニルメタンジイソシアネート、ナフタレン－１，５－ジイソシアネート、トリジンジイソシアネート等の芳香族ジイソシアネート、ヘキサメチレンジイソシアネート、リジンメチルエステルジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート、ダイマー酸ジイソシアネート等の脂肪族ジイソシアネート、イソホロンジイソシアネート、４，４′－メチレンビス（シクロヘキシルイソシアネート）、ω，ω′－ジイソシネートジメチルシクロヘキサン等の脂環族ジイソシアネート、キシリレンジイソシアネート、α，α，α′，α′－テトラメチルキシリレンジイソシアネート等の芳香環を有する脂肪族ジイソシアネート、リジンエステルトリイソシアネート、１，６，１１－ウンデカントリイソシアネート、１，８－ジイソシアネート－４－イソシアネートメチルオクタン、１，３，６－ヘキサメチレントリイソシアネート、ビシクロヘプタントリイソシアネート、トリス（イソシアネートフェニルメタン）、トリス（イソシアネートフェニル）チオホスフェート等のトリイソシアネート、及びこれらの三量体、水付加物、及びこれらのポリオール付加物等が挙げられる。ポリイソシアネートとして好ましいのは有機ジイソシアネートの三量体で、最も好ましいのはトリレンジイソシアネートの三量体とイソホロンジイソシアネートの三量体である。これらは１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the above polyisocyanate compounds include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω Alicyclic diisocyanates such as '-diisocyanate dimethylcyclohexane, xylylene diisocyanate, α, α, α', α'-tetra Aliphatic diisocyanates having an aromatic ring such as tilxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate Examples thereof include triisocyanates such as isocyanate, bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, trimers thereof, water adducts, and polyol adducts thereof. Preferred as the polyisocyanate are trimers of organic diisocyanate, and most preferred are trimerene of tolylene diisocyanate and trimer of isophorone diisocyanate. These may be used alone or in combination of two or more.
　イソシアネートの三量体の製造方法としては、前記ポリイソシアネート類を適当な三量化触媒、例えば第三級アミン類、ホスフィン類、アルコキシド類、金属酸化物、カルボン酸塩類等を用いてイソシアネート基の部分的な三量化を行い、触媒毒の添加により三量化を停止させた後、未反応のポリイソシアネートを溶剤抽出、薄膜蒸留により除去して目的のイソシアヌレート基含有ポリイソシアネートを得る方法が挙げられる。 As a method for producing an isocyanate trimer, the polyisocyanate may be converted into a part of an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.
　同一分子内に水酸基を１個又は２個有する数平均分子量３００～１０，０００の化合物としては、ポリエーテルグリコール、ポリエステルグリコール、ポリカーボネートグリコール、ポリオレフィングリコール等、及びこれらの化合物の片末端水酸基が炭素数１～２５のアルキル基でアルコキシ化されたもの及びこれら２種類以上の混合物が挙げられる。 Examples of the compound having one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 10,000 include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, and one terminal hydroxyl group of these compounds has a carbon number. Examples thereof include those alkoxylated with 1 to 25 alkyl groups and mixtures of two or more thereof.
　ポリエーテルグリコールとしては、ポリエーテルジオール、ポリエーテルエステルジオール、及びこれら２種類以上の混合物が挙げられる。ポリエーテルジオールとしては、アルキレンオキシドを単独又は共重合させて得られるもの、例えばポリエチレングリコール、ポリプロピレングリコール、ポリエチレン－プロピレングリコール、ポリオキシテトラメチレングリコール、ポリオキシヘキサメチレングリコール、ポリオキシオクタメチレングリコール及びそれらの２種以上の混合物が挙げられる。 Examples of the polyether glycol include polyether diol, polyether ester diol, and a mixture of two or more of these. Examples of polyether diols are those obtained by homopolymerizing or copolymerizing alkylene oxides such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. The mixture of 2 or more types of these is mentioned.
　ポリエーテルエステルジオールとしては、エーテル基含有ジオールもしくは他のグリコールとの混合物をジカルボン酸又はそれらの無水物と反応させるか、又はポリエステルグリコールにアルキレンオキシドを反応させることによって得られるもの、例えばポリ（ポリオキシテトラメチレン）アジペート等が挙げられる。ポリエーテルグリコールとして最も好ましいのはポリエチレングリコール、ポリプロピレングリコール、ポリオキシテトラメチレングリコール又はこれらの化合物の片末端水酸基が炭素数１～２５のアルキル基でアルコキシ化された化合物である。 Polyether ester diols include those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides or reacting polyester glycols with alkylene oxides, such as poly (poly And oxytetramethylene) adipate. Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.
　ポリエステルグリコールとしては、ジカルボン酸（コハク酸、グルタル酸、アジピン酸、セバシン酸、フマル酸、マレイン酸、フタル酸等）又はそれらの無水物とグリコール（エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、２，３－ブタンジオール、３－メチル－１，５－ペンタンジオール、ネオペンチルグリコール、２－メチル－１，３－プロパンジオール、２－メチル－２－プロピル－１，３－プロパンジオール、２－ブチル－２－エチル－１，３－プロパンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、２－メチル－２，４－ペンタンジオール、２，２，４－トリメチル－１，３－ペンタンジオール、２－エチル－１，３－ヘキサンジオール、２，５－ジメチル－２，５－ヘキサンジオール、１，８－オクタメチレングリコール、２－メチル－１，８－オクタメチレングリコール、１，９－ノナンジオール等の脂肪族グリコール、ビスヒドロキシメチルシクロヘキサン等の脂環族グリコール、キシリレングリコール、ビスヒドロキシエトキシベンゼン等の芳香族グリコール、Ｎ－メチルジエタノールアミン等のＮ－アルキルジアルカノールアミン等）とを重縮合させて得られたもの、例えばポリエチレンアジペート、ポリブチレンアジペート、ポリヘキサメチレンアジペート、ポリエチレン／プロピレンアジペート等、又は前記ジオール類又は炭素数１～２５の１価アルコールを開始剤として用いて得られるポリラクトンジオール又はポリラクトンモノオール、例えばポリカプロラクトングリコール、ポリメチルバレロラクトン及びこれらの２種以上の混合物が挙げられる。ポリエステルグリコールとして最も好ましいのはポリカプロラクトングリコール又は炭素数１～２５のアルコールを開始剤としたポリカプロラクトンである。 Polyester glycol includes dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, , 6-hexanediol, 2-methyl-2,4 Pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, Aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, N Obtained by polycondensation with N-alkyl dialkanolamine such as methyldiethanolamine), such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc., or the diols or carbon number 1-25 1 Alcohol polylactone diol obtained by using as an initiator or polylactone monool, for example polycaprolactone glycol, polymethyl valerolactone and mixtures of two or more thereof. Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone initiated with an alcohol having 1 to 25 carbon atoms.
　ポリカーボネートグリコールとしては、ポリ（１，６－ヘキシレン）カーボネート、ポリ（３－メチル－１，５－ペンチレン）カーボネート等、ポリオレフィングリコールとしてはポリブタジエングリコール、水素添加型ポリブタジエングリコール、水素添加型ポリイソプレングリコール等が挙げられる。
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。 Polycarbonate glycols include poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate, and polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, etc. Is mentioned.
These may be used alone or in combination of two or more.
　同一分子内に水酸基を１個又は２個有する化合物の数平均分子量は、通常３００～１０，０００、好ましくは５００～６，０００、更に好ましくは１，０００～４，０００である。
　本発明に用いられる同一分子内に活性水素と三級アミノ基を有する化合物を説明する。活性水素、即ち、酸素原子、窒素原子又はイオウ原子に直接結合している水素原子としては、水酸基、アミノ基、チオール基等の官能基中の水素原子が挙げられ、中でもアミノ基、特に一級のアミノ基の水素原子が好ましい。 The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, more preferably 1,000 to 4,000.
A compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described. Active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom includes a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. A hydrogen atom of an amino group is preferred.
　三級アミノ基は、特に限定されないが、例えば炭素数１～４のアルキル基を有するアミノ基、又はヘテロ環構造、より具体的にはイミダゾール環又はトリアゾール環などが挙げられる。
　このような同一分子内に活性水素と三級アミノ基を有する化合物を例示するならば、Ｎ，Ｎ－ジメチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジエチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジプロピル－１，３－プロパンジアミン、Ｎ，Ｎ－ジブチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジメチルエチレンジアミン、Ｎ，Ｎ－ジエチルエチレンジアミン、Ｎ，Ｎ－ジプロピルエチレンジアミン、Ｎ，Ｎ－ジブチルエチレンジアミン、Ｎ，Ｎ－ジメチル－１，４－ブタンジアミン、Ｎ，Ｎ－ジエチル－１，４－ブタンジアミン、Ｎ，Ｎ－ジプロピル－１，４－ブタンジアミン、Ｎ，Ｎ－ジブチル－１，４－ブタンジアミン等が挙げられる。 The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.
Examples of such compounds having active hydrogen and tertiary amino group in the same molecule are N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.
　また、三級アミノ基が含窒素ヘテロ環構造である場合の該含窒素ヘテロ環としては、ピラゾール環、イミダゾール環、トリアゾール環、テトラゾール環、インドール環、カルバゾール環、インダゾール環、ベンズイミダゾール環、ベンゾトリアゾール環、ベンゾオキサゾール環、ベンゾチアゾール環、ベンゾチアジアゾール環等の含窒素ヘテロ５員環、ピリジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、アクリジン環、イソキノリン環等の含窒素ヘテロ６員環が挙げられる。これらの含窒素ヘテロ環のうち好ましいものはイミダゾール環又はトリアゾール環である。 In addition, when the tertiary amino group has a nitrogen-containing heterocyclic structure, examples of the nitrogen-containing heterocyclic ring include pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzo Nitrogen-containing hetero 6-membered rings such as triazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, etc., pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring A ring is mentioned. Among these nitrogen-containing heterocycles, preferred are an imidazole ring or a triazole ring.
　これらのイミダゾール環とアミノ基を有する化合物を具体的に例示するならば、１－（３－アミノプロピル）イミダゾール、ヒスチジン、２－アミノイミダゾール、１－（２－アミノエチル）イミダゾール等が挙げられる。また、トリアゾール環とアミノ基を有する化合物を具体的に例示するならば、３－アミノ－１，２，４－トリアゾール、５－（２－アミノ－５－クロロフェニル）－３－フェニル－１Ｈ－１，２，４－トリアゾール、４－アミノ－４Ｈ－１，２，４－トリアゾール－３，５－ジオール、３－アミノ－５－フェニル－１Ｈ－１，３，４－トリアゾール、５－アミノ－１，４－ジフェニル－１，２，３－トリアゾール、３－アミノ－１－ベンジル－１Ｈ－２，４－トリアゾール等が挙げられる。中でも、Ｎ，Ｎ－ジメチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジエチル－１，３－プロパンジアミン、１－（３－アミノプロピル）イミダゾール、３－アミノ－１，２，４－トリアゾールが好ましい。 Specific examples of these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. Further, specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among these, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, and 3-amino-1,2,4-triazole preferable.
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。
　ウレタン系高分子分散剤を製造する際の原料の好ましい配合比率はポリイソシアネート化合物１００質量部に対し、同一分子内に水酸基を１個又は２個有する数平均分子量３００～１０，０００の化合物が１０～２００質量部、好ましくは２０～１９０質量部、更に好ましくは３０～１８０質量部、同一分子内に活性水素と三級アミノ基を有する化合物が０．２～２５質量部、好ましくは０．３～２４質量部である。 These may be used alone or in combination of two or more.
The preferred blending ratio of the raw materials for producing the urethane polymer dispersant is 10 compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by mass of the polyisocyanate compound. To 200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and 0.2 to 25 parts by mass of the compound having an active hydrogen and a tertiary amino group in the same molecule, preferably 0.3 ~ 24 parts by mass.
　ウレタン系高分子分散剤の製造はポリウレタン樹脂製造の公知の方法に従って行われる。製造する際の溶媒としては、通常、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノン、イソホロン等のケトン類、酢酸エチル、酢酸ブチル、酢酸セロソルブ等のエステル類、ベンゼン、トルエン、キシレン、ヘキサン等の炭化水素類、ダイアセトンアルコール、イソプロパノール、第二ブタノール、第三ブタノール等一部のアルコール類、塩化メチレン、クロロホルム等の塩化物、テトラヒドロフラン、ジエチルエーテル等のエーテル類、ジメチルホルムアミド、Ｎ－メチルピロリドン、ジメチルスルホキサイド等の非プロトン性極性溶媒等が用いられる。これらは１種を単独で用いてもよく、２種以上を併用してもよい。 The production of the urethane-based polymer dispersant is performed according to a known method for producing a polyurethane resin. As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used. These may be used alone or in combination of two or more.
　上記製造に際して、通常、ウレタン化反応触媒が用いられる。この触媒としては、例えば、ジブチルチンジラウレート、ジオクチルチンジラウレート、ジブチルチンジオクトエート、スタナスオクトエート等の錫系、鉄アセチルアセトナート、塩化第二鉄等の鉄系、トリエチルアミン、トリエチレンジアミン等の三級アミン系等の１種又は２種以上が挙げられる。 In the above production, a urethanization reaction catalyst is usually used. Examples of the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and stannous octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. 1 type, or 2 or more types, such as a secondary amine type | system | group, are mentioned.
