WO2016052328A1 - Composition de résine noire photosensible, procédé de fabrication de film durci noir, filtre colore, et appareil d'affichage el organique - Google Patents

Composition de résine noire photosensible, procédé de fabrication de film durci noir, filtre colore, et appareil d'affichage el organique Download PDF

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WO2016052328A1
WO2016052328A1 PCT/JP2015/077093 JP2015077093W WO2016052328A1 WO 2016052328 A1 WO2016052328 A1 WO 2016052328A1 JP 2015077093 W JP2015077093 W JP 2015077093W WO 2016052328 A1 WO2016052328 A1 WO 2016052328A1
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group
black
cured film
resin composition
mass
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PCT/JP2015/077093
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English (en)
Japanese (ja)
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浜田　大輔
久保田　誠
江副　利秀
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富士フイルム株式会社
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Priority to JP2016551968A priority Critical patent/JP6476198B2/ja
Publication of WO2016052328A1 publication Critical patent/WO2016052328A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces

Definitions

  • the present invention relates to a photosensitive black resin composition, a method for producing a black cured film, a color filter, and an organic EL display device.
  • a color filter when using a white light emitting element, light of the three primary colors of red, green and blue is used by using a color filter.
  • a color filter may be used for the purpose of improving color purity.
  • Such a color filter may include a light-shielding film to improve contrast.
  • a color filter having a light shielding film provided in a part of a transmission color region is disclosed.
  • a material constituting the light shielding film for example, titanium is disclosed. ing.
  • the light shielding film is preferably formed using a photosensitive composition under low temperature conditions. If the light-shielding film can be formed under low temperature conditions, damage to other members (for example, a light-emitting layer in the light-emitting element) and the like during heating can be reduced.
  • various demands are also demanded for the light shielding film in recent years. For example, from the viewpoint of further improving the contrast, further improvement in the light shielding property of the light shielding film is required. Further, it is desirable that the thickness of the light shielding film is thin in order to cope with the thinning of the display device. Further, from the viewpoint of improving the display performance of the display device, it is necessary to further reduce the size of the sub-pixels in the color filter, and further miniaturization of the light shielding film is required.
  • the present invention provides a photosensitive black resin composition that is capable of forming a black cured film having a thin film thickness and excellent light shielding properties under low temperature conditions and excellent resolution.
  • the task is to do.
  • Another object of the present invention is to provide a method for producing a black cured film using the above composition, a color filter, and an organic EL display device.
  • the present inventor has found that the above-mentioned problems can be solved by using a composition containing a predetermined component, and has completed the present invention. That is, the present inventors have found that the above problem can be solved by the following configuration.
  • a photosensitive black resin composition for forming a black cured film disposed inside a color filter containing a black pigment and having subpixels each having a side length of 15 ⁇ m or less (2) A photosensitive black resin composition for forming a black cured film disposed inside a color filter having a subpixel having a side length of 15 ⁇ m or less, Including titanium black, dispersant, polymerizable compound, polymerization initiator, alkali-soluble resin, and solvent, The polymerizable compound satisfies at least one of requirements 1 and 2; The titanium black content is 55% by mass or more based on the total solid content of the photosensitive black resin composition, A photosensitive black resin composition having a solid content of 13 to 22% by mass.
  • Requirement 1 Having 5 or more ethylenically unsaturated groups in one molecule
  • Requirement 2 The amount of ethylenically unsaturated groups in one molecule is 7 mmol / g or more (3)
  • an ultraviolet absorber is included ( The photosensitive black resin composition as described in 1) or (2).
  • (10) The manufacturing method of the black cured film as described in (8) or (9) whose thickness of a black cured film is 1 micrometer or less.
  • (11) A black cured film obtained by the manufacturing method according to any one of (8) to (10), and at least one sub selected from the group consisting of a red sub-pixel, a green sub-pixel, and a blue sub-pixel A color filter having pixels.
  • (12) An organic EL display device having the color filter according to (11).
  • a black cured film having a thin film thickness and excellent light shielding properties can be formed under low temperature conditions, and a photosensitive black resin composition excellent in resolution can be provided.
  • the manufacturing method of a black cured film using the said composition, a color filter, and an organic electroluminescence display can also be provided.
  • composition each component that can be contained in the photosensitive black resin composition of the present invention (hereinafter also simply referred to as “composition”) will be described in detail.
  • group (atomic group) in this specification the description which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • radiation in the present specification means visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • a photosensitive black for forming a black cured film disposed inside a color filter including a black pigment and having subpixels each having a side length of 15 ⁇ m or less.
  • a resin composition is mentioned.
  • the black pigment used include black pigments described in a second embodiment described later, and examples thereof include titanium black and carbon black. Of these, titanium black is preferable.
  • various components disersant, polymerizable compound, polymerization initiator, alkali-soluble resin, solvent, etc. described in the second embodiment to be described later are included in a predetermined amount. May be.
  • a second embodiment which is a preferred embodiment of the composition of the present invention includes a composition containing a predetermined amount of a black pigment, a dispersant, a polymerizable compound, a polymerization initiator, an alkali-soluble resin, and a solvent.
  • the said composition is used in order to form the black cured film (black light shielding film) arrange
  • the composition of the present invention contains a black pigment, and preferably contains titanium black as a black pigment.
  • Titanium black is black particles containing titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride.
  • the surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and can also be treated with a water-repellent substance as disclosed in Japanese Patent Application Laid-Open No. 2007-302836. is there.
  • the titanium black is typically titanium black particles, and it is preferable that both the primary particle size and the average primary particle size of each particle are small.
  • the average primary particle diameter is preferably in the range of 10 nm to 45 nm, and more preferably in the range of 12 nm to 20 nm.
  • the particle diameter that is, the particle diameter is a diameter of a circle having an area equal to the projected area of the outer surface of the particle.
  • the projected area of the particles can be obtained by measuring the area obtained by photographing with an electron micrograph and correcting the photographing magnification.
  • the specific surface area of titanium black is not particularly limited, but the water repellency after surface treatment of such titanium black with a water repellent agent has a predetermined performance, and therefore the value measured by the BET method is usually 5 m 2 / g to 150 m 2 / g or less, particularly preferably 20 m 2 / g to 100 m 2 / g.
  • Examples of commercially available titanium black products include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade names: above, manufactured by Mitsubishi Materials Corporation), Tilac ( Tilac) D (trade name: manufactured by Ako Kasei Co., Ltd.).
  • Titanium black particles can be modified on the particle surface as necessary for the purpose of improving dispersibility and suppressing aggregation.
  • modification of the particle surface for example, coating treatment with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide or the like is possible, and repellent properties as disclosed in JP-A-2007-302836 are also possible. Treatment with an aqueous material is also possible.
  • the composition of the present invention contains titanium black as a dispersion containing titanium black and Si atoms.
  • titanium black is contained as a dispersion in the composition, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more in terms of mass.
  • the to-be-dispersed bodies include both those in which titanium black is in the state of primary particles and those in the state of aggregates (secondary particles). If the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion in the present invention exceeds 0.5, it tends to be difficult to produce a pigment dispersion using the dispersion.
  • the upper limit is preferably 0.5. Further, if the Si / Ti of the dispersion is too small, when the black cured film using the dispersion in the present invention is patterned by photolithography or the like, the residue tends to remain in the removed portion, and the Si of the dispersion When / Ti is too large, the light shielding ability tends to decrease. Therefore, Si / Ti of the dispersion is more preferably 0.05 or more and 0.5 or less, and 0.07 or more and 0.4 or less. More preferably. In order to change the Si / Ti of the object to be dispersed (for example, 0.05 or more), the following means can be used.
