CN116806327A - Photosensitive green resin composition, cured product, color filter, display device, and method for producing laminate of organic light-emitting element and anti-external light reflection film - Google Patents

Photosensitive green resin composition, cured product, color filter, display device, and method for producing laminate of organic light-emitting element and anti-external light reflection film Download PDF

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Publication number
CN116806327A
CN116806327A CN202280013059.7A CN202280013059A CN116806327A CN 116806327 A CN116806327 A CN 116806327A CN 202280013059 A CN202280013059 A CN 202280013059A CN 116806327 A CN116806327 A CN 116806327A
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group
mass
resin composition
pigment
film
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石原星儿
藤田麻希
小野充史
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DNP Fine Chemicals Co Ltd
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DNP Fine Chemicals Co Ltd
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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
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B25/00—Quinophthalones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
    • C09B29/0074—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms
    • C09B29/0077—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms containing a five-membered heterocyclic ring with one nitrogen and one sulfur as heteroatoms
    • C09B29/0085—Thiazoles or condensed thiazoles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
    • C09B47/10—Obtaining compounds having halogen atoms directly bound to the phthalocyanine skeleton
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/04—Isoindoline dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • 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
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/122—Pixel-defining structures or layers, e.g. banks
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Theoretical Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Optical Filters (AREA)
  • Materials For Photolithography (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The photosensitive green resin composition of the present invention comprises a coloring material, a photopolymerizable compound, and a photoinitiator, wherein the coloring material comprises a blue pigment and a yellow pigment, the yellow pigment comprises C.I. pigment yellow 139, the halogenated metal phthalocyanine pigment is 10% or less, and when a cured film is formed with a film thickness of 3.0 [ mu ] m, the spectral transmittance at 360nm to 370nm is 0.7% or more.

Description

Photosensitive green resin composition, cured product, color filter, display device, and method for producing laminate of organic light-emitting element and anti-external light reflection film
Technical Field
The present invention relates to a photosensitive green resin composition, a cured product, a color filter, a display device, and a method for producing a laminate of an organic light-emitting element and an anti-external light reflection film using the photosensitive green resin composition.
Background
In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays has increased. The popularity of mobile displays (mobile phones, smartphones, tablet PCs (personal computer, personal computers)) is also increasing, and the market for liquid crystal displays is expanding. Organic light emitting display devices such as organic EL (Electroluminescence) displays which are highly visible due to self-luminescence are also attracting attention as next-generation image display devices.
Color filters may be used in these liquid crystal display devices and organic light emitting display devices. For example, with respect to formation of a color image of a liquid crystal display device, light passing through a color filter is directly colored into colors of respective pixels constituting the color filter, and the lights of these colors are combined to form the color image. As the light source at this time, an organic light-emitting element that emits white light and an inorganic light-emitting element that emits white light may be used in addition to the conventional cold cathode tube. In the organic light emitting display device, a color filter is used for color adjustment or the like.
Here, the color filter generally has: a substrate; a coloring layer formed on the substrate and including coloring patterns of three primary colors of red, green and blue; and a light shielding portion formed on the substrate so as to divide each of the coloring patterns.
As a method for forming a colored layer in a color filter, for example, a colored resin composition obtained by adding a binder resin, a photopolymerizable compound and a photoinitiator to a colorant dispersion liquid obtained by dispersing a colorant with a dispersant or the like is applied to a substrate, dried, exposed using a photomask, developed, and fixed by heating to form a colored pattern. Alternatively, the colored resin composition is applied in a pattern to a substrate by an inkjet method or the like, dried, and then cured to form a colored pattern, and the pattern is fixed by heating to form a colored layer. These steps are repeated for each color to form a color filter.
In recent years, in the course of increasing demands for higher brightness of color filters, the concentration of coloring materials in the colored layers of color filters has been higher than ever before, and thus the curable components have been relatively reduced, making patterning difficult. In order to further improve the productivity of the color filter, it is required to reduce the cumulative exposure amount required for patterning, and how to secure the curability required for patterning is a big problem.
Conventionally, as green pigments, halogenated metal phthalocyanine pigments such as c.i. Pigment Green (PG) 7, 36, 58, and 59 have been used in many cases in photosensitive green resin compositions for color filters. However, since the photosensitive green resin composition containing a large amount of halogenated metal phthalocyanine pigment has low transmittance of i-rays (365 nm spectral lines) as main wavelengths of exposure, it is difficult to uniformly cure the composition to deep portions of the film, and therefore there is a problem that the bottom portion of the film is removed during development and the pattern shape is deteriorated.
On the other hand, patent document l discloses a green colorant composition for a color filter containing a blue pigment and a yellow pigment.
Patent document 2 discloses a coloring composition comprising at least one selected from color index pigment blue 15:3 and color index pigment blue 15:4 and color index pigment yellow 150, wherein the total content of the color index pigment blue 15:3 and the color index pigment blue 15:4 is 35 to 55 parts by mass per 100 parts by mass of the color index pigment yellow 150, the coloring composition has a minimum value of absorbance in a range of 495 to 525nm among absorbance to light having a wavelength of 400 to 700nm, and absorbance a of light having a wavelength of 450nm is present in a range of 474 to 494nm and 530 to 570nm, respectively, when absorbance to light having a wavelength of 450nm is 1, and absorbance a of light having an absorbance of 0.14 is present in a range of 474 to 494nm and 530 to 570nm, respectively 450 Absorbance A to light of wavelength 620nm 620 Is a ratio of A 450 /A 620 1.08 to 2.05.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2011-242568
Patent document 2: international publication No. 2020/196393
Disclosure of Invention
Problems to be solved by the invention
Conventionally, a color filter has been formed on a glass substrate, but in recent years, it has been demanded to directly form a color filter on an element substrate.
Since the heat resistance of an element such as an organic light-emitting element is low, the heat treatment in the process of directly forming a color filter on an element substrate is preferably performed at 130 ℃ or lower, more preferably at 100 ℃ or lower, for example. In a typical color filter manufacturing process, a glass substrate is subjected to a heat treatment at about 230 ℃ to cure a colored layer, whereas in a heat treatment at 130 ℃ or less or at 100 ℃ or less, it is difficult to cure the colored layer by heat. Therefore, in order to impart solvent resistance required in the subsequent steps to the colored layer, the colored layer needs to be sufficiently cured by exposure to light. Since the photosensitive green resin composition containing a large amount of halogenated metal phthalocyanine pigment has low transmittance of i-rays (365 nm spectral lines) as main wavelengths of exposure, it is difficult to uniformly cure the composition to deep portions of the film, and therefore there is a problem in solvent resistance of the cured film particularly when low-temperature heat treatment is performed.
The patent document 1 aims to provide a technique for a color filter substrate which is halogen-free, has a high contrast ratio, and has a high adhesion, and is not described at all in a pattern shape and solvent resistance of a cured film when a low-temperature heat treatment is performed. As shown in comparative examples described below, the cured film obtained by low-temperature heat treatment using the composition specifically described in patent document 1 still has a problem of deteriorated pattern shape and insufficient solvent resistance.
Patent document 2 is aimed at obtaining a coloring composition capable of forming a cured film excellent in light resistance and color separation from other colors, and is not described at all in pattern shape and solvent resistance of the cured film when subjected to low-temperature heat treatment. As shown in comparative examples described below, the cured film obtained by low-temperature heat treatment using the composition specifically described in patent document 2 has a problem of deteriorated pattern shape and insufficient solvent resistance.
The present invention has been made in view of the above-described circumstances, and an object thereof is to provide a photosensitive green resin composition capable of forming a colored layer having good solvent resistance and good pattern shape even by low-temperature heat treatment. The present invention also provides a color filter and a display device using the photosensitive green resin composition, and a method for producing a laminate of an organic light-emitting element and an anti-external light reflection film using the photosensitive green resin composition.
Means for solving the problems
The photosensitive green resin composition of the invention comprises a coloring material, an alkali-soluble resin, a photopolymerizable compound and a photoinitiator,
the colorant comprises a blue pigment and a yellow pigment, wherein the yellow pigment comprises C.I. pigment yellow 139, and the halogenated metal phthalocyanine pigment is 10% or less,
when a cured film is formed with a film thickness of 3.0 μm, the spectral transmittance at 360nm to 370nm is 0.7% or more.
The cured product of the present invention is a cured product of the photosensitive green resin composition of the present invention.
The color filter of the present invention comprises at least a substrate and a colored layer provided on the substrate, and at least 1 of the colored layers is a cured product of the photosensitive green resin composition of the present invention.
The display device of the present invention has the color filter of the present invention described above.
The display device of the present invention has the cured film of the photosensitive green resin composition of the present invention described above on an organic light emitting element.
The method for producing a laminate of an organic light-emitting element and an anti-external light reflection film according to the present invention comprises a step of forming a cured film of the photosensitive green resin composition according to the present invention on the organic light-emitting element by comprising:
A step of forming a coating film by applying the photosensitive green resin composition of the present invention to an organic light-emitting element;
a step of irradiating the coating film with light;
a post-baking step of heating the film after the irradiation with light; and
and developing the film after the light irradiation.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a photosensitive green resin composition can be provided which can form a colored layer having good solvent resistance and good pattern shape even by low-temperature heat treatment. Further, according to the present invention, a color filter and a display device formed using the photosensitive green resin composition, and a method for manufacturing a laminate of an organic light-emitting element and an anti-external light reflection film using the photosensitive green resin composition can be provided.
Drawings
Fig. 1 is a schematic cross-sectional view showing an example of a color filter according to the present invention.
Fig. 2 is a schematic cross-sectional view showing an example of the liquid crystal display device of the present invention.
Fig. 3 is a schematic cross-sectional view showing an example of the organic light-emitting display device of the present invention.
Fig. 4 is a schematic cross-sectional view showing another example of a display device provided with the organic light-emitting element of the present invention.
Fig. 5 is a schematic cross-sectional view illustrating a taper angle (θ1) of a cross-sectional shape of a colored layer of a fine line pattern.
Detailed Description
Embodiments, examples, and the like of the present invention will be described below with reference to the drawings. However, the present invention can be implemented in various different modes, and is not limited to the description of the embodiments, examples, and the like illustrated below. For the sake of more clear explanation, the drawings may schematically show the width, thickness, shape, etc. of each part in comparison with the actual embodiment, but this is merely an example and not limiting the explanation of the present invention. In the present specification and the drawings, elements similar to those described above with reference to the drawings already appearing may be denoted by the same reference numerals, and detailed description thereof may be omitted as appropriate. For convenience of explanation, the description will be given using terms above or below, but the vertical direction may be reversed.
In the present specification, when a certain structure such as a certain member or a certain region is located "on (or under)" another structure such as another member or another region, the above is not particularly limited, but includes not only the case of being located directly above (or directly below) the other structure but also the case of being located above (or below) the other structure, that is, the case of including other structural elements between the above and the other structure (or below) is also included.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and also includes radiation, including microwaves and electron beams, for example. Specifically, electromagnetic waves having a wavelength of 5 μm or less and electron beams.
In the present invention, (meth) acryl means any one of acryl and methacryl, (meth) acrylic means any one of acrylic and methacrylic, and (meth) acrylate means any one of acrylate and methacrylate.
In the present specification, "to" representing a numerical range is used in a meaning including numerical values described before and after the numerical value as a lower limit value and an upper limit value.
In the present invention, the spectral transmittance in the wavelength range of X nm to Y nm being Z% or more means that the spectral transmittance is Z% or more in the entire wavelength range of X nm to Y nm.
Hereinafter, the photosensitive green resin composition, cured product, color filter, display device, and method for producing a laminate of an organic light-emitting element and an anti-external light reflection film according to the present invention will be described in detail.
I. Photosensitive green resin composition
The photosensitive green resin composition of the invention comprises a coloring material, an alkali-soluble resin, a photopolymerizable compound and a photoinitiator,
The colorant comprises a blue pigment and a yellow pigment, wherein the yellow pigment comprises C.I. pigment yellow 139, and the halogenated metal phthalocyanine pigment is 10% or less,
when a cured film is formed with a film thickness of 3.0um, the spectral transmittance at 360nm to 370nm is 0.7% or more.
In the photosensitive green resin composition of the present invention, the coloring material contains a blue pigment and a yellow pigment, the yellow pigment contains c.i. pigment yellow 139, and the halogenated metal phthalocyanine pigment is 10% or less, and a colored layer having good solvent resistance and good pattern shape can be formed even by heat treatment at low temperature by satisfying a specific spectral transmittance in the specific wavelength region.
The coloring material contains a blue pigment and a yellow pigment, and the yellow pigment contains c.i. pigment yellow 139, and the halogenated metal phthalocyanine pigment is 10% or less, so that when a cured film is formed at a film thickness of 3.0 μm, the spectral transmittance of 360nm to 370nm is easily 0.7% or more. Since c.i. pigment yellow 139 has high coloring power, the concentration of coloring material in the cured film can be reduced, and the concentration of curable components can be relatively increased, so that a colored layer having good solvent resistance and good pattern shape can be formed even by low-temperature heat treatment. When the transmittance of 360nm to 370nm is 0.7% or more in forming a cured film having a film thickness of 3.0 μm, the transmittance of i-rays (365 nm spectral lines) which are the main wavelengths of exposure at the time of curing a coating film of the composition is ensured, and the cured film is easily and uniformly cured to a deep portion of the film, and deterioration of the pattern shape due to removal of the bottom portion of the film at the time of development can be suppressed. Further, since the film is easily and uniformly cured to the deep portion of the film, the solvent resistance is excellent even in the low-temperature heat treatment.
The photosensitive green resin composition of the present invention can form a colored layer having good solvent resistance and good pattern shape even by low-temperature heat treatment, and therefore can be suitably used for a cured film formed on an organic light-emitting element. That is, the photosensitive green resin composition of the present invention can be suitably used for a cured film directly formed on an element substrate provided with an organic light-emitting element. In the case where the photosensitive green resin composition of the present invention is used for a cured film formed adjacently on an organic light emitting element or a cured film formed with at least 1 layer interposed, the following display device can be manufactured: the thickness and flexibility of the display device are improved as compared with those of a display device in which an externally mounted color filter formed on a substrate such as a glass substrate is bonded to an organic light emitting element. In the case where the photosensitive green resin composition of the present invention is used for a cured film formed adjacently on an organic light emitting element or a cured film formed via at least 1 layer, it can also be used as a polarizing plate for suppressing reflection of external light instead of a color filter.
Further, since the cured film formed on the organic light-emitting element by using the photosensitive green resin composition of the present invention has a content of the halogenated metal phthalocyanine pigment of 10 mass% or less relative to the total amount of the coloring material, green is realized, and therefore, even if a weather resistance test is performed in a state where glass is bonded by using a transparent adhesive, a decrease in transmittance is suppressed, and a display device excellent in weather resistance can be realized.
The photosensitive green resin composition of the present invention contains at least a coloring material, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator, and may further contain other components within a range that does not impair the effects of the present invention.
The respective components of the photosensitive green resin composition of the present invention will be described in detail below in order.
< colorant >
In the present invention, the coloring material is not particularly limited as long as it can perform a desired color development when forming a colored layer of a color filter, and various organic pigments, inorganic pigments, dispersible dyes, salt-forming compounds of dyes, and the like can be mixed and used, and is characterized in that: comprises a blue pigment and a yellow pigment, wherein the yellow pigment comprises C.I. pigment yellow 139 and the halogenated metal phthalocyanine pigment is 10% or less.
Among them, organic pigments are preferably used because they have high color developability and high heat resistance. Examples of the organic Pigment include a compound classified as a Pigment (Pigment) in a color index (c.i.; issued by The Society of Dyers and Colourists company), specifically, a compound to which a color index (c.i.) number as described below is attached.
Examples of the blue pigment include: c.i. pigment blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 61, 79, 80, etc.
The blue pigment is preferably at least one selected from the group consisting of c.i. pigment blue 15:3, c.i. pigment blue 15:4, pigment blue 15:6, and c.i. pigment blue 16, in order to easily obtain a desired transmission spectrum and to easily improve the effect of suppressing external light reflection.
Regarding c.i. pigment blue 15:3, c.i. pigment blue 15:4, and c.i. pigment blue 16, the rising wavelengths of the transmission spectra are gradually shifted from the long wavelength side to the short wavelength side to be different, respectively, and therefore, it is preferable to use one kind or two or more kinds in combination by appropriately selecting them in consideration of the transmitted wavelength region and the transmittance, and the emission spectrum of the combined light-emitting element. From the aspect of weather resistance, c.i. pigment blue 15:4 is particularly preferred.