＜アミン価の測定方法＞
　分散剤の三級アミン価は、分散剤試料中の溶剤を除いた固形分１ｇあたりの塩基量と当量のＫＯＨの質量で表し、次の方法により測定することができる。
　１００ｍＬのビーカーに分散剤試料の０．５～１．５ｇを精秤し、５０ｍＬの酢酸で溶解する。ｐＨ電極を備えた自動滴定装置を使って、この溶液を０．１ｍｏｌ／ＬのＨＣｌＯ４（過塩素酸）酢酸溶液にて中和滴定する。滴定ｐＨ曲線の変曲点を滴定終点とし次式によりアミン価を求める。 <Method of measuring amine value>
The tertiary amine value of the dispersant is represented by the mass of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and can be measured by the following method.
Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized and titrated with 0.1 mol / L HClO 4 (perchloric acid) acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.
　アミン価［ｍｇＫＯＨ／ｇ］＝（５６１×Ｖ）／（Ｗ×Ｓ）
〔但し、Ｗ：分散剤試料秤取量［ｇ］、Ｖ：滴定終点での滴定量［ｍＬ］、Ｓ：分散剤試料の固形分濃度［質量％］を表す。〕
　同一分子内に活性水素と三級アミノ基を有する化合物の導入量は反応後のアミン価で１～１００ｍｇＫＯＨ／ｇの範囲に制御するのが好ましい。より好ましくは５～９５ｍｇＫＯＨ／ｇの範囲である。アミン価は、塩基性アミノ基を酸により中和滴定し、酸価に対応させてＫＯＨのｍｇ数で表した値である。アミン価を前記下限値以上とすることで分散能力が良好となる傾向があり、また、前記上限値以下とすることで現像性が良好となる傾向がある。 Amine value [mgKOH / g] = (561 × V) / (W × S)
[However, W: Weighing amount of dispersant sample [g], V: Titration amount at the end of titration [mL], S: Solid content concentration [mass%] of the dispersant sample. ]
The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g in terms of amine value after reaction. More preferably, it is in the range of 5 to 95 mgKOH / g. The amine value is a value obtained by neutralizing and titrating a basic amino group with an acid, and representing the acid value in mg of KOH. When the amine value is not less than the lower limit value, the dispersibility tends to be good, and when the amine value is not more than the upper limit value, the developability tends to be good.
　なお、以上の反応で高分子分散剤にイソシアネート基が残存する場合には更に、アルコールやアミノ化合物でイソシアネート基を潰すと生成物の経時安定性が高くなるので好ましい。
　ウレタン系高分子分散剤の重量平均分子量（Ｍｗ）は通常１，０００～２００，０００、好ましくは２，０００～１００，０００、より好ましくは３，０００～５０，０００の範囲である。ウレタン系高分子分散剤の重量平均分子量（Ｍｗ）は、特に３０，０００以下が好ましい。重量平均分子量（Ｍｗ）を前記下限値以上とすることで分散性及び分散安定性が良好となる傾向があり、前記上限値以下とすることで溶解性が良好となり、分散性も良好となる傾向がある。分子量が３０，０００以下であると、特に顔料濃度の高い場合でも、アルカリ現像性が良好となる傾向がある。このような特に好ましい市販のウレタン分散剤の例としてＤＩＳＰＥＲＢＹＫ－１６７、１８２（ビックケミー社）などが挙げられる。 In addition, when an isocyanate group remains in the polymer dispersant by the above reaction, it is preferable to further crush the isocyanate group with an alcohol or an amino compound because the stability of the product with time is increased.
The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. The weight average molecular weight (Mw) of the urethane polymer dispersant is particularly preferably 30,000 or less. When the weight average molecular weight (Mw) is at least the lower limit, the dispersibility and dispersion stability tend to be good. There is. When the molecular weight is 30,000 or less, alkali developability tends to be good even when the pigment concentration is particularly high. Examples of such a particularly preferred commercially available urethane dispersant include DISPERBYK-167 and 182 (Bic Chemie).
　（ｅ）分散剤の含有割合は、感光性樹脂組成物の全固形分中、通常５０質量％以下、好ましくは３０質量％以下、より好ましくは２０質量％以下、さらに好ましくは１５質量％以下、特に好ましくは１０質量％以下であり、通常１質量％以上、好ましくは３質量％以上、より好ましくは５質量％以上、さらに好ましくは７質量％以上である。また、分散剤の含有割合は、（ｄ）色材１００質量部に対して、通常５質量部以上であり、１０質量部以上が好ましく、通常２００質量部以下であり、８０質量部以下が好ましく、５０質量部以下がより好ましく、３０質量部以下がさらに好ましく、２０質量部以下が特に好ましい。分散剤の含有割合を前記下限値以上とすることで十分な分散性を確保しやすい傾向があり、また、前記上限値以下とすることで他の成分の割合を減らすことなく、色濃度、感度、成膜性などを十分なものとしやすい傾向がある。 (E) The content of the dispersant is usually 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less in the total solid content of the photosensitive resin composition. Especially preferably, it is 10 mass% or less, Usually 1 mass% or more, Preferably it is 3 mass% or more, More preferably, it is 5 mass% or more, More preferably, it is 7 mass% or more. The content of the dispersant is usually 5 parts by mass or more, preferably 10 parts by mass or more, and usually 200 parts by mass or less, preferably 80 parts by mass or less, with respect to 100 parts by mass of the colorant (d). 50 parts by mass or less is more preferable, 30 parts by mass or less is more preferable, and 20 parts by mass or less is particularly preferable. There is a tendency to ensure sufficient dispersibility by setting the content ratio of the dispersant to the above lower limit value or more, and by reducing it to the upper limit value or less, the color density and sensitivity are reduced without reducing the ratio of other components. There is a tendency that the film-forming property tends to be sufficient.
　特に、分散剤としては、高分子分散剤と顔料誘導体（分散助剤）とを併用することが好ましいが、この場合、顔料誘導体の含有割合は本発明の感光性樹脂組成物の全固形分に対して、通常０．１質量％以上、好ましくは０．５質量％以上、通常１０質量％以下、好ましくは５質量％以下、より好ましくは２質量％以下である。 In particular, as the dispersant, it is preferable to use a polymer dispersant and a pigment derivative (dispersion aid) in combination. In this case, the content ratio of the pigment derivative is the total solid content of the photosensitive resin composition of the present invention. On the other hand, it is usually 0.1% by mass or more, preferably 0.5% by mass or more, usually 10% by mass or less, preferably 5% by mass or less, more preferably 2% by mass or less.
＜チオール類＞
　本発明の感光性樹脂組成物は、高感度化、基板への密着性の向上のため、チオール類を含有することが好ましい。チオール類の種類としては、ヘキサンジチオール、デカンジチオール、１，４－ジメチルメルカプトベンゼン、ブタンジオールビスチオプロピオネート、ブタンジオールビスチオグリコレート、エチレングリコールビスチオグリコレート、トリメチロールプロパントリスチオグリコレート、ブタンジオールビスチオプロピオネート、トリメチロールプロパントリスチオプロピオネート、トリメチロールプロパントリスチオグリコレート、ペンタエリスリトールテトラキスチオプロピオネート、ペンタエリスリトールテトラキスチオグリコレート、トリスヒドロキシエチルトリスチオプロピオネート、エチレングリコールビス（３－メルカプトブチレート）、プロピレングリコールビス（３－メルカプトブチレート）；（略してＰＧＭＢ）、ブタンジオールビス（３－メルカプトブチレート）、１，４－ビス（３－メルカプトブチリルオキシ）ブタン；（商品名；カレンズＭＴ　ＢＤ１、昭和電工（株）製）、ブタンジオールトリメチロールプロパントリス（３－メルカプトブチレート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）；（商品名；カレンズＭＴ　ＰＥ１、昭和電工（株）製）、ペンタエリスリトールトリス（３－メルカプトブチレート）、エチレングリコールビス（３－メルカプトイソブチレート）、ブタンジオールビス（３－メルカプトイソブチレート）、トリメチロールプロパントリス（３－メルカプトイソブチレート）、トリメチロールプロパントリス（３－メルカプトブチレート）；（略してＴＰＭＢ）、トリメチロールプロパントリス（２－メルカプトイソブチレート）；（略してＴＰＭＩＢ）、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン；（商品名；カレンズＭＴ　ＮＲ１、昭和電工（株）製）等が挙げられ、これらは種々のものが１種を単独で、或いは２種以上を混合して使用できる。好ましくは上記、ＰＧＭＢ、ＴＰＭＢ、ＴＰＭＩＢ、カレンズＭＴ　ＢＤ１、カレンズＭＴ　ＰＥ１、カレンズＭＴ　ＮＲ１などの多官能チオールが好ましく、その中でもカレンズＭＴ　ＢＤ１、カレンズＭＴ　ＰＥ１、カレンズＭＴ　ＮＲ１がさらに好ましく、カレンズＭＴ　ＰＥ１が特に好ましい。 <Thiols>
The photosensitive resin composition of the present invention preferably contains a thiol for increasing sensitivity and improving adhesion to the substrate. Types of thiols include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate , Butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, Ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate); (PGMB for short), Diol (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane; (trade name; Karenz MT BD1, manufactured by Showa Denko KK), butanediol trimethylolpropane tris (3-mercapto) (Butyrate), pentaerythritol tetrakis (3-mercaptobutyrate); (trade name; Karenz MT PE1, manufactured by Showa Denko KK), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoiso) (Butyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptobutyrate); (TPMB for short), trimethylolpropane Tris (2 -Mercaptoisobutyrate); (TPMIB for short), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H)- (Trade name; Karenz MT NR1, manufactured by Showa Denko K.K.) and the like, and various of these may be used alone or in combination of two or more. Preferred are polyfunctional thiols such as PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1, Karenz MT NR1, among which Karenz MT BD1, Karenz MT PE1 and Karenz MT NR1 are more preferable, and Karenz MT PE1 is Particularly preferred.
　チオール化合物を用いる場合、チオール化合物の含有割合は、本発明の感光性樹脂組成物の全固形分に対して、通常０．１質量％以上、好ましくは０．３質量％以上、更に好ましくは０．５質量％以上であり、通常１０質量％以下、好ましくは５質量％以下である。チオール化合物の含有割合を前記下限値以上とすることで感度低下を抑制できる傾向があり、前記上限値以下とすることで保存安定性を良好なものとしやすい傾向がある。 When using a thiol compound, the content ratio of the thiol compound is usually 0.1% by mass or more, preferably 0.3% by mass or more, and more preferably 0% with respect to the total solid content of the photosensitive resin composition of the present invention. 0.5 mass% or more, usually 10 mass% or less, preferably 5 mass% or less. There exists a tendency which can suppress a sensitivity fall by making the content rate of a thiol compound more than the said lower limit, and there exists a tendency which is easy to make a storage stability favorable by making it the said upper limit or less.
＜溶剤＞
　本発明の感光性樹脂組成物は、通常、（ａ）アルカリ可溶性樹脂、（ｂ）光重合性モノマー、（ｃ）光重合開始剤、（ｄ）色材及び必要に応じて使用される各種材料が、有機溶剤に溶解又は分散した状態で使用される。
　有機溶剤としては、沸点（圧力１０１３．２５［ｈＰａ］条件下。以下、沸点に関しては全て同様。）が１００～３００℃の範囲のものを選択するのが好ましい。より好ましくは１２０～２８０℃の沸点をもつ溶剤である。
　このような有機溶剤としては、例えば、次のようなものが挙げられる。 <Solvent>
The photosensitive resin composition of the present invention usually comprises (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, (d) a coloring material, and various materials used as necessary. Is used in a state dissolved or dispersed in an organic solvent.
As the organic solvent, it is preferable to select an organic solvent having a boiling point (under a pressure of 101.25 [hPa], hereinafter the same for the boiling point) in the range of 100 to 300 ° C. A solvent having a boiling point of 120 to 280 ° C. is more preferable.
Examples of such organic solvents include the following.
　エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ－ｎ－ブチルエーテル、プロピレングリコール－ｔ－ブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ－ｎ－ブチルエーテル、メトキシメチルペンタノール、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、３－メチル－３－メトキシブタノール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリプロピレングリコールメチルエーテルのようなグリコールモノアルキルエーテル類； Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol mono Chirueteru, glycol monoalkyl ethers such as tripropylene glycol methyl ether;
　エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル、ジプロピレングリコールジメチルエーテルのようなグリコールジアルキルエーテル類；
　エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノ－ｎ－ブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、メトキシブチルアセテート、３－メトキシブチルアセテート、メトキシペンチルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノ－ｎ－ブチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノエチルエーテルアセテート、３－メチル－３－メトキシブチルアセテートのようなグリコールアルキルエーテルアセテート類； Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, glycol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
　エチレングリコールジアセテート、１，３－ブチレングリコールジアセテート、１，６－ヘキサノールジアセテートなどのグリコールジアセテート類；
　シクロヘキサノールアセテートなどのアルキルアセテート類；
　アミルエーテル、ジエチルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、ジブチルエーテル、ジアミルエーテル、エチルイソブチルエーテル、ジヘキシルエーテルのようなエーテル類；
　アセトン、メチルエチルケトン、メチルアミルケトン、メチルイソプロピルケトン、メチルイソアミルケトン、ジイソプロピルケトン、ジイソブチルケトン、メチルイソブチルケトン、シクロヘキサノン、エチルアミルケトン、メチルブチルケトン、メチルヘキシルケトン、メチルノニルケトン、メトキシメチルペンタノンのようなケトン類；
　エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、エチレングリコール、プロピレングリコール、ブタンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、メトキシメチルペンタノール、グリセリン、ベンジルアルコールのような１価又は多価アルコール類；
　ｎ－ペンタン、ｎ－オクタン、ジイソブチレン、ｎ－ヘキサン、ヘキセン、イソプレン、ジペンテン、ドデカンのような脂肪族炭化水素類；
　シクロヘキサン、メチルシクロヘキサン、メチルシクロヘキセン、ビシクロヘキシルのような脂環式炭化水素類； Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
　ベンゼン、トルエン、キシレン、クメンのような芳香族炭化水素類；
　アミルホルメート、エチルホルメート、酢酸エチル、酢酸ブチル、酢酸プロピル、酢酸アミル、メチルイソブチレート、エチレングリコールアセテート、エチルプロピオネート、プロピルプロピオネート、酪酸ブチル、酪酸イソブチル、イソ酪酸メチル、エチルカプリレート、ブチルステアレート、エチルベンゾエート、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－メトキシプロピオン酸プロピル、３－メトキシプロピオン酸ブチル、γ－ブチロラクトンのような鎖状又は環状エステル類；
　３－メトキシプロピオン酸、３－エトキシプロピオン酸のようなアルコキシカルボン酸類； Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
　ブチルクロライド、アミルクロライドのようなハロゲン化炭化水素類；
　メトキシメチルペンタノンのようなエーテルケトン類；
　アセトニトリル、ベンゾニトリルのようなニトリル類等。
　上記に該当する市販の溶剤としては、ミネラルスピリット、バルソル＃２、アプコ＃１８ソルベント、アプコシンナー、ソーカルソルベントＮｏ．１及びＮｏ．２、ソルベッソ＃１５０、シェルＴＳ２８　ソルベント、カルビトール、エチルカルビトール、ブチルカルビトール、メチルセロソルブ（「セロソルブ」は登録商標。以下同じ。）、エチルセロソルブ、エチルセロソルブアセテート、メチルセロソルブアセテート、ジグライム（いずれも商品名）などが挙げられる。 Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile.
Commercially available solvents corresponding to the above include mineral spirits, Barsol # 2, Apco # 18 solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve (“Cerosolve” is a registered trademark, the same applies hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (any Product name).
　これらの有機溶剤は、単独で用いてもよく、２種以上を併用してもよい。
　フォトリソグラフィー法にてカラーフィルターの画素又はブラックマトリックスを形成する場合、有機溶剤としては沸点が１００～２５０℃の範囲のものを選択するのが好ましい。より好ましくは１２０～２３０℃の沸点を持つものである。
　上記有機溶剤のうち、塗布性、表面張力などのバランスが良く、組成物中の構成成分の溶解度が比較的高い点からは、グリコールアルキルエーテルアセテート類が好ましい。 These organic solvents may be used alone or in combination of two or more.
When forming a pixel or black matrix of a color filter by photolithography, it is preferable to select an organic solvent having a boiling point in the range of 100 to 250 ° C. More preferably, it has a boiling point of 120 to 230 ° C.
Of the above organic solvents, glycol alkyl ether acetates are preferred from the viewpoints of good balance of coatability, surface tension and the like, and relatively high solubility of the constituent components in the composition.
　また、グリコールアルキルエーテルアセテート類は、単独で使用してもよいが、他の有機溶剤を併用してもよい。併用してもよい他の有機溶剤として、特に好ましいのはグリコールモノアルキルエーテル類である。中でも、特に組成物中の構成成分の溶解性からプロピレングリコールモノメチルエーテルが好ましい。なお、グリコールモノアルキルエーテル類は極性が高く、添加量が多すぎると顔料が凝集しやすく、後に得られる感光性樹脂組成物の粘度が上がっていくなどの保存安定性が低下する傾向があるので、溶剤中のグリコールモノアルキルエーテル類の割合は５質量％～３０質量％が好ましく、５質量％～２０質量％がより好ましい。 In addition, glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As other organic solvents that may be used in combination, glycol monoalkyl ethers are particularly preferred. Of these, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition. Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment tends to aggregate, and the storage stability tends to decrease such as the viscosity of the photosensitive resin composition obtained later increases. The proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.
　また、２００℃以上の沸点をもつ有機溶剤（以下「高沸点溶剤」と称す場合がある。）を併用することも好ましい。このような高沸点溶剤を併用することにより、感光性樹脂組成物は乾きにくくなるが、組成物中における顔料の均一な分散状態が、急激な乾燥により破壊されることを防止する効果がある。すなわち、例えばスリットノズル先端における、色材などの析出・固化による異物欠陥の発生を防止する効果がある。このような効果が高い点から、上述の各種溶剤の中でも、特にジプロピレングリコールメチルエーテルアセテート、ジエチレングリコールモノ－ｎ－ブチルエーテルアセテート、及びジエチレングリコールモノエチルエーテルアセテート、１，４－ブタンジオールジアセテート、１，３－ブチレングリコールジアセテート、トリアセチン、１，６－ヘキサンジオールジアセテートが好ましい。 It is also preferable to use an organic solvent having a boiling point of 200 ° C. or higher (hereinafter sometimes referred to as “high boiling point solvent”). By using such a high boiling point solvent together, the photosensitive resin composition becomes difficult to dry, but there is an effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of a foreign matter defect due to precipitation or solidification of a color material or the like at the tip of the slit nozzle. Because of such high effects, among the above-mentioned various solvents, dipropylene glycol methyl ether acetate, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, 1,4-butanediol diacetate, 1, 3-butylene glycol diacetate, triacetin, and 1,6-hexanediol diacetate are preferred.
　有機溶剤中の高沸点溶剤の含有割合は、０質量％～５０質量％が好ましく、０．５質量％～４０質量％がより好ましく、１質量％～３０質量％が特に好ましい。高沸点溶剤の含有割合を前記下限値以上とすることで、例えばスリットノズル先端で色材などが析出・固化して異物欠陥を惹き起こすことを回避できる傾向があり、また前記上限値以下とすることで組成物の乾燥温度が遅くなって減圧乾燥プロセスのタクト不良やプリベークのピン跡といった問題を回避できる傾向がある。 The content of the high boiling point solvent in the organic solvent is preferably 0% by mass to 50% by mass, more preferably 0.5% by mass to 40% by mass, and particularly preferably 1% by mass to 30% by mass. By setting the content of the high-boiling solvent to the above lower limit value or more, for example, there is a tendency that it can be avoided that the coloring material precipitates and solidifies at the tip of the slit nozzle and causes foreign matter defects, and is set to the upper limit value or less. As a result, the drying temperature of the composition is delayed, and there is a tendency that problems such as a tact defect in a vacuum drying process and a pin mark of prebaking can be avoided.
　本発明の感光性樹脂組成物において、有機溶剤の含有割合は特に限定されないが、塗布し易さや粘度安定性の観点から、感光性樹脂組成物中の全固形分量が好ましくは５質量％以上、より好ましくは８質量％以上、さらに好ましくは１０質量％以上、特に好ましくは１２質量％以上、また、好ましくは４０質量％以下、より好ましくは３０質量％以下、さらに好ましくは２５質量％以下、特に好ましくは２０質量％以下である。 In the photosensitive resin composition of the present invention, the content of the organic solvent is not particularly limited, but from the viewpoint of ease of application and viscosity stability, the total solid content in the photosensitive resin composition is preferably 5% by mass or more, More preferably 8% by mass or more, further preferably 10% by mass or more, particularly preferably 12% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, particularly Preferably it is 20 mass% or less.
＜感光性樹脂組成物のその他の配合成分＞
　本発明の感光性樹脂組成物には、上述の成分の他、密着向上剤、塗布性向上剤、顔料誘導体、現像改良剤、紫外線吸収剤、酸化防止剤等を適宜配合することができる。 <Other ingredients of the photosensitive resin composition>
In addition to the above-described components, the photosensitive resin composition of the present invention can be appropriately mixed with an adhesion improver, a coatability improver, a pigment derivative, a development improver, an ultraviolet absorber, an antioxidant, and the like.
＜密着向上剤＞
　基板との密着性を改善するため、密着向上剤を含有させてもよく、例えば、シランカップリング剤、チタンカップリング剤等が挙げられるが、特にシランカップリング剤が好ましい。
　このようなシランカップリング剤としては、例えば、ＫＢＭ－４０２、ＫＢＭ－４０３、ＫＢＭ－５０２、ＫＢＭ－５１０３、ＫＢＥ－９００７、Ｘ－１２－１０４８、Ｘ１２－１０５０（信越シリコーン社製）、Ｚ－６０４０、Ｚ－６０４３、Ｚ－６０６２（東レ・ダウコーニング社製）等が挙げられる。なお、シランカップリング剤は、１種を用いてもよく、２種以上を任意の組み合わせ及び比率で併用してもよい。
　さらに、シランカップリング剤以外の密着向上剤を本発明の感光性樹脂組成物に含有させてもよく、例えば、リン酸系密着向上剤、その他の密着向上剤等が挙げられる。 <Adhesion improver>
In order to improve the adhesion to the substrate, an adhesion improver may be included, and examples thereof include a silane coupling agent and a titanium coupling agent, and a silane coupling agent is particularly preferable.
Examples of such silane coupling agents include KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, X12-1050 (manufactured by Shin-Etsu Silicone), Z- 6040, Z-6043, Z-6062 (manufactured by Toray Dow Corning) and the like. In addition, 1 type may be used for a silane coupling agent and it may use 2 or more types together by arbitrary combinations and a ratio.
Furthermore, you may make the photosensitive resin composition of this invention contain adhesion improvers other than a silane coupling agent, For example, a phosphoric acid type adhesion improver, other adhesion improvers, etc. are mentioned.
　リン酸系密着向上剤としては、（メタ）アクリロイルオキシ基含有ホスフェート類が好ましく、中でも下記一般式（ｇ１）、（ｇ２）、（ｇ３）で表されるものが好ましい。 As the phosphate-based adhesion improver, (meth) acryloyloxy group-containing phosphates are preferable, and those represented by the following general formulas (g1), (g2), and (g3) are particularly preferable.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　上記一般式（ｇ１）、（ｇ２）、（ｇ３）において、Ｒ５１は各々独立に水素原子又はメチル基を示し、ｌ及びｌ’は各々独立に１～１０の整数、ｍは各々独立に１、２又は３である。
　その他の密着向上剤としては、ＴＥＧＯ＊Ａｄｄ　Ｂｏｎｄ　ＬＴＨ（Ｅｖｏｎｉｋ社製）などが挙げられる。これらの燐酸基含有化合物やその他の密着剤も１種類を単独で用いても、２種以上を組み合わせて使用してもよい。 In the general formulas (g1), (g2), and (g3), R 51 each independently represents a hydrogen atom or a methyl group, l and l ′ are each independently an integer of 1 to 10, and m is each independently 1 2 or 3.
Examples of other adhesion improvers include TEGO * Add Bond LTH (manufactured by Evonik). These phosphoric acid group-containing compounds and other adhesives may be used alone or in combination of two or more.
　感光性樹脂組成物中の密着向上剤の含有割合は特に限定されないが、全固形分中０．１質量％以上であることが好ましく、０．３質量％以上であることがより好ましく、０．５質量％以上がさらに好ましく、１質量％以上が特に好ましく、また、２５質量％以下であることが好ましく、２０質量％以下であることがより好ましく、１０質量％以下であることがさらに好ましく、８質量％以下であることが特に好ましく、６質量％以下であることが最も好ましい。前記下限値以上とすることで基板との密着性を良好にできる傾向があり、また、前記上限値以下とすることでアルカリ現像時の残渣を抑制できる傾向がある。 Although the content rate of the adhesion improving agent in the photosensitive resin composition is not particularly limited, it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, based on the total solid content. 5% by mass or more is more preferable, 1% by mass or more is particularly preferable, 25% by mass or less is preferable, 20% by mass or less is more preferable, and 10% by mass or less is more preferable. The content is particularly preferably 8% by mass or less, and most preferably 6% by mass or less. There exists a tendency which can make favorable adhesiveness with a board | substrate by setting it as the said lower limit or more, and there exists a tendency which can suppress the residue at the time of alkali image development by setting it as the said upper limit or less.
＜塗布性向上剤＞
　本発明の感光性樹脂組成物には、塗布性向上のため、塗布性向上剤として界面活性剤を含有させてもよい。界面活性剤としては、例えば、アニオン系、カチオン系、非イオン系および両性界面活性剤等各種のものを用いることができる。中でも、諸特性に悪影響を及ぼす可能性が低い点で、非イオン系界面活性剤を用いるのが好ましく、中でもフッ素系またはシリコン系の界面活性剤が塗布性の面で効果的である。 <Applicability improver>
The photosensitive resin composition of the present invention may contain a surfactant as a coatability improver for improving coatability. As the surfactant, for example, anionic, cationic, nonionic and amphoteric surfactants can be used. Among these, nonionic surfactants are preferably used because they are less likely to adversely affect various properties, and among them, fluorine-based or silicon-based surfactants are effective in terms of coatability.