  • a dispersion is obtained by dispersing titanium oxide and silica particles using a disperser, and the mixture is subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C.), whereby titanium black particles are mainly contained.
  • a dispersion containing Si and Ti can be obtained.
  • Titanium black whose Si / Ti is adjusted to 0.05 or more, for example, is prepared by the method described in paragraph numbers [0005] and paragraph numbers [0016] to [0021] of Japanese Patent Application Laid-Open No. 2008-266045, for example. Can do.
  • the present invention by adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion containing titanium black and Si atoms to a suitable range (for example, 0.05 or more), this coverage is achieved.
  • a black cured film is formed using the composition of the present invention containing a dispersion, the residue derived from the composition outside the region where the black cured film is formed is reduced.
  • the residue includes components derived from the photosensitive composition such as titanium black particles and a resin component. The reason why the residue is reduced is not yet clear, but the above-mentioned dispersed material tends to have a small particle size (for example, a particle size of 30 nm or less).
  • the adsorptivity of the entire film with the undercoat is reduced, and this is presumed to contribute to the improvement of development and removal of uncured compositions (particularly titanium black) in the formation of black cured films.
  • titanium black is excellent in light-shielding property for light in a wide wavelength range from ultraviolet to infrared. Therefore, the above-described dispersion containing titanium black and Si atoms (preferably Si / Ti is 0 in terms of mass).
  • a black cured film formed using a .05 or more) exhibits excellent light shielding properties.
  • the content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP2013-249417A ).
  • the content ratio (Si / Ti) of Si atom and Ti atom in the to-be-dispersed body is 0.05. In order to determine whether or not this is the case, the method (2) described in paragraph 0035 of JP2013-249417A is used.
  • the above-described titanium black can be used.
  • complex oxides such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, carbon black, aniline
  • this dispersion for the purpose of adjusting the light shielding property, other colorants (such as organic pigments and dyes) may be used in combination with titanium black as long as the effects of the present invention are not impaired. Good.
  • materials used for introducing Si atoms into the dispersion will be described.
  • a Si-containing material such as silica may be used.
  • the silica that can be used in the present invention include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These may be appropriately selected and used.
  • the particle size of the silica particles is about the same as the film thickness when the black cured film is formed, the light-shielding property is lowered. Therefore, it is preferable to use fine particle type silica as the silica particles.
  • the fine particle type silica include silica described in paragraph 0039 of JP2013-249417A, and the contents thereof are incorporated in the present specification.
  • the composition of the present invention may contain only one type of titanium black, or may contain two or more types.
  • the content of titanium black is preferably 55% by mass or more with respect to the total solid content (total solid mass) of the composition, and the light-shielding property, low-temperature curability, and resolution of the black cured film to be formed. In terms of more excellent balance, 55 to 80% by mass is more preferable, and 55 to 70% by mass is more preferable. In addition, solid content can become a component which comprises a black cured film, and a solvent is not contained.
  • a black pigment for the composition of this invention may mix and use things other than titanium black as a black pigment for the composition of this invention.
  • a black pigment that can be mixed is not particularly limited as long as it has an absorbance in the visible light region.
  • examples thereof include organic pigments such as Pigment Black 1 and inorganic pigments such as Pigment Black 7.
  • Examples of mixing black pigments other than titanium black include a mixture of titanium black and carbon black in a ratio of 6: 1, a mixture of titanium black and titanium oxide in a ratio of 3: 1, and the like.
  • the black pigment other than titanium black to be mixed can be used in the range of 0.01 to 99.99 parts by mass with respect to 100 parts by mass of titanium black. Preferably, it is in the range of 20 to 70 parts by mass.
  • the composition of the present invention may contain extender pigments as necessary in addition to black pigments.
  • extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, titanium white, and hydrotalcite. These extender pigments can be used alone or in admixture of two or more.
  • the amount of extender used is usually 0 to 100 parts by weight, preferably 5 to 50 parts by weight, and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the black pigment.
  • the black pigment and extender pigment can be used after the surface thereof is modified with a polymer in some cases.
  • the composition of the present invention preferably contains a dispersant.
  • the dispersant contributes to the improvement of the dispersibility of the black pigment such as titanium black described above.
  • a known pigment dispersant or surfactant can be appropriately selected and used.
  • polymer compounds are preferable.
  • the polymer compound include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic.
  • polystyrene resin -Based copolymers, naphthalenesulfonic acid formalin condensates], polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, and pigment derivatives.
  • the polymer compounds can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.
  • the polymer compound is adsorbed on the surface of a dispersion such as a black pigment and, if desired, a pigment used together, and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures.
  • adsorbing the surface of titanium black or the above-described dispersion to be dispersed containing titanium black and Si atoms it is possible to promote the adsorptivity of the polymer compound to these.
  • the polymer compound preferably has a structural unit having a graft chain.
  • structural unit is synonymous with “repeating unit”. Since the polymer compound having such a structural unit having a graft chain has an affinity for a solvent by the graft chain, it is excellent in dispersibility of the black pigment and dispersion stability after aging. In addition, since the composition has an affinity with a polymerizable compound or other resin that can be used in combination due to the presence of the graft chain, a residue is hardly generated by alkali development. When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility is improved.
  • the graft chain preferably has a number of atoms excluding hydrogen atoms in the range of 40 to 10,000, more preferably a number of atoms excluding hydrogen atoms of 50 to 2000, and atoms excluding hydrogen atoms. More preferably, the number is from 60 to 500.
  • the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain.
  • the graft chain preferably has a polymer structure.
  • a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide structure. And a polyether structure.
  • the graft chain is at least one selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure.
  • the graft chain is preferably a graft chain having at least one of a polyester structure and a polyether structure.
  • the structure of the macromonomer having such a polymer structure as a graft chain is not particularly limited, but a macromonomer having a reactive double bond group can be preferably used.
  • AA-6 trade name, Toa Gosei Co., Ltd.
  • AA-10 Product name, manufactured by Toa Gosei Co., Ltd.
  • AB-6 trade name, manufactured by Toa Gosei Co., Ltd.
  • AS-6 trade name, produced by Toa Gosei Co., Ltd.
  • AN-6 trade name, manufactured by Toa Gosei Co., Ltd.
  • Co., Ltd. AW-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-707 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-5 (trade name, manufactured by Toa Gosei Co., Ltd.
  • AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.) AS-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.), Bremer PME-4000 (trade name, manufactured by NOF Corporation), and the like.
  • the polymer compound preferably includes a structural unit represented by any one of the following formulas (1) to (4) as a structural unit having a graft chain, and includes the following formula (1A), the following formula (2A), More preferably, it contains a structural unit represented by any one of the following formula (3A), the following formula (3B), and the following (4).
  • W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH.
  • W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
  • X 1 , X 2 , X 3 , X 4 , and X 5 each independently represent a hydrogen atom or a monovalent organic group.
  • X 1 , X 2 , X 3 , X 4 , and X 5 are preferably each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and each independently represents hydrogen.
  • An atom or a methyl group is more preferable, and a methyl group is particularly preferable.
  • Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly limited in structure.
  • Specific examples of the divalent linking group represented by Y 1 , Y 2 , Y 3 , and Y 4 include the following (Y-1) to (Y-21) linking groups.
  • a and B represent binding sites with the left end group and the right end group in Formulas (1) to (4), respectively.
  • (Y-2) or (Y-13) is more preferable from the viewpoint of ease of synthesis.
  • Z 1 , Z 2 , Z 3 , and Z 4 each independently represent a monovalent organic group.
  • the structure of the organic group is not particularly limited, and specific examples include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group. Is mentioned.
  • the organic group represented by Z 1 , Z 2 , Z 3 , and Z 4 those having a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms.