The yellow pigment contains c.i. pigment yellow 139 as an essential component. Since c.i. pigment yellow 139 has high coloring power, the concentration of coloring material in the cured film can be reduced, and the concentration of curable components can be relatively increased, so that even if the cured film is subjected to low-temperature heat treatment, a colored layer having good solvent resistance and good pattern shape can be formed. In addition, in the case of the combination with the blue pigment, c.i. pigment yellow 139 is easy to achieve a wavelength of 525nm to 545nm which is a maximum transmittance of the transmission spectrum, and is easy to reduce a half-peak width of a peak of the transmission spectrum in a wavelength range of 525nm to 545nm, so that the effect of suppressing external light reflection is easy to be improved in the case of using the cured film as an antireflection film.
Examples of the other yellow pigment include: pigment yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 15, 16, 17, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 60, 61, 62, 62:1, 63, 65, 71, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 98, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136, 138, 142, 147, 148, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 166, 167, 168, 175, 185, 194, 211, 214, 215, 231, 150, and c.i. pigment, etc.
In the case of combination with a blue pigment, the yellow pigment may further contain at least one selected from the group consisting of pigment yellow 138, pigment yellow 150, and pigment yellow 185, and more preferably further contains pigment yellow 150, in view of easy adjustment to a desired transmission spectrum.
As the coloring material, the blue pigment contains at least one selected from c.i. pigment blue 15:3, c.i. pigment blue 15:4, and c.i. pigment blue 16, and the yellow pigment may further contain at least one selected from c.i. pigment yellow 138, c.i. pigment yellow 150, and c.i. pigment yellow 185.
Other coloring materials may be used in order to adjust the color tone of the cured film and to suppress external light reflection when the film is used as an antireflection film. Examples of the other coloring material include: green pigment, violet pigment, orange pigment, etc.
Examples of the green pigment include: c.i. pigment green 7, 36, 58, 59, 62, 63, etc. In the case of using a green pigment, the halogenated metal phthalocyanine pigment is set to 10 mass% or less based on the total amount of the coloring material, in order to improve weather resistance.
Examples of the violet pigment include: c.i. pigment violet 1, 19, 23, 29, 32, 36, 38, etc.
Examples of the orange pigment include: c.i. pigment orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, etc.
The blue pigment, the yellow pigment, and other coloring materials which may be contained as needed in the present invention are contained in such a proportion that the transmittance of 360nm to 370nm is adjusted to 0.7% or more when a cured film is formed from the photosensitive green resin composition at a film thickness of 3.0. Mu.m.
When a cured film is formed with a film thickness of 3.0 μm from the photosensitive green resin composition, if the transmittance of 360nm to 370nm is 0.7% or more, the transmittance of i-rays (365 nm spectral lines) which are the main wavelengths of exposure at the time of curing the coating film of the composition is ensured, and the cured film is easily and uniformly cured to the deep portion of the film, and the bottom portion of the film at the time of development can be suppressed from being cut off and the pattern shape is deteriorated. Further, since the film is easily and uniformly cured to the deep portion of the film, the solvent resistance is excellent even in the low-temperature heat treatment. When a cured film is formed with a film thickness of 3.0. Mu.m, the transmittance at 360nm to 370nm may be 0.8% or more, or 0.9% or more.
In the present invention, the spectral transmittance when a cured film was formed at a film thickness of 3.0 μm was measured by the method specifically described in examples.
When the photosensitive green resin composition is used as an external light reflection preventing film, the content of the blue pigment, the yellow pigment, and other coloring materials which may be contained in the present invention is preferably such that when a cured film is formed with a film thickness of 3.0 μm, the spectral transmittance in the wavelength range of 380nm to 480nm is adjusted to 20% or less, the spectral transmittance in the wavelength range of 580nm to 700nm is 25% or less, and the spectral transmittance in the wavelength range of 510nm to 550nm is 40% or more and 80% or less.
When a cured film is formed with a film thickness of 3.0. Mu.m, if the spectral transmittance at a wavelength of 380nm to 480nm is 20% or less, the decrease in the color purity of green is suppressed, and the decrease in the color purity of a self-light emitting element is easily suppressed, so that the antireflection performance is easily excellent. When a cured film is formed with a film thickness of 3.0. Mu.m, the spectral transmittance at a wavelength of 380nm to 480nm may be 18% or less, or 13% or less.
On the other hand, when a cured film is formed with a film thickness of 3.0 μm, if the spectral transmittance at a wavelength of 510nm to 550nm is 40% or more and 80% or less, the luminance decrease and visibility defects of the display device are easily suppressed. When a cured film is formed with a film thickness of 3.0. Mu.m, the spectral transmittance at a wavelength of 510nm to 550nm may be 45% or more, 75% or less, and further 70% or less.
Further, when a cured film is formed with a film thickness of 3.0. Mu.m, the anti-reflection performance tends to be excellent if the spectral transmittance at a wavelength of 580nm to 700nm is 30% or less. When a cured film is formed with a film thickness of 3.0. Mu.m, the spectral transmittance at a wavelength of 580nm to 700nm may be 25% or less, 20% or less, or 18% or less.
In addition, in view of improving the luminance when combined with a specific organic light-emitting element and improving the external light reflection suppressing effect when used as an external light reflection preventing film, when a cured film is formed at a film thickness of 3.0 μm, the wavelength exhibiting the maximum transmittance in the wavelength range of 380nm to 700nm of the transmission spectrum is preferably in the range of 525nm to 545nm, more preferably in the range of 525nm to 540nm, still more preferably in the range of 526nm to 540nm, and may be in the range of 527nm to 535 nm.
In addition, in view of the improvement of the antireflection performance when used as an antireflection film and the improvement of the color purity and the expansion of the color reproduction region, it is preferable that the half-width of the peak of the transmission spectrum in the wavelength range of 525nm to 545nm is 70nm or less when a cured film is formed with a film thickness of 3.0 μm. When a cured film is formed with a film thickness of 3.0. Mu.m, the half-width of the peak of the transmission spectrum in the wavelength range of 525nm to 545nm may be 65nm or less, 63nm or less, or 60nm or less.
The content of the coloring material used in the present invention is not particularly limited as long as it satisfies a specific spectral transmittance in the specific wavelength region.
In the coloring material used in the present invention, the content of the blue pigment may be, for example, 1% by mass or more and 60% by mass or less, preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and still more preferably 50% by mass or less, and still more preferably 40% by mass or less, relative to the total amount of the coloring material.
In the coloring material used in the present invention, the content of the yellow pigment may be, for example, 20% by mass or more and 99% by mass or less, preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably 60% by mass or more, and still more preferably 90% by mass or less, and still more preferably 85% by mass or less, relative to the total amount of the coloring material.
The content of pigment yellow 139 may be 1 mass% or more, more preferably 5 mass% or more, still more preferably 10 mass% or more, and may be 80 mass% or less, more preferably 70 mass% or less, relative to the total amount of the yellow pigment.
When pigment yellow 139 and pigment yellow 150 are included as the yellow pigment, the total content of pigment yellow 139 and pigment yellow 150 may be 40 mass% or more, more preferably 60 mass% or more, still more preferably 80 mass% or more, and may be 100 mass% or less, relative to the total amount of the yellow pigment.
The content of pigment yellow 139 may be 1% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, and may be 75% by mass or less, more preferably 70% by mass or less, still more preferably 65% by mass or less, relative to the total amount of the coloring material.
The content of the blue pigment in the coloring material used in the present invention is not particularly limited as long as the total of the blue pigment and the yellow pigment satisfies a specific spectral transmittance in the specific wavelength region, and may be, for example, 1% by mass or more and 60% by mass or less, preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and still more preferably 50% by mass or less, and still more preferably 40% by mass or less.
In the colorant used in the present invention, the total content of the blue pigment and the yellow pigment may be usually 80 mass% or more, preferably 90 mass% or more, more preferably 95 mass% or more, and 100 mass% or less based on the total amount of the colorant, but may be 90 mass% or less in the case of containing a colorant other than the halogenated metal phthalocyanine pigment.
In the coloring material used in the present invention, the total content of the other coloring materials may be 0 mass% or more, 1 mass% or more, or 5 mass% or more, and on the other hand, is usually 20 mass% or less, preferably 10 mass% or less, relative to the total amount of the coloring materials.
The total content of the halogenated metal phthalocyanine pigments used as the other coloring material is 10 mass% or less, usually 0.1 mass% or more and 10 mass% or less, preferably 1 mass% or more, more preferably 3 mass% or more, and even more preferably 9.5 mass% or less, based on the total amount of the coloring material. The halogenated metal phthalocyanine pigment may be 0% by mass based on the total amount of the coloring material.
The average primary particle diameter of the coloring material used in the present invention is not particularly limited as long as it can suppress external light reflection and can transmit light necessary for the light-emitting element to suppress the decrease in luminance of the display device when the cured film is formed, and is preferably in the range of 10nm to 100nm, more preferably 15nm to 60nm, depending on the type of the coloring material used. By having the average primary particle diameter of the coloring material in the above range, a display device having a cured film produced using the photosensitive green resin composition of the present invention can be made to be a display device which can suppress external light reflection, has high contrast and is high in quality.
The average dispersion particle diameter of the coloring material in the photosensitive green resin composition varies depending on the type of the coloring material used, and is preferably in the range of 10nm to 100nm, more preferably in the range of 15nm to 60 nm.
The average dispersion particle diameter of the coloring material in the photosensitive green resin composition is the dispersion particle diameter of the coloring material particles dispersed in the dispersion medium containing at least the solvent, and is the dispersion particle diameter measured by a laser scattering particle size distribution meter. As the measurement of the particle diameter by the laser scattering particle size distribution meter, the photosensitive green resin composition may be diluted (for example, 1000 times or the like) appropriately to a concentration that can be measured by the laser scattering particle size distribution meter by using a solvent used in the photosensitive green resin composition, and the measurement may be performed at 23 ℃ by a dynamic light scattering method using the laser scattering particle size distribution meter (for example, nanotrac particle size distribution measuring apparatus UPA-EX150 manufactured by daily nectar corporation). The average distribution particle diameter herein is a volume average particle diameter.
The coloring material used in the present invention can be produced by a known method such as recrystallization or solvent salt milling. Further, commercially available coloring materials may be used by subjecting them to a fine treatment.
In the photosensitive green resin composition of the present invention, the content of the coloring material is not particularly limited. The content of the coloring material is preferably in the range of 3 to 65 mass%, more preferably in the range of 4 to 60 mass%, based on the total solid content of the photosensitive green resin composition, in terms of dispersibility and dispersion stability. When the lower limit is not less than the above, the cured film tends to have a sufficient color density when the photosensitive green resin composition is applied to a specific film thickness (usually 1.0 μm to 5.0 μm, for example, 3.0 μm). In addition, when the upper limit value is less than or equal to the above, a cured film having excellent storage stability and sufficient hardness and adhesion to a substrate can be obtained. When the low-temperature heat treatment is performed, the content of the coloring material (coloring material concentration) is preferably in the range of 3 to 50 mass%, more preferably in the range of 4 to 40 mass%, relative to the total solid content of the photosensitive green resin composition.
In the present invention, the solid component is all the substances except the solvent described below, and includes monomers dissolved in the solvent and the like.
< alkali-soluble resin >
The alkali-soluble resin used in the present invention has an acidic group, functions as a binder resin, and can be appropriately selected from resins soluble in an alkali developer used in pattern formation.
In the present invention, the alkali-soluble resin may have an acid value of 40mgKOH/g or more.
The alkali-soluble resin may be appropriately selected from conventionally known alkali-soluble resins, and for example, the alkali-soluble resin described in International publication No. 2016/104493 may be appropriately selected and used.
Preferred alkali-soluble resins in the present invention are resins having an acidic group, usually resins having a carboxyl group, and specifically, there can be mentioned: acrylic resins such as acrylic copolymer having carboxyl groups, styrene-acrylic copolymer having carboxyl groups, epoxy (meth) acrylate resin having carboxyl groups, and the like, and acrylic resins such as acrylic copolymer having carboxyl groups and styrene-acrylic copolymer having carboxyl groups can be suitably used. Of these, particularly preferred is an alkali-soluble resin having a carboxyl group in a side chain and a photopolymerizable functional group such as an ethylenically unsaturated group in a side chain. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. Further, two or more types of acrylic resins such as an acrylic copolymer and a styrene-acrylic copolymer, and an epoxy acrylate resin may be used in combination.
The alkali-soluble resin used in the photosensitive green resin composition may be used singly or in combination of two or more. The content of the alkali-soluble resin is not particularly limited, but is preferably in the range of 5 to 60 mass%, more preferably in the range of 10 to 40 mass%, based on the total solid content of the photosensitive green resin composition. When the content of the alkali-soluble resin is not less than the above-mentioned lower limit, sufficient alkali developability can be obtained, and when the content of the alkali-soluble resin is not more than the above-mentioned upper limit, film roughness and pattern defects can be suppressed at the time of development.
< photopolymerizable Compound >
As the photopolymerizable compound used in the photosensitive green resin composition, a compound having a photopolymerizable group in a molecule can be mentioned. The photopolymerizable group is not particularly limited as long as it can be polymerized by a photoinitiator, and examples thereof include ethylenically unsaturated double bonds: vinyl, allyl, acryl, methacryl, and the like. Among them, from the viewpoint of ultraviolet curability, an acryl group or a methacryl group can be suitably used as the photopolymerizable group.
The photopolymerizable compound is preferably a compound having 2 or more photopolymerizable groups in 1 molecule, and more preferably a compound having 3 or more photopolymerizable groups in 1 molecule, from the viewpoint of curability.
As the photopolymerizable compound, a compound having 2 or more ethylenically unsaturated double bonds can be suitably used, and a polyfunctional (meth) acrylate having 2 or more acryl groups or methacryl groups is particularly preferable.
Such a multifunctional (meth) acrylate may be appropriately selected from conventionally known multifunctional (meth) acrylates. Specific examples thereof include multifunctional (meth) acrylates described in JP-A2013-029832.
These polyfunctional (meth) acrylates may be used singly or in combination of two or more. In the case where excellent photocurability (high sensitivity) is required for the photosensitive green resin composition of the present invention, the multifunctional (meth) acrylate preferably has 3 or more (trifunctional) double bonds capable of polymerization, and the poly (meth) acrylate of a polyhydric alcohol of three or more or a dicarboxylic acid modified product thereof is preferable, and specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, succinic acid modified product of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, succinic acid modified product of dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like are preferable.
The content of the photopolymerizable compound used in the photosensitive green resin composition is not particularly limited, but is preferably in the range of, for example, 5 to 60 mass%, and more preferably in the range of 10 to 40 mass%, based on the total solid content of the photosensitive green resin composition. When the content of the photopolymerizable compound is not less than the above-mentioned lower limit, photocuring can be sufficiently performed to suppress elution of the exposed portion during development, and when the content of the photopolymerizable compound is not more than the above-mentioned upper limit, alkali developability is sufficient.
< photoinitiator >
The photoinitiator used in the photosensitive green resin composition of the present invention may be one or a combination of two or more of various conventionally known photoinitiators.
Examples of the photoinitiator include: aromatic ketones, benzoin ethers, halomethyl oxadiazole compounds, α -aminoketones, bisimidazoles, N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, thioxanthones, oxime esters, and the like. As such a photoinitiator, conventionally known photoinitiators can be used, and examples thereof include those described in international publication No. 2018/062105.
The oxime ester-based photoinitiator used in the present invention may be appropriately selected from, for example, oxime ester-based photoinitiators described in 1, 2-octanedione-1- [4- (phenylthio) phenyl ] -,2- (o-benzoyl oxime), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (o-acetyl oxime), japanese patent application laid-open No. 2000-80068, japanese patent application laid-open No. 2001-233842, japanese patent application laid-open No. 2010-527339, japanese patent application laid-open No. 2010-527338, japanese patent application laid-open No. 2013-04153, international publication No. 2015/152153, japanese patent application laid-open No. 2010-256891, and the like.
The photoinitiator preferably contains at least one compound represented by the following general formula (a) in particular, from the viewpoint that the solvent resistance of the cured film is easily improved even by low-temperature heat treatment.
