Photocurable green resin composition, display device, and method for manufacturing laminate of organic light-emitting element and external light antireflection film

Abstract

Provided is a photocurable green resin composition which can be used for a cured film to be formed on an organic light-emitting element, the photocurable green resin composition comprising a color material, a photopolymerizable compound, and a photo initiator, in which the color material comprises a blue pigment and a yellow pigment, the content of a halogenated metal phthalocyanine pigment is 10% by mass or less relative to the whole amount of the color material, and, when a cured film having a thickness of 3.0 μm is formed, a spectral transmittance at a wavelength falling within the range from 380 nm to 480 nm is 20% or less, a spectral transmittance at a wavelength falling within the range from 580 nm to 700 nm is 30% or less, and a spectral transmittance at a wavelength falling within the range from 510 nm to 550 nm is 40% to 80% inclusive.

Description

[Technical Field]

[0001] The present invention relates to a photocurable green resin composition, a display device containing a cured product of the photocurable green resin composition, and a method for producing a laminate of an organic light-emitting element and an external light antireflection film using the photocurable green resin composition. [Background technology]

[0002] In recent years, organic light-emitting devices have been attracting attention as display elements for mobile devices and televisions because they are advantageous in terms of thinness and flexibility compared to conventional liquid crystal display elements and, in principle, have high light utilization efficiency.

[0003] Such organic light-emitting elements, particularly in mobile devices intended for outdoor use, are equipped with a circular polarizer as an anti-reflection film to prevent a decrease in visibility due to reflection of external light. However, this circular polarizer blocks not only external light but also light emitted by the organic light-emitting element, significantly reducing light utilization efficiency. Furthermore, because circular polarizers have hard properties, they reduce flexibility, making them a disadvantage for flexible displays. Therefore, there has been a demand for the development of a display device using organic light-emitting elements that has good outdoor visibility without using a circular polarizer.

[0004] In contrast, Patent Document 1 discloses a green photosensitive resin composition for forming pixels that suppresses reflection of external light using a color filter that can replace a polarizing plate, and that can achieve high color reproducibility while being able to replace a polarizing plate. The green photosensitive resin composition comprises a pigment dispersion composition, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and the pigment dispersion composition contains a green pigment, a yellow pigment, and a black pigment. The green photosensitive resin composition, when formed into a cured film having a thickness of 2.2 μm, has a spectral transmittance of 25% or less at wavelengths of 380 nm to 480 nm and at wavelengths of 580 nm to 780 nm, and a spectral transmittance of 30% or more but less than 70% at wavelengths of 500 nm to 560 nm.

[0005] On the other hand, Patent Document 2 discloses a green colorant composition for color filters that is composed of a blue pigment and a yellow pigment so as to be halogen-free. However, Patent Document 2 is a technology that aims to provide a color filter substrate that is halogen-free, has a high contrast ratio, and has high adhesion, and does not describe at all its use as a substitute for a polarizing plate, nor does it describe at all any problems that may arise when using it as a substitute for a polarizing plate. Patent Document 3 also describes a colorant that contains at least one selected from Color Index Pigment Blue 15:3 and Color Index Pigment Blue 15:4, and Color Index Pigment Yellow 150, and that contains 35 to 55 parts by mass of Color Index Pigment Blue 15:3 and Color Index Pigment Blue 15:4 in total relative to 100 parts by mass of Color Index Pigment Yellow 150. The colored composition has a minimum absorbance value in the wavelength range of 495 to 525 nm among absorbance values ​​for light with wavelengths of 400 to 700 nm, and when the absorbance for light with a wavelength of 450 nm is taken as 1, wavelengths at which the absorbance is 0.14 exist in the ranges of 474 to 494 nm and 530 to 570 nm, respectively. 450 and absorbance A for light with a wavelength of 620 nm 620 A is the ratio of 450 / A 620 However, Patent Document 3 does not describe at all the use of the coloring composition in a cured film formed on an organic light-emitting element or the use of the coloring composition as a substitute for a polarizing plate, nor does it describe at all the problems that arise when the coloring composition is used as a substitute for a polarizing plate. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2017-182067 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-242568 [Patent Document 3] International Publication No. 2020-196393 Summary of the Invention [Problem to be solved by the invention]

[0007] The color filters used as polarizer substitutes in Patent Document 1 are formed on a glass substrate, which poses further problems when manufacturing thinner and more flexible display devices. Furthermore, in green resin compositions for color filters, halogenated metal phthalocyanine pigments such as Pigment Green (PG) 7, 36, 58, and 59 have traditionally been used as the green pigment. The color filter in place of a polarizing plate, as disclosed in Patent Document 1, also uses a halogenated metal phthalocyanine pigment to achieve green. However, display devices using organic light-emitting elements are typically used with glass or film attached to the surface as a cover material using a transparent adhesive. A green-colored layer formed on an organic light-emitting element using a photocurable green resin composition containing a large amount of halogenated metal phthalocyanine pigment has a problem in that its transmittance decreases when a weather resistance test is conducted with glass attached, even via a sealing film. On the other hand, the green colored layer specifically disclosed in Patent Documents 2 and 3 has insufficient spectral characteristics for use as a color filter in place of a polarizing plate to suppress external light reflection, as shown in the comparative examples described below, and also has problems with solvent resistance.

[0008] The present invention has been made in view of the above-mentioned circumstances, and aims to provide a photocurable green resin composition that can be used to produce an organic light-emitting display device that has excellent weather resistance, is capable of suppressing external light reflection, and is thin and has improved flexibility. The present invention also aims to provide a display device that has excellent weather resistance, is capable of suppressing external light reflection, and is thin and has improved flexibility, which contains a cured product of the photocurable green resin composition, and a method for producing a laminate of an organic light-emitting element and an external light anti-reflection film using the photocurable green resin composition. [Means for solving the problem]

[0009] The photocurable green resin composition according to the present invention is a photocurable green resin composition used for a cured film formed on an organic light-emitting device, the photocurable green resin composition contains a colorant, a photopolymerizable compound, and a photoinitiator; the coloring material contains a blue pigment and a yellow pigment, and the halogenated metal phthalocyanine pigment is 10 mass % or less based on the total amount of the coloring material; When a cured film having a thickness of 3.0 μm is formed, the spectral transmittance in the wavelength range of 380 nm to 480 nm is 20% or less, the spectral transmittance in the wavelength range of 580 nm to 700 nm is 30% or less, and the spectral transmittance in the wavelength range of 510 nm to 550 nm is 40% or more and 80% or less.

[0010] The display device according to the present invention has a cured film of the photocurable green resin composition according to the present invention on an organic light-emitting element.

[0011] The method for producing a laminate of an organic light-emitting element and an external light antireflection film according to the present invention comprises the steps of: a step of forming a coating film by applying the photocurable green resin composition according to the present invention onto an organic light-emitting element; a step of irradiating the coating film with light; a post-baking step of heating the film after the light irradiation; and By including a step of developing the film after the light irradiation, The method includes a step of forming a cured film of the photocurable green resin composition according to the present invention on an organic light-emitting element. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a photocurable green resin composition that can be used to produce an organic light-emitting display device that has excellent weather resistance, is capable of suppressing external light reflection, and is thin and has improved flexibility.The present invention also provides a display device that has excellent weather resistance, is capable of suppressing external light reflection, and is thin and has improved flexibility, which contains a cured product of the photocurable green resin composition, and a method for producing a laminate of an organic light-emitting element and an external light anti-reflection film using the photocurable green resin composition. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of a display device including an organic light-emitting element according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0014] Hereinafter, embodiments and examples of the present invention will be described with reference to the drawings. However, the present invention can be implemented in many different forms, and should not be construed as being limited to the description of the embodiments and examples exemplified below. Furthermore, to clarify the explanation, the drawings may show the width, thickness, shape, etc. of each part schematically compared to the actual form, but these are merely examples and do not limit the interpretation of the present invention. Furthermore, in this specification and each drawing, elements similar to those described above with reference to the previous drawings are given the same reference numerals, and detailed descriptions may be omitted as appropriate. Furthermore, for convenience of explanation, the terms "upper" and "lower" may be used in some cases, but the up-down direction may be reversed. In this specification, when a certain component, region, or other structure is said to be "on (or under)" another component, region, or other structure, unless otherwise specified, this includes not only the case where it is directly above (or directly below) the other structure, but also the case where it is above (or below) the other structure, i.e., the case where another component is included between the other structure and above (or below) the other structure. In the present invention, light includes electromagnetic waves with wavelengths in the visible and invisible regions, as well as radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves with wavelengths of 5 μm or less and electron beams. In the present invention, (meth)acryloyl refers to each of acryloyl and methacryloyl, (meth)acrylic refers to each of acrylic and methacrylic, and (meth)acrylate refers to each of acrylate and methacrylate. In addition, in this specification, the use of "to" to indicate a range of values ​​means that the values ​​before and after it are included as the lower limit and upper limit. In the present invention, the spectral transmittance in the wavelength range of X nm to Y nm being Z % or less means that the spectral transmittance is Z % or less over the entire wavelength range of X nm to Y nm. The photocurable green resin composition, the display device, and the method for producing a laminate of an organic light-emitting element and an external light antireflection film according to the present invention will be described in detail below.

[0015] I. Photocurable green resin composition The photocurable green resin composition according to the present invention is a photocurable green resin composition used for a cured film formed on an organic light-emitting device, the photocurable green resin composition contains a colorant, a photopolymerizable compound, and a photoinitiator; the coloring material contains a blue pigment and a yellow pigment, and the halogenated metal phthalocyanine pigment is 10 mass % or less based on the total amount of the coloring material; When a cured film having a thickness of 3.0 μm is formed, the spectral transmittance in the wavelength range of 380 nm to 480 nm is 20% or less, the spectral transmittance in the wavelength range of 580 nm to 700 nm is 30% or less, and the spectral transmittance in the wavelength range of 510 nm to 550 nm is 40% or more and 80% or less.