  • a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is particularly preferable.
  • the alkyl group contained in the alkoxy group may be linear, branched or cyclic.
  • n, m, p, and q are each independently an integer of 1 to 500.
  • j and k each independently represent an integer of 2 to 8.
  • J and k in the formulas (1) and (2) are preferably integers of 4 to 6 and most preferably 5 from the viewpoints of dispersion stability and developability.
  • R 3 represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R 3 may be the same or different from each other.
  • R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure.
  • R 4 preferably includes a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and more preferably a hydrogen atom or an alkyl group.
  • the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable.
  • a plurality of X 5 and R 4 present in the graft copolymer may be the same or different from each other.
  • the polymer compound may have a structural unit having a graft chain, which has two or more different structures. That is, the polymer compound molecule may contain structural units represented by formulas (1) to (4) having different structures, and n, m in formulas (1) to (4). , P, and q each represent an integer of 2 or more, in formula (1) and formula (2), j and k may contain structures different from each other in the side chain. In the formula (4), a plurality of R 3 , R 4 and X 5 present in the molecule may be the same or different from each other.
  • the structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoints of dispersion stability and developability.
  • the structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of dispersion stability and developability.
  • X 1, Y 1, Z 1 and n are as defined X 1, Y 1, Z 1 and n in Formula (1), and preferred ranges are also the same.
  • X 2, Y 2, Z 2 and m are as defined X 2, Y 2, Z 2 and m in the formula (2), and preferred ranges are also the same.
  • the structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or (3B) from the viewpoints of dispersion stability and developability.
  • X 3, Y 3, Z 3 and p are as defined X 3, Y 3, Z 3 and p in formula (3), and preferred ranges are also the same.
  • the polymer compound has a structural unit represented by the formula (1A) as a structural unit having a graft chain.
  • the structural unit having a graft chain (for example, the structural unit represented by the above formulas (1) to (4)) is 10% to 90% in terms of mass with respect to the total mass of the polymer compound. It is preferably included within the range of 30% to 70%. When the structural unit having a graft chain is contained within this range, the dispersibility of the black pigment (particularly titanium black particles) is high, and the developability when forming a black cured film is good.
  • the polymer compound preferably has a hydrophobic structural unit different from the structural unit having a graft chain (that is, not corresponding to the structural unit having a graft chain).
  • the hydrophobic structural unit is a structural unit having no acid group (for example, carboxylic acid group, sulfonic acid group, phosphoric acid group, phenolic hydroxyl group, etc.).
  • the hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, more preferably derived from a compound having a ClogP value of 1.2 to 8. A structural unit. Thereby, the effect of this invention can be expressed more reliably.
  • ClogP values can be obtained from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used. A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J. et al. B.
  • log P means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is represented by the following formula.
  • logP log (Coil / Cwater)
  • Coil represents the molar concentration of the compound in the oil phase
  • Cwater represents the molar concentration of the compound in the aqueous phase.
  • the polymer compound preferably has one or more structural units selected from structural units derived from monomers represented by the following general formulas (i) to (iii) as hydrophobic structural units.
  • R 1 , R 2 , and R 3 each independently represent a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or a carbon atom number of 1 to 6
  • An alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.).
  • R 1 , R 2 , and R 3 are more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably a hydrogen atom or a methyl group.
  • R 2 and R 3 are particularly preferably a hydrogen atom.
  • X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • L is a single bond or a divalent linking group.
  • a divalent aliphatic group for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group
  • a divalent aromatic group for example, an arylene group
  • Substituted arylene group divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR 31 —, where R 31 Are aliphatic groups, aromatic groups or heterocyclic groups), carbonyl groups (—CO—), or combinations thereof.
  • the divalent aliphatic group may have a cyclic structure or a branched structure.
  • the number of carbon atoms in the aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-10.
  • the aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group.
  • the number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.
  • the divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle.
  • Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring.
  • the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group, or heterocyclic group.
  • L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
  • the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
  • L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
  • the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
  • the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
  • Z is an aliphatic group (eg, alkyl group, substituted alkyl group, unsaturated alkyl group, substituted unsaturated alkyl group), aromatic group (eg, aryl group, substituted aryl group, arylene group, substituted arylene group). , A heterocyclic group, or a combination thereof. These groups include an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR 31 —, wherein R 31 is an aliphatic group, an aromatic group Group or heterocyclic group) or a carbonyl group (—CO—) may be contained.
  • the aliphatic group may have a cyclic structure or a branched structure.
  • the number of carbon atoms in the aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-10.
  • the aliphatic group further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4-cyclohexyl. A phenyl group and the like are included.
  • bridged cyclic hydrocarbon ring for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.)
  • Hydrocarbon rings and tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo [5.2.1.02,6] decane, tricyclo [4.3.1.12,5] undecane ring, tetracyclo [4 4.0.12, 5.17,10] dodecane, tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring, and the like.
  • the bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene.
  • a condensed ring formed by condensing a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring is also included.
  • the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.
  • the number of carbon atoms in the aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.
  • the heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.
  • R 4 , R 5 , and R 6 are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms ( For example, it represents a methyl group, an ethyl group, a propyl group, etc.), Z, or -LZ.
  • L and Z are as defined above.
  • R 4 , R 5 and R 6 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • R 1 , R 2 , and R 3 are a hydrogen atom or a methyl group, and L is a single bond, an alkylene group, or an oxyalkylene structure.
  • a compound in which X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.
  • R 1 is a hydrogen atom or a methyl group
  • L is an alkylene group
  • Z is an aliphatic group, a heterocyclic group or an aromatic group. Is preferred.
  • R 4 , R 5 , and R 6 are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Certain compounds are preferred.
  • Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.
  • Examples of typical compounds represented by formulas (i) to (iii) the compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are described in the present specification. Incorporated into.
  • the hydrophobic structural unit is preferably contained in a range of 10% to 90% and more preferably in a range of 20% to 80% with respect to the total mass of the polymer compound in terms of mass. Preferably, it is contained in the range of 30% to 70%. When the content is in the above range, sufficient pattern formation can be obtained.
  • the high molecular compound can introduce a functional group capable of forming an interaction with a black pigment (particularly, titanium black).
  • the polymer compound preferably further has a structural unit having a functional group capable of forming an interaction with the black pigment.
  • the functional group capable of forming an interaction with the black pigment include an acid group, a basic group, a coordination group, and a reactive functional group.
  • the polymer compound has an acid group, a basic group, a coordinating group, or a reactive functional group
  • the structural unit having an acid group, the structural unit having a basic group, or a coordinating group respectively. It is preferable to have a structural unit having or a structural unit having reactivity.
  • the polymer compound when the polymer compound further has an alkali-soluble group such as a carboxylic acid group as an acid group, developability for pattern formation by alkali development can be imparted to the polymer compound. That is, by introducing an alkali-soluble group into the polymer compound, the polymer compound as a dispersant that contributes to the dispersion of the black pigment has alkali solubility in the composition of the present invention.
  • a composition containing such a polymer compound has excellent light-shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
  • a high molecular compound has a structural unit which has an acid group
  • the acid group in the structural unit having an acid group easily interacts with the black pigment, the polymer compound stably disperses the black pigment, and the viscosity of the polymer compound that disperses the black pigment is the above-described polyester. This is presumed to be because it is lowered by the graft chain having a structure and the polymer compound itself is easily dispersed stably.
  • the structural unit having an alkali-soluble group as an acid group may be the same structural unit as the above-described structural unit having a graft chain or a different structural unit. Is a structural unit different from the hydrophobic structural unit described above (that is, does not correspond to the hydrophobic structural unit described above).