　このような界面活性剤としては、例えば、ＴＳＦ４４６０（モメンティブ・パフォーマンス・マテリアルズ社製）、ＤＦＸ－１８（ネオス社製）、ＢＹＫ－３００、ＢＹＫ－３２５、ＢＹＫ－３３０（ビックケミー社製）、ＫＰ３４０（信越シリコーン社製）、Ｆ－４７０、Ｆ－４７５、Ｆ－４７８、Ｆ－５５４、Ｆ－５５９（ＤＩＣ社製）、ＳＨ７ＰＡ（東レ・ダウコーニング社製）、ＤＳ－４０１（ダイキン社製）、Ｌ－７７（日本ユニカー社製）およびＦＣ４４３０（３Ｍジャパン社製）等が挙げられる。なお、界面活性剤は、１種を用いてもよく、２種以上を任意の組み合わせ及び比率で併用してもよい。
　感光性樹脂組成物中の界面活性剤の含有割合は特に限定されないが、全固形分中０．０１質量％以上であることが好ましく、０．０５質量％以上であることがより好ましく、０．１０質量％以上であることがさらに好ましく、また、１．０質量％以下であることが好ましく、０．７質量％以下であることがより好ましく、０．５質量％以下であることがさらに好ましく、０．３質量％以下であることが特に好ましい。界面活性剤の含有割合を前記下限値以上とすることでレジスト塗布均一性がよくなる傾向があり、また、前記上限値以下とすることでレジスト感度が下がらない傾向がある。 Examples of such surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), KP340. (Manufactured by Shin-Etsu Silicone), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC), SH7PA (manufactured by Dow Corning Toray), DS-401 (manufactured by Daikin) , L-77 (manufactured by Nihon Unicar) and FC4430 (manufactured by 3M Japan). In addition, 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and a ratio.
The content of the surfactant in the photosensitive resin composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on the total solid content. More preferably, it is 10% by mass or more, preferably 1.0% by mass or less, more preferably 0.7% by mass or less, and further preferably 0.5% by mass or less. The content is particularly preferably 0.3% by mass or less. When the content of the surfactant is set to the lower limit value or more, the resist coating uniformity tends to be improved, and when the surfactant content is set to the upper limit value or less, the resist sensitivity tends not to decrease.
＜顔料誘導体＞
　本発明の感光性樹脂組成物には、分散性、保存性向上のため、顔料誘導体を含有させてもよい。顔料誘導体としてはアゾ系、フタロシアニン系、キナクリドン系、ベンズイミダゾロン系、キノフタロン系、イソインドリノン系、ジオキサジン系、アントラキノン系、インダンスレン系、ペリレン系、ペリノン系、ジケトピロロピロール系、ジオキサジン系等の誘導体が挙げられるが、中でもフタロシアニン系、キノフタロン系が好ましい。 <Pigment derivative>
The photosensitive resin composition of the present invention may contain a pigment derivative for improving dispersibility and storage stability. As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine Among them, derivatives such as phthalocyanines and quinophthalones are preferable.
　顔料誘導体の置換基としてはスルホン酸基、スルホンアミド基及びその四級塩、フタルイミドメチル基、ジアルキルアミノアルキル基、水酸基、カルボキシル基、アミド基等が顔料骨格に直接又はアルキル基、アリール基、複素環基等を介して結合したものが挙げられ、好ましくはスルホン酸基である。またこれら置換基は一つの顔料骨格に複数置換していてもよい。顔料誘導体の具体例としてはフタロシアニンのスルホン酸誘導体、キノフタロンのスルホン酸誘導体、アントラキノンのスルホン酸誘導体、キナクリドンのスルホン酸誘導体、ジケトピロロピロールのスルホン酸誘導体、ジオキサジンのスルホン酸誘導体等が挙げられる。これらは１種を単独で用いてもよく、２種以上を併用してもよい。 As substituents of pigment derivatives, sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. can be directly in the pigment skeleton or alkyl groups, aryl groups, complex groups. Examples thereof include those bonded via a ring group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton. Specific examples of the pigment derivative include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. These may be used alone or in combination of two or more.
＜感光性樹脂組成物の製造方法＞
　本発明の感光性樹脂組成物（以下、「レジスト」と称することがある。）は、常法に従って製造される。
　通常、（ｄ）色材は、予めペイントコンディショナー、サンドグラインダー、ボールミル、ロールミル、ストーンミル、ジェットミル、ホモジナイザー等を用いて分散処理するのが好ましい。分散処理により（ｄ）色材が微粒子化されるため、レジストの塗布特性が向上する。また、（ｄ）色材として黒色色材を使用した場合は遮光能力の向上に寄与する。 <Method for producing photosensitive resin composition>
The photosensitive resin composition of the present invention (hereinafter sometimes referred to as “resist”) is produced according to a conventional method.
Usually, (d) the color material is preferably preliminarily dispersed using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like. Since (d) the color material is made into fine particles by the dispersion treatment, the resist coating characteristics are improved. Moreover, (d) When a black color material is used as a color material, it contributes to the improvement of a light-shielding capability.
　分散処理は、通常、（ｄ）色材、溶剤、及び必要に応じて（ｅ）分散剤、（ａ）アルカリ可溶性樹脂の一部又は全部を併用した系にて行うことが好ましい。（以下、分散処理に供する混合物、及び該処理にて得られた組成物を「インク」又は「顔料分散液」と称することがある。）特に分散剤として高分子分散剤を用いると、得られたインク及びレジストの経時の増粘が抑制される（分散安定性に優れる）ので好ましい。
　なお、感光性樹脂組成物に配合する全成分を含有する液に対して分散処理を行った場合、分散処理時に生じる発熱のため、高反応性の成分が変性する可能性がある。従って、高分子分散剤を含む系にて分散処理を行うことが好ましい。 The dispersion treatment is usually preferably carried out in a system in which (d) a color material, a solvent, and if necessary, (e) a dispersant and (a) a part or all of an alkali-soluble resin are used in combination. (Hereinafter, the mixture to be subjected to the dispersion treatment and the composition obtained by the treatment may be referred to as “ink” or “pigment dispersion”.) Particularly, when a polymer dispersant is used as the dispersant, the mixture is obtained. In addition, it is preferable because thickening of the ink and resist over time is suppressed (excellent dispersion stability).
In addition, when a dispersion treatment is performed on a liquid containing all components to be blended in the photosensitive resin composition, a highly reactive component may be modified due to heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.
　サンドグラインダーで（ｄ）色材を分散させる場合には、０．１～８ｍｍ程度の径のガラスビーズ又はジルコニアビーズが好ましく用いられる。分散処理条件は、温度は通常、０℃から１００℃であり、好ましくは、室温から８０℃の範囲である。分散時間は液の組成及び分散処理装置のサイズ等により適正時間が異なるため適宜調節する。レジストの２０度鏡面光沢度（ＪＩＳ　Ｚ８７４１）が１００～２００の範囲となるように、インキの光沢を制御するのが分散の目安である。レジストの光沢度が前記下限値以上の場合には、分散処理が十分となり、荒い顔料（色材）粒子が残っていることが少なく、現像性、密着性、解像性等が十分となる傾向がある。また、光沢値が前記上限値以下の場合には、顔料が破砕して超微粒子が多数生じ、却って分散安定性が損なわれるのを回避できる傾向がある。 When (d) the color material is dispersed with a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used. In the dispersion treatment conditions, the temperature is usually from 0 ° C. to 100 ° C., and preferably from room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment apparatus. The standard of dispersion is to control the gloss of the ink so that the 20-degree specular gloss of the resist (JIS Z8741) is in the range of 100 to 200. When the glossiness of the resist is not less than the above lower limit value, the dispersion treatment is sufficient, and there are few remaining rough pigment (coloring material) particles, and the developability, adhesion, resolution, etc. tend to be sufficient. There is. On the other hand, when the gloss value is less than or equal to the above upper limit value, there is a tendency that the pigment is crushed and a large number of ultrafine particles are produced, and on the contrary, the dispersion stability is impaired.
　次に、上記分散処理により得られたインキと、レジスト中に含まれる、上記の他の成分を混合し、均一な溶液とする。レジストの製造工程においては、微細なゴミが液中に混じることが多いため、得られたレジストはフィルター等により濾過処理するのが望ましい。 Next, the ink obtained by the dispersion treatment and the other components contained in the resist are mixed to obtain a uniform solution. In the resist manufacturing process, fine dust is often mixed in the liquid, and thus the obtained resist is preferably filtered by a filter or the like.
［硬化物］
　本発明の感光性樹脂組成物を硬化させることで、硬化物を得ることができる。感光性樹脂組成物を硬化してなる硬化物は、画素、ブラックマトリックスや着色スペーサーなどのカラーフィルターを構成する部材として好適に用いることができる。 [Cured product]
A cured product can be obtained by curing the photosensitive resin composition of the present invention. A cured product obtained by curing the photosensitive resin composition can be suitably used as a member constituting a color filter such as a pixel, a black matrix, or a colored spacer.
［ブラックマトリックス］
　次に、本発明の感光性樹脂組成物を用いたブラックマトリックスについて、その製造方法に従って説明する。 [Black Matrix]
Next, the black matrix using the photosensitive resin composition of the present invention will be described in accordance with its production method.
　（１）　支持体
　ブラックマトリックスを形成するための支持体としては、適度の強度があれば、その材質は特に限定されるものではない。おもに透明基板が使用されるが、材質としては、例えば、ポリエチレンテレフタレートなどのポリエステル系樹脂、ポリプロピレン、ポリエチレンなどのポリオレフィン系樹脂、ポリカーボネート、ポリメチルメタクリレート、ポリスルフォンなどの熱可塑性樹脂製シート、エポキシ樹脂、不飽和ポリエステル樹脂、ポリ（メタ）アクリル系樹脂などの熱硬化性樹脂シート、又は各種ガラスなどが挙げられる。この中でも、耐熱性の観点からガラス、耐熱性樹脂が好ましい。また、基板の表面にＩＴＯ、ＩＺＯ等の透明電極が成膜されている場合もある。透明基板以外では、ＴＦＴアレイ上に形成することも可能である。 (1) Support The support for forming the black matrix is not particularly limited as long as it has an appropriate strength. A transparent substrate is mainly used, but the material is, for example, a polyester resin such as polyethylene terephthalate, a polyolefin resin such as polypropylene or polyethylene, a sheet made of a thermoplastic resin such as polycarbonate, polymethyl methacrylate or polysulfone, or an epoxy resin. And thermosetting resin sheets such as unsaturated polyester resins and poly (meth) acrylic resins, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance. In some cases, a transparent electrode such as ITO or IZO is formed on the surface of the substrate. Other than the transparent substrate, it can be formed on the TFT array.
　支持体には、接着性などの表面物性の改良のため、必要に応じ、コロナ放電処理、オゾン処理、大気圧プラズマ処理、シランカップリング剤や、ウレタン系樹脂などの各種樹脂の薄膜形成処理などを行ってもよい。
　透明基板の厚さは、通常０．０５～１０ｍｍ、好ましくは０．１～７ｍｍの範囲とされる。また各種樹脂の薄膜形成処理を行う場合、その膜厚は、通常０．０１～１０μｍ、好ましくは０．０５～５μｍの範囲である。 For the support, to improve surface properties such as adhesiveness, corona discharge treatment, ozone treatment, atmospheric pressure plasma treatment, silane coupling agents, and thin film formation treatment of various resins such as urethane resins, etc. May be performed.
The thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. When a thin film forming process of various resins is performed, the film thickness is usually 0.01 to 10 μm, preferably 0.05 to 5 μm.
　（２）　ブラックマトリックス
　上述の本発明の感光性樹脂組成物により、本発明のブラックマトリックスを形成するには、透明基板上に本発明の感光性樹脂組成物を塗布して乾燥した後、塗膜の上にフォトマスクを置き、該フォトマスクを介して画像露光、現像、必要に応じて熱硬化或いは光硬化することによりブラックマトリックスを形成させる。 (2) Black Matrix In order to form the black matrix of the present invention by the above-described photosensitive resin composition of the present invention, the photosensitive resin composition of the present invention is applied on a transparent substrate and dried, and then a coating film is formed. A black mask is formed by placing a photomask on the substrate and exposing the image through the photomask, developing, and thermosetting or photocuring as necessary.
　（３）　ブラックマトリックスの形成
　（３－１）　感光性樹脂組成物の塗布
　ブラックマトリックス用の感光性樹脂組成物の透明基板上への塗布は、スピナー法、ワイヤーバー法、フローコート法、ダイコート法、ロールコート法、又はスプレーコート法などによって行うことができる。中でも、ダイコート法によれば、塗布液使用量が大幅に削減され、かつ、スピンコート法により行った際に付着するミストなどの影響が全くなく、異物発生が抑制されるなど、総合的な観点から好ましい。 (3) Formation of black matrix (3-1) Application of photosensitive resin composition The photosensitive resin composition for black matrix is applied on a transparent substrate by spinner method, wire bar method, flow coating method, die coating method. , Roll coating method or spray coating method. Above all, according to the die coating method, the amount of coating solution used is greatly reduced, and there is no influence of mist adhering when performed by the spin coating method, so that the generation of foreign matters is suppressed. To preferred.