[0016] In the photocurable green resin composition according to the present invention, the colorant contains a blue pigment and a yellow pigment, the halogenated metal phthalocyanine pigment accounts for 10 mass % or less of the total amount of the colorant, and the composition satisfies the specified spectral transmittance in the specified wavelength range. As a result, a cured film of the photocurable green resin composition can effectively reduce the transmittance of the film and can suppress external light reflection as an alternative to a polarizing plate. The photocurable green resin composition according to the present invention is also characterized by its use in a cured film formed on an organic light-emitting element. That is, the photocurable green resin composition according to the present invention is used in a cured film formed directly on an element substrate equipped with an organic light-emitting element. Because the photocurable green resin composition according to the present invention is a photocurable green resin composition used in a cured film formed adjacent to or via at least one layer on an organic light-emitting element, it is possible to produce a display device that is thinner and more flexible than a display device in which an external color filter formed on a substrate such as a glass substrate is bonded to an organic light-emitting element. Furthermore, the cured film formed on an organic light-emitting element made from the photocurable green resin composition according to the present invention achieves a green color with a halogenated metal phthalocyanine pigment content of 10 mass % or less based on the total amount of coloring materials. Therefore, even when a weather resistance test is conducted in a state where glass is bonded to the cured film with a transparent adhesive, a decrease in transmittance is suppressed, and a display device with excellent weather resistance can be realized.

[0017] The photocurable green resin composition according to the present invention contains at least a colorant, 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. Each component of the photocurable green resin composition according to the present invention will be described in detail below.

[0018] <Colorant> In the present invention, the coloring material is not particularly limited as long as it can produce the desired color when a colored layer of a color filter is formed, and a mixture of two or more of various organic pigments, inorganic pigments, dispersible dyes, dye salt-forming compounds, etc. can be used. However, the coloring material is characterized by containing at least a blue pigment and a yellow pigment, and the amount of a halogenated metal phthalocyanine pigment is 10 mass % or less of the total amount of the coloring material.

[0019] Among coloring materials, organic pigments are particularly preferred because they have high color development and heat resistance. Examples of organic pigments include compounds classified as pigments in the Color Index (CI; published by The Society of Dyers and Colourists), specifically compounds assigned the following Color Index (CI) numbers:

[0020] Examples of blue pigments include CI Pigment Blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 61, 79, and 80.

[0021] As the blue pigment, at least one selected from the group consisting of CI Pigment Blue 15:3, CI Pigment Blue 15:4, and CI Pigment Blue 16 is preferred, since it is easy to satisfy the predetermined spectral transmittance in the predetermined wavelength range and to improve the effect of suppressing external light reflection.

[0022] CI Pigment Blue 15:3, CI Pigment Blue 15:4, and CI Pigment Blue 16 each have a different wavelength at the start of their transmission spectra, which are shifted slightly from the long wavelength side to the short wavelength side, and therefore, it is preferable to select them individually or in combination of two or more types in consideration of the spectrum of the green light-emitting layer of the organic light-emitting element to be combined for reflecting ambient light. Of these, CI Pigment Blue 15:4 is preferred from the viewpoint of weather resistance.

[0023] Examples of yellow pigments include CI 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, 139, 142, 147, 148, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 173, 175, 185, 194, 211, 214, 215, 231, and derivative pigments of CI Pigment Yellow 150.

[0024] The yellow pigment preferably contains CI Pigment Yellow 139, because when combined with a blue pigment, it is easy to achieve a predetermined spectral transmittance in the predetermined wavelength range, it is easy to reduce the half-width of the peak showing the maximum transmittance of the transmission spectrum, it is easy to make the wavelength showing the maximum transmittance of the transmission spectrum fall within the range of 525 nm to 545 nm, and it is easy to improve the effect of suppressing external light reflection. The yellow pigment preferably contains Pigment Yellow 139 and may further contain at least one pigment selected from the group consisting of Pigment Yellow 138, Pigment Yellow 150, and Pigment Yellow 185, and more preferably contains Pigment Yellow 139 and further contains Pigment Yellow 150, because when combined with a blue pigment, this easily satisfies the specified spectral transmittance in the specified wavelength range, makes it easy to reduce the half-width of the peak showing the maximum transmittance of the transmission spectrum, makes it easy to keep the wavelength showing the maximum transmittance of the transmission spectrum within the range of 525 nm to 545 nm, and makes it easy to improve the effect of suppressing external light reflection.

[0025] Other coloring materials may also be used to adjust the effect of suppressing external light reflection, such as green pigments, purple pigments, orange pigments, and the like. Examples of green pigments include CI Pigment Green 7, 36, 58, 59, 62, and 63. However, even when a green pigment is used, the amount of the halogenated metal phthalocyanine pigment is set to 10% by mass or less of the total amount of coloring materials in order to improve weather resistance.

[0026] Examples of purple pigments include CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38. Examples of orange pigments include CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, and 73.

[0027] The content ratios of the blue pigment and yellow pigment used in the present invention, and any other coloring materials that may be included as needed, are adjusted so that when a cured film having a thickness of 3.0 μm is formed from the photocurable green resin composition, the spectral transmittance in the wavelength range of 380 nm to 480 nm is 20% or less, the spectral transmittance in the wavelength range of 580 nm to 700 nm is 30% or less, and the spectral transmittance in the wavelength range of 510 nm to 550 nm is 40% or more and 80% or less. When a cured film is formed to a thickness of 3.0 μm, if the spectral transmittance at wavelengths of 380 nm to 480 nm is 20% or less, the decrease in green color purity is suppressed, the decrease in color purity from the light-emitting element is also easily suppressed, and anti-reflection performance is likely to be excellent. When a cured film is formed to a thickness of 3.0 μm, the spectral transmittance at wavelengths of 380 nm to 480 nm may be 18% or less, or may be 13% or less. On the other hand, when a cured film is formed to a thickness of 3.0 μm, if the spectral transmittance at wavelengths of 510 nm to 550 nm is 40% or more and 80% or less, it is easy to suppress a decrease in brightness and poor visibility of a display device. When a cured film is formed to a thickness of 3.0 μm, the spectral transmittance at wavelengths of 510 nm to 550 nm may be 45% or more, and may be 75% or less, or even 70% or less. Furthermore, when a cured film is formed to a thickness of 3.0 μm, if the spectral transmittance at wavelengths of 580 nm to 700 nm is 30% or less, the antireflection performance is likely to be excellent. When a cured film is formed to a thickness of 3.0 μm, the spectral transmittance at wavelengths of 580 nm to 700 nm may be 25% or less, 20% or less, or 18% or less. In the present invention, the spectral transmittance when a cured film having a thickness of 3.0 μm is formed can be measured specifically by the method described in the Examples.

[0028] Furthermore, from the viewpoint of improving antireflection performance, it is preferable that when a cured film is formed to a thickness of 3.0 μm, the half-width of the peak showing the maximum transmittance in the wavelength range of 380 nm to 700 nm in the transmission spectrum be 70 nm or less. When a cured film is formed to a thickness of 3.0 μm, the half-width of the peak showing the maximum transmittance in the transmission spectrum may be 65 nm or less, 63 nm or less, or 60 nm or less. Furthermore, in order to achieve excellent color separation between blue and red, when a cured film having a thickness of 3.0 μm is formed, the peak wavelength showing maximum transmittance in the wavelength range of 380 nm to 700 nm is preferably in the range of 510 nm to 550 nm, more preferably in the range of 525 nm to 545 nm, even more preferably in the range of 526 nm to 540 nm, and may be in the range of 527 nm to 535 nm.

[0029] The content of the coloring material used in the present invention is not particularly limited as long as it is used so as to satisfy the predetermined spectral transmittance in the above-mentioned predetermined wavelength range. In the colorant 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, even more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, relative to the total amount of the colorant.

[0030] In the colorant used in the present invention, the content of the yellow pigment may be, for example, 20% by mass or more and 90% by mass or less, preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, and still more preferably 60% by mass or more, and preferably 85% by mass or less, and more preferably 80% by mass or less, relative to the total amount of the colorant.

[0031] When Pigment Yellow 139 is contained as the yellow pigment, the content of Pigment Yellow 139 may be 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total amount of the yellow pigment, and may be 50% by mass or less, and preferably 30% by mass or less. When the yellow pigment contains Pigment Yellow 139 and Pigment Yellow 150, the total content of Pigment Yellow 139 and Pigment Yellow 150 may be 40% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more, or may be 100% by mass or 40% by mass or less, based on the total amount of the yellow pigment.

[0032] In the colorant used in the present invention, the content ratio of the blue pigment relative to the total of the blue pigment and the yellow pigment is not particularly limited as long as the specified spectral transmittance is satisfied in the specified wavelength range, but 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, even more preferably 15% by mass or more, and preferably 50% by mass or less, 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% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, or may be 100% by mass, based on the total amount of the colorant. However, when other colorants different from the halogenated metal phthalocyanine pigment are contained, the total content may be 90% by mass or less.

[0033] In the colorant used in the present invention, the total content of other colorants may be 0% by mass, or may be 1% by mass or more, or may be 5% by mass or more, relative to the total amount of colorants, and is usually 20% by mass or less, and preferably 10% by mass or less. However, when a halogenated metal phthalocyanine pigment is used as another coloring material, the total content is 10% by mass or less, and may usually be 0.1% by mass or more and 10% by mass or less, preferably 1% by mass or more, more preferably 3% by mass or more, and preferably 9.5% by mass or less, based on the total amount of coloring materials. The halogenated metal phthalocyanine pigment may be 0% by mass based on the total amount of coloring materials.