  • the acid group that is a functional group capable of forming an interaction with the black pigment examples include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group.
  • the polymer compound may have one or more structural units having an acid group.
  • the polymer compound may or may not contain a structural unit having an acid group. However, when it is contained, the content of the structural unit having an acid group is based on the total mass of the polymer compound in terms of mass.
  • the ratio is preferably 5% or more and 80% or less, and more preferably 10% or more and 60% or less from the viewpoint of suppressing damage to the image strength due to alkali development.
  • Examples of the basic group that is a functional group capable of forming an interaction with the black pigment include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, and an amide group. Among them, particularly preferred is a tertiary amino group having a good adsorptive power to a black pigment and high dispersibility.
  • the polymer compound can have one or more of these basic groups.
  • the polymer compound may or may not contain a structural unit having a basic group, but when it is contained, the content of the structural unit having a basic group is calculated by mass conversion to the total mass of the polymer compound. On the other hand, it is preferably 0.01% or more and 50% or less, and more preferably 0.01% or more and 30% or less from the viewpoint of suppressing developability inhibition.
  • Examples of the coordinating group that is a functional group capable of forming an interaction with the black pigment and the reactive functional group include an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, and an acid chloride. Is mentioned. Particularly preferred is an acetylacetoxy group which has a good adsorptive power to black pigments and a high dispersibility.
  • the polymer compound may have one or more of these groups.
  • the polymer compound may or may not contain a structural unit having a coordinating group or a structural unit having a reactive functional group, but when it is contained, the content of these structural units is: In terms of mass, it is preferably 10% or more and 80% or less, and more preferably 20% or more and 60% or less from the viewpoint of inhibition of developability inhibition with respect to the total mass of the polymer compound.
  • polymer compound in the present invention When the polymer compound in the present invention has a functional group capable of interacting with a black pigment in addition to the graft chain, it contains a functional group capable of interacting with various black pigments as described above. There is no particular limitation on how these functional groups are introduced, but polymer compounds are structural units derived from monomers represented by the following general formulas (iv) to (vi) It is preferable to have one or more structural units selected from
  • R 11 , R 12 , and R 13 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon atom It represents an alkyl group having 1 to 6 numbers (for example, a methyl group, an ethyl group, a propyl group, etc.).
  • R 11 , R 12 and R 13 are more preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, most preferably Are each independently a hydrogen atom or a methyl group.
  • R 12 and R 13 are each particularly preferably a hydrogen atom.
  • X 1 in the general formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • Y in the general formula (v) represents a methine group or a nitrogen atom.
  • L 1 represents a single bond or a divalent linking group.
  • the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene groups and substituted arylene groups), divalent heterocyclic groups, oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino bonds (—NR 31 ′ —
  • R 31 ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), or a combination thereof.
  • the divalent aliphatic group may have a cyclic structure or a branched structure.
  • the number of carbon atoms in the aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-10.
  • the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.
  • the number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.
  • the divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle.
  • One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle.
  • the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.
  • L 1 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
  • the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
  • L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
  • the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
  • the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
  • Z 1 represents a functional group capable of interacting with the black pigment other than the graft site, and is preferably a carboxylic acid group or a tertiary amino group. A carboxylic acid group is more preferable.
  • R 14 , R 15 , and R 16 are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms (eg, , methyl group, ethyl group, propyl group, etc.), - represents a Z 1, or -L 1 -Z 1.
  • L 1 and Z 1 are the same meaning as L 1 and Z 1 in the above, it is the preferable examples.
  • R 14 , R 15 and R 16 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • R 11 , R 12 , and R 13 are each independently a hydrogen atom or a methyl group, and L 1 is an alkylene group or an oxyalkylene structure.
  • a compound in which X is an oxygen atom or an imino group and Z is a carboxylic acid group is preferable.
  • R 11 is a hydrogen atom or a methyl group
  • L 1 is an alkylene group
  • Z 1 is a carboxylic acid group
  • Y is methine. Compounds that are groups are preferred.
  • R 14 , R 15 and R 16 are each independently a hydrogen atom or a methyl group, L is a single bond or an alkylene group, and Z A compound in which is a carboxylic acid group is preferred.
  • monomers represented by general formula (iv) to general formula (vi).
  • monomers include methacrylic acid, crotonic acid, isocrotonic acid, a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride, Reaction product of compound having addition polymerizable double bond and hydroxyl group in molecule and phthalic anhydride, reaction product of compound having addition polymerizable double bond and hydroxyl group in molecule and tetrahydroxyphthalic anhydride, intramolecular A reaction product of a compound having an addition polymerizable double bond and a hydroxyl group and trimellitic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and pyromellitic anhydride, acrylic acid, acrylic acid Dimer, acrylic acid oligomer, maleic acid, itaconic
  • the content of the structural unit having a functional group capable of forming an interaction with the black pigment is, in terms of mass, from the viewpoint of the interaction with the black pigment, the dispersion stability, and the permeability to the developer. 0.05% to 90% by weight, preferably 1.0% to 80% by weight, more preferably 10% to 70% by weight, based on the total weight.
  • the polymer compound forms an interaction with the structural unit having a graft chain, the hydrophobic structural unit, and the black pigment as long as the effects of the present invention are not impaired.
  • other structural units having various functions for example, a structural unit having a functional group having affinity with a dispersion medium used in the dispersion).
  • Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
  • the polymer compound may use one or more of these other structural units, and the content thereof is preferably 0% or more and 80% or less in terms of mass with respect to the total mass of the polymer compound. Especially preferably, it is 10% or more and 60% or less. When the content is in the above range, sufficient pattern formability is maintained.
  • the acid value of the polymer compound is preferably in the range of 0 mgKOH / g to 160 mgKOH / g, more preferably in the range of 10 mgKOH / g to 140 mgKOH / g, and still more preferably in the range of 20 mgKOH / g to 120 mgKOH / g.
  • the range is as follows. When the acid value of the polymer compound is 160 mgKOH / g or less, pattern peeling during development when forming a black cured film is more effectively suppressed. Moreover, if the acid value of a high molecular compound is 10 mgKOH / g or more, alkali developability will become more favorable.
  • the acid value of the polymer compound is 20 mgKOH / g or more, the precipitation of the black pigment (particularly titanium black) or the dispersion to be dispersed containing titanium black and Si atoms can be further suppressed, and the number of coarse particles can be reduced. And the stability over time of the composition can be further improved.
  • the acid value of the polymer compound can be calculated, for example, from the average content of acid groups in the polymer compound.
  • the resin which has a desired acid value can be obtained by changing content of the structural unit containing the acid group which is a structural component of a high molecular compound.
  • the weight average molecular weight of the polymer compound in the present invention is 4,000 as a polystyrene conversion value by GPC (Gel permeation chromatography) method from the viewpoint of pattern peeling inhibition and developability during development when forming a black cured film. It is preferably 300 or more and 300 or less, more preferably 5,000 or more and 200,000 or less, further preferably 6,000 or more and 100,000 or less, and 10,000 or more and 50,000 or less. It is particularly preferred.
  • the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID ⁇ 15 cm) as columns and THF (tetrahydrofuran) as an eluent. ).
  • the polymer compound can be synthesized based on a known method, and examples of the solvent used for synthesizing the polymer compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, and ethylene glycol monomethyl.
  • Ether ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene,
  • Examples include ethyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or in combination of two or more.
  • polymer compound As specific examples of the polymer compound, the polymer compounds described in paragraphs 0127 to 0129 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification.
  • graft copolymers described in JP-A 2010-106268, paragraphs 0037 to 0115 corresponding to paragraphs 0075 to 0133 in US2011 / 0124824.