[ chemical formula 1]
General formula (A)
(wherein R is 1 And R is 2 R is independently represented by 11 、OR 11 、COR 11 、SR 11 、CONR 12 R 13 Or the CN of the two-dimensional network,
R 11 、R 12 and R is 13 Respectively independent earth's surfaceA hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,
R 11 、R 12 and R is 13 The hydrogen atom of the group represented may be further represented by R 21 、OR 21 、COR 21 、SR 21 、NR 22 R 23 、CONR 22 R 23 、-NR 22 -OR 23 、-NCOR 22 -OCOR 23 、NR 22 COR 21 、OCOR 21 、COOR 21 、SCOR 21 、OCSR 21 、COSR 21 、CSOR 21 Substituted by hydroxy, nitro, CN, or halogen atoms,
R 21 、R 22 And R is 23 Independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,
R 21 、R 22 and R is 23 The hydrogen atom of the represented group may be further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, or a carboxyl group,
R 11 、R 12 、R 13 、R 21 、R 22 and R is 23 The alkylene portion of the radicals represented may contain 1 to 5-O-, under the condition that the oxygen atoms are not adjacent-S-, -COO-, -OCO-, -NR 24 -、-NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-; OCS-or-CSO-,
R 24 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,
R 11 、R 12 、R 13 、R 21 、R 22 、R 23 and R is 24 The alkyl portion of the group represented may have a branched side chain or may be a cyclic alkyl group,
R 3 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, R 3 Of the radicals representedThe alkyl moiety may have a branched side chain, may be a cyclic alkyl group, and R 3 And R is R 7 And R is 3 And R is R 8 Each of which may be formed together to form a ring,
R 3 the hydrogen atom of the group represented may be further represented by R 21 、OR 21 、COR 21 、SR 21 、NR 22 R 23 、CONR 22 R 23 、-NR 22 -OR 23 、-NCOR 22 -OCOR 23 、NR 22 COR 21 、OCOR 21 、COOR 21 、SCOR 21 、OCSR 21 、COSR 21 、CSOR 21 Substituted by hydroxy, nitro, CN, or halogen atoms,
R 4 、R 5 、R 6 and R is 7 R is independently represented by 11 、OR 11 、SR 11 、COR 14 、CONR 15 R 16 、NR 12 COR 11 、OCOR 11 、COOR 14 、SCOR 11 、OCSR 11 、COSR 14 、CSOR 11 A hydroxyl group, CN or halogen atom, R 4 And R is R 5 、R 5 And R is R 6 And R is 6 And R is R 7 Each of which may be formed together to form a ring,
R 14 、R 15 and R is 16 Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R 14 、R 15 And R is 16 The alkyl portion of the group represented may have a branched side chain or may be a cyclic alkyl group, R 8 R represents 11 、OR 11 、SR 11 、COR 11 、CONR 12 R 13 、NR 12 COR 11 、OCOR 11 、COOR 11 、SCOR 11 、OCSR 11 、COSR 11 、CSOR 11 A hydroxyl group, a CN or a halogen atom,
k represents 0 or 1. )
The oxime ester compound represented by the above general formula (a) contains geometrical isomers formed by the double bond of oxime, but they are not distinguished. That is, in the present specification, the compound represented by the general formula (a) and a preferable form of the compound described below, that is, the compound represented by the general formula (a') described below and an exemplified compound thereof represent a mixture of both or any of them, and are not limited to the structure representing an isomer.
R in the above general formula (A) 3 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 21 、R 22 、R 23 And R is 24 Examples of the alkyl group having 1 to 20 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, and the like.
R in the above general formula (A) 3 、R 11 、R 12 、R 13 、R 21 、R 22 、R 23 And R is 24 Examples of the aryl group having 6 to 30 carbon atoms include: phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthryl, phenyl substituted with 1 or more of the above alkyl groups, biphenyl, naphthyl, anthryl, and the like.
R in the above general formula (A) 3 、R 11 、R 12 、R 13 、R 21 、R 22 、R 23 And R is 24 Examples of the aralkyl group having 7 to 30 carbon atoms include: benzyl, α -methylbenzyl, α -dimethylbenzyl, phenylethyl and the like.
R in the above general formula (A) 3 、R 11 、R 12 、R 13 、R 21 、R 22 、R 23 And R 24 Examples of the heterocyclic group having 2 to 20 carbon atoms include: pyridyl, pyrimidinyl, furyl, thienyl, tetrahydrofuranyl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidinyl, imidazolidinyl,Pyrazolidines, thiazolidines, isothiazolidines, oxazolidines, isoxazolidines, piperidines, piperazines, morpholines, and the like, and 5-to 7-membered heterocycles.
R in the above general formula (A) 4 And R is R 5 、R 5 And R is R 6 And R is 6 And R is R 7 R is as follows 3 And R is R 7 And R is 3 And R is R 8 The rings which can be formed together can be preferably exemplified, for example: cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, lactam ring and other 5-to 7-membered rings.
In addition, R in the general formula (A) 4 、R 5 、R 6 、R 7 And R is 8 A halogen atom represented by the general formula (A) above, and a substitutable R 3 、R 11 、R 12 、R 13 、R 21 、R 22 And R is 23 Examples of the halogen atom of (2) include: fluorine, chlorine, bromine, iodine.
R in the above general formula (A) 11 、R 12 、R 13 、R 21 、R 22 And R is 23 The alkylene portion of the radicals represented may contain 1 to 5-O-, under the condition that the oxygen atoms are not adjacent-S-, -COO-, -OCO-, -NR 24 -、-NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-; OCS-or-CSO-, the divalent group contained at this time may be one or two or more groups, in the case of a group which can be contained continuously, 2 or more groups may be contained continuously.
In addition, R in the above general formula (A) 11 、R 12 、R 13 、R 21 、R 22 、R 23 And R is 24 The alkyl (alkylene) moiety of the indicated group may have a branched side chain or may be a cyclic alkyl group.
In the compound represented by the above general formula (A), R 3 The compound having a condensable aromatic ring or the compound represented by the general formula (a') is preferable because it has high sensitivity and is easy to produce.
[ chemical formula 2]
General formula (A')
(wherein R is 1 、R 2 、R 4 、R 5 、R 6 、R 7 、R 8 And k is the same as the above formula (A), R 31 、R 32 、R 33 、R 34 And R is 35 R is independently represented by 11 、OR 11 、SR 11 、COR 11 、CONR 15 R 16 、NR 12 COR 11 、OCOR 11 、COOR 14 、SCOR 11 、OCSR 11 、COSR 14 、CSOR 11 Hydroxy, nitro, CN, or halogen atoms, R 31 And R is R 32 、R 32 And R is R 33 、R 33 And R is R 34 And R is 34 And R is R 35 Each may together form a ring. )
As R 31 And R is R 32 、R 32 And R is R 33 、R 33 And R is R 34 And R is 34 And R is R 35 Examples of the ring formed together include R 4 And R is R 5 、R 5 And R is R 6 And R is 6 And R is R 7 R is as follows 3 And R is R 7 And R is 3 And R is R 8 Examples of rings that may be formed together are the same rings as those listed above.
In the above general formulae (A) and (A'), an alkyl group having 1 to 12 carbon atoms or an aralkyl group having 7 to 15 carbon atoms is used as R 1 And R is 11 Compounds which are C6-C12 aryl groups or C1-C8 alkyl groups are preferred as R because of their high solvent solubility 2 Compounds which are methyl, ethyl or phenyl are preferred as R because of their relatively high reactivity 4 ～R 7 Compounds which are hydrogen atoms or cyano groups, especially hydrogen atoms, are preferred as R because they are easy to synthesize 8 The compound having a hydrogen atom is preferably a compound having k of 1 because of easy synthesis, and the compound having k of 1 is preferably a compound having R in the above general formula (A') 31 ～R 35 At least 1 of them is nitro, CN, halogen atom, COR 11 And R is 11 The compound having an aryl group having 6 to 12 carbon atoms or an alkyl group having 1 to 8 carbon atoms is preferable because of its high sensitivity, and R is more preferable 31 ～R 35 Compounds in which at least 1 is nitro, CN or a halogen atom, R being particularly preferred 35 A compound which is a nitro group, a CN or a halogen atom.
Preferable specific examples of the compound represented by the general formula (a) include the following compounds. Further, examples of the compounds include compounds No.1 to No.212 described in International publication No. 2015/152153.
[ chemical formula 3]
The compound represented by the general formula (a) can be synthesized by appropriately selecting a solvent, a reaction temperature, a reaction time, a purification method, and the like according to the material used, for example, by referring to international publication No. 2015/152153. Further, commercially available products may be suitably obtained and used.
The total content of the photoinitiators used in the photosensitive green resin composition of the present invention is not particularly limited as long as the effect of the present invention is not impaired, and is preferably in the range of 0.1 to 15.0 mass%, and more preferably in the range of 1.0 to 10.0 mass%, relative to the total solid content of the photosensitive green resin composition. If the content is not less than the above-mentioned lower limit, the photo-curing is easily performed sufficiently, solvent resistance and substrate adhesion are easily improved, while if it is not more than the above-mentioned upper limit, line width deviation is suppressed, and a high-definition pattern is easily formed.
The total content of at least one compound represented by the general formula (a) is preferably 30.0 mass% or more, more preferably 50.0 mass% or more, still more preferably 70.0 mass% or more, and may be 100 mass% or more, based on the total amount of the photoinitiator, in terms of forming a cured film excellent in substrate adhesion and solvent resistance even by low-temperature heat treatment.
< solvent >
The photosensitive green resin composition of the present invention may contain a solvent. The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with the components in the photosensitive green resin composition and can dissolve or disperse them. The solvents may be used singly or in combination of two or more.
Specific examples of the solvent include, for example: alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, and cyclohexanol acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, and ethoxyethyl acetate; carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl Carbitol Acetate (BCA); diacetates such as propylene glycol diacetate and 1, 3-butanediol diacetate; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether, and the like; aprotic amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as gamma-butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; organic solvents such as aromatic hydrocarbons including toluene and xylene. Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are suitably used in view of the solubility of other components. Among them, the solvent used in the present invention is preferably one or more selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl Carbitol Acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate, in terms of solubility of other components and coating suitability.
In the photosensitive green resin composition of the present invention, the content of the solvent may be appropriately set within a range in which the colored layer can be formed with high accuracy. The content of the solvent is generally preferably in the range of 55 to 95 mass%, more preferably in the range of 65 to 88 mass%, relative to the total amount of the photosensitive green resin composition containing the solvent. The content of the solvent is within the above range, and a composition excellent in coatability can be obtained.
< dispersant >
In the photosensitive green resin composition of the present invention, when the coloring material is dispersed, a dispersant may be further contained in terms of the dispersibility of the coloring material and the dispersion stability of the coloring material.
In the present invention, the dispersant may be appropriately selected from conventionally known dispersants. As the dispersant, for example, surfactants such as cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants can be used. Among the surfactants, polymeric dispersants are preferred in terms of being uniformly and finely dispersible.
Examples of the polymer dispersant include: a (meth) acrylate copolymer dispersant; polyurethanes; unsaturated polyamides; polysiloxanes; long chain polyaminoamide phosphates; polyethyleneimine derivatives (amides obtained by reaction of poly (lower alkylene imine) with free carboxyl group-containing polyesters or their bases); polyallylamine derivatives (reaction products obtained by reacting polyallylamine with at least one compound selected from 3 compounds including polyesters having free carboxyl groups, polyamides, or cocondensates of esters and amides (polyesteramides)), and the like.
In the present invention, a (meth) acrylate copolymer-based dispersant is preferably used as the dispersant in view of the fact that solvent resistance is easily improved even by low-temperature heat treatment. Regarding the (meth) acrylate copolymer-based dispersant, it is presumed that since the compatibility of the photopolymerizable compound with the photoinitiator containing the compound represented by the general formula (a) is good, the initiator is likely to be uniformly present in the colored layer, the colored layer is uniformly cured, the unreacted components are reduced, and the internal stress of the colored layer is also reduced, so that the change of the colored layer upon immersion in a solvent is reduced.
In the present invention, the (meth) acrylate copolymer-based dispersant is a dispersant which is a copolymer and contains at least a structural unit derived from a (meth) acrylate.
The (meth) acrylate copolymer dispersant is preferably a copolymer containing a structural unit functioning as a coloring material adsorption site and a structural unit functioning as a solvent affinity site, and it is preferable that at least a structural unit derived from a (meth) acrylate is contained in the structural unit functioning as a solvent affinity site.
Examples of the structural unit functioning as the coloring material adsorption site include structural units derived from an ethylenically unsaturated monomer copolymerizable with the structural unit derived from (meth) acrylic acid ester. The coloring material adsorption site may be a structural unit derived from an ethylenically unsaturated monomer having an acidic group or a structural unit derived from an ethylenically unsaturated monomer having a basic group.
The structural unit derived from the basic group-containing ethylenically unsaturated monomer is preferably a structural unit represented by the following general formula (I) in view of excellent dispersibility.
[ chemical formula 4]
(in the general formula (I), R 71 Represents a hydrogen atom or a methyl group, A 1 Is a divalent linking group, R 72 And R is 73 Each independently represents a hydrogen atom, or a hydrocarbon group which may contain a hetero atom, R 72 And R is 73 Or can be bonded to each other to form a ring structure. )
In the general formula (I), A 1 Is a divalent linking group. Examples of the divalent linking group include: linear, branched or cyclic alkylene, linear, branched or cyclic alkylene having a hydroxyl group, arylene, -CONH-group, -COO-group, -NHCOO-group, ether group (-O-group), thioether group (-S-group), combinations thereof, and the like. In the present invention, the bonding direction of the divalent linking group is arbitrary. That is, when-CONH-is contained in the divalent linking group, can be-CO as the carbon atom side of the main chain and-NH as the nitrogen atom side of the side chain, conversely, -NH may be the carbon atom side of the main chain and-CO may be the nitrogen atom side of the side chain.
Wherein A in the general formula (I) is from the aspect of dispersibility 1 Preferably a divalent linking group comprising a-CONH-group or-COO-group, more preferably a divalent linking group comprising a-CONH-or-COO-group and an alkylene group having 1 to 10 carbon atoms.
R 72 And R is 73 Examples of the hydrocarbon group in the hydrocarbon group which may contain a heteroatom include: alkyl, aralkyl, aryl, and the like.
Examples of the alkyl group include: methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, etc., the carbon number of the alkyl group is preferably 1 to 18, and among them, methyl or ethyl is more preferred.
Examples of the aralkyl group include: benzyl, phenethyl, naphthylmethyl, biphenylmethyl, and the like. The carbon number of the aralkyl group is preferably 7 to 20, more preferably 7 to 14.
Further, examples of the aryl group include: phenyl, biphenyl, naphthyl, tolyl, xylyl, and the like. The carbon number of the aryl group is preferably 6 to 24, more preferably 6 to 12. The preferable carbon number does not contain a substituent.
The heteroatom-containing hydrocarbon group has a structure in which a carbon atom in the above-mentioned hydrocarbon group is substituted with a heteroatom, or a structure in which a hydrogen atom in the above-mentioned hydrocarbon group is substituted with a heteroatom-containing substituent. Examples of the hetero atom which the hydrocarbon group may contain include: oxygen atom, nitrogen atom, sulfur atom, silicon atom, etc.
The hydrogen atom in the hydrocarbon group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom.
R 72 And R is 73 The R is R 72 And R is 73 A ring structure is formed via a nitrogen atom. At R 72 And R is 73 Heteroatoms may also be included in the ring structure formed. The ring structure is not particularly limited, and examples thereof include: pyrrolidine ring, piperidine ring, morpholine ring, and the like.
In the present invention, R is particularly preferable 72 And R is 73 Independently of each other, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R 12 And R is 73 Bonding to form a pyrrolidine ring, a piperidine ring, a morpholine ring.
Examples of the monomer from which the structural unit represented by the above general formula (I) is derived include: alkyl-substituted amino group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, and the like; and (meth) acrylamides containing an alkyl-substituted amino group such as dimethylaminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide. Among them, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide are preferably used in view of improving dispersibility and dispersion stability.
In the polymer, the structural unit represented by the general formula (I) may contain one kind or two or more kinds of structural units.
The structural unit represented by the general formula (I) may have a nitrogen site at least partially forming a salt with at least one member selected from the group consisting of organic acid compounds and halogenated hydrocarbons (hereinafter, such a copolymer may be referred to as a salt-type copolymer).
The organic acid compound is particularly preferably a compound represented by the following general formula (1) or a compound represented by the following general formula (3), and the halogenated hydrocarbon is particularly preferably a compound represented by the following general formula (2). That is, as at least one selected from the above-mentioned organic acid compounds and halogenated hydrocarbons, one or more compounds selected from the following general formulae (1) to (3) can be preferably used.
[ chemical formula 5]
(in the general formula (1), R a Represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or-O-R e ，R e Represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or a (meth) acryloyl group of an alkylene group having 1 to 4 carbon atoms. In the general formula (2), R b 、R b′ And R b″ Each independently represents a hydrogen atom, an acidic group or an ester group thereof, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a vinyl group which may have a substituent, a phenyl group or benzyl group which may have a substituent, or-O-R f ，R f A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or a (meth) acryloyl group of an alkylene group having 1 to 4 carbon atoms via a carbon atom, X represents a chlorine atom, a bromine atom, or an iodine atom. In the general formula (3), R c And R is d Independently of one another, represents a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl or benzyl group which may have a substituent, or-O-R e ，R e Represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or a (meth) acryloyl group of an alkylene group having 1 to 4 carbon atoms. Wherein R is c And R is d Comprises carbon atoms. )
The symbols of the general formulae (1) to (3) may be the same as those described in International publication No. 2016/104493.