[0034] The average primary particle size of the colorant used in the present invention is not particularly limited as long as it can suppress external light reflection and transmit desired light from the light-emitting element to suppress a decrease in brightness of the display device when formed into a cured film, and although it varies depending on the type of colorant used, it is preferably in the range of 10 nm to 200 nm, more preferably 15 nm to 100 nm. When the average primary particle size of the colorant is in the above range, a display device including a cured film produced using the photocurable green resin composition of the present invention can suppress external light reflection, have excellent color separation, and be of high quality.

[0035] The average dispersed particle size of the colorant in the photocurable green resin composition varies depending on the type of colorant used, but is preferably in the range of 10 nm to 200 nm, and more preferably in the range of 15 nm to 100 nm. The average dispersed particle size of the colorant in the photocurable green resin composition is the dispersed particle size of colorant particles dispersed in a dispersion medium containing at least a solvent, and is measured using a laser light scattering particle size distribution analyzer. The particle size can be measured using a laser light scattering particle size distribution analyzer by diluting the photocurable green resin composition with the solvent used in the photocurable green resin composition to a concentration measurable with the laser light scattering particle size distribution analyzer (e.g., 1000 times), and measuring the particle size at 23°C using a laser light scattering particle size distribution analyzer (e.g., a Nanotrac particle size distribution analyzer UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average dispersed particle size here is the volume average particle size.

[0036] The coloring material used in the present invention can be produced by known methods such as recrystallization, solvent salt milling, etc. Alternatively, commercially available coloring materials may be used after being subjected to a micronization treatment.

[0037] The content of the colorant in the photocurable green resin composition according to the present invention is not particularly limited. From the viewpoints of dispersibility and dispersion stability, the content of the colorant is, for example, preferably 3% to 65% by mass, more preferably 4% to 60% by mass, even more preferably 5% to 55% by mass, and even more preferably 6% to 50% by mass, based on the total solid content of the photocurable green resin composition. From the viewpoints of dispersibility and dispersion stability, the content of the colorant may be 10% to 45% by mass, or even 10% to 35% by mass, based on the total solid content of the photocurable green resin composition. When the content is equal to or greater than the above lower limit, the photocurable green resin composition, when applied to a predetermined film thickness (usually 1.0 μm to 5.0 μm, for example, 3.0 μm), provides a cured film with sufficient color density and a favorable external light reflection suppression effect. When the content is equal to or less than the above upper limit, a cured film with excellent storage stability, sufficient hardness, and adhesion to a substrate can be obtained. In the present invention, the solid content refers to everything other than the solvent, which will be described later, and also includes monomers dissolved in the solvent.

[0038] <Photopolymerizable compound> The photopolymerizable compound used in the photocurable green resin composition includes a compound having a photopolymerizable group in the molecule. The photopolymerizable group is not particularly limited as long as it can be polymerized by a photoinitiator, and examples thereof include an ethylenically unsaturated double bond, such as a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group. Among these, an acryloyl group or a methacryloyl group is preferably used as the photopolymerizable group from the viewpoint of ultraviolet curability. From the viewpoint of curability, the photopolymerizable compound preferably contains a compound having two or more photopolymerizable groups in one molecule, and more preferably contains a compound having three or more photopolymerizable groups in one molecule.

[0039] As the photopolymerizable compound, a compound having two or more ethylenically unsaturated double bonds is preferably used, and in particular, a polyfunctional (meth)acrylate having two or more acryloyl groups or methacryloyl groups is preferred. Such a polyfunctional (meth)acrylate may be appropriately selected from conventionally known compounds, and specific examples include those described in JP-A-2013-029832.

[0040] These polyfunctional (meth)acrylates may be used alone or in combination of two or more. When excellent photocurability (high sensitivity) is required for the photocurable green resin composition of the present invention, the polyfunctional (meth)acrylate is preferably one having three (trifunctional) or more polymerizable double bonds, and poly(meth)acrylates of trihydric or higher polyhydric alcohols or dicarboxylic acid modified products thereof are preferred. Specifically, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, succinic acid modified pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, succinic acid modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are preferred.

[0041] The content of the photopolymerizable compound used in the photocurable green resin composition is not particularly limited, but is, for example, preferably in the range of 5% by mass to 60% by mass, and more preferably 10% by mass to 40% by mass, based on the total solid content of the photocurable green resin composition. When the content of the photopolymerizable compound is equal to or greater than the lower limit, photocuring proceeds sufficiently, and elution of the exposed portion during development can be suppressed. When the content of the photopolymerizable compound is equal to or less than the upper limit, alkaline developability is sufficient.

[0042] <Photoinitiator> As the photoinitiator used in the photocurable green resin composition of the present invention, one or a combination of two or more of various conventionally known photoinitiators can be used. Examples of the photoinitiator include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, α-aminoketones, biimidazoles, N,N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, thioxanthone, oxime esters, etc. As such a photoinitiator, conventionally known photoinitiators can be used, and examples thereof include the photoinitiators described in WO 2018 / 062105.

[0043] The oxime ester photoinitiator used in the present invention can be appropriately selected from oxime ester photoinitiators described in, for example, 1,2-octadione-1-[4-(phenylthio)phenyl]-, 2-(o-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime), JP 2000-80068 A, JP 2001-233842 A, JP 2010-527339 A, JP 2010-527338 A, JP 2013-041153 A, WO 2015 / 152153 A, JP 2010-256891 A, and the like.

[0044] When a cured film is formed on an element substrate as in the present invention, because the heat resistance of organic light-emitting elements is low, it is preferable to perform heating in the manufacturing process at a low temperature of 130°C or less, and even more preferably at 100°C or less. In a typical color filter manufacturing process, a cured film is cured by performing a heat treatment on a glass substrate at about 230°C, whereas heat treatment at 130°C or less does not allow the cured film to harden due to heat. In other words, a cured film manufactured by low-temperature heat treatment has the problem that it is likely to have insufficient substrate adhesion and solvent resistance. To address these issues, it is preferable that the photoinitiator contains at least one compound represented by the following general formula (A), since this improves the substrate adhesion and solvent resistance of the cured film even when subjected to low-temperature heat treatment.

[0045] [ka] (In the formula, R 1 and R 2 are each independently R 11 , OR 11 , C.O.R. 11 , S.R. 11 ,CONR 12 R 13 or CN, R 11 , R 12 and R 13 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, R 11 , R 12 and R 13 The hydrogen atoms of the group represented by 21 , OR 21 , C.O.R. 21 , S.R. 21 , N.R. 22 R 23 ,CONR 22 R 23 , -NR 22 -OR 23 , -NCOR 22 -OCOR 23 , N.R. 22 COR21 ,OCOR 21 , COOR 21 , SCOR 21 , OCSR 21 , COSR 21 , CSOR 21 , optionally substituted with a hydroxyl group, a nitro group, CN, or a halogen atom; R 21 , R 22 and R 23 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, R 21 , R 22 and R 23 A hydrogen atom of the group represented by the formula (I) may be further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, or a carboxy group, R 11 , R 12 , R 13 , R 21 , R 22 and R 23 The alkylene portion of the group represented by the formula: 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR 24 may contain 1 to 5 -, -SCO-, -COS-, -OCS- or -CSO-, provided that no oxygen atoms are adjacent to each other; 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 arylalkyl 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 24 The alkyl portion of the group represented by the formula (I) may have a branched side chain or may be a cyclic alkyl, R 3represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms; R 3 The alkyl portion of the group represented by R may have a branched side chain or may be a cyclic alkyl. 3 and R 7 , and R 3 and R 8 may be joined together to form a ring, R 3 The hydrogen atoms of the group represented by 21 , OR 21 , C.O.R. 21 , S.R. 21 , N.R. 22 R 23 ,CONR 22 R 23 , -NR 22 -OR 23 , -NCOR 22 -OCOR 23 , N.R. 22 COR 21 ,OCOR 21 , COOR 21 , SCOR 21 , OCSR 21 , COSR 21 , CSOR 21 , optionally substituted with a hydroxyl group, a nitro group, CN, or a halogen atom; R 4 , R 5 , R 6 and R 7 are each independently R 11 , OR 11 , S.R. 11 , C.O.R. 14 ,CONR 15 R 16 , N.R. 12 COR 11 ,OCOR 11 , COOR 14 , SCOR 11 , OCSR 11 , COSR 14 , CSOR 11 , a hydroxyl group, CN or a halogen atom, R 4 and R 5 , R 5and R 6 , and R 6 and R 7 may be joined together to form a ring, R 14 , R 15 and R 16 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R 14 , R 15 and R 16 The alkyl portion of the group represented by R may have a branched side chain or may be a cyclic alkyl. 8 is R 11 , OR 11 , S.R. 11 , C.O.R. 11 ,CONR 12 R 13 , N.R. 12 COR 11 ,OCOR 11 , COOR 11 , SCOR 11 , OCSR 11 , COSR 11 , CSOR 11 , a hydroxyl group, CN, or a halogen atom; k represents 0 or 1.

[0046] The oxime ester compound represented by the general formula (A) has geometric isomers due to the double bond of the oxime, but these are not distinguished from each other. That is, in this specification, the compound represented by the general formula (A) and the compound represented by the following general formula (A') which is a preferred form of the compound described later, and its exemplified compounds represent a mixture of both or either one of them, and are not limited to the structures showing the isomers.

[0047] In the above general formula (A), R 3 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 21 , R 22 , R 23 and R 24Examples of the alkyl group having 1 to 20 carbon atoms represented by the formula (I) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, and cyclohexylethyl.

[0048] In the above general formula (A), R 3 , R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 Examples of the aryl group having 6 to 30 carbon atoms represented by the formula (I) include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl substituted with one or more of the above alkyl groups, biphenylyl, naphthyl, anthryl, and the like.

[0049] In the above general formula (A), R 3 , R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 Examples of the arylalkyl group having 7 to 30 carbon atoms represented by the formula (I) include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl.