  • it has a side chain structure in which acidic groups in paragraphs 0028 to 0084 (corresponding to columns 0075 to 0133 of US 2011/0279759) of JP 2011-153283 A are bonded via a linking group.
  • Polymeric compounds containing components can be used, the contents of which can be incorporated and incorporated herein.
  • the content of the dispersant in the composition of the present invention is preferably 0.1% by mass to 50% by mass and more preferably 0.5% by mass to 30% by mass with respect to the total solid content of the composition.
  • the composition of the present invention preferably contains a polymerizable compound.
  • the polymerizable compound preferably satisfies at least one of the following requirements 1 and 2.
  • Requirement 1 Having 5 or more ethylenically unsaturated groups in one molecule
  • Requirement 2 The amount of ethylenically unsaturated groups in one molecule is 7 mmol / g or more
  • Requirement 1 is ethylene in one molecule of a polymerizable compound
  • the number of the unsaturated groups is intended to be 5 or more, and 5 to 20 is preferable and 5 to 8 is more preferable in terms of better resolution.
  • Requirement 2 intends that the amount of ethylenically unsaturated groups in one molecule of the polymerizable compound is 7 mmol / g or more, and is preferably 7 to 30 mmol / g, more preferably 7 to 15 mmol in terms of better resolution. / G is more preferable.
  • the ethylenically unsaturated group is a group having a carbon-carbon double bond, and this carbon-carbon double bond may be conjugated with other saturated bonds, but is stable like a benzene ring. It does not include double bonds in aromatic rings.
  • Examples of the ethylenically unsaturated group include a vinyl group (—CH ⁇ CH 2 ), a (meth) acryloyl group [—C ( ⁇ O) CH ⁇ CH 2 , —C ( ⁇ O) C (CH 3 ) ⁇ CH. 2 ], vinylsulfonyl group (—SO 2 CH ⁇ CH 2 ), and groups having a partial structure of —C ( ⁇ O) CH ⁇ CHC ( ⁇ O) — such as maleimide.
  • the polymerizable compound preferably satisfies one of the above requirements 1 and 2, and more preferably satisfies both.
  • examples of the polymerizable compound include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, and trimethylolpropane tri (acryloyloxypropyl) ether.
  • Tri (acryloyloxyethyl) isocyanurate Tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane and the addition of ethylene oxide and propylene oxide followed by (meth) acrylate conversion, pentaerythritol or dipentaerythritol poly (meta) )
  • Polyfunctional acrylates and methacrylates such as epoxy acrylates that are reaction products of acrylated and epoxy resins with (meth) acrylic acid It can be mentioned.
  • the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308, which are introduced as photocurable monomers and oligomers can also be used.
  • urethane oligomers UAS-10, UAB-140 (trade name, manufactured by Nippon Paper Chemicals Co., Ltd.), A-TMMT, UA-7200 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA, DPHA-40H, DPCA-20 (trade names, manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (trade names, Kyoeisha Chemical ( Etc.). Further, ethylenically unsaturated compounds having an acid group are also suitable, and examples of commercially available products include TO-1382, which is a carboxyl group-containing pentafunctional acrylate.
  • a polymeric compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the combination aspect can be suitably set according to the physical property etc. which are requested
  • a suitable combination mode of the polymerizable compound for example, a mode in which two or more polymerizable compounds selected from the polyfunctional acrylate compounds described above are combined, and an example thereof is dipentaerythritol hexaacrylate. And a combination of pentaerythritol triacrylate.
  • the content of the polymerizable compound in the composition of the present invention is preferably 3% by mass to 55% by mass, more preferably 10% by mass to 50% by mass with respect to the total solid content of the composition, and 10 to 25% by mass. Is more preferable.
  • the composition of the present invention preferably contains a polymerization initiator.
  • a polymerization initiator There is no restriction
  • it may be an activator that generates an active radical by causing some action with a photoexcited sensitizer, and may be an initiator that initiates cationic polymerization according to the type of monomer.
  • the polymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).
  • polymerization initiator examples include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, oximes such as hexaarylbiimidazole and oxime derivatives.
  • acylphosphine compounds such as acylphosphine oxide
  • oximes such as hexaarylbiimidazole and oxime derivatives.
  • examples thereof include compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
  • IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by Ciba Japan) can be used.
  • aminoacetophenone initiator commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by Ciba Japan Co., Ltd.) can be used.
  • aminoacetophenone-based initiator a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source of 365 nm or 405 nm can also be used.
  • acylphosphine-based initiator commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by Ciba Japan) can be used.
  • oxime initiator oxime compound
  • oxime initiator oxime compound
  • Specific compound names of the oxime initiator include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [ 4- (phenylthio) phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O -Benzoyloxime) -1- [4- (methyl
  • oxime initiators examples include TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD).
  • Commercial products can be used.
  • the description of oxime initiators described in paragraphs 0092 to 0096 of JP2012-113104A can be referred to, and the contents thereof are incorporated in the present specification. By using such an oxime initiator, a composition having high curing sensitivity and good developability can be provided.
  • the oxime-based initiator is a compound described in paragraphs 0030 and later of JP2012-113104A.
  • the general formula is represented by the general formula (I) described in claim 1 of JP2012-113104A, and more preferably expressed by the general formula (IA) described in claim 3. Yes, these descriptions can be referred to, and the contents thereof are incorporated in the present specification.
  • IRGACURE OXE 01 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]
  • IRGACURE manufactured by BASF Japan OXE 02 ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime)
  • the content of the polymerization initiator in the composition of the present invention is preferably 0.1% by mass to 30% by mass, and preferably 1% by mass to 25% by mass with respect to the total solid content of the composition. More preferably, the content is 1% by mass to 10% by mass.
  • the composition of the present invention preferably contains an alkali-soluble resin.
  • the alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable. From the viewpoint of development control, acrylic resins and acrylamide resins are preferable.
  • Resins and acrylic / acrylamide copolymer resins are preferred.
  • examples of the group that promotes alkali solubility include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group.
  • the group is soluble in an organic solvent and developed with a weak alkaline aqueous solution. Possible are preferable, and (meth) acrylic acid is particularly preferable.
  • These acid groups may be used alone or in combination of two or more.
  • alkali-soluble resin examples include resins having a carboxylic acid group in the side chain (for example, radical polymer), such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-sho. Nos.
  • Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and examples of monomers having an acid anhydride include maleic anhydride.
  • An acid etc. are mentioned.
  • an acidic cellulose derivative having a carboxylic acid group in the side chain is also exemplified.
  • those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.
  • 993966, 120204000, and 2001-318463 has an excellent balance of film strength and developability. It is preferable.
  • polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer.
  • alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) propane and epichlorohydrin are also useful.
  • a known radical polymerization method can be applied.
  • Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.
  • the content of the alkali-soluble resin in the composition of the present invention is preferably 0.1% by mass to 25% by mass, and 0.3% by mass to 20% by mass with respect to the total solid content of the composition. More preferably, the content is 0.5 to 10% by mass.
  • the composition of the present invention preferably contains a solvent.
  • the solvent include water or an organic solvent.
  • organic solvents include, for example, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether.
  • Acetylacetone, cyclohexanone, cyclopentanone, diacetone alcohol ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol Nomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, ⁇ -butyrolactone, acetic acid Examples include, but are not limited to, ethyl, butyl acetate, methyl lactate, and ethyl lactate.
  • a solvent may be used individually by 1 type and may be used in combination of 2 or more type.
  • two or more solvents are used in combination, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate 2-heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
  • the amount of the solvent contained in the composition is preferably 10% by mass to 90% by mass and more preferably 20% by mass to 85% by mass with respect to the total amount of the composition.
  • the composition of the present invention may contain components other than those described above.