　塗膜の厚さは、乾燥後の膜厚として、通常０．２～１０μｍの範囲とするのが好ましく、より好ましいのは０．５～６μｍの範囲、更に好ましいのは１～４μｍの範囲である。前記上限値以下とすることでパターン現像が容易となり、液晶セル化工程でのギャップ調整も容易となる傾向がある。また前記下限値以上とすることで所望の色発現が容易となる傾向がある。 The thickness of the coating film is usually preferably in the range of 0.2 to 10 μm, more preferably in the range of 0.5 to 6 μm, and still more preferably in the range of 1 to 4 μm, as the film thickness after drying. is there. By setting it to the upper limit or less, pattern development becomes easy, and gap adjustment in the liquid crystal cell forming step tends to be easy. Moreover, there exists a tendency for desired color expression to become easy by setting it as the said lower limit or more.
　（３－２）　塗膜の乾燥
　基板に感光性樹脂組成物を塗布した後の塗膜の乾燥は、ホットプレート、ＩＲオーブン、又はコンベクションオーブンを使用した乾燥法によるのが好ましい。乾燥の条件は、前記溶剤成分の種類、使用する乾燥機の性能などに応じて適宜選択することができる。乾燥時間は、溶剤成分の種類、使用する乾燥機の性能などに応じて、通常は、４０～２００℃の温度で１５秒～５分間の範囲で選ばれ、好ましくは５０～１３０℃の温度で３０秒～３分間の範囲で選ばれる。 (3-2) Drying of the coating film The coating film after the photosensitive resin composition is applied to the substrate is preferably dried by a drying method using a hot plate, IR oven, or convection oven. Drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying time is usually selected within the range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably 50 to 130 ° C., depending on the type of solvent component and the performance of the dryer used. It is selected in the range of 30 seconds to 3 minutes.
　乾燥温度は、高いほど透明基板に対する塗膜の接着性が向上するが、高すぎるとアルカリ可溶性樹脂が分解し、熱重合を誘発して現像不良を生ずる場合がある。なお、この塗膜の乾燥工程は、温度を高めず、減圧チャンバー内で乾燥を行う、減圧乾燥法であってもよい。 The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. However, when the drying temperature is too high, the alkali-soluble resin is decomposed, and thermal polymerization may be induced to cause development failure. In addition, the drying process of this coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.
　（３－３）露光
　画像露光は、感光性樹脂組成物の塗膜上に、ネガのマスクパターンを重ね、このマスクパターンを介し、紫外域から可視域に至る波長の光を照射して行う。この際、必要に応じ、酸素による光重合性層の感度の低下を防ぐため、光重合性の塗膜上にポリビニルアルコール層などの酸素遮断層を形成した後に露光を行ってもよい。上記の画像露光に使用される光源は、特に限定されるものではない。光源としては、例えば、キセノンランプ、ハロゲンランプ、タングステンランプ、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、中圧水銀灯、低圧水銀灯、カーボンアークなどのランプ光源などが挙げられる。特定の波長の光を照射して使用する場合には、光学フィルタを利用することもできる。 (3-3) Exposure Image exposure is performed by overlaying a negative mask pattern on the coating film of the photosensitive resin composition and irradiating light of a wavelength from the ultraviolet region to the visible region through this mask pattern. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable coating film in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said image exposure is not specifically limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, and a lamp light source such as a carbon arc. An optical filter can also be used when used by irradiating light of a specific wavelength.
　（３－４）現像
　本発明に係るブラックマトリックスは、感光性樹脂組成物による塗膜を、上記の光源によって画像露光を行った後、有機溶剤、又は、界面活性剤とアルカリ性化合物とを含む水溶液を用いる現像によって、基板上に画像を形成して作製することができる。この水溶液には、更に有機溶剤、緩衝剤、錯化剤、染料又は顔料を含ませることができる。 (3-4) Development The black matrix according to the present invention comprises an organic solvent or an aqueous solution containing a surfactant and an alkaline compound after the coating film made of the photosensitive resin composition is image-exposed with the above-mentioned light source. An image can be formed on a substrate by development using a film. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.
　アルカリ性化合物としては、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、ケイ酸ナトリウム、ケイ酸カリウム、メタケイ酸ナトリウム、リン酸ナトリウム、リン酸カリウム、リン酸水素ナトリウム、リン酸水素カリウム、リン酸二水素ナトリウム、リン酸二水素カリウム、水酸化アンモニウムなどの無機アルカリ性化合物や、モノ－・ジ－又はトリエタノールアミン、モノ－・ジ－又はトリメチルアミン、モノ－・ジ－又はトリエチルアミン、モノ－又はジイソプロピルアミン、ｎ－ブチルアミン、モノ－・ジ－又はトリイソプロパノールアミン、エチレンイミン、エチレンジイミン、テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）、コリンなどの有機アルカリ性化合物が挙げられる。これらのアルカリ性化合物は、２種以上の混合物であってもよい。 Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine , Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Organic alkaline compounds. These alkaline compounds may be a mixture of two or more.
　界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルアリールエーテル類、ポリオキシエチレンアルキルエステル類、ソルビタンアルキルエステル類、モノグリセリドアルキルエステル類などのノニオン系界面活性剤、アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、アルキル硫酸塩類、アルキルスルホン酸塩類、スルホコハク酸エステル塩類などのアニオン性界面活性剤、アルキルベタイン類、アミノ酸類などの両性界面活性剤が挙げられる。 Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.
　有機溶剤としては、例えば、イソプロピルアルコール、ベンジルアルコール、エチルセロソルブ、ブチルセロソルブ、フェニルセロソルブ、プロピレングリコール、ジアセトンアルコールなどが挙げられる。有機溶剤は、単独で用いてもよく、また、水溶液と併用してもよい。
　現像処理の条件は特に制限はなく、通常、現像温度は１０～５０℃の範囲、中でも１５～４５℃、特に好ましくは２０～４０℃で、現像方法は、浸漬現像法、スプレー現像法、ブラシ現像法、超音波現像法などのいずれかの方法によることができる。 Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent may be used alone or in combination with an aqueous solution.
The development processing conditions are not particularly limited, and the development temperature is usually in the range of 10 to 50 ° C., particularly 15 to 45 ° C., particularly preferably 20 to 40 ° C. The development methods are immersion development, spray development, brush Any of a developing method, an ultrasonic developing method and the like can be used.
　（３－５）熱硬化処理
　現像の後の基板には、熱硬化処理又は光硬化処理、好ましくは熱硬化処理を施す。この際の熱硬化処理条件は、温度は１００～２８０℃の範囲、好ましくは１５０～２５０℃の範囲で選ばれ、時間は５～６０分間の範囲で選ばれる。
　以上のようにして形成させたブラックマトリックスの高さは通常０．５～５μｍ、好ましくは０．８～４μｍである。
　さらに、厚さ１μｍ当たりの光学濃度（ＯＤ）が３．０以上、好ましくは３．５以上、より好ましくは３．８以上、特に好ましくは４．０以上、最も好ましくは４．２以上である。 (3-5) Thermosetting treatment The substrate after development is subjected to thermosetting treatment or photocuring treatment, preferably thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C., preferably in the range of 150 to 250 ° C., and the time is in the range of 5 to 60 minutes.
The height of the black matrix formed as described above is usually 0.5 to 5 μm, preferably 0.8 to 4 μm.
Furthermore, the optical density (OD) per 1 μm thickness is 3.0 or more, preferably 3.5 or more, more preferably 3.8 or more, particularly preferably 4.0 or more, and most preferably 4.2 or more. .
［その他のカラーフィルター画像の形成］
　ブラックマトリックスを設けた透明基板上に、上記（３－１）～（３－５）と同じプロセスで赤色、緑色、青色のうち一色の色材を含有する感光性樹脂組成物を塗布し、乾燥した後、塗膜の上にフォトマスクを重ね、このフォトマスクを介して画像露光、現像、必要に応じて熱硬化又は光硬化により画素画像を形成させ、着色層を作製する。この操作を、赤色、緑色、青色の三色の感光性樹脂組成物についてそれぞれ行うことによって、カラーフィルター画像を形成することができる。これらの順番は上記に限定されるものではない。 [Formation of other color filter images]
On a transparent substrate provided with a black matrix, a photosensitive resin composition containing a color material of one color of red, green, and blue is applied by the same process as (3-1) to (3-5) above, and dried. After that, a photomask is overlaid on the coating film, and a pixel image is formed through image exposure, development, and thermal curing or photocuring as necessary through this photomask to produce a colored layer. A color filter image can be formed by performing this operation for each of the three color photosensitive resin compositions of red, green, and blue. The order of these is not limited to the above.
［着色スペーサー］
　本発明の感光性樹脂組成物は、ブラックマトリックス以外に着色スペーサー用のレジストとして使用することも可能である。スペーサーをＴＦＴ型ＬＣＤに使用する場合、ＴＦＴに入射する光によりスイッチング素子としてＴＦＴが誤作動を起こすことがあり、着色スペーサーはこれを防止するために用いられ、例えば、日本国特開平８－２３４２１２号公報にスペーサーを遮光性とすることが記載されている。着色スペーサーは着色スペーサー用のマスクを用いる以外は前述のブラックマトリックスと同様の方法で形成することができる。 [Coloring spacer]
The photosensitive resin composition of the present invention can be used as a resist for colored spacers in addition to the black matrix. When a spacer is used in a TFT type LCD, the TFT may malfunction as a switching element due to light incident on the TFT, and a colored spacer is used to prevent this, for example, Japanese Patent Application Laid-Open No. 8-234212. The publication discloses that the spacer is light-shielding. The colored spacer can be formed in the same manner as the black matrix described above except that a mask for the colored spacer is used.
　（３－６）　透明電極の形成
　カラーフィルターは、このままの状態で画像上にＩＴＯなどの透明電極を形成して、カラーディスプレー、液晶表示装置などの部品の一部として使用されるが、表面平滑性や耐久性を高めるため、必要に応じ、画像上にポリアミド、ポリイミドなどのトップコート層を設けることもできる。また一部、平面配向型駆動方式（ＩＰＳモード）などの用途においては、透明電極を形成しないこともある。 (3-6) Formation of transparent electrode The color filter is used as part of components such as color displays and liquid crystal display devices by forming transparent electrodes such as ITO on the image in this state. In order to enhance the property and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.
［画像表示装置］
　本発明の画像表示装置は、本発明の感光性樹脂組成物を硬化させた硬化物を有する。画像表示装置としては、画像や映像を表示する装置であれば特に限定は受けないが、後述する液晶表示装置や有機ＥＬディスプレイ等が挙げられる。 [Image display device]
The image display device of the present invention has a cured product obtained by curing the photosensitive resin composition of the present invention. The image display device is not particularly limited as long as it is a device that displays an image or video, and examples thereof include a liquid crystal display device and an organic EL display described later.
［液晶表示装置］
　本発明の液晶表示装置は、上述の本発明のブラックマトリックス、カラーフィルター画素、着色スペーサー等の硬化物を有するものであり、カラー画素やブラックマトリックスの形成順序や形成位置等特に制限を受けるものではない。 [Liquid Crystal Display]
The liquid crystal display device of the present invention has a cured product such as the above-described black matrix, color filter pixel, and colored spacer of the present invention, and is not particularly limited in terms of the order of formation and formation position of the color pixels and black matrix. Absent.
　液晶表示装置は、通常、カラーフィルター上に配向膜を形成し、この配向膜上にスペーサーを散布した後、対向基板と貼り合わせて液晶セルを形成し、形成した液晶セルに液晶を注入し、対向電極に結線して完成する。配向膜としては、ポリイミド等の樹脂膜が好適である。配向膜の形成には、通常、グラビア印刷法及び／又はフレキソ印刷法が採用され、配向膜の厚さは数１０ｎｍとされる。熱焼成によって配向膜の硬化処理を行った後、紫外線の照射やラビング布による処理によって表面処理し、液晶の傾きを調整しうる表面状態に加工される。 A liquid crystal display device usually forms an alignment film on a color filter, spreads spacers on the alignment film, and then bonds to the counter substrate to form a liquid crystal cell, injects liquid crystal into the formed liquid crystal cell, Complete by connecting to the counter electrode. As the alignment film, a resin film such as polyimide is suitable. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to be processed into a surface state in which the tilt of the liquid crystal can be adjusted.
　スペーサーとしては、対向基板とのギャップ（隙間）に応じた大きさのものが用いられ、通常２～８μｍのものが好適である。カラーフィルター基板上に、フォトリソグラフィ法によって透明樹脂膜のフォトスペーサー（ＰＳ）を形成し、これをスペーサーの代わりに活用することもできる。対向基板としては、通常、アレイ基板が用いられ、特にＴＦＴ（薄膜トランジスタ）基板が好適である。 As the spacer, a spacer having a size corresponding to the gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by photolithography, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.
