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WO2018052024A1 - Composition de résine photosensible, produit durci et dispositif d'affichage d'image - Google Patents

Composition de résine photosensible, produit durci et dispositif d'affichage d'image 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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Prior art keywords
ring
group
mass
resin composition
photopolymerization initiator
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English (en)
Japanese (ja)
Inventor
植松　卓也
直人 関口
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Application filed by Mitsubishi Chemical Corp filed Critical Mitsubishi Chemical Corp
Priority to JP2018511166A priority Critical patent/JP6341351B1/ja
Priority to KR1020197007411A priority patent/KR102402726B1/ko
Priority to CN201780056225.0A priority patent/CN109791357B/zh
Publication of WO2018052024A1 publication Critical patent/WO2018052024A1/fr
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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.

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Abstract

La présente invention aborde le problème de la réalisation d'une composition de résine photosensible qui présente une sensibilité élevée et une excellente adhérence sur fil mince. Une composition de résine photosensible selon la présente invention contient (a) une résine soluble dans les alcalis, (b) un monomère photopolymérisable, (c) un initiateur de photopolymérisation et (d) un colorant ; et l'initiateur de photopolymérisation (c) contient un initiateur de photopolymérisation (c1) représenté par la formule générale (I) et un initiateur de photopolymérisation (c2) qui a une longueur d'onde d'absorption maximale de 334 nm ou plus dans une plage de longueurs d'onde allant de 320 nm à 400 nm. (Dans la formule (I), R1-R6, k, l, m, n et o sont tels que définis dans la description.)
PCT/JP2017/033037 2016-09-16 2017-09-13 Composition de résine photosensible, produit durci et dispositif d'affichage d'image Ceased WO2018052024A1 (fr)

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