[0050] In the above general formula (A), R 3 , R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , and R 24Examples of the heterocyclic group having 2 to 20 carbon atoms represented by the formula (I) include 5- to 7-membered heterocyclic rings such as pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl, and morpholinyl. In the above general formula (A), R 4 and R 5 , R 5 and R 6 and R 6 and R 7 and R 3 and R 7 and R 3 and R 8 Preferred examples of the ring that can be formed by combining with each other include 5- to 7-membered rings such as a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring, and a lactam ring.

[0051] In addition, in the general formula (A), R 4 , R 5 , R 6 , R 7 and R 8 and R in the above general formula (A). 3 , R 11 , R 12 , R 13 , R 21 , R 22 and R 23 Examples of halogen atoms which may substitute include fluorine, chlorine, bromine and iodine.

[0052] In the above general formula (A), R 11 , R 12 , R 13 , R 21 , R 22 and R 23 The alkylene portion of the group represented by the formula: 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR24 -, -SCO-, -COS-, -OCS- or -CSO- of The oxygen atom may contain 1 to 5 oxygen atoms provided that they are not adjacent to each other, and the divalent group contained in this case may be one type or two or more types of groups, and in the case of groups that can be contained consecutively, two or more of them may be contained consecutively.

[0053] In addition, in the general formula (A), R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 The alkyl (alkylene) portion of the group represented by the formula (I) may have a branched side chain or may be a cyclic alkyl. Among the compounds represented by the above general formula (A), R 3 The compounds represented by the following general formula (A') are preferred because they have high sensitivity and are easy to produce.

[0054] [ka] (In the formula, R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 and k are the same as in the general formula (A), and R 31 , R 32 , R 33 , R 34 and R 35 are each independently R 11 , OR 11 , S.R. 11 , C.O.R. 11 ,CONR 15 R 16 , N.R. 12 COR 11 ,OCOR 11 , COOR 14 , SCOR 11 , OCSR 11 , COSR 14 , CSOR11 , a hydroxyl group, a nitro group, CN, or a halogen atom; R 31 and R 32 , R 32 and R 33 , R 33 and R 34 and R 34 and R 35 may be joined together to form a ring.

[0055] R 31 and R 32 , R 32 and R 33 , R 33 and R 34 and R 34 and R 35 An example of a ring formed by combining the 4 and R 5 , R 5 and R 6 and R 6 and R 7 and R 3 and R 7 and R 3 and R 8 Examples of the ring that can be formed by combining with each other include the same rings as those listed above.

[0056] In the above general formulas (A) and (A'), R 1 is an alkyl group having 1 to 12 carbon atoms or an arylalkyl group having 7 to 15 carbon atoms, R 11 is preferably an aryl group having 6 to 12 carbon atoms or an alkyl group having 1 to 8 carbon atoms, since these groups have high solubility in solvents. 2 As R, a methyl group, an ethyl group, or a phenyl group is preferred because of its high reactivity. 4 ~R 7 is preferably a hydrogen atom or a cyano group, particularly a hydrogen atom, because of ease of synthesis. 8 In the above general formula (A'), R is preferably a hydrogen atom because it is easy to synthesize, and k is preferably 1 because it has high sensitivity. 31 ~R 35 At least one of the following is a nitro group, CN, halogen atom, or COR 11 and R 11is preferably an aryl group having 6 to 12 carbon atoms or an alkyl group having 1 to 8 carbon atoms, since this has high sensitivity. 31 ~R 35 More preferably, at least one of R is a nitro group, CN, or a halogen atom. 33 is particularly preferably a nitro group, CN or a halogen atom.

[0057] Specific preferred examples of the compound represented by the general formula (A) include the following compounds: Further examples include compounds No. 1 to No. 212 described in WO 2015 / 152153.

[0058] [ka]

[0059] The compound represented by the general formula (A) can be synthesized by appropriately selecting the solvent, reaction temperature, reaction time, purification method, etc. depending on the materials to be used, for example, with reference to WO 2015 / 152153. Alternatively, a commercially available product may be obtained and used as appropriate.

[0060] The total content of photoinitiators used in the photocurable green resin composition of the present invention is not particularly limited as long as the effects of the present invention are not impaired, but is preferably in the range of 0.1 to 15.0 mass% and more preferably 1.0 to 10.0 mass% based on the total solids content of the photocurable green resin composition. When this content is equal to or greater than the lower limit, photocuring proceeds sufficiently and solvent resistance and substrate adhesion tend to be good, while when it is equal to or less than the upper limit, line width shift is suppressed and high-resolution patterns can be easily formed.

[0061] 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, and even more preferably 70.0 mass% or more, relative to the total amount of the photoinitiator, from the viewpoint of being able to form a cured film having good substrate adhesion and solvent resistance even by low-temperature heat treatment, and may be 100 mass%.

[0062] The photocurable green resin composition according to the present invention contains a colorant, a photopolymerizable compound, and a photoinitiator. By using a liquid photopolymerizable compound, it is possible to form a coating film without containing a solvent, and by using a means for applying the composition in a pattern, such as an inkjet method, it is possible to form a patterned colored layer. The photocurable green resin composition according to the present invention may further contain an alkali-soluble resin and a solvent, and may be an alkali-developable photocurable green resin composition.

[0063] <Alkali-soluble resin> The alkali-soluble resin used in the present invention has an acidic group, acts as a binder resin, and can be appropriately selected from those that are soluble in an alkaline developer used in pattern formation. In the present invention, an alkali-soluble resin can be defined as one having an acid value of 40 mgKOH / g or more.

[0064] As the alkali-soluble resin, any conventionally known alkali-soluble resin can be appropriately selected and used. For example, the alkali-soluble resins described in WO 2016 / 104493 can be appropriately selected and used. The preferred alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxy group. Specific examples include acrylic resins such as acrylic copolymers having a carboxy group and styrene-acrylic copolymers having a carboxy group, and epoxy (meth)acrylate resins having a carboxy group. Of these, acrylic resins such as acrylic copolymers having a carboxy group and styrene-acrylic copolymers having a carboxy group are preferably used. Among these, particularly preferred are those having a carboxy group in the side chain and a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. This is because the inclusion of a photopolymerizable functional group improves the film strength of the cured film formed. Furthermore, two or more of these acrylic resins, such as acrylic copolymers and styrene-acrylic copolymers, and epoxy acrylate resins may be used in combination.

[0065] The alkali-soluble resin used in the photocurable green resin composition may be used alone or in combination of two or more. The content of the alkali-soluble resin is not particularly limited, but is preferably within the range of 5% to 60% by mass, and more preferably 10% to 40% by mass, based on the total solid content of the photocurable green resin composition. When the content of the alkali-soluble resin is equal to or greater than the lower limit, sufficient alkali developability is obtained. When the content of the alkali-soluble resin is equal to or less than the upper limit, film roughness and pattern chipping during development can be suppressed.

[0066] <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 photocurable green resin composition and can dissolve or disperse them. The solvents can be used alone or in combination of two or more. Specific examples of the solvent include alcohol-based solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, methoxy alcohol, and ethoxy alcohol; carbitol-based solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, and isobutyl acetate. Ester solvents such as 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; and methoxyethoxyethyl acetate. carbitol acetate solvents such as ethoxyethoxyethyl acetate and butyl carbitol acetate (BCA); diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether and dipropylene glycol dimethyl ether; aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; lactone solvents such as γ-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; and aromatic hydrocarbons such as toluene and xylene.Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used in terms of the solubility of other components. Among them, the solvent used in the present invention is preferably one or more selected from the group consisting of 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 the solubility of other components and coating suitability.

[0067] In the photocurable green resin composition according to the present invention, the content of the solvent may be appropriately set within a range that allows for accurate formation of a colored layer. The content of the solvent is usually preferably within a range of 55% by mass to 95% by mass, more preferably 65% ​​by mass to 88% by mass, based on the total amount of the photocurable green resin composition including the solvent. By having the content of the solvent within the above range, excellent coatability can be achieved.

[0068] <Dispersant> When a colorant is dispersed in the photocurable green resin composition of the present invention, the composition may further contain a dispersant from the viewpoints of colorant dispersibility and colorant dispersion stability. In the present invention, the dispersant can be appropriately selected from conventionally known dispersants. As the dispersant, for example, cationic, anionic, nonionic, amphoteric, silicone, fluorine-based surfactants can be used. Among surfactants, polymer dispersants are preferred because they can be dispersed uniformly and finely.

[0069] Examples of polymer dispersants include (meth)acrylate copolymer dispersants; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (amides obtained by reacting poly(lower alkyleneimine) with polyesters containing free carboxy groups, or bases thereof); and polyallylamine derivatives (reaction products obtained by reacting polyallylamine with one or more compounds selected from three types of compounds: polyesters having free carboxy groups, polyamides, or co-condensates of esters and amides (polyesteramides)).

[0070] In the present invention, it is preferable to use a (meth)acrylate copolymer dispersant as the dispersant, since it is likely to provide good solvent resistance even in low-temperature heat treatment. The (meth)acrylate copolymer dispersant has good compatibility with the photopolymerizable compound and the photoinitiator containing the compound represented by general formula (A), making it easier for the initiator to be uniformly present in the colored layer, and the colored layer is uniformly cured, reducing unreacted components and reducing internal stress in the colored layer, which is presumed to result in less change in the colored layer when immersed in a solvent.

[0071] In the present invention, the (meth)acrylate copolymer-based dispersant refers to a dispersant that is a copolymer and contains at least a structural unit derived from (meth)acrylate. The (meth)acrylate copolymer dispersant is preferably a copolymer containing a structural unit that functions as a colorant adsorption site and a structural unit that functions as a solvent affinity site, and it is preferable that the structural unit that functions as a solvent affinity site contains at least a structural unit derived from (meth)acrylate.