　対向基板との貼り合わせのギャップは、液晶表示装置の用途によって異なるが、通常２～８μｍの範囲で選ばれる。対向基板と貼り合わせた後、液晶注入口以外の部分は、エポキシ樹脂等のシール材によって封止する。シール材は、ＵＶ照射及び／又は加熱することによって硬化させ、液晶セル周辺がシールされる。
　周辺をシールされた液晶セルは、パネル単位に切断した後、真空チャンバー内で減圧とし、上記液晶注入口を液晶に浸漬した後、チャンバー内をリークすることによって、液晶を液晶セル内に注入する。液晶セル内の減圧度は、通常、１×１０－２～１×１０－７Ｐａであるが、好ましくは１×１０－３～１×１０－６Ｐａである。また、減圧時に液晶セルを加温するのが好ましく、加温温度は通常３０～１００℃であり、より好ましくは５０～９０℃である。減圧時の加温保持は、通常１０～６０分間の範囲とされ、その後液晶中に浸漬される。液晶を注入した液晶セルは、液晶注入口をＵＶ硬化樹脂を硬化させて封止することによって、液晶表示装置（パネル）が完成する。 The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of decompression in the liquid crystal cell is usually 1 × 10 −2 to 1 × 10 −7 Pa, preferably 1 × 10 −3 to 1 × 10 −6 Pa. Further, it is preferable to heat the liquid crystal cell during decompression, and the heating temperature is usually 30 to 100 ° C., more preferably 50 to 90 ° C. The warming holding at the time of depressurization is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected has a liquid crystal display device (panel) completed by sealing the liquid crystal injection port by curing the UV curable resin.
　液晶の種類には特に制限がなく、芳香族系、脂肪族系、多環状化合物等、従来から知られている液晶であって、リオトロピック液晶、サーモトロピック液晶等のいずれでもよい。サーモトロピック液晶には、ネマティック液晶、スメスティック液晶及びコレステリック液晶等が知られているが、いずれであってもよい。 There are no particular restrictions on the type of liquid crystal, and it is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of lyotropic liquid crystal, thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, and the like are known, but any of them may be used.
［有機ＥＬディスプレイ］
　本発明の有機ＥＬディスプレイは、本発明のカラーフィルターを用いて作製されたものである。 [Organic EL display]
The organic EL display of the present invention is produced using the color filter of the present invention.
　本発明のカラーフィルターを用いて有機ＥＬディスプレイを作製する場合、例えば図１に示すように、まず透明支持基板１０上に、感光性樹脂組成物により形成されたパターン（すなわち、画素２０、及び隣接する画素２０の間に設けられた樹脂ブラックマトリックス（図示せず））が形成されてなるカラーフィルターを作製し、該カラーフィルター上に有機保護層３０及び無機酸化膜４０を介して有機発光体５００を積層することによって、有機ＥＬ素子１００を作製することができる。なお、画素２０及び樹脂ブラックマトリックスの内、少なくとも一つは本発明の感光性樹脂組成物を用いて作製されたものである。有機発光体５００の積層方法としては、カラーフィルター上面へ透明陽極５０、正孔注入層５１、正孔輸送層５２、発光層５３、電子注入層５４、及び陰極５５を逐次形成していく方法や、別基板上へ形成した有機発光体５００を無機酸化膜４０上に貼り合わせる方法などが挙げられる。このようにして作製された有機ＥＬ素子１００を用い、例えば「有機ＥＬディスプレイ」（オーム社，２００４年８月２０日発光，時任静士、安達千波矢、村田英幸著）に記載された方法等にて、有機ＥＬディスプレイを作製することができる。 When an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. 1, first, a pattern (that is, the pixel 20 and the adjacent region) formed on the transparent support substrate 10 by the photosensitive resin composition. A color filter in which a resin black matrix (not shown) provided between the pixels 20 to be formed is formed, and the organic light-emitting body 500 is formed on the color filter via the organic protective layer 30 and the inorganic oxide film 40. The organic EL element 100 can be manufactured by stacking layers. In addition, at least one of the pixel 20 and the resin black matrix is manufactured using the photosensitive resin composition of the present invention. As a method for laminating the organic light-emitting body 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. A method described in, for example, “Organic EL display” (Ohm, Inc., August 20, 2004, light emission, Shizushi Tokito, Chiba Adachi, Hideyuki Murata) using the organic EL element 100 manufactured in this manner, etc. Thus, an organic EL display can be produced.
　なお、本発明のカラーフィルターは、パッシブ駆動方式の有機ＥＬディスプレイにもアクティブ駆動方式の有機ＥＬディスプレイにも適用可能である。 It should be noted that the color filter of the present invention can be applied to both passive drive type organic EL displays and active drive type organic EL displays.
　次に、合成例、実施例及び比較例を挙げて本発明をより具体的に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。 Next, the present invention will be described more specifically with reference to synthesis examples, examples and comparative examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
＜カーボンブラックインクの調製＞
　以下の組成及び方法で顔料、分散剤、分散助剤（顔料誘導体）、溶剤を調合し、カーボンブラックインクを調製した。
　具体的にはまず、顔料、分散剤、分散助剤の固形分と溶剤が以下の量比となるように調合した。
・顔料：ＲＡＶＥＮ１０６０Ｕ（ビルラー社製、カーボンブラック）；５２．００質量部
・分散剤：ＤＩＳＰＥＲＢＹＫ－１６７（ビックケミー社製、塩基性ウレタン分散剤）；７．３０質量部（固形分換算）
・分散助剤（顔料誘導体）：Ｓ１２０００（ルーブリゾール社製、酸性基を有するフタロシアニン系顔料誘導体）；１．０３質量部
・溶剤：プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）；１１２．０４質量部 <Preparation of carbon black ink>
A carbon black ink was prepared by preparing a pigment, a dispersant, a dispersion aid (pigment derivative), and a solvent by the following composition and method.
Specifically, first, the solid content of the pigment, the dispersant, and the dispersion aid and the solvent were prepared so as to have the following quantitative ratio.
Pigment: RAVEN 1060U (manufactured by Birler, carbon black); 52.00 parts by mass Dispersant: DISPERBYK-167 (manufactured by Big Chemie, basic urethane dispersant); 7.30 parts by mass (solid content conversion)
Dispersing aid (pigment derivative): S12000 (manufactured by Lubrizol, phthalocyanine pigment derivative having an acidic group); 1.03 parts by mass; Solvent: propylene glycol monomethyl ether acetate (PGMEA); 112.04 parts by mass
　これらを十分に攪拌・混合し、分散液を得た。
　次に、ペイントシェーカーにより２５～４５℃の範囲で６時間分散処理を行った。ビーズとしては、直径０．５ｍｍのジルコニアビーズを用い、分散液６０質量部に対しビーズ１８０質量部の割合で加えた。分散終了後、フィルターによりビーズと分散液を分離して、固形分３５質量％のカーボンブラックインクを調製した。 These were sufficiently stirred and mixed to obtain a dispersion.
Next, a dispersion treatment was carried out in the range of 25 to 45 ° C. for 6 hours using a paint shaker. As beads, zirconia beads having a diameter of 0.5 mm were used and added at a ratio of 180 parts by mass of beads to 60 parts by mass of the dispersion. After the dispersion, the beads and the dispersion were separated by a filter to prepare a carbon black ink having a solid content of 35% by mass.
＜合成例１：アルカリ可溶性樹脂（１）の合成＞ <Synthesis Example 1: Synthesis of alkali-soluble resin (1)>
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　上記化学構造のエポキシ化合物（エポキシ当量２６４）５０ｇ、アクリル酸１３．６５ｇ、３－メトキシブチルアセテート６０．５ｇ、トリフェニルホスフィン０．９３６ｇ、及びパラメトキシフェノール０．０３２ｇを、温度計、攪拌機、冷却管を取り付けたフラスコに入れ、攪拌しながら９０℃で酸価が５ｍｇＫＯＨ／ｇ以下になるまで反応させた。反応には１２時間を要し、エポキシアクリレート溶液を得た。
　得られたエポキシアクリレート溶液２５質量部及び、トリメチロールプロパン（ＴＭＰ）０．７６質量部、ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）３．３質量部、テトラヒドロフタル酸無水物（ＴＨＰＡ）３．５質量部を、温度計、攪拌機、冷却管を取り付けたフラスコに入れ、攪拌しながら１０５℃までゆっくり昇温し反応させた。
　樹脂溶液が透明になったところで、３－メトキシブチルアセテート（ＭＢＡ）で希釈し、固形分５０質量％となるよう調製し、酸価１１５ｍｇＫＯＨ／ｇ、ＧＰＣで測定したポリスチレン換算の重量平均分子量（Ｍｗ）２，６００のアルカリ可溶性樹脂（１）を得た。 50 g of an epoxy compound having the above chemical structure (epoxy equivalent 264), 13.65 g of acrylic acid, 60.5 g of 3-methoxybutyl acetate, 0.936 g of triphenylphosphine, and 0.032 g of paramethoxyphenol were added to a thermometer, a stirrer, and a cooling device. The mixture was placed in a flask equipped with a tube and reacted at 90 ° C. with stirring until the acid value was 5 mgKOH / g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.
25 parts by mass of the resulting epoxy acrylate solution, 0.76 parts by mass of trimethylolpropane (TMP), 3.3 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), 3.5 parts of tetrahydrophthalic anhydride (THPA) The mass part was put into a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105 ° C. while stirring to react.
When the resin solution became transparent, it was diluted with 3-methoxybutyl acetate (MBA) to prepare a solid content of 50% by mass, an acid value of 115 mg KOH / g, and a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC. ) 2,600 alkali-soluble resins (1) were obtained.
＜合成例２：アルカリ可溶性樹脂（２）の合成＞ <Synthesis Example 2: Synthesis of alkali-soluble resin (2)>
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　上記化学構造のエポキシ化合物（エポキシ当量２４０）７．３ｇ、アクリル酸２．２ｇ、プロピレングリコールモノメチルエーテルアセテート６．４ｇ、テトラエチルアンモニウムクロライド０．１８ｇ、及びｐ－メトキシフェノール０．００７ｇを温度計、攪拌機、冷却管を取り付けたフラスコに入れ、攪拌しながら１００℃で酸価が５ｍｇＫＯＨ／ｇ以下になるまで反応させた。反応には９時間を要し、エポキシアクリレート溶液を得た。
　得られたエポキシアクリレート溶液１６質量部、トリメチロールプロパン（ＴＭＰ）０．４質量部、ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）３．５質量部、テトラヒドロフタル酸無水物（ＴＨＰＡ）０．０６質量部、及びプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）１４質量部を、温度計、攪拌機、冷却管を取り付けたフラスコに入れ、攪拌しながら１０５℃までゆっくり昇温して反応させ、固形分４０質量％、酸価１００ｍｇＫＯＨ／ｇ、ＧＰＣで測定したポリスチレン換算の重量平均分子量（Ｍｗ）１０，４００のアルカリ可溶性樹脂（２）を得た。 7.3 g of epoxy compound having the above chemical structure (epoxy equivalent 240), 2.2 g of acrylic acid, 6.4 g of propylene glycol monomethyl ether acetate, 0.18 g of tetraethylammonium chloride, and 0.007 g of p-methoxyphenol were thermometer and stirrer. The mixture was placed in a flask equipped with a condenser and allowed to react at 100 ° C. with stirring until the acid value was 5 mgKOH / g or less. The reaction took 9 hours to obtain an epoxy acrylate solution.
16 parts by mass of the resulting epoxy acrylate solution, 0.4 parts by mass of trimethylolpropane (TMP), 3.5 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), 0.06 parts by mass of tetrahydrophthalic anhydride (THPA) Part, and 14 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) were put into a flask equipped with a thermometer, a stirrer and a cooling tube, and the reaction was carried out by slowly raising the temperature to 105 ° C. while stirring, An alkali-soluble resin (2) having an acid value of 100 mgKOH / g and a weight average molecular weight (Mw) of 10,400 in terms of polystyrene measured by GPC was obtained.
＜光重合開始剤（１）＞ <Photopolymerization initiator (1)>
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　国際公開第第２０１５／０３６９１０号に記載の方法で合成した上記化学構造の光重合開始剤（１）を用いた。得られた光重合開始剤（１）をプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）に溶解して０．０１質量％溶液を調製し、分光光度計Ｕ－３９００Ｈ（日立ハイテクサイエンス社製）を用いて吸収スペクトルを測定したところ、波長３２０ｎｍ～４００ｎｍの範囲における極大吸収波長は３３１ｎｍであった。 A photopolymerization initiator (1) having the above chemical structure synthesized by the method described in International Publication No. 2015/036910 was used. The obtained photopolymerization initiator (1) is dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a 0.01% by mass solution, which is absorbed using a spectrophotometer U-3900H (manufactured by Hitachi High-Tech Science Co., Ltd.). When the spectrum was measured, the maximum absorption wavelength in the wavelength range of 320 nm to 400 nm was 331 nm.
＜光重合開始剤（２）＞ <Photopolymerization initiator (2)>
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　国際公開第２００８／０７８６７８号に記載の方法で合成した上記化学構造の光重合開始剤（２）を用いた。光重合開始剤（１）と同様の方法で吸収スペクトルを測定したところ、極大吸収波長は３６８ｎｍであった。 A photopolymerization initiator (2) having the above chemical structure synthesized by the method described in International Publication No. 2008/078678 was used. When the absorption spectrum was measured by the same method as that for the photopolymerization initiator (1), the maximum absorption wavelength was 368 nm.