  • the composition of the present invention may contain an adhesive.
  • the adhesion agent include a silane coupling agent and a titanium coupling agent.
  • a silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule. Note that a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
  • silane coupling agents examples include N- ⁇ -aminoethyl- ⁇ -aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), N- ⁇ -aminoethyl- ⁇ -aminopropyl-trimethoxy.
  • Silane (trade name KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.), N- ⁇ -aminoethyl- ⁇ -aminopropyl-triethoxysilane (trade name KBE-602, manufactured by Shin-Etsu Chemical Co., Ltd.), ⁇ -aminopropyl-trimethoxysilane (Trade name KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.), ⁇ -aminopropyl-triethoxysilane (trade name KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (trade name manufactured by Shin-Etsu Chemical Co., Ltd.) KBM-503) and the like.
  • a silane coupling agent Y having at least a silicon atom, a nitrogen atom and a curable functional group in the molecule and having a hydrolyzable group bonded to the silicon atom is provided.
  • the silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms and substituents. They may be the same atom, substituent or different.
  • Atoms and substituents that can be bonded are a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an alkyl group and / or an aryl group, a silyl group Group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group, and the like.
  • substituents further include amino groups, halogen atoms, sulfonamide groups, which can be substituted with silyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, thioalkoxy groups, alkyl groups and / or aryl groups, It may be substituted with an alkoxycarbonyl group, an amide group, a urea group, an ammonium group, an alkylammonium group, a carboxyl group, a salt thereof, a sulfo group, or a salt thereof.
  • at least one hydrolyzable group is bonded to the silicon atom. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group.
  • the silane coupling agent Y has at least one nitrogen atom in the molecule, and the nitrogen atom is preferably present in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom is used as a substituent. It preferably has at least one organic group.
  • the amino group structure may exist in the molecule in the form of a partial structure of a nitrogen-containing heterocycle, or may exist as a substituted amino group such as aniline.
  • examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof.
  • substituents that can be introduced include silyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, thioalkoxy group, amino group, halogen atom, and sulfonamide.
  • the nitrogen atom is couple
  • Preferred examples of the organic linking group include the above-described nitrogen atom and a substituent that can be introduced into the organic group bonded thereto.
  • Examples of the curable functional group contained in the silane coupling agent Y include a (meth) acryloyloxy group, an epoxy group, and an oxetanyl group.
  • the silane coupling agent Y only needs to have at least one curable functional group in one molecule, but it is also possible to take an embodiment having two or more curable functional groups, sensitivity, stability. From this viewpoint, it is preferable to have 2 to 20 curable functional groups, more preferably 4 to 15, and most preferably 6 to 10 curable functional groups in the molecule.
  • the content of the adhesion agent is preferably 0.5% by mass to 30% by mass, more preferably 0.7% by mass to 20% by mass, based on the total solid content of the composition. More preferably, the content is 7% by mass to 5% by mass.
  • the composition of the present invention may contain an ultraviolet absorber.
  • an ultraviolet absorber As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.
  • compounds in paragraphs 0137 to 0142 of JP2012-068418A corresponding to paragraphs 0251 to 0254 of US2012 / 0068292 can be used, and the contents thereof can be incorporated herein. Incorporated.
  • a diethylamino-phenylsulfonyl ultraviolet absorber (trade name: UV-503, manufactured by Daito Chemical Co., Ltd.) is also preferably used.
  • the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP2012-32556A.
  • the composition may or may not contain an ultraviolet absorber, but when included, the content of the ultraviolet absorber is preferably 0.001% by mass to 15% by mass with respect to the total solid content of the composition, It is more preferably 0.01% by mass to 10% by mass, and further preferably 0.1% by mass to 5% by mass.
  • surfactants may be added to the composition from the viewpoint of further improving coatability.
  • various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • the composition of the present invention contains a fluorosurfactant, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved. Sex can be improved more.
  • fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.) and the like.
  • surfactants include, for example, surfactants described in paragraphs 0174 to 0177 of JP2013-249417A, the contents of which are incorporated herein. Only one type of surfactant may be used, or two or more types may be combined.
  • the addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass and more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the composition.
  • the following components may be further added to the composition.
  • examples include sensitizers, co-sensitizers, cross-linking agents, curing accelerators, fillers, thermosetting accelerators, polymerization inhibitors, plasticizers, diluents, sensitizers, and the like.
  • Adhesion promoters and other auxiliaries for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.
  • These known additives may be added as necessary.
  • These components include, for example, paragraph numbers 0183 to 0228 of JP2012-003225A (corresponding US Patent Application Publication No.
  • JP2008-250074A Paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, paragraph numbers 0159 to 0184 in JP 2013-195480 A, and the like can be referred to, and the contents thereof are incorporated in the present specification. .
  • the solid content concentration of the composition of the present invention is preferably 13 to 22% by mass, more preferably 15 to 21% by mass in terms of the balance between the thickness of the black cured film to be formed and the light shielding property, More preferably, it is 17 to 20% by mass.
  • the composition of the present invention can be prepared by mixing the above-described various components by a known mixing method (for example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser).
  • the composition of the present invention (the first embodiment and the second embodiment of the photosensitive black resin composition) is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration.
  • a filter made of fluorine resin such as PTFE (polytetrafluoroethylene), polyamide resin such as nylon, polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP), and the like can be given.
  • polypropylene (including high density polypropylene) and nylon are preferable.
  • the pore size of the filter is suitably about 0.1 to 7.0 ⁇ m, preferably about 0.2 to 2.5 ⁇ m, more preferably about 0.2 to 1.5 ⁇ m, and still more preferably 0.3 to 0.0 ⁇ m. 7 ⁇ m.
  • the filtering by the first filter may be performed only once or may be performed twice or more.
  • the second and subsequent hole diameters are the same or larger than the first filtering hole diameter.
  • the pore diameter here can refer to the nominal value of the filter manufacturer.
  • a filter As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
  • the second filter a filter formed of the same material as the first filter described above can be used.
  • the pore size of the second filter is suitably about 0.2 to 10.0 ⁇ m, preferably about 0.2 to 7.0 ⁇ m, more preferably about 0.3 to 6.0 ⁇ m. By setting it as this range, the foreign material mixed in the liquid mixture can be removed while the component particles contained in the liquid mixture remain.
  • the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.
  • the method for producing the black cured film is not particularly limited, but the above-described composition is applied on a substrate (preferably, a SiN film) to form a coating film, and the coating film is subjected to a curing treatment.
  • the method of manufacturing is mentioned.
  • the method for the curing treatment is not particularly limited, and examples thereof include a photocuring treatment or a thermosetting treatment, and a photocuring treatment (particularly, an ultraviolet irradiation treatment) is preferable because pattern formation is easy.
  • substrate used is not restrict
  • composition layer forming step As a preferred embodiment of the method for producing a black cured film of the present invention, a step of applying a composition of the present invention on a substrate to form a composition layer (hereinafter, abbreviated as “composition layer forming step” as appropriate). ), A step of exposing the composition layer through a mask (hereinafter abbreviated as “exposure step” where appropriate), and developing the exposed composition layer to form a colored pattern (patterned black cured film). (Hereinafter, abbreviated as “development step” where appropriate). Specifically, the composition of the present invention is applied on a substrate directly or via another layer to form a composition layer (composition layer forming step), and exposed through a predetermined mask pattern. By curing only the coating film portion irradiated with light (exposure process) and developing with a developer (development process), a patterned black cured film can be produced. Hereinafter, each process in the said aspect is demonstrated.
  • composition layer forming step a composition layer is formed by applying the composition of the present invention on a substrate.