[0072] Examples of the structural unit that functions as a colorant adsorption site include a structural unit derived from an ethylenically unsaturated monomer that is copolymerizable with a structural unit derived from a (meth)acrylate. The colorant adsorption site may be a structural unit derived from an acidic group-containing ethylenically unsaturated monomer or a structural unit derived from a basic group-containing ethylenically unsaturated monomer. As the constituent unit derived from a basic group-containing ethylenically unsaturated monomer, a constituent unit represented by the following general formula (I) is preferred from the viewpoint of excellent dispersibility.

[0073] [ka] (In general formula (I), R 71 is a hydrogen atom or a methyl group, A 1 is a divalent linking group, R 72 and R 73 each independently represents a hydrogen atom or a hydrocarbon group which may contain a heteroatom; R 72 and R 73 may be bonded to each other to form a ring structure.

[0074] In general formula (I), A 1 is a divalent linking group. Examples of the divalent linking group include a linear, branched, or cyclic alkylene group, a linear, branched, or cyclic alkylene group having a hydroxyl group, an arylene group, a -CONH- group, a -COO- group, a -NHCOO- group, an ether group (-O- group), a thioether group (-S- group), and combinations thereof. In the present invention, the bond direction of the divalent linking group is arbitrary. That is, when the divalent linking group contains -CONH-, -CO may be on the carbon atom side of the main chain and -NH may be on the nitrogen atom side of the side chain, or conversely, -NH may be on the carbon atom side of the main chain and -CO may be on the nitrogen atom side of the side chain. Among these, from the viewpoint of dispersibility, A in general formula (I) 1 is preferably a divalent linking group containing a -CONH- group or a -COO- group, and more preferably a divalent linking group containing a -CONH- group or a -COO- group and an alkylene group having 1 to 10 carbon atoms.

[0075] R 72 and R 73 Examples of the hydrocarbon group in the hydrocarbon group which may contain a heteroatom include an alkyl group, an aralkyl group, and an aryl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2-ethylhexyl group, a cyclopentyl group, and a cyclohexyl group. The number of carbon atoms in the alkyl group is preferably 1 to 18, and among these, a methyl group or an ethyl group is more preferred. Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. The aralkyl group preferably has 7 to 20 carbon atoms, more preferably 7 to 14 carbon atoms. Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. The number of carbon atoms in the aryl group is preferably 6 to 24, and more preferably 6 to 12. The above preferred number of carbon atoms does not include the number of carbon atoms in the substituent. The hydrocarbon group containing a heteroatom has a structure in which a carbon atom in the above hydrocarbon group is replaced with a heteroatom, or a hydrogen atom in the above hydrocarbon group is replaced with a substituent containing a heteroatom. Examples of the heteroatom that may be contained in the hydrocarbon group include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. Furthermore, the hydrogen atoms in the hydrocarbon group may be substituted with halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms.

[0076] R 72 and R 73 are bonded to each other to form a ring structure, R 72 and R 73 forms a ring structure via a nitrogen atom. 72 and R 73 The ring structure formed by the formula (I) may contain a heteroatom. The ring structure is not particularly limited, but examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

[0077] In the present invention, among others, R 72 and R 73 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or R 72 and R 73are preferably bonded to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

[0078] Examples of monomers that derive the structural unit represented by the general formula (I) include alkyl group-substituted amino group-containing (meth)acrylates such as dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and diethylaminopropyl (meth)acrylate, as well as alkyl group-substituted amino group-containing (meth)acrylamides such as dimethylaminoethyl (meth)acrylamide and dimethylaminopropyl (meth)acrylamide. Among these, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylamide are preferred in terms of improving dispersibility and dispersion stability. In the polymer, the constitutional unit represented by general formula (I) may be composed of one type, or may contain two or more types of constitutional units.

[0079] Furthermore, as a structural unit that functions as a colorant adsorption site, at least a portion of the nitrogen moieties of the structural unit represented by general formula (I) may form 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). Among the organic acid compounds, compounds represented by the following general formula (1) and compounds represented by the following general formula (3) are preferred, and among the halogenated hydrocarbons, compounds represented by the following general formula (2) are preferred. That is, as the at least one compound selected from the group consisting of organic acid compounds and halogenated hydrocarbons, one or more compounds selected from the group consisting of the following general formulas (1) to (3) can be preferably used.

[0080] [ka] (In general formula (1), R arepresents 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 -OR e represents 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 connected via an alkylene group having 1 to 4 carbon atoms. 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 a benzyl group which may have a substituent, or -OR f represents R f represents 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 connected via an alkylene group having 1 to 4 carbon atoms, and X represents a chlorine atom, a bromine atom, or an iodine atom. c and R d each independently 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 group or a benzyl group which may have a substituent, or -OR e represents R e 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 a (meth)acryloyl group connected via an alkylene group having 1 to 4 carbon atoms. c and R d At least one of the groups contains a carbon atom.

[0081] The symbols in the general formulae (1) to (3) may be the same as those described in WO 2016 / 104493. The organic acid compound is preferably an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid, because it has excellent dispersibility and dispersion stability of the colorant. Specific examples of the organic acid compound used in such a dispersant include the organic acid compounds described in JP-A-2012-236882. The halogenated hydrocarbon is preferably at least one of allyl halides and aralkyl halides, such as allyl bromide and benzyl chloride, from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.

[0082] In the salt-type copolymer, the content of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons forms a salt with the terminal nitrogen moiety of the structural unit represented by general formula (I). Therefore, the total amount of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons is preferably 0.01 mol or more, more preferably 0.05 mol or more, even more preferably 0.1 mol or more, and particularly preferably 0.2 mol or more, relative to the terminal nitrogen moiety of the structural unit represented by general formula (I). When the amount is above the lower limit, the effect of improving colorant dispersibility due to salt formation is easily obtained. Similarly, the amount is preferably 1 mol or less, more preferably 0.8 mol or less, even more preferably 0.7 mol or less, and particularly preferably 0.6 mol or less. When the amount is below the upper limit, excellent development adhesion and solvent resolubility can be achieved. The 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 types are combined, the total content thereof is preferably within the above range.

[0083] Examples of a method for preparing the salt-type copolymer include a method in which at least one selected from the group consisting of the organic acid compounds and halogenated hydrocarbons described above is added to a solvent in which the copolymer before salt formation has been dissolved or dispersed, followed by stirring and, if necessary, heating. The fact that the terminal nitrogen moiety of the structural unit represented by general formula (I) of the copolymer forms a salt with at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon, and the ratio thereof, can be confirmed by known techniques such as NMR.

[0084] From the viewpoint of dispersibility and dispersion stability, the copolymer having the structural unit represented by the general formula (I) is more preferably at least one of a graft copolymer having the structural unit represented by the general formula (I) and having a structural unit derived from (meth)acrylate in the graft polymer chain, and a block copolymer having an A block containing the structural unit represented by the general formula (I) and a B block containing a structural unit derived from (meth)acrylate. The graft copolymer and the block copolymer will be described below in order.

[0085] Examples of the graft copolymer having a structural unit represented by the general formula (I) and having a structural unit derived from a (meth)acrylate in the graft polymer chain include a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the following general formula (II), and at least one salt-type graft copolymer in which at least a portion of the nitrogen moieties of the structural unit represented by the general formula (I) of the graft copolymer form a salt with at least one member selected from the group consisting of an organic acid compound and a halogenated hydrocarbon.

[0086] [ka] (In general formula (II), R 71’ is a hydrogen atom or a methyl group, A 2 represents a direct bond or a divalent linking group, and Polymer represents a polymer chain, and the structural units of the polymer chain include structural units derived from (meth)acrylate.

[0087] In the general formula (II), A 2 is a direct bond or a divalent linking group. 2The divalent linking group in A is not particularly limited as long as it can link the carbon atom derived from the ethylenically unsaturated double bond to the polymer chain. 2 Examples of the divalent linking group in A include 1 Examples of the divalent linking group include the same as the divalent linking group in the above. Among these, from the viewpoint of dispersibility, A in general formula (II) 2 is preferably a divalent linking group containing a -CONH- group or a -COO- group, and more preferably a divalent linking group containing a -CONH- group or a -COO- group and an alkylene group having 1 to 10 carbon atoms.

[0088] In the general formula (II), Polymer represents a polymer chain, and the structural units of the polymer chain include structural units derived from (meth)acrylate. By having a structural unit represented by the general formula (II) having a specific polymer chain, the graft copolymer has good solvent affinity, good dispersibility and dispersion stability of the colorant, and good compatibility with the photoinitiator. The structural unit of the polymer chain includes a structural unit represented by the following general formula (III).

[0089] [ka] (In general formula (III), R 74” is a hydrogen atom or a methyl group, A 4 is a divalent linking group, R 80 is a hydrogen atom or a hydrocarbon group which may contain a heteroatom.

[0090] A 4 Examples of the divalent linking group include the above-mentioned A 1 In the present invention, the (meth)acrylate-derived structural unit may be the same as the divalent linking group in general formula (III): 4 In view of solubility in organic solvents used in color filters, the structural unit represented by general formula (III) in which A is a divalent linking group containing a -COO- group is included.4 may contain a divalent linking group containing a -CONH- group.