＜光重合開始剤（３）＞
　光重合開始剤（３）として、常州強力電子新材料社製のＴＲ－ＰＢＧ－３１４（以下の化学構造を有する化合物）を用いた。 <Photopolymerization initiator (3)>
As the photopolymerization initiator (3), TR-PBG-314 (compound having the following chemical structure) manufactured by Changzhou Strong Electronic New Materials Co., Ltd. was used.
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
　光重合開始剤（１）と同様の方法で吸収スペクトルを測定したところ、極大吸収波長は３３９ｎｍであった。 When the absorption spectrum was measured by the same method as that for the photopolymerization initiator (1), the maximum absorption wavelength was 339 nm.
＜光重合開始剤（４）＞
　光重合開始剤（４）として、常州強力電子新材料社製のＴＲ－ＰＢＧ－３５８（以下の化学構造を有する化合物）を用いた。 <Photopolymerization initiator (4)>
As the photopolymerization initiator (4), TR-PBG-358 (compound having the following chemical structure) manufactured by Changzhou Strong Electronic New Materials Co., Ltd. was used.
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
　光重合開始剤（１）と同様の方法で吸収スペクトルを測定したところ、極大吸収波長は３４４ｎｍであった。 When the absorption spectrum was measured in the same manner as for the photopolymerization initiator (1), the maximum absorption wavelength was 344 nm.
＜光重合性モノマー＞
　光重合性モノマーとして共栄社化学社製のライトアクリレートＰＥ－４Ａ、日本化薬製のＫＡＹＡＲＡＤ　ＤＰＣＡ－２０を準備した。 <Photopolymerizable monomer>
Light acrylate PE-4A manufactured by Kyoeisha Chemical Co., Ltd. and KAYARAD DPCA-20 manufactured by Nippon Kayaku were prepared as photopolymerizable monomers.
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
＜密着向上剤＞
　密着向上剤として、シランカップリング剤である信越化学工業社製のＫＢＭ－５１０３、及び、リン酸系密着向上剤である日本化薬社製のＫＡＹＡＭＥＲ　ＰＭ－２１を準備した。 <Adhesion improver>
As an adhesion improver, KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd., which is a silane coupling agent, and KAYAMER PM-21, manufactured by Nippon Kayaku Co., Ltd., which is a phosphate adhesion improver, were prepared.
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
＜塗布性向上剤＞
　塗布性向上剤として界面活性剤であるＤＩＣ社製のメガファックＦ－５５４（含フッ素基・親油性基含有オリゴマー、ノニオン型界面活性剤）を準備した。 <Applicability improver>
Megafac F-554 (fluorine-containing / lipophilic group-containing oligomer, nonionic surfactant) manufactured by DIC, which is a surfactant, was prepared as a coating property improver.
＜実施例１＞
（ブラックレジスト１の調製）
　前記＜カーボンブラックインクの調製＞で調製したカーボンブラックインクを用いて、表１に記載の割合となるように各成分を加え、スターラーにより攪拌、溶解させて、ブラックレジスト１を調製した。ブラックレジスト１中の全固形分は１５質量％である。 <Example 1>
(Preparation of black resist 1)
Using the carbon black ink prepared in <Preparation of carbon black ink>, each component was added so as to have the ratio shown in Table 1, and stirred and dissolved with a stirrer to prepare black resist 1. The total solid content in the black resist 1 is 15% by mass.
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000034
　なお、表１中の溶剤の略称の意味は以下のとおりである。
　　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
　　ＭＢＡ：　　　３－メトキシブチルアセテート
　　ＥＤＧＡＣ：　ジエチレングリコールモノエチルエーテルアセテート In addition, the meaning of the abbreviation of the solvent in Table 1 is as follows.
PGMEA: Propylene glycol monomethyl ether acetate MBA: 3-methoxybutyl acetate EDGAC: Diethylene glycol monoethyl ether acetate
＜実施例２＞
（ブラックレジスト２の調製）
　表１に示すブラックレジスト１において、光重合開始剤の合計量はそのままで、光重合開始剤（１）及び（２）の混合比率（質量％）を表２に示すように変更したこと以外は、ブラックレジスト１と同じ方法で固形分濃度１５質量％のブラックレジスト２を調製した。 <Example 2>
(Preparation of black resist 2)
In the black resist 1 shown in Table 1, the total amount of the photopolymerization initiator is kept as it is, except that the mixing ratio (% by mass) of the photopolymerization initiators (1) and (2) is changed as shown in Table 2. A black resist 2 having a solid concentration of 15% by mass was prepared in the same manner as the black resist 1.
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000035
＜実施例３＞
（ブラックレジスト３の調製）
　表１に示すブラックレジスト１において、光重合開始剤の合計量はそのままで、光重合開始剤（１）及び（２）の混合比率（質量％）を表２に示すように変更したこと以外は、ブラックレジスト１と同じ方法で固形分濃度１５質量％のブラックレジスト３を調製した。 <Example 3>
(Preparation of black resist 3)
In the black resist 1 shown in Table 1, the total amount of the photopolymerization initiator is kept as it is, except that the mixing ratio (% by mass) of the photopolymerization initiators (1) and (2) is changed as shown in Table 2. A black resist 3 having a solid concentration of 15% by mass was prepared by the same method as that for black resist 1.
＜比較例１＞
（ブラックレジスト４の調製）
　表１に示すブラックレジスト１において、光重合開始剤の合計量はそのままで、光重合開始剤（１）及び（２）の混合比率（質量％）を表２に示すように変更したこと以外は、ブラックレジスト１と同じ方法で固形分濃度１５質量％のブラックレジスト４を調製した。 <Comparative Example 1>
(Preparation of black resist 4)
In the black resist 1 shown in Table 1, the total amount of the photopolymerization initiator is kept as it is, except that the mixing ratio (% by mass) of the photopolymerization initiators (1) and (2) is changed as shown in Table 2. A black resist 4 having a solid content concentration of 15% by mass was prepared in the same manner as black resist 1.
＜比較例２＞
（ブラックレジスト５の調製）
　表１に示すブラックレジスト１において、光重合開始剤の合計量はそのままで、光重合開始剤（１）及び（２）の混合比率（質量％）を表２に示すように変更したこと以外は、ブラックレジスト１と同じ方法で固形分濃度１５質量％のブラックレジスト５を調製した。 <Comparative example 2>
(Preparation of black resist 5)
In the black resist 1 shown in Table 1, the total amount of the photopolymerization initiator is kept as it is, except that the mixing ratio (% by mass) of the photopolymerization initiators (1) and (2) is changed as shown in Table 2. A black resist 5 having a solid concentration of 15% by mass was prepared in the same manner as the black resist 1.
＜実施例４＞
（ブラックレジスト６の調製）
　実施例２のブラックレジスト２において、光重合開始剤の合計量はそのままで、光重合開始剤（２）を光重合開始剤（３）に変更したこと以外は、ブラックレジスト２と同じ方法で固形分濃度１５質量％のブラックレジスト６を調製した。 <Example 4>
(Preparation of black resist 6)
In the black resist 2 of Example 2, the total amount of the photopolymerization initiator is kept as it is, and the solid state is the same as that of the black resist 2 except that the photopolymerization initiator (2) is changed to the photopolymerization initiator (3). A black resist 6 having a partial concentration of 15% by mass was prepared.
＜実施例５＞
（ブラックレジスト７の調製）
　実施例２のブラックレジスト２において、光重合開始剤の合計量はそのままで、光重合開始剤（２）を光重合開始剤（４）に変更したこと以外は、ブラックレジスト２と同じ方法で固形分濃度１５質量％のブラックレジスト７を調製した。 <Example 5>
(Preparation of black resist 7)
In the black resist 2 of Example 2, the total amount of the photopolymerization initiator was kept as it was, and the solid state was the same as that of the black resist 2 except that the photopolymerization initiator (2) was changed to the photopolymerization initiator (4). A black resist 7 having a partial concentration of 15% by mass was prepared.
（ブラックレジストの評価）
（１）ブラックマトリックス（ＢＭ）細線パターンの作製
　調製したブラックレジスト１～７をスピンコーターにてガラス基板に塗布し、減圧乾燥後、ホットプレートで９０℃にて１００秒間乾燥した。なお、それぞれ塗布膜厚が約１．２μｍとなるように塗布条件を調整した。続いて、得られた乾燥塗布膜に対し、露光機（オーク製作所社製ＥＸＦ－２８２９－Ｆ－００）を用いて、高圧水銀灯（オーク製作所社製ＡＤＨ－３０００Ｍ－Ｆ－Ｎ、光学フィルターなし）により３５ｍＪ／ｃｍ２で、開口幅１～１０μｍ（１μｍ刻み）および１５μｍの直線状開口部を有する露光マスクを介してパターン露光（プロキシミティギャップ：１８０μｍ）を行った。その後、室温（２３℃）下、超純水で０．０４質量％に調製したＫＯＨ水溶液をアルカリ現像液として用いて溶解時間の２．２倍の時間、スプレー現像（スプレー圧力：０．１ＭＰａ）して、未露光部を除去した後、超純水でスプレー洗浄（スプレー圧力：０．１ＭＰａ）を行い、ＢＭ細線パターンを形成した。なお、溶解時間とは、現像処理時に未露光部のブラックレジスト膜が溶解して基板表面が見え始めるまでの時間であり、各々のブラックレジストの溶解時間は２０～３０秒の範囲であった。 (Evaluation of black resist)
(1) Production of Black Matrix (BM) Fine Wire Pattern The prepared black resists 1 to 7 were applied to a glass substrate with a spin coater, dried under reduced pressure, and then dried at 90 ° C. for 100 seconds with a hot plate. The coating conditions were adjusted so that the coating film thickness was about 1.2 μm. Subsequently, a high pressure mercury lamp (ADH-3000M-FN, manufactured by Oak Manufacturing Co., Ltd., no optical filter) was used for the resulting dried coating film using an exposure machine (EXF-2829-F-00 manufactured by Oak Manufacturing Co., Ltd.). Pattern exposure (proximity gap: 180 μm) through an exposure mask having an opening width of 1 to 10 μm (in 1 μm increments) and a linear opening of 15 μm at 35 mJ / cm 2 . Then, spray development (spray pressure: 0.1 MPa) at room temperature (23 ° C.) using an aqueous KOH solution prepared to 0.04% by mass with ultrapure water as an alkaline developer for 2.2 times the dissolution time. Then, after removing the unexposed portion, spray cleaning (spray pressure: 0.1 MPa) with ultrapure water was performed to form a BM fine line pattern. The dissolution time is the time from the development of the unexposed portion of the black resist film until the substrate surface begins to be visible, and the dissolution time of each black resist was in the range of 20 to 30 seconds.
（２）ＢＭ細線パターン評価
　作製した現像後のＢＭ細線パターンに対して光学顕微鏡観察を行い、ＢＭ細線形成状態を確認し、細線密着と感度の評価を行った。結果を表３に示した。なお、細線密着と感度の評価は以下の基準にて行った。 (2) BM fine line pattern evaluation The developed BM fine line pattern was observed with an optical microscope, the BM fine line formation state was confirmed, and fine line adhesion and sensitivity were evaluated. The results are shown in Table 3. The fine wire adhesion and sensitivity were evaluated according to the following criteria.
（細線密着評価）
　ＢＭ細線は、アルカリ現像中にＢＭ細線／ガラス基板の接着面が浸食されて差込みが発生し、細線密着性が悪くなる場合がある。光学顕微鏡により１０μｍ以下のラインパターン部分を観察し、例えば、８μｍ以上のパターンが密着し７μｍ以下のパターンが剥離していた場合には、細線密着を８μｍと評価し、以下の通り分類した（ここでは例えば、露光マスクの開口部の幅が７μｍに対応するパターンを、７μｍのパターンと記載している。）。なお、評価が「○」であれば細線密着性が良好であり、「◎」であればさらに良好であると評価でき、「×」は細線密着性が悪いと評価される。
　◎：７μｍ以上のパターンの細線が密着している。
　〇：８μｍ以上のパターンの細線が密着している（７μｍ以下のパターンは剥離）。
　×：９μｍ以上のパターンの細線が密着している（８μｍ以下のパターンは剥離）。 (Thin wire adhesion evaluation)
In the BM fine wire, the adhesion surface of the BM fine wire / glass substrate is eroded during alkali development, and insertion may occur, resulting in poor fine wire adhesion. The line pattern portion of 10 μm or less was observed with an optical microscope. For example, when a pattern of 8 μm or more adhered and a pattern of 7 μm or less peeled, the fine line adhesion was evaluated as 8 μm and classified as follows (here (For example, a pattern in which the width of the opening of the exposure mask corresponds to 7 μm is described as a 7 μm pattern.) If the evaluation is “◯”, the fine line adhesion is good, and if “◎”, it can be evaluated that the fine line adhesion is better, and “x” is evaluated as poor fine line adhesion.
A: Fine lines with a pattern of 7 μm or more are in close contact.
A: Fine lines of a pattern of 8 μm or more are in close contact (patterns of 7 μm or less are peeled).