  • the substrate for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and the like in which a transparent conductive film is attached thereto, a solid-state imaging device, etc.
  • the photoelectric conversion element substrate include a silicon substrate and a complementary metal oxide semiconductor (CMOS).
  • CMOS complementary metal oxide semiconductor
  • a SiN film may be used as the substrate.
  • composition of the present invention As a coating method of the composition of the present invention on the substrate, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing method can be applied.
  • the coating thickness of the composition layer is preferably from 0.35 ⁇ m to 1.5 ⁇ m, more preferably from 0.40 ⁇ m to 1.0 ⁇ m, from the viewpoint of resolution and developability.
  • the composition coated on the substrate is usually dried at 70 ° C. to 110 ° C. for about 2 minutes to 4 minutes to form a composition layer.
  • the composition layer formed in the composition layer forming step is exposed through a mask, and only the coating film portion irradiated with light is cured.
  • the exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are preferably used, and a high-pressure mercury lamp is more preferable.
  • the irradiation intensity is preferably 5 mJ / cm 2 or more 1500 mJ / cm 2 or less, more preferably 10 mJ / cm 2 or more 1000 mJ / cm 2 or less, 10 mJ / cm 2 or more 800 mJ / cm 2 or less is most preferable.
  • an alkali development treatment (development step) is performed, and the light non-irradiated part in the exposure step is eluted in an alkaline aqueous solution.
  • an organic alkali developer is desirable.
  • the development temperature is usually from 20 ° C. to 30 ° C., and the development time is from 20 seconds to 90 seconds.
  • the alkaline aqueous solution include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate as the inorganic developer, ammonia water, ethylamine, diethylamine as the organic alkali developer.
  • Alkaline compounds such as dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, and the concentration is 0.001
  • An aqueous alkali solution dissolved in an amount of ⁇ 10% by mass, preferably 0.01 to 1% by mass is exemplified.
  • An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.
  • a developer composed of such an alkaline aqueous solution it is generally washed (rinsed) with pure water after development.
  • the black cured film obtained from the composition described above has a small thickness and exhibits excellent light shielding properties. Moreover, it can be cured by low temperature curing and has excellent developability.
  • the black cured film functions as a so-called light shielding film.
  • the thickness of the black cured film is not particularly limited, but is preferably 1 ⁇ m or less, more preferably 0.8 ⁇ m or less, and even more preferably 0.5 ⁇ m or less from the viewpoint of thinning. Although a minimum in particular is not restrict
  • the pattern size (length of one side) is preferably 5 ⁇ m or less and more preferably 1 ⁇ m or less from the viewpoint of obtaining the effect of the present invention more effectively.
  • a minimum in particular is not restrict
  • the pattern shape is preferably a square shape, and may be square or rectangular. The length of the long side of the quadrangle should satisfy the above condition.
  • the black cured film is disposed inside a color filter having subpixels each having a side length of 15 ⁇ m or less.
  • the subpixel include a red subpixel, a green subpixel, and a blue subpixel.
  • the size (length of one side) of the sub pixel in the color filter in which the black cured film is disposed is 15 ⁇ m or less, preferably 10 ⁇ m or less, and more preferably 5 ⁇ m or less.
  • the lower limit is not particularly limited, but is often 0.5 ⁇ m or more.
  • the shape of the subpixel is preferably a square shape. In the case of a square shape, the length of each side may be 15 ⁇ m or less.
  • the black cured film is disposed inside the color filter, but the position thereof is not particularly limited.
  • the subpixel red subpixel, green subpixel, or blue subpixel
  • the black cured film is preferably disposed so as to be in contact with the subpixel (at least one of the red subpixel, the green subpixel, and the blue subpixel).
  • the color filter including the black cured film obtained from the composition of the present invention can be applied to various uses.
  • a color filter of a display device for example, an organic EL display device (OLED), a liquid crystal display device, etc.
  • OLED organic EL display device
  • solid-state imaging Examples thereof include color filters of elements.
  • an embodiment of an organic EL display device including a color filter including a black cured film of the present invention will be described with reference to the drawings. It is sectional drawing of one embodiment of the organic electroluminescent display apparatus containing the color filter containing the black cured film of this invention shown in FIG.
  • the organic EL display device 10 includes a substrate 12, a plurality of organic EL elements 14 arranged in a matrix on the substrate 12, a protective layer 16 covering the organic EL elements 14, and a color filter disposed on the protective layer 16. 18 and a sealing substrate 24 disposed on the color filter 18.
  • the color filter 18 includes a square red subpixel (red area) 20R, a square green subpixel (green area) 20G, a square blue subpixel (blue area) 20B, and two rectangular black colors.
  • a cured film 22 is disposed between the red subpixel 20R and the green subpixel 20G, and the other black cured film 22 is disposed between the green subpixel 20G and the blue subpixel 20B. That is, each subpixel is disposed on the black cured film. Further, the black cured film is located between the sub-pixels.
  • the sub-pixel means each point of RGB single color constituting one pixel (pixel).
  • a combination of a plurality of organic EL elements 14 that generate white light and a color filter 18 generates light of any of the three primary colors (red, green, and blue).
  • the pitch (center-to-center distance) P of the plurality of organic EL elements 14 is, for example, 30 ⁇ m or less, specifically, for example, about 2 ⁇ m to 3 ⁇ m. That is, this organic EL display device is a so-called micro display (micro OLED) in which the size of the organic EL element 14 is extremely small.
  • the protective film 16 has a thickness of 0.5 ⁇ m to 10 ⁇ m and is made of silicon nitride (SiN).
  • the sealing substrate 24 seals the organic EL element and is made of a material such as transparent glass.
  • Each subpixel (the red subpixel 20R, the green subpixel 20G, and the blue subpixel 20B) in the color filter 18 has a square shape, the length of one side thereof is 15 ⁇ m or less, and 10 ⁇ m or less from the viewpoint of miniaturization. Is preferable, and 5 ⁇ m or less is more preferable.
  • the lower limit is not particularly limited, but is often 0.5 ⁇ m or more due to manufacturing problems.
  • the aspect of the square-shaped subpixel was shown in FIG. 1, it is not limited to this aspect, What is necessary is just square shape, and rectangular shape may be sufficient.
  • the black cured film 20 is a rectangular layer that is disposed between the sub-pixels and extends parallel to the interface between the sub-pixels.
  • the shape of the black cured film 20 is not limited to the aspect of FIG. 1, and any form may be sufficient. Further, in the embodiment shown in FIG. 1, the black cured film 20 exists over two subpixels, but the position thereof is not particularly limited as long as it is disposed in the color filter.
  • Titanium Black A-1 100 g of titanium oxide MT-150A having an average particle diameter of 15 nm (trade name: manufactured by Teika Co., Ltd.), 25 g of silica particles AROPERL (registered trademark) 300/30 (manufactured by Evonik) having a BET surface area of 300 m 2 / g, and dispersion 100 g of the agent Disperbyk190 (trade name: manufactured by Big Chemie), add 71 g of ion-exchange water, and use MURASTAR KK-400W manufactured by KURABO for 20 minutes at a revolution speed of 1360 rpm and a rotation speed of 1047 rpm.
  • Gave a homogeneous aqueous mixture.
  • This aqueous solution is filled in a quartz container, heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.), then the atmosphere is replaced with nitrogen, and ammonia gas is kept at 100 mL / min for 5 hours at the same temperature.
  • the nitriding reduction treatment was carried out by flowing. After the completion, the collected powder was pulverized in a mortar to obtain titanium black A-1 [dispersed material containing titanium black particles and Si atoms] containing Si atoms and having a powdery specific surface area of 73 m 2 / g.