[0091] R 80 Examples of the hydrocarbon group in the hydrocarbon group which may contain a heteroatom in R include an alkyl group, an alkenyl group, an aryl group, and combinations thereof such as an aralkyl group and an alkyl-substituted aryl group. 80 In the above, 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, and combinations thereof such as aralkyl groups and alkyl-substituted aryl groups. The alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-nonyl group, an n-lauryl group, an n-stearyl group, a cyclopentyl group, a cyclohexyl group, a bornyl group, an isobornyl group, a dicyclopentanyl group, an adamantyl group, a lower alkyl group-substituted adamantyl group, etc. The number of carbon atoms in the alkyl group is preferably 1 to 12, and more preferably 1 to 6. The alkenyl group having 2 to 18 carbon atoms may be linear, branched, or cyclic. Examples of such alkenyl groups include vinyl groups, allyl groups, and propenyl groups. There are no limitations on the position of the double bond in the alkenyl group, but from the viewpoint of the reactivity of the resulting polymer, it is preferable that the double bond is located at the terminal of the alkenyl group. The number of carbon atoms in the alkenyl group is preferably 2 to 12, and more preferably 2 to 8. Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, etc. The aryl group preferably has 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms. Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, and a biphenylmethyl group, and the aralkyl group may further have a substituent. The number of carbon atoms in the aralkyl group is preferably 7 to 20, and more preferably 7 to 14. Furthermore, the aromatic ring of the aryl group or aralkyl group may have a linear or branched alkyl group having 1 to 30 carbon atoms bonded thereto as a substituent.

[0092] R 80 In terms of dispersion stability, the hydrocarbon group in is preferably at least one selected from the group consisting of alkyl groups having 1 to 18 carbon atoms, aryl groups having 6 to 12 carbon atoms which may be substituted with an alkyl group, and aralkyl groups having 7 to 14 carbon atoms which may be substituted with an alkyl group, and is preferably at least one selected from the group consisting of methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, n-nonyl groups, n-lauryl groups, n-stearyl groups, phenyl groups which may be substituted with an alkyl group, and benzyl groups.

[0093] Examples of heteroatoms that may be contained in the hydrocarbon group include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, etc. Examples of hydrocarbon groups that may contain a heteroatom include structures in which the carbon chain of the hydrocarbon group contains a linking group such as -CO-, -COO-, -OCO-, -O-, -S-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, or -O-NH-. The hydrocarbon group may have a substituent within the range that does not impair the dispersibility of the graft copolymer. Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group, an alkoxy group, a nitro group, a cyano group, an epoxy group, an isocyanate group, and a thiol group.

[0094] Also, R 80 The hydrocarbon group which may contain a heteroatom in the formula (III) may have a structure in which a polymerizable group such as an alkenyl group is added to the end of the hydrocarbon group via a linking group containing a heteroatom. For example, the structural unit represented by the formula (III) may have a structure in which a structural unit derived from (meth)acrylic acid is reacted with glycidyl (meth)acrylate. That is, -A in the formula (III) may have a structure in which a polymerizable group such as an alkenyl group is added to the end of the hydrocarbon group via a linking group containing a heteroatom. 4 -R80 The structure of the formula (III) may be a structure represented by -COO-CH2CH(OH)CH2-OCO-CR=CH2 (where R is a hydrogen atom or a methyl group). In addition, the structural unit represented by 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. That is, R in general formula (III) 80 However, it may also have a structure represented by -R'-OCONH-R"-OCO-CR=CH2 (wherein R' and R" each independently represent an alkylene group, and R represents a hydrogen atom or a methyl group).

[0095] Examples of monomers that derive the structural unit represented by general formula (III) include methyl(meth)acrylate, ethyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, tert-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, and adamantyl(meth)acrylate. Preferred are those having structural units derived from acrylate, (meth)acrylic acid, 2-methacryloyloxyethyl succinate, 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, etc. However, they are not limited to these.

[0096] In the present invention, the R 80Among them, it is preferable to use one that has excellent solubility in the organic solvent described below, and it may be selected appropriately according to the organic solvent used in the colorant dispersion liquid. Specifically, for example, when the organic solvent is an ether alcohol acetate-based, ether-based, ester-based, or alcohol-based organic solvent that is generally used as an organic solvent for the colorant dispersion liquid, a methyl group, an ethyl group, an isobutyl group, an n-butyl group, a 2-ethylhexyl group, a benzyl group, a cyclohexyl group, a dicyclopentanyl group, a hydroxyethyl group, a phenoxyethyl group, an adamantyl group, a methoxypolyethylene glycol group, a methoxypolypropylene glycol group, a polyethylene glycol group, etc. are preferred.

[0097] In the graft copolymer, it is preferable that the structural units of the polymer chain in the structural unit represented by general formula (II) include at least one structural unit selected from the group consisting of structural units represented by general formula (IV) below and structural units represented by general formula (IV') below, in order to further improve the solvent resistance of the cured product of the photocurable green resin composition and to shorten the development time of the photocurable green resin composition. The constitutional unit represented by the following general formula (IV) and the constitutional unit represented by the following general formula (IV') are constitutional units encompassed by the constitutional unit represented by the above general formula (III).

[0098] [ka] (In general formula (IV), R 74 is a hydrogen atom or a methyl group, A 3 is a divalent linking group, R 75 is an ethylene group or a propylene group, R 76 is a hydrogen atom or a hydrocarbon group, and m is a number of 3 or more and 80 or less. In general formula (IV'), R 74’ is a hydrogen atom or a methyl group, A 3’ is a divalent linking group, R 77 is an alkylene group having 1 to 10 carbon atoms, R 78 is an alkylene group having 3 to 7 carbon atoms, R 79is a hydrogen atom or a hydrocarbon group, and n is a number of 1 or more and 40 or less.

[0099] A 3 Examples of the divalent linking group include the above-mentioned A 1 Among them, from the viewpoint of solubility in organic solvents used for color filters, A in general formula (IV) is preferred. 3 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.

[0100] The m represents the number of repeating units of the ethylene oxide chain or propylene oxide chain and is a number of 3 or more. In particular, from the viewpoints of suppressing water stains and solvent resistance, it is preferably 19 or more, and more preferably 21 or more. When m is 19 or greater, the graft copolymer contains a main chain portion having a structural unit represented by general formula (I) and a structural unit represented by general formula (II), and the structural unit represented by general formula (II) contains a structural unit represented by general formula (IV) containing a polyethylene oxide chain or polypropylene oxide chain having a specific repeat number in the polymer chain. In the specific graft copolymer used in the present invention, the structural units of the grafted polymer chain contain a structural unit having a polyethylene oxide chain or polypropylene oxide chain having a specific repeat number, and the grafted polymer chain itself has a branched structure. The multiple grafted polymer chains spread three-dimensionally in the film, increasing the specific surface area, which is presumed to further inhibit solvents from penetrating the coating film and reaching the colorant. On the other hand, the upper limit of m is 80 or less, but is preferably 50 or less from the viewpoint of solubility in organic solvents used in color filters.

[0101] R 76 The hydrocarbon group in R 80 may be the same as the hydrocarbon group in R76 In terms of dispersion stability and compatibility, the hydrocarbon group in is preferably at least one selected from the group consisting of alkyl groups having 1 to 18 carbon atoms, aryl groups having 6 to 12 carbon atoms which may be substituted with an alkyl group, and aralkyl groups having 7 to 14 carbon atoms which may be substituted with an alkyl group, and is preferably at least one selected from the group consisting of methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, n-nonyl groups, n-lauryl groups, n-stearyl groups, phenyl groups which may be substituted with an alkyl group, and benzyl groups.

[0102] In addition, in the general formula (IV'), A 3’ Examples of the divalent linking group include the above-mentioned A 1 Among them, from the viewpoint of solubility in organic solvents used for color filters, A 3’ 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. In the general formula (IV'), R 77 is an alkylene group having 1 to 10 carbon atoms, and among these, an alkylene group having 2 to 8 carbon atoms is preferred from the viewpoint of solvent resolubility. R 78 is an alkylene group having 3 to 7 carbon atoms, and among these, an alkylene group having 3 to 5 carbon atoms, and more preferably an alkylene group having 5 carbon atoms, is preferred from the viewpoint of adhesion to the substrate. R 79 is a hydrogen atom or a hydrocarbon group, and 79 The hydrocarbon group in R 76 may be the same as the hydrocarbon group in

[0103] In the general formula (IV'), n represents the number of repeating units of the ester chain and is a number of 1 or more. In particular, from the viewpoint of simultaneously achieving a shorter development time and excellent solvent resistance, n is preferably 2 or more, and more preferably 3 or more. On the other hand, the upper limit of n is 40 or less, but is preferably 20 or less from the viewpoint of solubility in organic solvents used in color filters.

[0104] In the polymer chain, the at least one structural unit selected from the group consisting of the structural unit represented by the general formula (IV) above and the structural unit represented by the following general formula (IV') may be a single type or a mixture of two or more types. It is preferable that the polymer chain contains a structural unit represented by general formula (IV) because the effect of the solvent affinity moiety due to the oxygen atom becomes more pronounced, thereby shortening the development time of the photocurable green resin composition and improving the solvent resistance.

[0105] Among these, from the viewpoints of improving solvent resistance, improving the effect of suppressing water stains, and improving the effect of suppressing development residues, it is more preferable that the structural units of the polymer chain in the structural unit represented by general formula (II) contain a combination of at least one selected from the group consisting of structural units represented by general formula (IV) in which m is 19 or more and 80 or less, and at least one selected from the group consisting of structural units represented by general formula (IV) in which m is 3 or more and 10 or less, and it is even more preferable that the structural units contain a combination of at least one selected from the group consisting of structural units represented by general formula (IV) in which m is 19 or more and 50 or less, and at least one selected from the group consisting of structural units represented by general formula (IV) in which m is 3 or more and 8 or less.

[0106] When the structural units of the polymer chain in the structural unit represented by general formula (II) contain at least one selected from the group consisting of structural units represented by general formula (IV) in which m is 19 or more and 80 or less, the total proportion of structural units represented by general formula (IV) in which m is 19 or more and 80 or less, when all structural units of the polymer chain are taken as 100% by mass, is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 4% by mass or more, from the viewpoint of the water stain suppression effect; on the other hand, from the viewpoint of solvent resolubility and the water stain suppression effect, it is preferably 75% by mass or less, more preferably 65% ​​by mass or less, and even more preferably 50% by mass or less.