X: Fine lines with a pattern of 9 μm or more are in close contact (patterns of 8 μm or less are peeled).
（感度評価）
　ブラックレジストは感光性樹脂組成物としての露光感度が上がると、形成されるＢＭ細線の線幅が増える傾向にある。光学顕微鏡により１５μｍのラインパターンの線幅を測長して、感度の判定を以下の通り分類した（ここで例えば、露光マスクの開口部の幅が１５μｍに対応するパターンを、１５μｍのパターンと記載している。）。なお、評価が「○」であれば感度が良好であると評価でき、「×」は感度が低いと評価される。
　○：１５μｍのパターンの線幅が１５μｍ以上。
　×：１５μｍのパターンの線幅が１５μｍ未満。 (Sensitivity evaluation)
When the exposure sensitivity as a photosensitive resin composition increases, the black resist tends to increase the line width of the formed BM thin line. The line width of a 15 μm line pattern was measured with an optical microscope, and the sensitivity determination was classified as follows (here, for example, a pattern corresponding to an exposure mask opening width of 15 μm is described as a 15 μm pattern) is doing.). If the evaluation is “◯”, it can be evaluated that the sensitivity is good, and “X” is evaluated that the sensitivity is low.
A: The line width of a 15 μm pattern is 15 μm or more.
X: The line width of the pattern of 15 micrometers is less than 15 micrometers.
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000036
　表３に示すように、実施例１～５のＢＭ細線は、いずれも細線密着と感度が共に良好であった。比較例１のＢＭ細線は、高感度を示す一方で細線密着が低い結果となった。また、比較例２のＢＭ細線は、良好な細線密着を示す一方で感度が低い結果となった。 As shown in Table 3, all of the BM thin wires of Examples 1 to 5 had good fine wire adhesion and sensitivity. The BM fine wire of Comparative Example 1 showed high sensitivity while the fine wire adhesion was low. In addition, the BM fine wire of Comparative Example 2 showed good thin wire adhesion while having low sensitivity.
　比較例１では、ＢＭ表面の硬化が強いがＢＭ内部の硬化は不十分なため、線幅が太い割りに細線密着が悪い結果となっていると考えられる。比較例２では、ＢＭ表面の硬化が緩いがＢＭ内部の硬化は強めのため線幅が細い割りに、細線密着が良い結果となっていると考えられる。また、実施例１～５では、ＢＭ表面と内部の硬化がバランスよく進んでいることが細線密着と高感度の両立に繋がっていると考えられる。 In Comparative Example 1, the BM surface is strongly cured but the inside of the BM is insufficiently cured, so that it is considered that the thin line adhesion is poor although the line width is large. In Comparative Example 2, it is considered that the fine line adhesion is good for the thin line width because the hardening of the BM surface is loose but the hardening inside the BM is strong. In Examples 1 to 5, it is considered that the progress of the BM surface and internal curing in a well-balanced manner leads to both fine line adhesion and high sensitivity.
　実施例１～５は高感度であることで線幅は太くなるが、以下に挙げる観点からメリットが多く望ましいことである。
・感度に余裕がある分、光重合開始剤の減量が可能で、減量分をアルカリ可溶性樹脂や光重合性モノマーなどに置換えることで耐現像性や基板密着性等の性能向上に振り分けられること。
・目標線幅の形成に必要な露光量が下がる分、露光速度が増加できて生産性が向上する。一方、比較例１も高感度の結果であるが、ＢＭ内部の硬化は不十分であるため、光重合開始剤の減量や露光量の低減を行うと更なる細線密着悪化を引き起こす。 In Examples 1 to 5, the line width becomes thick due to high sensitivity, but many advantages are desirable from the following viewpoints.
-The amount of photopolymerization initiator can be reduced by the margin of sensitivity, and can be distributed to improve performance such as development resistance and substrate adhesion by replacing the reduced amount with alkali-soluble resin or photopolymerizable monomer. .
・ As the exposure amount necessary for forming the target line width decreases, the exposure speed can be increased and the productivity is improved. On the other hand, although Comparative Example 1 is also a result of high sensitivity, since the curing inside the BM is insufficient, further reduction in the adhesion of fine wires is caused when the amount of the photopolymerization initiator is reduced or the exposure amount is reduced.
　本発明の効果に関して詳細な機構は明らかになっていないが以下のように考えられる。すなわち、フェニルスルフィド系の光重合開始剤は３３０ｎｍ付近のＵＶ吸収能力に優れているが、一般式（Ｉ）で示される光重合開始剤（ｃ１）が持つ縮合複素環のベンゾフラン部は色材、特にカーボンブラックとの相互作用力を高めることにより光重合開始剤（ｃ１）の色材粒子表面への吸着を促進する。色材に吸収された光は重合に寄与せず露光感度低下の大きな原因となるが、光重合開始剤が色材表面を覆うことで、光重合開始剤に対する光吸収率が向上する。また、光重合開始剤の色材への吸着は、相対的に樹脂成分中の光重合開始剤濃度を下げるため、深部への光透過性が向上する。これにより、レジスト膜の内部硬化性が向上し、細線密着性の改善に繋がると考えられる。 Although the detailed mechanism regarding the effect of the present invention is not clarified, it is considered as follows. That is, the phenyl sulfide photopolymerization initiator is excellent in UV absorption ability around 330 nm, but the benzofuran part of the condensed heterocyclic ring of the photopolymerization initiator (c1) represented by the general formula (I) is a coloring material, In particular, by increasing the interaction force with carbon black, the adsorption of the photopolymerization initiator (c1) to the surface of the colorant particles is promoted. The light absorbed by the color material does not contribute to the polymerization and causes a significant decrease in exposure sensitivity. However, the photopolymerization initiator covers the color material surface, so that the light absorption rate with respect to the photopolymerization initiator is improved. Further, the adsorption of the photopolymerization initiator to the coloring material relatively lowers the photopolymerization initiator concentration in the resin component, so that the light transmittance to the deep portion is improved. Thereby, it is considered that the internal curability of the resist film is improved and the fine wire adhesion is improved.
　ただし、光重合開始剤（ｃ１）だけでは、露光光源のＵＶ波長域の低波長側の一部しか利用しておらず、十分な感度が得られないため、極大吸収波長が長波長域にある光重合開始剤（ｃ２）と組合せることで感度、特に表面感度が底上げできる。光重合開始剤（ｃ１）と光重合開始剤（ｃ２）の間には極大吸収波長の差があるため、併用による内部硬化性への影響は抑えられる。これらにより、表面感度と内部硬化を同時に高めることができたと考えられる。
　以上より、本発明の感光性樹脂組成物を用いることにより、高感度かつ細線密着性能に優れる感光性樹脂組成物が提供可能であることがわかる。 However, only the photopolymerization initiator (c1) uses only a part of the low wavelength side of the UV wavelength range of the exposure light source, and sufficient sensitivity cannot be obtained, so the maximum absorption wavelength is in the long wavelength range. By combining with the photopolymerization initiator (c2), the sensitivity, particularly the surface sensitivity can be increased. Since there is a difference in the maximum absorption wavelength between the photopolymerization initiator (c1) and the photopolymerization initiator (c2), the influence on the internal curability due to the combined use can be suppressed. It is considered that the surface sensitivity and internal curing can be improved at the same time.
From the above, it can be seen that by using the photosensitive resin composition of the present invention, it is possible to provide a photosensitive resin composition excellent in high sensitivity and fine wire adhesion performance.
　本発明を特定の態様を用いて詳細に説明したが、本発明の意図と範囲を離れることなく様々な変更および変形が可能であることは、当業者にとって明らかである。なお、本出願は２０１６年９月１６日付で出願された日本特許出願（特願２０１６－１８１９３２）に基づいており、その全体が引用により援用される。 Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention. Note that this application is based on a Japanese patent application filed on September 16, 2016 (Japanese Patent Application No. 2016-181932), which is incorporated by reference in its entirety.
　１０　透明支持基板
　２０　画素
　３０　有機保護層
　４０　無機酸化膜
　５０　透明陽極
　５１　正孔注入層
　５２　正孔輸送層
　５３　発光層
　５４　電子注入層
　５５　陰極
　１００　有機ＥＬ素子
　５００　有機発光体 DESCRIPTION OF SYMBOLS 10 Transparent support substrate 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode 51 Hole injection layer 52 Hole transport layer 53 Light emitting layer 54 Electron injection layer 55 Cathode 100 Organic EL element 500 Organic light emitter

Claims (10)

  1. 　（ａ）アルカリ可溶性樹脂、（ｂ）光重合性モノマー、（ｃ）光重合開始剤及び（ｄ）色材を含有する感光性樹脂組成物であって、
    　前記（ｃ）光重合開始剤が、下記一般式（Ｉ）で表される光重合開始剤（ｃ１）、及び、波長３２０ｎｍ～４００ｎｍの範囲における極大吸収波長が３３４ｎｍ以上である光重合開始剤（ｃ２）を含有することを特徴とする感光性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式（Ｉ）中、Ｒ１は置換基を有していてもよいアルキル基又は置換基を有していてもよい芳香族環基を表す。
    　Ｒ２は置換基を有していてもよいアルキル基又は置換基を有していてもよい芳香族環基を表す。
    　ｋは０又は１を表す。
    　Ｒ３～Ｒ６は各々独立に、任意の１価の置換基を表す。
    　ｌ、ｍ及びｏは各々独立に、０～３の整数を表す。ｎは０又は１を表す。）     A photosensitive resin composition comprising (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, and (d) a coloring material,
    The photopolymerization initiator (c) is a photopolymerization initiator (c1) represented by the following general formula (I), and a photopolymerization initiator having a maximum absorption wavelength of 334 nm or more in the wavelength range of 320 nm to 400 nm ( A photosensitive resin composition comprising c2).
    Figure JPOXMLDOC01-appb-C000001
     (In formula (I), R 1 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
    R 2 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
    k represents 0 or 1;
    R 3 to R 6 each independently represents an arbitrary monovalent substituent.
    l, m and o each independently represents an integer of 0 to 3. n represents 0 or 1. )
  2. 　全固形分に対する前記（ｃ）光重合開始剤の含有割合が２質量％以上である、請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein a content ratio of the photopolymerization initiator (c) with respect to the total solid content is 2% by mass or more.
  3. 　前記（ｃ）光重合開始剤における、前記光重合開始剤（ｃ１）の含有割合が１質量％以上である、請求項１又は２に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1 or 2, wherein the content ratio of the photopolymerization initiator (c1) in the (c) photopolymerization initiator is 1% by mass or more.
  4. 　前記光重合開始剤（ｃ２）が、フルオレン骨格又はカルバゾール骨格を有する光重合開始剤である、請求項１～３のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 3, wherein the photopolymerization initiator (c2) is a photopolymerization initiator having a fluorene skeleton or a carbazole skeleton.
  5. 　前記光重合開始剤（ｃ２）が、下記一般式（ＩＩ）で表される光重合開始剤である、請求項４に記載の感光性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000002
     （式（ＩＩ）中、Ｒ７は置換基を有していてもよいアルキル基又は置換基を有していてもよい芳香族環基を表す。
    　Ｒ８は置換基を有していてもよいアルキル基又は置換基を有していてもよい芳香族環基を表す。
    　ｐは０又は１を表す。
    　Ｒ９は任意の１価の置換基を表す。ｑは０～３の整数を表す。
    　Ｘは－Ｎ（Ｒ１０）－又は－Ｃ（Ｒ１１）（Ｒ１２）－を表す。
    　Ｒ１０～Ｒ１２は各々独立に、水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよい芳香族環基を表す。Ｒ１１とＲ１２は相互に結合して環を形成していてもよい。）     The photosensitive resin composition of Claim 4 whose said photoinitiator (c2) is a photoinitiator represented by the following general formula (II).
    Figure JPOXMLDOC01-appb-C000002
     (In Formula (II), R 7 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
    R 8 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
    p represents 0 or 1;
    R 9 represents an arbitrary monovalent substituent. q represents an integer of 0 to 3.
    X represents —N (R 10 ) — or —C (R 11 ) (R 12 ) —.
    R 10 to R 12 each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R 11 and R 12 may be bonded to each other to form a ring. )
  6. 　前記（ｄ）色材がカーボンブラックである、請求項１～５のいずれか１項に記載の感光性樹脂組成物。 6. The photosensitive resin composition according to claim 1, wherein the color material (d) is carbon black.
  7. 　全固形分に対する前記（ｄ）色材の含有割合が３０質量％以上である、請求項１～６のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 6, wherein the content of the color material (d) with respect to the total solid content is 30% by mass or more.
  8. 　前記（ａ）アルカリ可溶性樹脂が、カルボキシル基を有するエポキシ（メタ）アクリレート樹脂を含有する、請求項１～７のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 7, wherein the (a) alkali-soluble resin contains an epoxy (meth) acrylate resin having a carboxyl group.
  9. 　請求項１～８のいずれか１項に記載の感光性樹脂組成物を硬化させた硬化物。 A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 8.
  10. 　請求項９に記載の硬化物を有する画像表示装置。 An image display device having the cured product according to claim 9.
PCT/JP2017/033037 2016-09-16 2017-09-13 Photosensitive resin composition, cured product and image display device WO2018052024A1 (en)

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