The organic acid compound is preferably an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid, in view of excellent dispersibility and dispersion stability of the colorant. Specific examples of the organic acid compound used for such a dispersant include, for example, those described in japanese patent application laid-open No. 2012-236882.
The halogenated hydrocarbon is preferably at least one of an allylhalogen such as allylbromine or benzyl chloride and a halogenated aralkyl group, in view of excellent dispersibility and dispersion stability of the coloring material.
In the salt-type copolymer, since the content of at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon forms a salt with the terminal nitrogen moiety of the structural unit represented by the general formula (I), the total of at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon is preferably 0.01 mol or more, more preferably 0.05 mol or more, still more preferably 0.1 mol or more, and particularly preferably 0.2 mol or more, with respect to the terminal nitrogen moiety of the structural unit represented by the general formula (I). When the lower limit is not less than the above, the effect of improving the dispersibility of the coloring material by salt formation is easily obtained. Similarly, the amount is preferably 1 mol or less, more preferably 0.8 mol or less, still more preferably 0.7 mol or less, and particularly preferably 0.6 mol or less. When the amount is not more than the above-mentioned upper limit, the development adhesion and the solvent resolubility can be improved.
At least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons may be used alone or in combination of two or more. When two or more of them are combined, the total content thereof is preferably within the above range.
The method for producing the salt-type copolymer includes the following methods: at least one selected from the group consisting of the organic acid compounds and halogenated hydrocarbons is added to a solvent in which the copolymer before salt formation is dissolved or dispersed, and the mixture is stirred and heated as necessary.
The nitrogen site at the terminal of the structural unit represented by the general formula (I) of the copolymer forms a salt with at least one selected from the group consisting of the organic acid compounds and halogenated hydrocarbons, and the ratio thereof can be confirmed by a known method such as NMR (Nuclear Magnetic Resonance ).
From the viewpoints of dispersibility and dispersion stability, the copolymer having the structural unit represented by the above general formula (I) is more preferably at least one of a graft copolymer having the structural unit represented by the above general formula (I) and having a structural unit derived from a (meth) acrylic ester in a graft polymer chain, and a block copolymer having an a block containing the structural unit represented by the above general formula (I) and a B block containing the structural unit derived from a (meth) acrylic ester.
The graft copolymer and the block copolymer will be described below in order.
Examples of the graft copolymer having a structural unit represented by the above general formula (I) and having a structural unit derived from a (meth) acrylic acid ester in the graft polymer chain include: a graft copolymer having a structural unit represented by the above general formula (I) and a structural unit represented by the following general formula (II), and a salt-type graft copolymer wherein at least a part of a nitrogen site of the structural unit represented by the general formula (I) of the graft copolymer forms a salt with at least one selected from an organic acid compound and a halogenated hydrocarbon.
[ chemical formula 6]
(in the general formula (II), R 71′ Represents a hydrogen atom or a methyl group, A 2 Represents a direct bond or a divalent linking group, and Polymer represents a Polymer chain containing a structural unit derived from a (meth) acrylate in a structural unit of the Polymer chain. )
In the above general formula (II), A 2 Is a direct bond or a divalent linking group. As A 2 The divalent linking group in (2) is not particularly limited as long as it can link a carbon atom derived from an ethylenically unsaturated double bond to the polymer chain. As A 2 Examples of the divalent linking group include those described above in connection with A 1 The divalent linking groups of (a) are the same.
Wherein A in the general formula (II) is from the aspect of dispersibility 2 Preferably a divalent linking group comprising a-CONH-group or-COO-group, more preferably a divalent linking group comprising a-CONH-or-COO-group and an alkylene group having 1 to 10 carbon atoms.
In the above general formula (II), the Polymer represents a Polymer chain, and the structural unit of the Polymer chain contains a structural unit derived from a (meth) acrylate. The graft copolymer has a structural unit represented by the general formula (II) having a specific polymer chain, so that the solvent affinity is good, the dispersibility and dispersion stability of the colorant are good, and the compatibility with the photoinitiator is also good.
The structural unit of the polymer chain includes a structural unit represented by the following general formula (III).
[ chemical formula 7]
(in the general formula (III), R 74″ Is a hydrogen atom or methyl group, A 4 Is a divalent linking group, R 80 Is a hydrogen atom, or a hydrocarbon group that may contain a heteroatom. )
As A 4 Examples of the divalent linking group include those described above in connection with A 1 The divalent linking groups of (a) are the same. In the present invention, at least A in the general formula (III) is contained as a structural unit derived from (meth) acrylic acid ester 4 A structural unit represented by the general formula (III) which contains a divalent linking group of-COO-group. From the aspect of solubility in organic solvents for color filter applications, A in formula (III) 4 Divalent linking groups containing-CONH-groups may also be included.
R 80 Examples of the hydrocarbon group in the hydrocarbon group which may contain a heteroatom include: alkyl, alkenyl, aryl, aralkyl or alkyl substituted aryl, and the like. As R 80 Examples of the hydrocarbon group in the hydrocarbon group which may contain a heteroatom include: alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, aryl groups, aralkyl groups, alkyl substituted aryl groups, and the like.
The alkyl group having 1 to 18 carbon atoms may be any of linear, branched, and cyclic, and examples thereof include: methyl, ethyl, n-propyl, isopropyl, n-butyl, n-nonyl, n-lauryl, n-stearyl, cyclopentyl, cyclohexyl, bornyl, isobornyl, dicyclopentyl, adamantyl, lower alkyl substituted adamantyl, and the like. The carbon number of the alkyl group is preferably 1 to 12, more preferably 1 to 6.
The alkenyl group having 2 to 18 carbon atoms may be any of linear, branched, and cyclic. Examples of such alkenyl groups include: vinyl, allyl, propenyl, and the like. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of reactivity of the obtained polymer, it is preferable that a double bond exists at the terminal of the alkenyl group. The carbon number of the alkenyl group is preferably 2 to 12, more preferably 2 to 8.
Examples of the aryl group include: phenyl, biphenyl, naphthyl, tolyl, xylyl, and the like. The carbon number of the aryl group is preferably 6 to 24, more preferably 6 to 12.
Further, examples of the aralkyl group include: benzyl, phenethyl, naphthylmethyl, biphenylmethyl and the like may further have a substituent. The carbon number of the aralkyl group is preferably 7 to 20, more preferably 7 to 14.
Further, a linear or branched alkyl group having 1 to 30 carbon atoms may be bonded to the aromatic ring such as an aryl group or an aralkyl group as a substituent.
Wherein R is as R from the aspect of dispersion stability 80 The hydrocarbon group in (2) is preferably one selected from alkyl groups having 1 to 18 carbon atoms, aryl groups having 6 to 12 carbon atoms which may be substituted with alkyl groups, and aralkyl groups having 7 to 14 carbon atoms which may be substituted with alkyl groupsThe above is preferably one or more selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, n-nonyl, n-lauryl, n-stearyl, phenyl optionally substituted with alkyl, and benzyl.
Examples of the hetero atom which the hydrocarbon group may contain include: oxygen atom, nitrogen atom, sulfur atom, silicon atom, etc. As the hydrocarbon group which may contain a hetero atom, examples include those wherein the carbon chain of the hydrocarbon group contains-CO-, -COO-, -OCO-, -O-, -S-, -CO-S-, -S-CO-, -O-CO-O-, and-CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-and the like.
The hydrocarbon group may have a substituent in a range that does not interfere with the dispersibility of the graft copolymer, and examples of the substituent include: halogen atom, hydroxyl group, carboxyl group, alkoxy group, nitro group, cyano group, epoxy group, isocyanate group, thiol group, and the like.
In addition, as R 80 The hydrocarbon group which may contain a heteroatom may be one in which a polymerizable group such as an alkenyl group is added to the hydrocarbon group at the terminal via a linking group containing a heteroatom. For example, the structural unit represented by the general formula (III) may be a structure obtained by reacting glycidyl (meth) acrylate with a structural unit derived from (meth) acrylic acid. Namely, -A in the general formula (III) 4 -R 80 The structure of (C) may also be-COO-CH 2 CH(OH)CH 2 -OCO-CR＝CH 2 (herein, R is a hydrogen atom or a methyl group). The structural unit represented by the general formula (III) may be a structure obtained by reacting a structural unit derived from a hydroxyalkyl (meth) acrylate with a 2-isocyanatoalkyl (meth) acrylate. Namely, R in the general formula (III) 80 or-R' -OCONH-R "-OCO-cr=ch 2 (Here, R 'and R' are each independently an alkylene group, and R is a hydrogen atom or a methyl group).
The monomer from which the structural unit represented by the general formula (III) is derived is preferably a structural unit derived from methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, 2-methacryloyloxy ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, or the like. However, these are not limited thereto.
In the present invention, R is as the above 80 In particular, a group having excellent solubility in an organic solvent to be described later is preferably used, and the group may be appropriately selected according to the organic solvent used in the colorant dispersion. Specifically, for example, when an ether alcohol acetate, ether, ester, alcohol or other organic solvent which is generally used as the organic solvent of the colorant dispersion is used as the organic solvent, methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, benzyl, cyclohexyl, dicyclopentyl, hydroxyethyl, phenoxyethyl, adamantyl, methoxypolyethylene glycol, methoxypolypropylene glycol, polyethylene glycol or the like is preferable.
In the graft copolymer, it is preferable that the structural unit of the polymer chain in the structural unit represented by the general formula (II) contains at least one structural unit selected from the structural units represented by the general formula (IV) and the structural units represented by the general formula (IV') below, in view of further improving the solvent resistance of the cured product of the photosensitive green resin composition and shortening the development time of the photosensitive green resin composition.
The structural unit represented by the above general formula (III) includes a structural unit represented by the following general formula (IV).
[ chemical formula 8]
(in the general formula (IV), R 74 Is a hydrogen atom or methyl group, A 3 Is a divalent linking group, R 75 Is ethylene or propylene, R 76 And m represents a number of 3 to 80 inclusive.
In the general formula (IV'), R 74′ Is a hydrogen atom or methyl group, A 3′ Is a divalent linking group, R 77 Is alkylene with 1-10 carbon atoms, R 78 Is alkylene of 3-7 carbon atoms, R 79 Is a hydrogen atom or a hydrocarbon group, and n represents a number of 1 to 40 inclusive. )
As A 3 Examples of the divalent linking group include those described above in connection with A 1 The divalent linking groups of (a) are the same. Among them, aw in the general formula (IV) is preferably a divalent linking group containing a-CONH-group or a-COO-group, more preferably a-CONH-group or a-COO-group, and even more preferably a-COO-group, from the viewpoint of solubility in an organic solvent for color filter use.
The number of repeating units of the ethylene oxide chain or the propylene oxide chain is 3 or more, and among them, 19 or more is preferable, and 21 or more is more preferable from the viewpoints of suppression of occurrence of water stains and solvent resistance.
When m is 19 or more, the graft copolymer contains a main chain portion having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II), the structural unit represented by the general formula (II) contains a structural unit represented by the general formula (IV) in a polymer chain, and the structural unit represented by the general formula (IV) contains a polyethylene oxide chain or a polypropylene oxide chain having a specific number of repetitions. In the specific graft copolymer used in the present invention, the structural unit containing a polyethylene oxide chain or polypropylene oxide chain having a specific number of repetitions is contained in the structural unit of the polymer chain thus grafted, and the polymer chain itself subjected to grafting has a branched structure. Since the plurality of polymer chains to be grafted are stereoscopically extended in the film and the specific surface area is increased, it is presumed that the penetration of the solvent into the coating film or the arrival of the coloring material can be further suppressed.
On the other hand, the upper limit value of m is 80 or less, but is preferably 50 or less in terms of solubility in an organic solvent used for color filter application.
As R 76 The hydrocarbon group of (B) may be the same as R 80 The hydrocarbon groups in (2) are the same.
Wherein R is as R from the aspects of dispersion stability and compatibility 76 The hydrocarbon group in (a) is preferably at least one selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group, and an aralkyl group having 7 to 14 carbon atoms which may be substituted with an alkyl group, and preferably at least one selected from the group consisting of a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a n-nonyl group, a n-lauryl group, a n-stearyl group, a phenyl group which may be substituted with an alkyl group, and a benzyl group.
In the general formula (IV '), A is represented by the formula (IV') 3′ Examples of the divalent linking group include those described above in connection with A 1 The divalent linking groups of (a) are the same. Wherein A in the general formula (IV ') is represented by the following formula (IV') in view of solubility in an organic solvent for color filter use 3′ Preferably a divalent linking group comprising a-CONH-group or-COO-group, more preferably-CONH-or-COO-group, further preferred is-COO-group.
In the above formula (IV'), R 77 The alkylene group has 1 to 10 carbon atoms, and among them, an alkylene group having 2 to 8 carbon atoms is preferable in view of the solvent resolubility.
R 78 Among them, an alkylene group having 3 to 7 carbon atoms is preferable, and an alkylene group having 3 to 5 carbon atoms and an alkylene group having 5 carbon atoms are more preferable in view of adhesion to a substrate.
R 79 Is a hydrogen atom or a hydrocarbon group as R 79 The hydrocarbon group of (B) may be the same as R 76 The hydrocarbon groups in (2) are the same.
The number of repeating units of the ester chain in the general formula (IV') is 1 or more, preferably 2 or more, more preferably 3 or more, from the viewpoint of satisfying both reduction of development time and excellent solvent resistance.
On the other hand, the upper limit value of n is 40 or less, but is preferably 20 or less in view of solubility in an organic solvent used for color filter application.
In the polymer chain, at least one structural unit selected from the structural units represented by the above general formula (IV) and the structural units represented by the following general formula (IV') may be a single structural unit, but two or more structural units may be mixed.
The polymer chain preferably contains a structural unit represented by the general formula (IV) because the action of the solvent affinity part by the oxygen atom becomes more remarkable, the development time of the photosensitive green resin composition is shortened, and the solvent resistance is improved.
Among them, from the viewpoint of improving solvent resistance, improving water stain inhibition effect, and improving development residue inhibition effect, it is more preferable to combine at least one structural unit selected from the structural units represented by the general formula (IV) having m of 19 to 80 and at least one structural unit selected from the structural units represented by the general formula (IV) having m of 3 to 10, and it is still more preferable to combine at least one structural unit selected from the structural units represented by the general formula (IV) having m of 19 to 50 and at least one structural unit selected from the structural units represented by the general formula (IV) having m of 3 to 8.
When at least one of the structural units represented by the general formula (IV) is contained in the structural units represented by the general formula (II), the total proportion of the structural units represented by the general formula (IV) in which m is 19 to 80 is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 4% by mass or more, and on the other hand, from the viewpoints of solvent resolubility and water stain inhibition effect, the total proportion of the structural units represented by the general formula (IV) in which m is 19 to 80 is preferably 75% by mass or less, more preferably 65% by mass or less, and even more preferably 50% by mass or less, based on 100% by mass of the total structural units of the polymer chain.
The total proportion of the structural units represented by the general formula (IV) in which m is 3 to 10 is preferably 20 mass% or more, when 100 mass% of the total structural units of the polymer chain are contained in the structural units of the general formula (II), the total proportion being obtained by combining at least one structural unit represented by the general formula (IV) in which m is 19 to 80 inclusive with at least one structural unit represented by the general formula (IV) in which m is 3 to 10 inclusive. On the other hand, in view of solvent resolubility, the total proportion of the structural units represented by the general formula (IV) in which m is 3 to 10 inclusive is preferably 80 mass% or less, more preferably 60 mass% or less, in the polymer chain, when the total structural units of the polymer chain are 100 mass%.
In the polymer chain, the total of the structural units represented by the general formula (IV) in which m is 19 to 80 inclusive and the structural units represented by the general formula (IV) in which m is 3 to 10 inclusive is preferably 3 parts by mass or more, more preferably 6 parts by mass or more, and still more preferably 80 parts by mass or less, and the total of the structural units represented by the general formula (IV) in which m is 19 to 80 inclusive and the structural units represented by the general formula (IV) in which m is 3 to 10 inclusive is 100 parts by mass, in terms of the improvement of the development residue suppressing effect.
In view of satisfying the dispersion stability, high contrast, shortened development time, and excellent solvent resistance at the same time, the total ratio of at least one structural unit selected from the structural units represented by the general formula (IV) and the structural units represented by the general formula (IV') is preferably 1 mass% or more, more preferably 2 mass% or more, and even more preferably 4 mass% or more, when the total structural units of the polymer chain is 100 mass%. In terms of solvent resolubility, when the total structural units of the polymer chain are 100% by mass, the total proportion of at least one structural unit selected from the structural units represented by the general formula (IV) and the structural units represented by the general formula (IV') is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less.