[0107] When the structural units of the polymer chain in the structural unit represented by general formula (II) contain a combination of at least one selected from the group consisting of structural units represented by general formula (IV) in which m is 19 or more and 80 or less and at least one selected from the group consisting of structural units represented by general formula (IV) in which m is 3 or more and 10 or less, the total proportion of structural units represented by general formula (IV) in which m is 3 or more and 10 or less is preferably 20% by mass or more, when all structural units of the polymer chain are taken as 100% by mass. On the other hand, from the viewpoint of solvent resolubility, the total proportion of structural units represented by general formula (IV) in which m is 3 or more and 10 or less in the polymer chain is preferably 80% by mass or less, and more preferably 60% by mass or less, when all structural units of the polymer chain are taken as 100% by mass. Furthermore, in the polymer chain, from the viewpoint of improving the development residue suppression effect, the mixing ratio of the structural units represented by general formula (IV) in which m is 19 or more and 80 or less and the structural units represented by general formula (IV) in which m is 3 or more and 10 or less is preferably such that, when the total of the structural units represented by general formula (IV) in which m is 19 or more and 80 or less and the structural units represented by general formula (IV) in which m is 3 or more and 10 or less is taken as 100 parts by mass, the total of the structural units represented by general formula (IV) in which m is 19 or more and 80 or less is 3 parts by mass or more, more preferably 6 parts by mass or more, and is preferably 80 parts by mass or less, and more preferably 60 parts by mass or less.

[0108] In order to simultaneously achieve dispersion stability, high contrast, reduced development time, and excellent solvent resistance, the total proportion of at least one structural unit selected from the group consisting of structural units represented by general formula (IV) and structural units represented by general formula (IV') is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 4% by mass or more, when all structural units in the polymer chain are taken as 100% by mass. In terms of solvent resolubility, the total proportion of at least one structural unit selected from the group consisting of structural units represented by general formula (IV) and structural units represented by general formula (IV') is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less, when all structural units in the polymer chain are taken as 100% by mass.

[0109] In the polymer chain, the structural unit represented by general formula (III), which includes the structural unit represented by general formula (IV) and the structural unit represented by general formula (IV'), may be of one type alone or may be a mixture of two or more types. From the viewpoint of dispersibility and dispersion stability of the colorant, the total proportion of the structural units represented by the general formula (III) is preferably 70% by mass or more, and more preferably 90% by mass or more, when all structural units in the polymer chain are taken as 100% by mass. On the other hand, from the viewpoint of simultaneously satisfying 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% by mass, when all structural units in the polymer chain are taken as 100% by mass. In particular, the total proportion of (meth)acrylate-derived structural units is preferably 60% by mass or more, and more preferably 80% by mass or more, when all structural units in the polymer chain are taken as 100% by mass, from the viewpoints of dispersion stability, solvent resistance, and compatibility with initiators. On the other hand, in order to simultaneously satisfy dispersion stability and excellent solvent resistance, the total proportion of (meth)acrylate-derived structural units in the polymer chain may be 100% by mass, when all structural units in the polymer chain are taken as 100% by mass.

[0110] The structural units 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). Examples of other structural units include structural units derived from monomers having an unsaturated double bond that are copolymerizable with the monomer that derives the structural unit represented by general formula (III). Examples of monomers from which other structural units are derived include styrenes such as styrene and α-methylstyrene, and vinyl ethers such as phenyl vinyl ether.

[0111] In the polymer chain of the structural unit represented by general formula (II) of the graft copolymer, the total proportion of other structural units is preferably 30% by mass or less, and more preferably 10% by mass or less, when all structural units of the polymer chain are taken as 100% by mass, from the viewpoint of the effects of the present invention.

[0112] The weight average molecular weight Mw of the polymer chain in the polymer is preferably 2000 or more, more preferably 3000 or more, and even more preferably 4000 or more, and more preferably 15000 or less, and even more preferably 12000 or less, from the viewpoint of dispersibility and dispersion stability of the colorant. By ensuring that the content is within this range, the dispersant can maintain a sufficient steric repulsion effect, and the specific surface area of ​​the solvent-compatible portion of the dispersant is increased, making it easier to prevent the solvent from penetrating the coating film or reaching the colorant.

[0113] Furthermore, as a guideline, the polymer chain in the Polymer preferably has a solubility at 23° C. of 20 (g / 100 g solvent) or more in the organic solvent used in combination. The solubility of the polymer chain can be determined by the solubility of the raw material into which the polymer chain is introduced when preparing the graft copolymer. For example, when a polymerizable oligomer (macromonomer) containing a polymer chain and a group having an ethylenically unsaturated double bond at its terminal is used to introduce a polymer chain into the graft copolymer, the polymerizable oligomer should have the solubility. Furthermore, when a copolymer is formed using a monomer containing a group having an ethylenically unsaturated double bond, and then a polymer chain is introduced using a polymer chain containing a reactive group capable of reacting with a reactive group contained in the copolymer, the polymer chain containing the reactive group should have the solubility.

[0114] In the graft copolymer, the content of the structural unit represented by general formula (I) is preferably 3% by mass to 60% by mass, more preferably 6% by mass to 45% by mass, and even more preferably 9% by mass to 30% by mass. When the content of the structural unit represented by general formula (I) in the graft copolymer is within the above range, the proportion of the portion having affinity with the colorant in the graft copolymer becomes appropriate and a decrease in solubility in organic solvents can be suppressed, resulting in good adsorption to the colorant and easy achievement of excellent dispersibility and dispersion stability. On the other hand, the graft copolymer preferably contains the structural unit represented by general formula (II) in a proportion of 40% to 97% by mass, more preferably 55% to 94% by mass, and even more preferably 70% to 91% by mass. If the structural unit represented by general formula (II) in the graft copolymer is within the above range, the proportion of the solvent-compatible moiety in the graft copolymer becomes appropriate, allowing the graft copolymer to maintain a sufficient steric repulsion effect as a dispersant, and the specific surface area of ​​the solvent-compatible moiety of the dispersant to be increased, making it easier to prevent the solvent from penetrating the coating film or reaching the colorant.

[0115] The graft copolymer used in the present invention may further contain other structural units in addition to the structural units represented by the general formula (I) and the structural units represented by the general formula (II), as long as the effects of the present invention are not impaired. As the other structural units, ethylenically unsaturated double bond-containing monomers copolymerizable with the ethylenically unsaturated double bond-containing monomers that derive the structural units represented by the general formula (I) can be appropriately selected and copolymerized to introduce the other structural units. Examples of other structural units copolymerized with the structural unit represented by the general formula (I) include structural units represented by the general formula (III). The content ratio of the structural units is calculated from the amounts of monomers used to derive the structural unit represented by general formula (I), the structural unit represented by general formula (II), and the structural unit represented by general formula (III) when synthesizing the graft copolymer during production.

[0116] From the viewpoints 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, while from the viewpoint of solvent resolubility, it is preferably 50000 or less, and more preferably 30000 or less. In the present invention, the mass average molecular weight Mw is a value measured by GPC (gel permeation chromatography). Measurements were performed using a Tosoh HLC-8120GPC, with N-methylpyrrolidone containing 0.01 mol / L of lithium bromide as the eluent, polystyrene standards for calibration curves of Mw 377,400, 210,500, 96,000, 50,400, 20,650, 10,850, 5,460, 2,930, 1,300, and 580 (all Easi PS-2 series, manufactured by Polymer Laboratories) and Mw 1,090,000 (manufactured by Tosoh), and two TSK-GEL ALPHA-M columns (manufactured by Tosoh).

[0117] (Method for producing graft copolymer) In the present invention, the method for producing the graft copolymer is not particularly limited as long as it can produce a graft copolymer having a constitutional unit represented by the general formula (I) and a constitutional unit represented by the general formula (II). When producing a graft copolymer having a constitutional unit represented by the general formula (I) and a constitutional unit represented by the general formula (II), for example, a method for producing a graft copolymer includes copolymerizing a monomer represented by the following general formula (Ia) and a polymerizable oligomer (macromonomer) consisting of the polymer chain and a group having an ethylenically unsaturated double bond at its terminal as copolymerization components. If necessary, other monomers may also be used to produce the graft copolymer by known polymerization means.

[0118] [ka] (In general formula (Ia), R 71 , A 1 , R 72 and R 73 is the same as in general formula (I).

[0119] Furthermore, when 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 may be introduced using a polymer chain having a reactive group capable of reacting with the reactive group contained in the copolymer after the copolymer is formed by addition polymerization of a monomer represented by the general formula (Ia) and another monomer having a group with an ethylenically unsaturated double bond. 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 the polymer chain may be introduced by reacting the copolymer with a polymer chain having a functional group reactive with the substituent. For example, a polymer chain can be introduced by reacting a copolymer having a glycidyl group in the side chain with a polymer chain having a carboxyl group at the end, or by reacting a copolymer having an isocyanate group in the side chain with a polymer chain having a hydroxyl group at the end. In the polymerization, additives generally used in polymerization, such as a polymerization initiator, a dispersion stabilizer, and a chain transfer agent, may be used.

[0120] Next, a block copolymer having an A block containing a structural unit represented by the 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 may be, for example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer, etc. Among these, an AB block copolymer or an ABA block copolymer is preferred in terms of excellent dispersibility.

[0121] The A block is a block that functions as a colorant adsorption site and contains at least a constituent unit represented by the general formula (I). The A block may be a salt-type block copolymer in which at least a portion of the nitrogen moieties of the constituent unit represented by the general formula (I) of the block copolymer forms a salt with at least one selected from the group consisting of an organic acid compound and a halogenated hydrocarbon. The A block may contain a structural unit other than the structural unit represented by general formula (I) as long as the object of the present invention is achieved, and may contain a structural unit that is copolymerizable with the structural unit represented by general formula (I). Specific examples include the structural unit represented by the above-mentioned general formula (III). In the A block of the block copolymer before salt formation, the content of the structural unit represented by general formula (I) is preferably 50% to 100% by mass, more preferably 80% to 100% by mass, and most preferably 100% by mass, relative to the total mass of all structural units in the A block. This is because the higher the proportion of the structural unit represented by general formula (I), the more improved the adsorption force to the colorant and the better the dispersibility and dispersion stability of the block copolymer. The content of the structural unit is calculated from the mass of the components charged when synthesizing the A block having the structural unit represented by general formula (I).