  • composition 1 The component shown in the following composition 1 was mixed for 15 minutes using a stirrer (EUROSTAR manufactured by IKA) to obtain dispersion a.
  • the specific resin 1 described below was synthesized with reference to the description in JP2013-249417A.
  • x was 30 mass%
  • y was 20 mass%
  • z was 50 mass%.
  • the specific resin 1 had a weight average molecular weight of 30000, an acid value of 60 mgKOH / g, and the number of graft chain atoms (excluding hydrogen atoms) was 117.
  • composition 1 -Titanium black (A-1) obtained as described above-25 parts by mass-30% by mass solution of propylene glycol monomethyl ether acetate in specific resin 1-25 parts by mass-Propylene glycol monomethyl ether acetate (PGMEA )(solvent) ... 50 parts by mass
  • the obtained dispersion a was subjected to a dispersion treatment using Ultra Apex Mill UAM015 manufactured by Kotobuki Industries Co., Ltd. under the following conditions to obtain a titanium black dispersion.
  • the black photosensitive resin composition 1 was obtained by mixing the following composition. Titanium black dispersion 45.48 parts by mass Alkali-soluble resin: Acrylic base FF-426 (Fujikura Kasei Co., Ltd., solid content 39%, solvent: propylene glycol monomethyl ether) 1.30 parts by mass Polymerization initiator: Irgacure OXE02 (Manufactured by BASF Japan) 0.75 parts by mass polymerizable compound: KAYARAD DPHA (trade name: manufactured by Nippon Kayaku Co., Ltd., hexafunctional polymerizable compound (amount of ethylenically unsaturated group: 10.4 mmol / g), And a pentafunctional polymerizable compound (a mixture of ethylenically unsaturated groups: 9.5 mmol / g)) 2.66 parts by mass of ultraviolet (UV) absorber: UV-503 (manufactured
  • Example 2 A black photosensitive resin composition 2 was obtained according to the same procedure as in Example 1 except that Irgacure OXE02, which is a polymerization initiator, was changed to NCI-831 (manufactured by Adeka).
  • Example 3 A black photosensitive resin composition 3 was obtained according to the same procedure as in Example 1 except that Irgacure OXE02, which is a polymerization initiator, was changed to N-1919 (manufactured by Adeka).
  • Example 4 Other than changing the polymerizable compound KAYARAD DPHA to KAYARAD DPCA-20 (manufactured by Nippon Kayaku Co., Ltd., number of ethylenically unsaturated groups: 6, amount of ethylenically unsaturated groups: 7.4 mmol / g) In accordance with the same procedure as in Example 1, a black photosensitive resin composition 4 was obtained.
  • KAYARAD DPHA which is a polymerizable compound, is changed to NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), number of ethylenically unsaturated groups: 4, amount of ethylenically unsaturated groups: 11.3 mmol / g)
  • a black photosensitive resin composition 5 was obtained according to the same procedure as in Example 1 except that.
  • Example 6 A black photosensitive resin composition 6 was obtained according to the same procedure as in Example 1 except that 0.3 parts by mass of KBM-502 (manufactured by Shin-Etsu Chemical Co., Ltd.) was further added as an adhesive.
  • Example 7 A black photosensitive resin composition 7 was obtained according to the same procedure as in Example 1 except that 0.3 parts by mass of a compound represented by the following formula was further added as an adhesive.
  • Example 8> A black photosensitive resin composition 8 was obtained according to the same procedure as in Example 1, except that 0.3 parts by mass of KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.) was further added as an adhesive.
  • Example 9 A black photosensitive resin composition 9 was obtained according to the same procedure as in Example 5 except that 0.3 parts by mass of KBM-502 (manufactured by Shin-Etsu Chemical Co., Ltd.) was further added as an adhesive.
  • Example 10 A black photosensitive resin composition 10 was obtained according to the same procedure as in Example 5 except that 0.3 parts by mass of a compound represented by the following formula was further added as an adhesive.
  • Example 11 A black photosensitive resin composition 11 was obtained according to the same procedure as in Example 5, except that 0.3 parts by mass of KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.) was further added as an adhesive.
  • Example 12 A black photosensitive resin composition 12 was obtained according to the same procedure as in Example 1 except that 35.1 parts by mass of cyclohexanone was further added as a solvent.
  • Each of the black photosensitive resin compositions obtained in the above examples was applied on a glass substrate by a spin coating method so as to have a film thickness of 0.4 ⁇ m, and then heated at 100 ° C. for 2 minutes on a hot plate. Thus, a coating film was obtained. Next, using an i-line stepper, the obtained coating film was exposed at 500 mJ / cm 2 . Thereafter, the light shielding property was evaluated using UV-3600 (manufactured by Hitachi, Ltd .: spectrophotometer) according to the evaluation criteria. A was within tolerance. “A”: Less than 20% transmittance at a wavelength of 400 to 700 nm “B”: More than 20% transmittance at a wavelength of 400 to 700 nm
  • the black cured film obtained in ⁇ Preparation of black cured film> is immersed in cyclohexanone for 10 minutes, and then UV cured before UV immersion in cyclohexanone using UV-3600 (manufactured by Hitachi, Ltd .: spectrophotometer).
  • UV-3600 manufactured by Hitachi, Ltd .: spectrophotometer.
  • the transmittance of the membrane and the transmittance of the black permeable membrane after being immersed in cyclohexanone were measured, and the light shielding property was evaluated according to the evaluation criteria. "3" or "2" was made into tolerance.
  • the following transmittance fluctuation is the difference in transmittance of the black transmissive film before and after immersion in cyclohexanone at a wavelength of 450 nm (transmittance of the black transmissive film at wavelength 450 nm after being immersed in cyclohexanone ⁇ wavelength before being immersed in cyclohexanone.
  • the “content (mass%) of titanium black” column intends the content (mass%) of titanium black with respect to the total solid content in the composition.
  • the “solid content concentration (mass%)” column intends the solid content concentration in the composition.
  • the “Requirements for polymerizable compound” column is the above requirement 1 (requirement 1: having 5 or more ethylenically unsaturated groups in one molecule) and the above requirement 2 (ethylenic non-molecular in one molecule). Whether the amount of saturated groups is 7 mmol / g or more).
  • a color filter and an organic EL display device including a black cured film as shown in FIG. 1 were produced.
  • the length of one side of each subpixel square red subpixel 20R, square green subpixel 20G, square blue subpixel 20B
  • the shape of the black cured film was rectangular, and the length of each side was 3.0 ⁇ m and 1.0 ⁇ m.
  • the black cured film was produced according to the same procedure as described above.

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  • Spectroscopy & Molecular Physics (AREA)
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Abstract

La présente invention concerne une composition de résine noire photosensible qui permet de former, dans des conditions de basse température, un film durci noir ayant une faible épaisseur et de meilleures propriétés de blocage de lumière et qui présente une meilleure résolution, ainsi qu'un procédé pour fabriquer un film durci noir, un filtre coloré, et un appareil d'affichage EL organique utilisant la composition. La composition de résine noire photosensible, selon la présente invention, contient un ingrédient prédéfini et est utilisée pour former un film durci noir qui est disposé dans un filtre coloré comprenant des sous-pixels avec une longueur inférieure ou égale à 15 μm sur chaque côté.
PCT/JP2015/077093 2014-09-30 2015-09-25 Composition de résine noire photosensible, procédé de fabrication de film durci noir, filtre colore, et appareil d'affichage el organique WO2016052328A1 (fr)

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TWI750292B (zh) * 2017-01-18 2021-12-21 南韓商東友精細化工有限公司 黑色感光性樹脂組合物、以及使用其所製造之用於圖像顯示裝置的黑矩陣、柱狀間隔物及黑矩陣一體型柱狀間隔物

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