The structural unit represented by the general formula (III) including the structural unit represented by the general formula (IV) and the structural unit represented by the general formula (IV') may be a single type, or two or more types may be mixed in the polymer chain.
In terms of dispersibility and dispersion stability of the coloring material, the total proportion of the structural units represented by the general formula (III) is preferably 70 mass% or more, more preferably 90 mass% or more, based on 100 mass% of the total structural units of the polymer chain. On the other hand, in view of satisfying both dispersion stability and excellent solvent resistance, the total proportion of the structural units represented by the general formula (III) in the polymer chain may be 100 mass% when the total structural units of the polymer chain are 100 mass%.
Among them, the total proportion of the structural units derived from the (meth) acrylic acid ester is preferably 60 mass% or more, more preferably 80 mass% or more, when the total structural units of the polymer chain are 100 mass% in terms of dispersion stability, solvent resistance, and compatibility with the initiator. On the other hand, in view of satisfying both dispersion stability and excellent solvent resistance, the total proportion of structural units derived from (meth) acrylic acid esters may be 100 mass% in the polymer chain, assuming that all structural units of the polymer chain are 100 mass%.
The structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer may contain other structural units in addition to the structural unit represented by the general formula (III).
As the other structural unit, a structural unit derived from a monomer having an unsaturated double bond copolymerizable with a monomer from which the structural unit represented by the above general formula (III) is derived may be mentioned.
Examples of the monomer from which the other structural unit is derived include: styrenes such as styrene and α -methylstyrene; vinyl ethers such as phenyl vinyl ether, and the like.
In the polymer chain of the structural units represented by the general formula (II) of the graft copolymer, the total proportion of the other structural units is preferably 30 mass% or less, more preferably 10 mass% or less, when the total structural units of the polymer chain is 100 mass% in view of the effects of the present invention.
The mass average molecular weight Mw of the Polymer chain in the Polymer (Polymer) is preferably 2000 or more, more preferably 3000 or more, still more preferably 4000 or more, and still more preferably 15000 or less, still more preferably 12000 or less, from the viewpoints of dispersibility and dispersion stability of the colorant.
By the above-mentioned range, the specific surface area of the solvent affinity portion of the dispersant increases while maintaining a sufficient steric repulsion effect as the dispersant, and thus penetration of the solvent into the coating film or arrival of the coloring material can be easily suppressed.
In addition, as a standard, the solubility of the Polymer chain in the Polymer (Polymer) at 23℃is preferably 20 (g/100 g solvent) or more with respect to the organic solvent used in combination.
Regarding the solubility of the polymer chain, the raw material into which the polymer chain is introduced in the preparation of the graft copolymer may be given as a standard. For example, in the case of using a polymerizable oligomer (macromer) containing a polymer chain and a group having an ethylenically unsaturated double bond at the terminal thereof for introducing a polymer chain into a graft copolymer, the polymerizable oligomer may have the above-mentioned solubility. In addition, when a polymer chain containing a reactive group capable of reacting with a reactive group contained in a copolymer is used to introduce the polymer chain after forming a copolymer using a monomer containing a group having an ethylenically unsaturated double bond, the polymer chain containing the reactive group may have the above-mentioned solubility.
The graft copolymer preferably contains the structural unit represented by the general formula (I) at a ratio of 3 to 60% by mass, more preferably 6 to 45% by mass, and still more preferably 9 to 30% by mass. When the structural unit represented by the general formula (I) in the graft copolymer is within the above range, the proportion of the affinity portion with the colorant in the graft copolymer becomes appropriate, and the decrease in solubility in the organic solvent can be suppressed, so that the adsorptivity to the colorant becomes good, and excellent dispersibility and dispersion stability can be easily obtained.
On the other hand, the graft copolymer preferably contains the structural unit represented by the general formula (II) at a ratio of 40 to 97% by mass, more preferably 55 to 94% by mass, and still more preferably 70 to 91% by mass. When the structural unit represented by the general formula (II) in the graft copolymer falls within the above range, the proportion of the solvent affinity portion in the graft copolymer becomes appropriate, a sufficient steric repulsion effect as a dispersant can be maintained, and the specific surface area of the solvent affinity portion of the dispersant increases, whereby penetration of the solvent into the coating film or arrival of the coloring material is easily suppressed.
The graft copolymer used in the present invention may further have other structural units in addition to the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) within a range that does not impair the effects of the present invention. As the other structural unit, an ethylenically unsaturated double bond-containing monomer which is copolymerizable with an ethylenically unsaturated double bond-containing monomer or the like which induces the structural unit represented by the above general formula (I) may be appropriately selected and copolymerized to introduce the other structural unit.
Examples of the other structural unit copolymerizable with the structural unit represented by the above general formula (I) include structural units represented by the above general formula (III).
The content of the structural unit is calculated from the amount of the monomer derived from the structural unit represented by the general formula (I), the structural unit represented by the general formula (II), the structural unit represented by the general formula (III), and the like when the graft copolymer is synthesized at the time of production.
In view of dispersibility and dispersion stability, the mass average molecular weight Mw of the graft copolymer is preferably 4000 or more, more preferably 6000 or more, and even more preferably 8000 or more. On the other hand, from the viewpoint of solvent resolubility, it is preferably 50000 or less, more preferably 30000 or less.
In the present invention, the mass average molecular weight Mw is a value measured by GPC (gel permeation chromatography). Measurement was performed using HLC-8120GPC manufactured by eason, using N-methylpyrrolidone to which 0.01 mol/l of lithium bromide was added as a dissolution solvent, using polystyrene standards for calibration curves, using Mw377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (Easi PS-2 series manufactured by Polymer Laboratories above) and Mw1090000 (east Cao Zhizao), and using measurement columns using TSK-GEL ALPHA-mx2 roots (east Cao Zhizao).
(Process for producing graft copolymer)
In the present invention, the method for producing the graft copolymer is not particularly limited as long as it is a method capable of producing a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II). In the case of producing a graft copolymer having a structural unit represented by the above general formula (I) and a structural unit represented by the above general formula (II), for example, the following method can be mentioned: a graft copolymer is produced by copolymerizing a monomer represented by the general formula (Ia) below and a polymerizable oligomer (macromer) containing the polymer chain and a group having an ethylenically unsaturated double bond at the terminal thereof as copolymerization components.
Other monomers may be further used as needed, and a known polymerization method may be used to produce the graft copolymer.
[ chemical formula 9]
(in the general formula (Ia), R 71 、A 1 、R 72 And R is 73 Is the same as the general formula (I). )
In the case of producing a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II), a polymer chain containing a reactive group capable of reacting with a reactive group contained in the copolymer may be used after addition-polymerizing a monomer represented by the general formula (Ia) with another monomer containing a group having an ethylenically unsaturated double bond to form a copolymer. Specifically, for example, a copolymer having a substituent such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, or a hydrogen bond forming group may be synthesized, and then reacted with a polymer chain containing a functional group reactive with the substituent to introduce the polymer chain.
For example, the polymer chain may be introduced by reacting a polymer chain having a carboxyl group at the end with a copolymer having a glycidyl group in the side chain, or by reacting a polymer chain having a hydroxyl group at the end with a copolymer having an isocyanate group in the side chain.
In the above polymerization, additives commonly used for polymerization, such as a polymerization initiator, a dispersion stabilizer, a chain transfer agent, and the like, may also be used.
Next, a block copolymer having an a block containing a structural unit represented by the above general formula (I) and a B block containing a structural unit derived from a (meth) acrylate will be described.
In the present invention, the arrangement of each block of the block copolymer is not particularly limited, and for example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer, or the like may be used. Among them, an AB block copolymer or an ABA block copolymer is preferable in view of excellent dispersibility.
The A block is a block functioning as a coloring material adsorption site, and includes at least a structural unit represented by the general formula (I). The block copolymer may be a salt block copolymer in which at least a part of the nitrogen moiety of the structural unit represented by the general formula (I) of the block copolymer and at least one member selected from the group consisting of an organic acid compound and a halogenated hydrocarbon form a salt.
Within the scope of achieving the object of the present invention, the A block may have a structural unit other than the structural unit represented by the general formula (I), and may be contained as long as it is a structural unit copolymerizable with the structural unit represented by the general formula (I). Specifically, the structural unit represented by the general formula (III) can be exemplified.
In the a block in the block copolymer before salt formation, the content of the structural unit represented by the general formula (I) is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and most preferably 100% by mass based on the total mass of all the structural units of the a block. This is because the higher the proportion of the structural unit represented by the general formula (I), the higher the adsorption force to the coloring material, and the better the dispersibility and dispersion stability of the block copolymer. The content of the structural unit is calculated from the mass added when synthesizing the a block having the structural unit represented by the general formula (I).
In the block copolymer before salt formation, the total content of all the structural units including the a block represented by the general formula (I) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, relative to the total mass of all the structural units of the block copolymer, from the viewpoint of improving dispersibility and dispersion stability.
In addition, in the block copolymer before salt formation, the content of the structural unit represented by the general formula (I) is preferably 5 to 60 mass%, more preferably 10 to 50 mass% with respect to the total mass of all the structural units of the block copolymer, from the viewpoint of improving dispersibility and dispersion stability. The content of each structural unit in the block copolymer was calculated from the mass of the block copolymer before formation of the synthetic salt.
The structural unit represented by the general formula (I) may be one or two or more structural units as long as it has affinity with the coloring material.
The B block is a block that functions as a solvent affinity site and includes at least a structural unit derived from a (meth) acrylate.
The structural unit derived from the (meth) acrylic acid ester may be the same as described above.
The B block is preferably selected from monomers having an unsaturated double bond copolymerizable with the monomer from which the structural unit represented by the general formula (I) is derived, and used appropriately depending on the solvent so as to have solvent affinity. As a standard, it is preferable to introduce the B block so that the solubility of the copolymer at 23℃becomes 20 (g/100 g of solvent) or more with respect to the solvent used in combination. The structural unit constituting the B block portion may include one kind or two or more kinds of structural units.
Examples of the structural unit contained in the B block include a structural unit represented by the above general formula (III).
In the block copolymer used as the dispersant, the ratio m/n of the number m of the structural units represented by the above general formula (I) to the number n of the other structural units constituting the block portion having affinity for the solvent is preferably in the range of 0.01 to 1, more preferably in the range of 0.05 to 0.7 in terms of dispersibility and dispersion stability of the colorant.
Among the block copolymers used as the dispersant, from the viewpoint of improving the substrate adhesion and solvent resistance of the cured film even by low-temperature heat treatment and suppressing the occurrence of development residues, it is preferable that the block copolymer contains at least one of an a block containing a structural unit represented by the above general formula (I) and a B block containing a structural unit derived from a carboxyl group-containing monomer and a structural unit derived from a (meth) acrylic ester, and a salt-type block copolymer is formed by forming a salt with at least a part of a nitrogen site of the structural unit represented by the above general formula (I) of the block copolymer and at least one selected from an organic acid compound and a halogenated hydrocarbon, and that the acid value of at least one of the block copolymer and the salt-type block copolymer is 1mgKOH/g to 18mgKOH/g, and that the glass transition temperature is 30 ℃. The specific dispersant is preferable in terms of further improvement in solvent resistance when combined with a photoinitiator comprising a compound represented by the general formula (a).
The B block in this case contains a structural unit derived from a (meth) acrylic acid ester as an essential component, and may be the same as the B block of International publication No. 2016/104493.
As the carboxyl group-containing monomer, a monomer which is copolymerizable with a monomer having a structural unit represented by the general formula (I) and which contains an unsaturated double bond and a carboxyl group can be used. Examples of such monomers include: (meth) acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl esters of maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimers, and the like. In addition, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride or phthalic anhydride, cyclohexane dicarboxylic anhydride, ω -carboxyl-polycaprolactone mono (meth) acrylate, or the like can also be used. Further, as the carboxyl group precursor, an anhydride group-containing monomer such as maleic anhydride, itaconic anhydride, citraconic anhydride, or the like can be used. Among them, (meth) acrylic acid is particularly preferred in view of copolymerizability, cost, solubility, glass transition temperature, and the like.
In the block copolymer before salt formation, the content of the structural unit derived from the carboxyl group-containing monomer is not particularly limited as long as the acid value of the block copolymer is appropriately set within the above-mentioned specific acid value range, and is preferably 0.05 to 4.5 mass%, more preferably 0.07 to 3.7 mass% relative to the total mass of all the structural units of the block copolymer.
The content ratio of the structural unit derived from the carboxyl group-containing monomer is not less than the above lower limit, whereby the effect of suppressing the development residue is exhibited, and the deterioration of the development adhesion and the deterioration of the solvent resolubility can be prevented by the content of the structural unit being not more than the above upper limit.
The structural unit derived from the carboxyl group-containing monomer may be one or two or more structural units as long as it has the above-mentioned specific acid value.
In addition, the B block of the block copolymer preferably contains a structural unit derived from a hydroxyl group-containing monomer in view of improving development adhesion. In the case where the B block contains a structural unit derived from a hydroxyl group-containing monomer, the development speed is further increased. The hydroxyl group herein means an alcoholic hydroxyl group bonded to an aliphatic hydrocarbon.
As the structural unit derived from the hydroxyl group-containing monomer, a monomer containing an unsaturated double bond and a hydroxyl group which is copolymerizable with a monomer from which the structural unit represented by the general formula (I) is derived can be used. Examples of such monomers include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, epsilon-caprolactone 1 molar adduct of 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like.
In particular, one or more selected from the group consisting of 2-hydroxyethyl methacrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate is preferable from the viewpoint of improving the development adhesion.
In the block copolymer before salt formation, the content of the structural units derived from the hydroxyl group-containing monomer is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and particularly preferably 4% by mass or more, based on the total mass of all the structural units of the block copolymer. If the lower limit is not less than the above, a block copolymer having preferable development adhesion can be produced. Similarly, the content is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass or less. If the ratio is not more than the upper limit, a block copolymer preferable from the viewpoint of increasing the ratio of other useful monomers to be introduced can be produced. The content of the structural unit is calculated from the mass of the block copolymer before formation of the synthetic salt.
The acid value of at least one of the block copolymer and the salt-type block copolymer is preferably 1mgKOH/g or more, more preferably 2mgKOH/g or more, from the viewpoint of the effect of suppressing the development residue. In addition, the acid value of at least one of the block copolymer and the salt-type block copolymer is preferably 18mgKOH/g or less, more preferably 16mgKOH/g or less, and even more preferably 14mgKOH/g or less, from the standpoint of preventing deterioration of development adhesion and deterioration of solvent resolubility.
The acid value of at least one of the block copolymer and the salt-type block copolymer can be obtained by the method described in International publication No. 2016/104493.
The glass transition temperature of at least one of the block copolymer and the salt-type block copolymer is preferably 30℃or higher, particularly preferably 32℃or higher, and more preferably 35℃or higher, from the viewpoint of development adhesion. On the other hand, from the viewpoint of ease of handling in use such as accurate weighing, it is preferably 200℃or less.
The glass transition temperature of at least one of the block copolymer and the salt-type block copolymer is determined by measurement by Differential Scanning Calorimetry (DSC) according to JIS K7121. When 2 or more peaks indicating the glass transition temperature are observed, the peak area, that is, the peak having the largest area of the portion protruding from the base line of the obtained graph is set as a representative value of the glass transition temperature.
The mass average molecular weight Mw of the block copolymer is not particularly limited, but is preferably 1000 to 20000, more preferably 2000 to 15000, and even more preferably 3000 to 12000, in view of improving the dispersibility and dispersion stability of the colorant.
The mass average molecular weight (Mw) can be measured in the same manner as described above.
In addition, the total proportion of the structural units derived from the (meth) acrylic acid ester is preferably 60 mass% or more, more preferably 80 mass% or more, and even more preferably 90 mass% or more, in terms of dispersion stability, solvent resistance, and compatibility with the photoinitiator, when the total structural units in the B block in the block copolymer are 100 mass%. On the other hand, in terms of satisfying both dispersion stability and excellent solvent resistance, the total proportion of structural units derived from the (meth) acrylic acid ester may be 100 mass% when the total of structural units in the B block is 100 mass%. When the structural unit derived from the carboxyl group-containing monomer is contained in the B block, the total proportion of the structural units derived from the (meth) acrylic acid ester may be 100 mass% when the total structural units in the B block other than the structural unit derived from the carboxyl group-containing monomer are 100 mass%.
In the block copolymer before salt formation, the total content of all the structural units of the B block is preferably 5 to 60 mass%, more preferably 10 to 50 mass%, relative to the total mass of all the structural units of the block copolymer, from the viewpoint of improving dispersibility and dispersion stability.
In the block copolymer before salt formation, the content of the structural unit represented by the general formula (III) is preferably 40 to 95% by mass, more preferably 50 to 90% by mass, based on the total mass of all the structural units of the block copolymer, in terms of improving the dispersibility of the coloring material. The content of the structural unit is calculated from the mass of the block copolymer before formation of the synthetic salt.
The (meth) acrylic acid ester-based copolymer containing the structural unit represented by the above general formula (I) is preferably a copolymer having an amine value of 40mgKOH/g to 120mgKOH/g, in view of good dispersibility, no precipitation of foreign matter at the time of coating film formation, and improvement of brightness and contrast.
When the amine number is within the above range, the viscosity is excellent in time stability and heat resistance, and the alkali developability and solvent resolubility are also excellent. In the present invention, the amine value of the (meth) acrylic acid ester copolymer containing the structural unit represented by the above general formula (I) is preferably 80mgKOH/g or more, more preferably 90mgKOH/g or more. On the other hand, from the viewpoint of solvent resolubility, the amine value of the (meth) acrylic copolymer containing the structural unit represented by the above general formula (I) is preferably 110mgKOH/g or less, more preferably 105mgKOH/g or less.
The amine number is the number of mg of potassium hydroxide equivalent to perchloric acid required for neutralizing the amine component contained in sample 1g, and can be measured by the method defined in JIS-K7237. In the case of measurement by this method, even if an amino group forming a salt with an organic acid compound in the dispersant is dissociated from the organic acid compound, the amine value of the block copolymer itself used as the dispersant can be measured.
The content (mol%) of each structural unit in the copolymer in the dispersant can be determined from the amount of the raw material added at the time of production, and can be measured by using an analytical device such as NMR (Nuclear Magnetic Resonance ). The structure of the dispersant can be measured by NMR, various mass spectrometry, or the like. The dispersant may be decomposed by thermal decomposition or the like as needed, and the decomposed product obtained may be obtained by using high performance liquid chromatography, gas chromatography mass spectrometry, NMR, elemental analysis, XPS/ESCA (X-ray photoelectron spectroscopy/Electron Spectroscopy for Chemical Analysis, X-ray photoelectron spectroscopy/chemical analysis electron spectroscopy), TOF-SIMS (Time-Of-Flight Secondary Ion Mass Spectrometry ) or the like.
The content of the dispersant in the photosensitive green resin composition of the present invention is not particularly limited as long as it is selected so that the dispersibility and dispersion stability of the colorant are excellent, and is preferably in the range of 2 to 30 mass%, more preferably in the range of 3 to 25 mass%, relative to the total amount of solid components in the photosensitive green resin composition. When the content is not less than the above lower limit, the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the photosensitive green resin composition is further excellent. In addition, if the upper limit value is less than or equal to the above, the development property becomes good. Particularly in the case of forming a cured film having a relatively high color material concentration, the content of the dispersant is preferably in the range of, for example, 2 to 25 mass%, and more preferably in the range of 3 to 20 mass%, relative to the total solid content of the photosensitive green resin composition.
< thiol Compound >
The photosensitive green resin composition of the present invention preferably further contains a thiol compound in terms of improving solvent resistance after low-temperature heat treatment and substrate adhesion.
Examples of the thiol compound include a monofunctional thiol compound having 1 thiol group and a polyfunctional thiol compound having 2 or more thiol groups. In view of suppressing line width deviation and improving substrate adhesion, it is more preferable to use a monofunctional thiol compound having 1 thiol group.
Examples of the monofunctional thiol compound include: 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, and the like.
Examples of the polyfunctional thiol compound include: 1, 4-bis (3-mercaptobutyryloxy) butane, 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), and tetraethyleneglycol bis (3-mercaptopropionate), and the like.
The thiol compound may be used alone or in combination of two or more, but among them, 2-mercaptobenzoxazole or 2-mercaptobenzothiazole is preferable in terms of improving solvent resistance after low-temperature heat treatment and substrate adhesion.
The content of the thiol compound is usually in the range of 0.5 to 10 mass%, preferably 1 to 5 mass%, based on the total solid content of the photosensitive green resin composition. When the lower limit is not less than the above, solvent resistance after the low-temperature heat treatment and substrate adhesion are excellent. On the other hand, when the ratio is equal to or less than the upper limit, the photosensitive green resin composition of the present invention is easily made to be a resin composition having good developability and suppressed line width deviation.
< other ingredients >
The photosensitive green resin composition of the present invention may further contain various additives as required. Examples of the additive include: antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like.
Specific examples of the surfactant and the plasticizer include those described in, for example, japanese patent application laid-open No. 2013-029832.
The photosensitive green resin composition of the present invention preferably further contains an antioxidant in terms of suppressing the line width shift amount of the cured film. The photosensitive green resin composition of the present invention, for example, by containing an antioxidant in combination with the compound represented by the general formula (a), can control excessive radical chain reaction without impairing curability when forming a cured film, and thus can further improve linearity when forming a fine line pattern or improve capability of forming a fine line pattern as in the design of a mask line width. In addition, heat resistance can be improved, and reduction in luminance after exposure and post baking can be suppressed, so that luminance can be improved.
The antioxidant used in the present invention is not particularly limited, and may be appropriately selected from conventionally known antioxidants. Specific examples of the antioxidant include, for example: hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, and the like are preferably used from the viewpoint of improving the ability to form fine line patterns as in the design of line width mask line widths, and from the viewpoint of heat resistance. A latent antioxidant as described in International publication No. 2014/021023 may also be used.
Examples of the hindered phenol-based antioxidant include: pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] (trade name: IRGANOX1010, manufactured by BASF corporation), 1,3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) isocyanurate (trade name: IRGANOX3114, manufactured by BASF), 2,4, 6-tris (4-hydroxy-3, 5-di-t-butylbenzyl) mesitylene (trade name: IRGANOX 1330, manufactured by BASF), 2 '-methylenebis (6-t-butyl-4-methylphenol) (trade name: sumizer MDP-S, manufactured by Sumitomo chemical corporation), 6' -thiobis (2-t-butyl-4-methylphenol) (trade name: IRGANOX1081, manufactured by BASF), diethyl 3, 5-di-t-butyl-4-hydroxybenzyl phosphonate (trade name: irgamod195, manufactured by BASF), and the like. Among them, pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] (trade name: IRGANOX1010, manufactured by BASF corporation) is preferable from the viewpoints of heat resistance and light resistance.
The content of the antioxidant is usually in the range of 0.1 to 10.0 mass%, preferably in the range of 0,5 to 5.0 mass% based on the total solid content of the photosensitive green resin composition. If the lower limit is not less than the above, the ability to form a thin line pattern is improved as in the design of the mask line width, and the heat resistance is excellent. On the other hand, if the upper limit value is less than the above, the photosensitive green resin composition of the present invention is easily made into a photosensitive green resin composition having high sensitivity.
Further, as the silane coupling agent, there may be mentioned, for example: KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-903, KBE-903, KBM573, KBM-403, KBE-402, KBE-403, KBM-303, KBM-802, KBM-803, KBE-9007, X-12-967C (manufactured by Shin-Etsu Silicones Co.) and the like. Among them, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103 having a methacryloyl group and an acryl group are preferable from the viewpoint of adhesion of SiN substrates.
The content of the silane coupling agent is usually in the range of 0.05 to 10.0 mass%, preferably in the range of 0.1 to 5.0 mass% based on the total amount of solid components in the photosensitive green resin composition. When the lower limit value is not less than the upper limit value, the substrate adhesion improving effect is easily improved.
< method for producing photosensitive Green resin composition >
The method for producing the photosensitive green resin composition of the present invention can be prepared by mixing a coloring material, a photopolymerizable compound, a photoinitiator, and various optional additives by a known mixing method.
In the case where the photosensitive green resin composition of the present invention contains a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, and various optional additives, examples of the method for producing the resin composition include: (1) A method comprising preparing a colorant dispersion by adding a colorant and a dispersant to a solvent, and mixing an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various optional additives into the dispersion; (2) A method of simultaneously adding and mixing a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various optional additives to a solvent; (3) A method in which a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various optional additives are added to a solvent and mixed, and then a coloring material is added and dispersed; (4) A method of preparing a colorant dispersion by adding a colorant, a dispersant, and an alkali-soluble resin to a solvent, and further adding and mixing the alkali-soluble resin, the solvent, the photopolymerizable compound, the photoinitiator, and various optional additives to the dispersion.
Among these methods, the methods (1) and (4) are preferable in that the coloring material can be effectively prevented from agglomerating and uniformly dispersed.
The method for preparing the colorant dispersion may be appropriately selected from conventionally known dispersion methods. Examples include: (1) The dispersant is mixed in a solvent in advance and stirred to prepare a dispersant solution, and then an organic acid compound is mixed as needed to form a salt of an amino group of the dispersant with the organic acid compound. A method of mixing the pigment with a coloring material and other components as required and dispersing the mixture using a known stirrer or a dispersing machine; (2) A method in which a dispersant is mixed with a solvent and stirred to prepare a dispersant solution, and then a colorant, an organic acid compound as required, and other components as required are mixed and dispersed by using a known stirrer or a dispersing machine; (3) A method in which a dispersant is mixed with a solvent and stirred to prepare a dispersant solution, then a colorant and other components as needed are mixed, and a known stirrer or a dispersing machine is used to prepare a dispersion, and then an organic acid compound is added as needed.
As a dispersing machine for carrying out the dispersing treatment, there can be mentioned: roller mills such as a two-roller mill and a three-roller mill; ball mills such as a ball mill and a vibration ball mill; coating regulators, continuous disc type bead mills, continuous ring type bead mills, etc. As preferable dispersion conditions of the bead mill, the bead particle diameter used is preferably 0.03mm to 2.00mm, more preferably 0.10mm to 1.0mm.
< use >
The photosensitive green resin composition of the present invention can be suitably used for color filter applications because a colored layer having good solvent resistance and good pattern shape can be formed even by low-temperature heat treatment, and can be suitably used for low-temperature heat treatment applications of 130 ℃ or less, further 100 ℃ or less, 90 ℃ or less for forming a color filter directly on a substrate on which an element having low heat resistance such as an organic light-emitting element is formed, and can be suitably used for a cured film formed on the organic light-emitting element.
In addition, the photosensitive green resin composition of the present invention can be used for a cured film formed on an organic light emitting element, and therefore can be suitably used for forming a circularly polarizing plate having an external light reflection suppressing effect instead of a colored cured film. When the cured film of the photosensitive green resin composition of the present invention is used as a substitute for a circularly polarizing plate, a display device free of a polarizing plate can be produced, and therefore the photosensitive green resin composition of the present invention can be suitably used for a display device use free of a polarizing plate.
The photosensitive green resin composition of the present invention is a photosensitive green resin composition for a cured film formed on an organic light-emitting element, and therefore can be suitably used for display device applications without an externally mounted color filter substrate and organic light-emitting display device applications in which flexibility is improved by a thin film.
II. cured product
The cured product of the present invention is a cured product of the photosensitive green resin composition of the present invention.
The cured product of the present invention can be obtained, for example, by forming a coating film of the photosensitive green resin composition of the present invention, drying the coating film, and then exposing the resultant to light, and optionally developing and heat-treating the resultant. The method of forming the coating film, exposing, developing, and heat treating may be, for example, the same method as that used for forming the colored layer provided in the color filter of the present invention described later.
The cured product of the present invention has good solvent resistance and good pattern shape even when heat-treated at a low temperature of 130 ℃ or less, further 100 ℃ or less, or 90 ℃ or less.
The cured product of the present invention has good solvent resistance even when subjected to low-temperature heat treatment, and has good pattern shape, and can be suitably used as a colored layer of a color filter and a cured film formed on an organic light-emitting element.
III color filter
The color filter of the present invention comprises at least a substrate and a colored layer provided on the substrate, and at least 1 of the colored layers is a cured product of the photosensitive green resin composition of the present invention.
The color filter according to the present invention will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an example of a color filter according to the present invention. According to fig. 1, a color filter 10 of the present invention includes a substrate 1, a light shielding portion 2, and a coloring layer 3.
< coloring layer >)
The colored layer used in the color filter of the present invention is at least 1 colored layer which is a cured product of the photosensitive green resin composition of the present invention.
The colored layer is usually formed in an opening of a light shielding portion on a substrate described later, and is usually composed of a colored pattern of 3 colors or more.
The arrangement of the colored layers is not particularly limited, and may be, for example, a typical arrangement such as a stripe type, a mosaic type, a delta type, or a 4-pixel arrangement type. The width, area, etc. of the colored layer may be arbitrarily set.
The thickness of the colored layer is suitably controlled by adjusting the coating method, the solid content concentration, viscosity, etc. of the photosensitive green resin composition, and is preferably in the range of 1 to 5 μm in general.
The colored layer can be formed by a method described later, for example.
First, the photosensitive green resin composition of the present invention is applied to a substrate described below by a coating method such as spray coating, dip coating, bar coating, roll coating, spin coating, or die coating, to form a wet coating film. Among them, spin coating and die coating may be preferably used.
Subsequently, the wet coating film is dried using a heating plate, an oven, or the like, and then exposed to light through a mask having a specific pattern, whereby an alkali-soluble resin, a polyfunctional monomer, or the like is photopolymerized to prepare a cured coating film. Examples of the light source for exposure include: ultraviolet rays, electron beams, etc. of low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, etc. The exposure amount can be appropriately adjusted by the light source used, the thickness of the coating film, and the like.
In addition, heat treatment may be performed after exposure to promote polymerization reaction. The heating conditions are appropriately selected depending on the blending ratio of each component in the photosensitive green resin composition to be used, the thickness of the coating film, and the like.
Next, a developing treatment is performed using a developer, and the unexposed portions are dissolved and removed, whereby a coating film is formed in a desired pattern. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is generally used. To the alkali solution, a surfactant or the like may be added in an appropriate amount. In addition, the development method may employ a usual method.
After the development treatment, the colored layer is usually formed by washing the developer and drying the cured coating film of the photosensitive green resin composition. After the development treatment, a heat treatment may be performed to sufficiently cure the coating film. The heating conditions are not particularly limited, and may be appropriately selected according to the application of the coating film.
The heating treatment in the step of directly forming the colored layer on the element substrate is preferably performed at 30 ℃ or higher and 100 ℃ or lower, more preferably at 35 ℃ or higher and 95 ℃ or lower, and still more preferably at 40 ℃ or higher and 90 ℃ or lower.
In the case where the photosensitive green resin composition of the present invention does not have alkali developability, the colored layer is formed into a desired pattern by a conventionally known method for forming a pattern-like coating film, such as an inkjet method, and then exposed to light to cause photopolymerization of a photopolymerizable compound or the like, thereby producing a cured coating film. In the same manner as described above, heat treatment may be performed after exposure to promote polymerization reaction.
< shading portion >)
The light shielding portion in the color filter of the present invention may be formed in a pattern on a substrate described later, and may be the same as that used as the light shielding portion in a normal color filter.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape, a matrix shape, and the like. The light shielding portion may be a metal thin film of chromium or the like formed by sputtering, vacuum deposition, or the like. Alternatively, the light shielding portion may be a resin layer containing light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in the resin binder. In the case of the resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, and the like.
The film thickness of the light shielding portion is set to about 0.2 to 0.4 μm in the case of a metal thin film, and about 0.5 to 2 μm in the case of dispersing or dissolving the black pigment in the binder resin.
< substrate >
As the substrate, a transparent substrate, a silicon substrate, a substrate having aluminum, silver/copper/palladium alloy thin films formed on a transparent substrate or a silicon substrate, which will be described later, or the like can be used. Other color filter layers, resin layers, transistors such as TFTs (Thin Film Transistor, thin film transistors), circuits, and the like may be formed over these substrates. The substrate may be an element substrate such as an organic light-emitting element described later.
The transparent substrate used in the color filter of the present invention is not particularly limited as long as it is a substrate transparent to visible light, and a transparent substrate used in a normal color filter can be used. Specifically, there may be mentioned: transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials such as transparent resin films, optical resin plates, and flexible glass, which have flexibility. Examples of the transparent resin film and the optical resin sheet include: among them, polyethylene terephthalate (PET) films, polyimide films, polycarbonate films, and the like, and PET films, polyimide films, and the like containing hetero atoms such as oxygen atoms, nitrogen atoms, and the like can be suitably used.
The thickness of the transparent substrate is not particularly limited, and for example, a transparent substrate of about 100 μm to 1mm can be used according to the application of the color filter of the present invention.
In addition to the substrate, the light shielding portion, and the coloring layer, the color filter of the present invention may be formed with, for example, a protective layer, a transparent electrode layer, an alignment film, a columnar spacer, and the like.
In addition, the color filter of the present invention may also be used as a substitute for a circular polarizing plate for preventing reflection of external light.
IV. display device
The display device of the present invention is characterized by having the color filter of the present invention described above. In the present invention, the configuration of the display device is not particularly limited, and may be appropriately selected from conventionally known display devices, and examples thereof include a liquid crystal display device and an organic light emitting display device.
[ liquid Crystal display device ]
As a liquid crystal display device of the present invention, for example, a liquid crystal display device having the color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate is mentioned.
The liquid crystal display device of the present invention will be described with reference to the drawings. Fig. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. As illustrated in fig. 2, the liquid crystal display device 40 of the present invention has: a color filter 10; a counter substrate 20 having a TFT array substrate or the like; and a liquid crystal layer 30 formed between the color filter 10 and the counter substrate 20.
The liquid crystal display device of the present invention is not limited to the configuration shown in fig. 2, and may be a configuration generally known as a liquid crystal display device using a color filter.
The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method used in a usual liquid crystal display device may be employed. Examples of such a driving method include: TN (Twisted nematic) mode, IPS (In-Plane Switching) mode, OCB (Optically Compensated Birefringence) mode, MVA (Multi-domain vertical alignment) mode, and the like. Any of these modes can be suitably used in the present invention.
The counter substrate may be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.
Further, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropies, and mixtures thereof can be used according to the driving method or the like of the liquid crystal display device of the present invention.
As a method for forming the liquid crystal layer, a method commonly used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method. After the liquid crystal layer is formed by the above method, the liquid crystal cell is cooled slowly to room temperature, whereby the enclosed liquid crystal can be aligned.
[ organic light-emitting display device ]
As the organic light emitting display device of the present invention, for example, an organic light emitting display device having the color filter and the organic light emitting element of the present invention described above can be cited.
Such an organic light emitting display device of the present invention will be described with reference to the drawings. Fig. 3 is a schematic diagram showing an example of the organic light emitting display device of the present invention. As illustrated in fig. 3, the organic light emitting display device 100 of the present invention has an organic light emitting element 80 and a sealing layer 90 formed on a substrate 50, and a color filter 10 formed thereon. As the substrate 50, a substrate having TFTs formed on a flexible substrate may be used. In the organic light emitting display device of fig. 3, the color filter 10 may be a circular polarizing plate instead of the color filter.
As a lamination method of the organic light emitting element 80, for example, the following method and the like are cited: on the substrate 50, a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 are sequentially formed. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 in the organic light emitting element 80, and other structures can be appropriately used. In addition, a known sealing layer may be used as the sealing layer 90. The organic light emitting display device 100 manufactured in the above manner can be applied to, for example, a passive driving type organic EL display, and can also be applied to an active driving type organic EL display.
The organic light-emitting display device of the present invention is not limited to the configuration shown in fig. 3, and may be a configuration generally known as an organic light-emitting display device using a color filter.
In addition, the display device of the present invention may have the cured film of the photosensitive green resin composition of the present invention described above on the organic light emitting element.
Since the cured film of the photosensitive green resin composition of the present invention is formed on the organic light emitting element, the display device of the present invention does not require an externally mounted circular polarizing plate or an externally mounted color filter substrate, and may not have any of them.
Since the photosensitive green resin composition of the present invention is used for forming a cured film on an organic light-emitting element, the display device of the present invention does not have a substrate between the organic light-emitting element and the cured film, such as a color filter substrate for external mounting, and thus, the thickness and flexibility are improved.
An organic light emitting display device including the organic light emitting element of the present invention will be described with reference to the drawings. Fig. 4 is a schematic cross-sectional view showing another example of a display device provided with the organic light-emitting element of the present invention. As illustrated in fig. 4, the display device 200 of the present invention includes: an element substrate 130 having an organic light emitting element, and an external light reflection preventing film 120 including colored cured films (109R, 109G, 109B) on the element substrate 130, and further having a sealing film 111 thereon.
The element substrate 130 including the organic light-emitting element includes a Thin Film Transistor (TFT) 102 as a driving element disposed on a substrate 101 so as to correspond to each sub-pixel, a sealing film 103 provided thereon, an electrode 104 (anode) corresponding to each sub-pixel and a partition 105 dividing each sub-pixel provided on the sealing film 103, organic light-emitting elements (106R, 106G, 106B) constituting R, G, B sub-pixels disposed in a block thereof, and an electrode 107 (cathode) provided on the organic light-emitting elements (106R, 106G, 106B). The element substrate 130 having the organic light-emitting element further includes a sealing layer 108 covering the organic light-emitting element thereon.
An external light reflection preventing film 120 is provided on the sealing layer 108 on the organic EL elements (106R, 106G, 106B) in the element substrate 130, and further a sealing film 111 is provided thereon, and the external light reflection preventing film 120 includes a 3-color colored cured film (109R, 109G, 109B) corresponding to each organic EL element formed using a photocurable colored resin composition, and a light shielding portion 110.
The display device 200 of the present invention of fig. 4 further includes a cover material 113 on the sealing film 111 via the transparent adhesive layer 112.
Although not shown, the display device 200 of the present invention may further include a touch sensor layer including an insulating film and a transparent electrode layer on the sealing film 111, and may further include a known structure such as a hard coat layer on the touch sensor layer, as appropriate.
As described above, the colored cured films (109R, 109G, 109B) and the layers of the light shielding portion 110 provided on the element substrate 130 including the organic light emitting element can be used as the external light reflection preventing film 120, and therefore, the external light reflection preventing film used in the present invention does not include other substrates such as an externally mounted circular polarizing plate or an externally mounted color filter substrate, and can improve the thinning and flexibility.
In the display device of the present invention, it is preferable that the color of the sub-pixels (106R, 106G, 106B) of the organic light emitting element is adjusted so as to be the same color as that of the colored cured film (109R, 109G, 109B) located directly above with at least 1 layer such as the sealing layer 108 interposed therebetween. The colored cured film provided on the organic light-emitting element causes external light to be shielded except for the color that the organic light-emitting element originally emits light, and the light emitted from the organic light-emitting element is not cut off, so that external light reflection can be suppressed without reducing the light utilization efficiency.
The cured film of the photosensitive green resin composition of the present invention may be a green cured film (109G) out of the 3-color colored cured films (109R, 109G, 109B).
The substrate 101, the Thin Film Transistor (TFT) 102, the sealing film 103, the electrode 104 (anode), the partition 105 dividing each sub-pixel, the organic light emitting elements (106R, 106G, 106B) constituting the sub-pixel, the electrode 107 (cathode) and the like used in the display device of the present invention can be appropriately selected from known structures and used.
The organic light-emitting element may have a known structure such as a hole injection layer, a hole transport layer, and an electron injection layer in addition to the light-emitting layer.
The sealing layer 108 on the organic EL element used in the display device of the present invention includes an inorganic film, an organic film, and a multilayer film in which these are laminated. From the viewpoint of high effect of suppressing penetration of moisture and oxygen, a multilayer film is preferably used.
Specifically, examples thereof include: metal film, metal oxide film, laminated SiO x 、SiN x And a multilayer film formed from an inorganic film and an organic film.
At least 1 of the colored cured films used in the display device of the present invention is the cured film of the photosensitive green resin composition of the present invention described above.
The colored cured film is usually formed in an opening of a light shielding portion described later on the sealing layer 108 on the organic light emitting element, and is usually composed of a colored pattern of 3 colors or more. They may be the same coloring pattern as the (106R, 106G, 106B) of the sub-pixels of the organic light emitting element.
The colored cured films (109R, 109G, 109B) may be arranged in a usual arrangement such as a stripe type, a mosaic type, a delta type, or a 4-pixel arrangement. The width, area, etc. of the colored layer can be appropriately set so as to be suitable for the sub-pixels (106R, 106G, 106B) of the organic light emitting element.
The thickness of the colored cured film is suitably controlled by adjusting the coating method, the solid content concentration or viscosity of the photosensitive green resin composition, etc., but is usually in the range of 1 μm to 5 μm.
The light shielding portion 110 used in the display device of the present invention is generally formed in a pattern on the sealing layer 108 on the organic light emitting element, and may be the same as that used as a light shielding portion in a general color filter.
The pattern shape of the light shielding portion may be appropriately selected according to the shape of the colored cured film, and examples thereof include a stripe shape, a matrix shape, and the like. The light shielding portion may be a metal thin film of chromium or the like formed by sputtering, vacuum deposition, or the like. Alternatively, the light shielding portion may be a resin layer containing light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in the resin binder. In the case of the resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, and the like.
The film thickness of the light shielding portion is set to about 0.2 μm to about 0.4 μm in the case of a metal thin film, and is set to about 0.5 μm to about 2 μm in the case of dispersing or dissolving the black pigment in the binder resin.
As the sealing film 111 provided on the colored cured films (109R, 109G, 109B) and the light shielding portion 110, a known material can be appropriately selected and used.
The transparent adhesive layer 112 and the cover material 113 provided on the sealing film 111 may be formed of known materials. In the present invention, even when glass is used as the covering material, glass may be used as the covering material in view of the weather resistance of the green cured film being good and the transmittance being suppressed from decreasing.
The display device of the present invention is not limited to the configuration shown in fig. 4, and may further include a display device having a known organic light emitting element.
V. method for manufacturing laminate of organic light-emitting element and external light reflection preventing film
The method for producing a laminate of an organic light-emitting element and an anti-external light reflection film according to the present invention comprises a step of forming a cured film of the photosensitive green resin composition according to the present invention on the organic light-emitting element by comprising:
A step of forming a coating film by applying the photosensitive green resin composition of the present invention to an organic light-emitting element;
a step of irradiating the coating film with light;
a post-baking step of heating the film after the irradiation with light; and
and developing the film after the light irradiation.
The following describes each step.
In the step of applying the photosensitive green resin composition of the present invention to the organic light-emitting element, the organic light-emitting element may be applied without being adjacent to the organic light-emitting element, or may be applied with at least 1 layer interposed therebetween. As shown in fig. 4, in the element substrate 130 including the organic light-emitting element, an electrode 107 and a sealing layer 108 for suppressing penetration of moisture and oxygen may be further provided on the sub-pixels (106R, 106G, 106B) of the organic light-emitting element, and thus the organic light-emitting element may be coated with the electrode, the sealing layer, and the like.
For example, the light shielding portion 110 may be provided in advance on the sealing layer 108 by a known method as exemplified above, and the colored cured films (109R, 109G, 109B) may be formed by coating the openings of the light shielding portion 110.
For example, the photosensitive green resin composition of the present invention is applied to the organic light-emitting element by a coating method such as spray coating, dip coating, bar coating, roll coating, spin coating, or die coating. As the coating method, among them, spin coating and die coating can be preferably used.
Subsequently, the wet coating film is dried using a heating plate, an oven, or the like, to form a coating film.
The obtained coating film is irradiated (exposed) with light through a mask having a specific pattern, and the photopolymerizable compound and, if necessary, the alkali-soluble resin or the like are subjected to photopolymerization. Examples of the light source for exposure include: ultraviolet rays, electron beams, etc. of low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, etc. The exposure amount is appropriately adjusted according to the light source used, the thickness of the coating film, and the like.
In order to promote the polymerization reaction after the exposure, a post-baking step of heating the film after the irradiation with the light may be performed. The heating conditions may be appropriately selected depending on the blending ratio of each component in the photosensitive green resin composition to be used, the thickness of the coating film, and the like.
The post baking step may be performed before the development step, after the development step, or before and after the development step.
In the present invention, since the colored cured film is directly formed on the element substrate provided with the organic light-emitting element, the heating temperature in the post-baking step is preferably 130 ℃ or lower. The heating temperature is more preferably 100℃or lower, and still more preferably 90℃or lower. The heating temperature may be 30℃or higher, 35℃or higher, or 40℃or higher.
Next, the film after the light irradiation is developed. The film after the development and the light irradiation may be a film after post baking.
In the development step, a development treatment is performed using a developer, and the unexposed portions are dissolved and removed, thereby forming a coating film in a desired pattern. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is generally used. To the alkali solution, a surfactant or the like may be added in an appropriate amount. In addition, the development method may employ a usual method.
After the development treatment, the cured film of the photosensitive green resin composition is usually dried by washing with a developer to form a colored cured film. After the development treatment, a heat treatment may be performed to sufficiently cure the coating film.
In the present invention, since the colored cured film is directly formed on the element substrate provided with the organic light-emitting element, the heating temperature in the post-baking step is preferably 130 ℃ or less, more preferably 100 ℃ or less, and even more preferably 90 ℃ or less. The heating temperature may be 30℃or higher, 35℃or higher, or 40℃or higher.
In order to further cure the film after the development treatment or after the post baking, light irradiation (exposure) may be additionally performed.
Examples
Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited by these descriptions.
The mass average molecular weight (Mw) of the copolymer before salt formation was determined as a standard polystyrene equivalent by GPC (gel permeation chromatography) according to the measurement method described in the above description of the present invention.
Synthesis example 1 Synthesis of Block copolymer 1
To a 500mL round bottom 4-necked separable flask equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of THF (Tetrahydrofuran) and 0.6 part by mass of lithium chloride were added, and nitrogen substitution was sufficiently performed. After cooling the reaction flask to-60 ℃, 4.9 parts by mass of butyllithium (15% by mass of hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 parts by mass of methyl isobutyrate were injected using a syringe. 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA), 29.1 parts by mass of 2- (trimethylsilyloxy) ethyl methacrylate (TMSM), 12.8 parts by mass of 2-ethylhexyl methacrylate (EHMA), 13.7 parts by mass of n-Butyl Methacrylate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), and 17.5 parts by mass of Methyl Methacrylate (MMA) were added dropwise over 60 minutes using an addition funnel. After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA) as a monomer for the A block was added dropwise over 20 minutes. After the reaction was performed for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained THF solution of the precursor block copolymer was purified by reprecipitation in hexane, filtration, and vacuum drying, and diluted with PGMEA to prepare a 30 mass% solution of solid content. 32.5 parts by mass of water was added thereto, and the temperature was raised to 100℃and the reaction was carried out for 7 hours, whereby a structural unit derived from EEMA was deprotected to give a structural unit derived from methacrylic acid (MAA), and a structural unit derived from TMSM was deprotected to give a structural unit derived from 2-hydroxyethyl methacrylate (HEMA). The obtained block copolymer PGMEA solution was purified by reprecipitation in hexane, filtration and vacuum drying, to obtain a block copolymer 1 (amine value: 95mgKOH/g, acid value: 8mgKOH/g, tg: 38 ℃ C.) containing a structural unit represented by the above general formula (I). The mass average molecular weight Mw was 7730.
( Synthesis example 2: synthesis of oxime ester photoinitiator represented by formula (A-2) )
An oxime ester photoinitiator represented by the above formula (A-2) was synthesized in the same manner as in the production of Compound No.73 of paragraphs 0114 to 0117 of International publication No. 2015/152153.
Preparation example 1 preparation of alkali-soluble resin A
To the polymerization vessel, 300 parts by mass of PGMEA was added, and after the temperature was raised to 100 ℃ under a nitrogen atmosphere, 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by mass of MMA, 36 parts by mass of methacrylic acid (MAA), 6 parts by mass of perbutylo (manufactured by daily oil corporation), and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. Thereafter, the reaction was continued at 100℃and after 2 hours from the completion of the dropping of the above-mentioned mixture for forming a main chain, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to stop the polymerization.
Then, while blowing air, 20 parts by mass of Glycidyl Methacrylate (GMA) as an epoxy group-containing compound was added, the temperature was raised to 110 ℃, 0.8 parts by mass of triethylamine was added, and an addition reaction was performed at 110 ℃ for 15 hours to obtain an alkali-soluble resin a solution (mass average molecular weight (Mw) 8500, acid value 75mgKOH/g, solid content 40 mass%).
In the above method for measuring mass average molecular weight, polystyrene was used as a standard substance, THF was used as an eluent, and the mass average molecular weight was measured by Shodex GPC system-21H (Shodex GPC System-21H). The method for measuring the acid value was carried out based on JIS K0070.
( Example 1: production of photosensitive Green resin composition G-1 )
(1) Production of colorant Dispersion B (1)
To a 225mL mayonnaise bottle, 64.9 parts by mass of PGMEA, 13.5 parts by mass of the alkali-soluble resin a solution of preparation example 1 (solid content 40% by mass), and 9.2 parts by mass of the PGMEA solution of block copolymer 1 of synthesis example 1 (solid content 35% by mass) were added and stirred. 0.39 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan chemical Co., ltd.) was added thereto, and stirred at room temperature for 30 minutes.
To this was added 12.0 parts by mass of C.I. pigment blue 15:4 (B15:4) as a blue pigment and 100 parts by mass of zirconia beads having a particle diameter of 2.0mm, followed by shaking with a paint shaker (manufactured by light Tian Tiegong Co.) for 1 hour as pre-crushing, followed by changing to 200 parts of zirconia beads having a particle diameter of 0.1mm, and dispersing with the paint shaker for 4 hours as main crushing, to obtain a colorant dispersion B (1). The block copolymer 1 is a salt block copolymer 1 formed by forming a salt with phenylphosphonic acid.
(2) Production of colorant Dispersion Y (1)
In the production of the colorant dispersion liquid B (1), the colorant dispersion liquid Y (1) was obtained in the same manner as in the production of the colorant dispersion liquid B (1), except that c.i. pigment blue 15:4 (B15:4) was changed to c.i. pigment yellow 139 (Y139).
(3) Production of colorant Dispersion Y (2)
In the production of the colorant dispersion liquid B (1), the colorant dispersion liquid Y (2) was obtained in the same manner as in the production of the colorant dispersion liquid B (1), except that c.i. pigment blue 15:4 (B15:4) was changed to c.i. pigment yellow 150 (Y150).
(4) Production of colorant Dispersion Y (3)
In the production of the colorant dispersion liquid B (1), a colorant dispersion liquid Y (3) was obtained in the same manner as in the production of the colorant dispersion liquid B (1), except that the C.I. pigment blue 15:4 (B15:4) was changed to the C.I. pigment yellow 138 (Y138).
(5) Production of photosensitive Green resin composition G-1
6.4 parts by mass of the colorant dispersion liquid B (1) obtained in the above, 5.2 parts by mass of the colorant dispersion liquid Y (1), 9.0 parts by mass of the colorant dispersion liquid Y (2), 15.0 parts by mass of the colorant dispersion liquid Y (3), 3.5 parts by mass of the alkali-soluble resin A solution obtained in preparation example 1, 5.6 parts by mass of a polyfunctional monomer (trade name ARONIXM-305, manufactured by Toyama Synthesis Co., ltd.), 0.5 part by mass of an oxime ester photoinitiator represented by the above formula (A-2), 0.03 part by mass of a fluorine-based surfactant (trade name MEGAFACR-08MH, manufactured by DIC Co., ltd.) and 54.6 parts by mass of PGMEEA were added to obtain a photosensitive green resin composition G-1.
( Examples 2 to 14: production of photosensitive Green resin compositions G-2 to G-14 )
In example 1, photosensitive green resin compositions G-2 to G-14 were obtained in the same manner as in the photosensitive green resin composition G-1 except that the types and/or mass ratios of the blue pigment, the yellow pigment, and the green pigment were changed as shown in table 1, and the ratio of the alkali-soluble resin a solution, the polyfunctional monomer, and the oxime ester photoinitiator represented by the above formula (a-2) was changed so that the color material concentration became the values shown in table 1 in the same state as in example 1.
In addition, the colorant dispersion liquid of c.i. pigment blue 15:6 (B15:6), c.i. pigment blue 15:3 (B15:3), c.i. pigment green 59 (G59) or c.i. pigment green 7 (G7) was obtained in the same manner as in the production of the colorant dispersion liquid B (1), except that the c.i. pigment blue 15:4 (B15:4) was changed to c.i. pigment blue 15:6 (B15:6), c.i. pigment blue 15:3 (B15:3), c.i. pigment green 59 (G59) or c.i. pigment green 7 (G7), respectively, to obtain the colorant dispersion liquid B (2), the colorant dispersion liquid B (3), the colorant dispersion liquid G (1) or the colorant dispersion liquid G (2).
( Comparative examples 1 to 4: production of comparative photosensitive Green resin compositions CG-1 to CG-4 )
In examples 6, 7, 13 and 14, comparative photosensitive green resin compositions CG-1 to CG-4 were obtained in the same manner as in photosensitive green resin compositions G-6, G-7, G-13 or G-14 except that the pigment proportions were changed so that the green pigment (halogenated phthalocyanine pigment) was used in an amount exceeding 10 mass% in the total amount of the colorant, as shown in Table 1, respectively.
( Comparative examples 5 to 6: production of comparative photosensitive Green resin compositions CG-5 to CG-6 )
In example 1, comparative photosensitive green resin compositions CG-5 to CG-6 were obtained in the same manner as in photosensitive green resin composition G-1 except that as shown in table 1, the types and/or mass ratios of blue pigment and yellow pigment, the types of initiator (Irgacure 907 (907 manufactured by basf) and Kayacure DETX-S (manufactured by DETX, japan chemical) were changed in the same manner as in examples 1 and 2 of patent document 2 (japanese patent application laid-open No. 2011-242568), and the amounts of the components other than the pigment were changed so as to become the pigment concentrations shown in table 1.
In the production of the colorant dispersion liquid B (1), the colorant dispersion liquid B (4) was produced in the same manner as in the production of the colorant dispersion liquid B (1), except that c.i. pigment blue 15:4 (B15:4) was changed to c.i. pigment blue 16 (B16).
( Comparative examples 7 to 10: production of comparative photosensitive Green resin compositions CG-7 to CG-10 )
In example 1, comparative photosensitive green resin compositions CG-7 to CG-10 were obtained in the same manner as in the photosensitive green resin composition G-1 except that as shown in table 1, the types and/or mass ratios of the blue pigment and the yellow pigment, the types of the initiator (Irgacure OXE02 (OXE 02, manufactured by BASF corporation) and the amounts of the components other than the pigment were changed so as to become the pigment concentrations shown in table 1 were changed in the same manner as in examples 2, 5, 7 and 10 of patent document 3 (international publication No. 2020/196393).
[ evaluation method ]
The photosensitive green resin compositions obtained in each example and each comparative example were applied to a GLASS substrate (manufactured by nhtechon gloss corporation, "NA 35") using a spin coater so that the finally obtained cured film became a thickness of 3.0 μm, and then dried at 80 ℃ for 3 minutes using a heating plate, thereby forming a coating film on the substrate. On the coating film, a super high pressure mercury lamp was used at 50mJ/cm via a photomask (chromium mask) having a pattern with an opening size of 2 μm to 100 μm for forming independent fine lines 2 By exposure to ultraviolet rays, a coating film is formed after the exposure. Then, a 0.05wt% aqueous potassium hydroxide solution was used as a developer, and after 60 seconds of contact with the developer, the film was washed with pure water to obtain an independent thin line pattern coating film. Thereafter, post-baking was performed with a clean oven at 90 ℃ for 30 minutes, thereby forming an independent fine line pattern-shaped cured film. The obtained cured film was evaluated for transmittance, cross-sectional shape, and solvent resistance.
< transmittance >
The transmission spectrum of the cured film was measured at 380nm to 780nm using a microscopic spectroscope (OSP-SP 200, manufactured by Olympus), and the difference between the minimum transmittance at 360nm to 370nm and the wavelength thereof, the maximum transmittance at 380nm to 480nm, the maximum transmittance at 510nm to 550nm and the minimum transmittance, the maximum transmittance at 580nm to 700nm, and the wavelength at 2 points at which the transmittance at the peak of the maximum transmittance is half the maximum transmittance in the wavelength range at 380nm to 700nm was calculated, to obtain the half-peak width.
< evaluation of the sectional shape of colored layer in thin line pattern >
The cross-sectional shape in the thickness direction of the obtained coloring layer in the form of an independent fine line pattern was observed by a scanning electron microscope (super scan model 220, magnification 10000 times, manufactured by shimadzu corporation), and the taper angle (θ1) of the cross-sectional shape of the coloring layer was evaluated by the following evaluation criteria (see fig. 5).
(evaluation criterion of the sectional shape of the patterned colored layer)
A: the taper angle (theta 1) is 15 DEG or more and less than 100 DEG
B: the taper angle (theta 1) is 100 DEG or more and less than 110 DEG
C: the taper angle (theta 1) is 110 DEG or more and less than 120 DEG
D: cone angle (theta 1) is 120 DEG or more
If the evaluation result is B, the cross-sectional shape of the colored layer is good, and if the evaluation result is a, the cross-sectional shape of the colored layer is excellent.
< evaluation of solvent resistance (PGME resistance)
After measuring the film thickness of the obtained colored layer, the film was immersed in Propylene Glycol Monomethyl Ether (PGME) for 10 minutes, and then air-dried, and the film thickness was measured again. The film thickness was measured using a stylus type step film thickness meter "P-15Tencor" (manufactured by Instruments). The film thickness after solvent immersion/the film thickness before solvent immersion was calculated as the residual film ratio by 100.
(solvent resistance evaluation criterion)
A: the residual film rate after the solvent dipping is more than 98 percent
B: the residual film rate after solvent impregnation is more than 96% and less than 98%
C: the residual film rate after solvent impregnation is more than 94% and less than 96%
D: the residual film rate after the solvent dipping is less than 94 percent
If the evaluation result is B, the solvent resistance is good, and if the evaluation result is a, the solvent resistance is excellent.
TABLE 1
[ summary of results ]
In comparative examples 1 to 4, in which a green pigment (halogenated phthalocyanine pigment) was used in an amount exceeding 10% by mass based on the total amount of the coloring material, the cured film formed at a film thickness of 3.0 μm had a spectral transmittance of 360nm to 370nm of less than 0.7%, and the cured film subjected to the low-temperature heat treatment had poor solvent resistance and pattern shape.
It is shown that, when the types and/or mass ratios of the blue pigment and the yellow pigment are set to be the same as those of comparative examples 5 and 6 of examples 1 and 2 of patent document 2 (Japanese patent application laid-open No. 2011-242568), respectively, the film thickness is 3.0 μm and the spectral transmittance at 360nm to 370nm is 0.7% or more, but the solvent resistance and pattern shape of the cured film subjected to the low-temperature heat treatment are poor.
In addition, it was shown that, when cured films were formed with film thicknesses of 3.0 μm in comparative examples 7 to 10 similar to examples 2, 5, 7 and 10 of patent document 3 (International publication No. 2020/196393), the spectral transmittance at 360nm to 370nm was 0.7% or more, but the pigment concentration was increased, and the solvent resistance and pattern shape of the cured films subjected to low-temperature heat treatment were poor.
In contrast, in examples 1 to 14, which are photosensitive green resin compositions of the present invention, when a cured film was formed at a film thickness of 3.0. Mu.m, a spectral transmittance of 360nm to 370nm was 0.7% or more, and the color material concentration was low, and even when the cured film was formed on an organic light-emitting element by post-baking at a low temperature (90 ℃) which was preferable, a colored layer having good solvent resistance and good pattern shape was formed.
Description of the reference numerals
1: substrate board
2: light shielding part
3: coloring layer (coloring solidified film)
10: color filter
20: counter substrate
30: liquid crystal layer
40: liquid crystal display device having a light shielding layer
50: substrate board
71: transparent anode
72: hole injection layer
73: hole transport layer
74: light-emitting layer
75: electron injection layer
76: cathode electrode
80: organic light-emitting element
90: sealing layer
100: organic light emitting display device
101: substrate board
102: thin Film Transistor (TFT)
103: sealing film
104: electrode
105: partition wall
106 r, 106G, 106 b: organic light-emitting element
107: electrode
108: sealing layer
109R, 109G, 109B: colored cured film
110: light shielding part
111: sealing film
112: transparent adhesive layer
113: covering material
120: external light reflection preventing film
130: element substrate having organic light-emitting element
200: a display device.

Claims (11)

1. A photosensitive green resin composition comprising a coloring material, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator,
the colorant comprises a blue pigment and a yellow pigment, the yellow pigment comprising C.I. pigment yellow 139, a halogenated metal phthalocyanine pigment being 10% or less,
when a cured film is formed with a film thickness of 3.0 μm, the spectral transmittance at 360nm to 370nm is 0.7% or more.
2. The photosensitive green resin composition according to claim 1, wherein the blue pigment comprises at least one selected from the group consisting of c.i. pigment blue 15:3, c.i. pigment blue 15:4, and c.i. pigment blue 16, and the yellow pigment optionally further comprises at least one selected from the group consisting of c.i. pigment yellow 138, c.i. pigment yellow 150, and c.i. pigment yellow 185.
3. The photosensitive green resin composition according to claim 1 or 2, wherein the photoinitiator comprises at least one of compounds represented by the following general formula (A),
general formula (A)
Wherein R is 1 And R is 2 R is independently represented by 11 、OR 11 、COR 11 、SR 11 、CONR 12 R 13 Or the CN of the two-dimensional network,
R 11 、R 12 and R is 13 Independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,
R 11 、R 12 and R is 13 The hydrogen atoms of the radicals represented are optionally further denoted by R 21 、OR 21 、COR 21 、SR 21 、NR 22 R 23 、CONR 22 R 23 、-NR 22 -OR 23 、-NCOR 22 -OCOR 23 、NR 22 COR 21 、OCOR 21 、COOR 21 、SCOR 21 、OCSR 21 、COSR 21 、CSOR 21 Substituted by hydroxy, nitro, CN, or halogen atoms,
R 21 、R 22 and R is 23 Independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,
R 21 、R 22 and R is 23 The hydrogen atom of the represented group is optionally further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, or a carboxyl group,
R 11 、R 12 、R 13 、R 21 、R 22 and R is 23 The alkylene portion of the radicals represented optionally contains 1 to 5-O-, optionally under conditions in which the oxygen atoms are not adjacent-S-, -COO-, -OCO-, -NR 24 -、-NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-; OCS-or-CSO-,
R 24 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,
R 11 、R 12 、R 13 、R 21 、R 22 、R 23 and R is 24 The alkyl portion of the group represented may have a branched side chain or may be a cyclic alkyl group,
R 3 Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, R 3 The alkyl moiety of the group represented may have a branched side chain, or may be a cyclic alkyl group, and R 3 And R is R 7 And R is 3 And R is R 8 Each optionally together with the formation of a ring,
R 3 the hydrogen atoms of the radicals represented are optionally further denoted by R 21 、OR 21 、COR 21 、SR 21 、NR 22 R 23 、CONR 22 R 23 、-NR 22 -OR 23 、-NCOR 22 -OCOR 23 、NR 22 COR 21 、OCOR 21 、COOR 21 、SCOR 21 、OCSR 21 、COSR 21 、CSOR 21 Substituted by hydroxy, nitro, CN, or halogen atoms,
R 4 、R 5 、R 6 and R is 7 R is independently represented by 11 、OR 11 、SR 11 、COR 14 、CONR 15 R 16 、NR 12 COR 11 、OCOR 11 、COOR 14 、SCOR 11 、OCSR 11 、COSR 14 、CSOR 11 A hydroxyl group, CN or halogen atom, R 4 And R is R 5 、R 5 And R is R 6 And R 6 And R is R 7 Each optionally together with the formation of a ring,
R 14 、R 15 and R is 16 Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R 14 、R 15 And R is 16 The alkyl portion of the group represented may have a branched side chain or may be a cyclic alkyl group, R 8 R represents 11 、OR 11 、SR 11 、COR 11 、CONR 12 R 13 、NR 12 COR 11 、OCOR 11 、COOR 11 、SCOR 11 、OCSR 11 、COSR 11 、CSOR 11 A hydroxyl group, a CN or a halogen atom,
k represents 0 or 1.
4. The photosensitive green resin composition according to any one of claims 1 to 3, wherein a wavelength exhibiting a maximum transmittance in a wavelength range of 380nm to 700nm of a transmission spectrum is in a range of 525nm to 545nm when a cured film is formed at a film thickness of 3.0 μm.
5. The photosensitive green resin composition according to any one of claims 1 to 4, which is used for a cured film formed on an organic light emitting element.
6. A cured product of the photosensitive green resin composition according to any one of claims 1 to 4.
7. A color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least 1 of the colored layers is a cured product of the photosensitive green resin composition according to claim 6.
8. A display device having the color filter of claim 7.
9. A display device having the cured film of the photosensitive green resin composition according to any one of claims 1 to 4 on an organic light-emitting element.
10. A method for producing a laminate of an organic light-emitting element and an anti-external light reflection film, comprising the step of forming a cured film of the photosensitive green resin composition according to any one of claims 1 to 4 on the organic light-emitting element by comprising the steps of:
a step of forming a coating film by applying the photosensitive green resin composition according to any one of claims 1 to 4 on an organic light-emitting element;
a step of irradiating the coating film with light;
a post-baking step of heating the film after the irradiation with light; and
and developing the film after the light irradiation.
11. The method for producing a laminate of an organic light-emitting element and an anti-external light reflection film according to claim 10, wherein a heating temperature in the post-baking step is 130 ℃ or lower.
CN202280013059.7A 2021-02-19 2022-02-15 Photosensitive green resin composition, cured product, color filter, display device, and method for producing laminate of organic light-emitting element and anti-external light reflection film Pending CN116806327A (en)

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