[0122] In the block copolymer before salt formation, the total content of all structural units of the A block, including the structural unit represented by general formula (I), is preferably 5% by mass to 60% by mass, and more preferably 10% by mass to 50% by mass, relative to the total mass of all structural units of the block copolymer, in order to achieve good dispersibility and dispersion stability. In order to improve dispersibility and dispersion stability, the content of the structural unit represented by general formula (I) in the block copolymer before salt formation is preferably 5% by mass to 60% by mass, and more preferably 10% by mass to 50% by mass, relative to the total mass of all structural units of the block copolymer. The content of each structural unit in the block copolymer is calculated from the mass of the components charged when synthesizing the block copolymer before salt formation. The structural unit represented by general formula (I) may be composed of one type or may contain two or more types of structural units as long as it has affinity with the colorant.

[0123] The B block is a block that functions as a solvent-affinity site and contains at least a structural unit derived from a (meth)acrylate. The (meth)acrylate-derived structural unit may be the same as described above. The B block is preferably selected from monomers having an unsaturated double bond that are copolymerizable with the monomer that derives the structural unit represented by general formula (I) and that have solvent affinity, depending on the solvent. As a guideline, it is preferable to introduce the B block so that the solubility of the copolymer at 23°C in the solvent used in combination is 20 (g / 100g solvent) or more. The structural unit that constitutes the B block portion may consist of one type, or may contain two or more types of structural units. Examples of the structural units contained in the B block include the structural units represented by the general formula (III) above.

[0124] In the block copolymer used as the dispersant of the present invention, the ratio m / n of the number of units m of the structural unit represented by general formula (I) to the number of units n of other structural units constituting the solvent-compatible block portion is preferably within the range of 0.01 or more and 1 or less, and more preferably within the range of 0.05 or more and 0.7 or less from the viewpoint of dispersibility and dispersion stability of the colorant.

[0125] Among the block copolymers used as dispersants in the present invention, those containing a block A containing structural units represented by general formula (I) and a block B containing structural units derived from a carboxyl group-containing monomer and a (meth)acrylate-derived structural unit, as well as at least one salt-type block copolymer in which at least a portion of the nitrogen moieties of the structural units represented by general formula (I) of the block copolymer form a salt with at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons, are preferred, as they provide good substrate adhesion and solvent resistance of the cured film even after low-temperature heat treatment and suppress the generation of development residues. Furthermore, these specific dispersants are preferred when combined with a photoinitiator containing the compound represented by general formula (A), as they further improve solvent resistance. In this case, the B block contains a structural unit derived from a (meth)acrylate as an essential component, and may be the same as the B block in WO 2016 / 104493.

[0126] The carboxyl group-containing monomer can be copolymerizable with a monomer having a structural unit represented by general formula (I) and can contain an unsaturated double bond and a carboxyl group. Examples of such monomers include (meth)acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl esters, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Other examples include addition reaction products of hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate with cyclic anhydrides such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, and ω-carboxy-polycaprolactone mono(meth)acrylate. Furthermore, acid anhydride group-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride can also be used as carboxyl group precursors. Among these, (meth)acrylic acid is particularly preferred in terms of copolymerizability, cost, solubility, and glass transition temperature.

[0127] The content of the structural units derived from the carboxyl group-containing monomer in the block copolymer before salt formation is not particularly limited, and may be appropriately set so that the acid value of the block copolymer falls within the above-mentioned specific acid value range. However, the content is preferably 0.05% by mass to 4.5% by mass, and more preferably 0.07% by mass to 3.7% by mass, relative to the total mass of all structural units of the block copolymer. When the content ratio of the structural unit derived from the carboxy group-containing monomer is equal to or more than the above-mentioned lower limit, the effect of suppressing development residues is exerted, and when it is equal to or less than the above-mentioned upper limit, deterioration of development adhesion and deterioration of solvent resolubility can be prevented. The structural unit derived from the carboxyl group-containing monomer may be one type or may contain two or more types of structural units as long as it has the above-mentioned specific acid value.

[0128] Furthermore, it is preferable that the B block of the block copolymer contains a structural unit derived from a hydroxyl group-containing monomer in order to improve development adhesion. When the B block contains a structural unit derived from a hydroxyl group-containing monomer, the development rate is further improved. Here, the hydroxyl group refers to an alcoholic hydroxyl group bonded to an aliphatic hydrocarbon.

[0129] The structural unit derived from a hydroxyl group-containing monomer can be a monomer containing an unsaturated double bond and a hydroxyl group that is copolymerizable with the monomer that derives the structural unit represented by general formula (I). Examples of such monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerin mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, an adduct of 2-hydroxyethyl (meth)acrylate with 1 mole of ε-caprolactone, and 2-hydroxy-3-phenoxypropyl (meth)acrylate. Among them, one or more selected from the group consisting of 2-hydroxyethyl methacrylate and 2-hydroxy-3-phenoxypropyl (meth)acrylate are preferred in terms of improving development adhesion.

[0130] In the block copolymer before salt formation, the content of the structural unit derived from the hydroxyl group-containing monomer is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, and particularly preferably 4% by mass or more, relative to the total mass of all structural units of the block copolymer. A content above the lower limit can ensure favorable development adhesion. Similarly, a content below the upper limit can be preferred in terms of increasing the introduction ratio of other useful monomers. The content of the structural unit is calculated from the mass of the components charged when synthesizing the block copolymer before salt formation.

[0131] The acid value of at least one of the block copolymers and salt-type block copolymers is preferably 1 mgKOH / g or more, more preferably 2 mgKOH / g or more, as a lower limit from the viewpoint of suppressing development residues, and is preferably 18 mgKOH / g or less, more preferably 16 mgKOH / g or less, and even more preferably 14 mgKOH / g or less, as an upper limit from the viewpoint of preventing deterioration of development adhesion and solvent resolubility. The acid value of at least one of the block copolymer and the salt-type block copolymer can be determined by the method described in WO 2016 / 104493.

[0132] The glass transition temperature of at least one of the block copolymers and salt-type block copolymers is preferably 30° C. or higher from the viewpoint of development adhesion, more preferably 32° C. or higher, and more preferably 35° C. or higher, while from the viewpoint of operability during use, such as ease of precise weighing, it is preferably 200° C. or lower. The glass transition temperature of at least one of the block copolymers and salt-type block copolymers is determined by differential scanning calorimetry (DSC) in accordance with JIS K 7121. When two or more peaks indicating the glass transition temperature are observed, the peak with the largest peak area, i.e., the largest area of ​​the part projecting from the baseline of the obtained chart, is taken as the representative value of the glass transition temperature.

[0133] The mass average molecular weight Mw of the block copolymer is not particularly limited, but from the viewpoint of improving colorant dispersibility and dispersion stability, it is preferably 1,000 to 20,000, more preferably 2,000 to 15,000, and even more preferably 3,000 to 12,000. Here, the mass average molecular weight (Mw) can be measured in the same manner as above.

[0134] Furthermore, from the viewpoints of dispersion stability, solvent resistance, and compatibility with photoinitiators, the total proportion of (meth)acrylate-derived structural units is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, when all structural units in the B block of the block copolymer are taken as 100% by mass. On the other hand, from the viewpoint of simultaneously satisfying dispersion stability and excellent solvent resistance, the total proportion of (meth)acrylate-derived structural units may be 100% by mass when all structural units in the B block are taken as 100% by mass. When the B block contains structural units derived from the carboxy group-containing monomer, the total proportion of (meth)acrylate-derived structural units may be 100% by mass when all structural units in the B block other than structural units derived from the carboxy group-containing monomer are taken as 100% by mass.

[0135] In the block copolymer before salt formation, the total content of all structural units of the B block is preferably 5% by mass to 60% by mass, and more preferably 10% by mass to 50% by mass, relative to the total mass of all structural units of the block copolymer, in order to achieve good dispersibility and dispersion stability. In order to improve colorant dispersibility, the content of the structural unit represented by the general formula (III) in the block copolymer before salt formation is preferably 40% by mass to 95% by mass, and more preferably 50% by mass to 90% by mass, based on the total mass of all structural units of the block copolymer. The content of the structural unit is calculated from the mass of the components used in synthesizing the block copolymer before salt formation.

[0136] As the (meth)acrylate copolymer containing the structural unit represented by the general formula (I), a copolymer having an amine value of 40 mgKOH / g to 120 mgKOH / g is preferred, as it has good dispersibility, does not precipitate foreign matter during coating film formation, and improves brightness and contrast. By having an amine value within the above range, the viscosity stability over time and heat resistance are excellent, and the composition is also excellent in alkali developability and solvent resolubility. In the present invention, the amine value of the (meth)acrylate copolymer containing the structural unit represented by the general formula (I) is preferably 80 mgKOH / g or more, and more preferably 90 mgKOH / g or more. On the other hand, from the viewpoint of solvent resolubility, the amine value of the (meth)acrylate copolymer containing the structural unit represented by the general formula (I) is preferably 110 mgKOH / g or less, and more preferably 105 mgKOH / g or less. The amine value refers to the number of milligrams of potassium hydroxide equivalent to the perchloric acid required to neutralize the amine components contained in 1 g of sample, and can be measured by the method defined in JIS-K 7237. When measured by this method, even if an amino group forms a salt with an organic acid compound in the dispersant, the organic acid compound usually dissociates, so the amine value of the block copolymer itself used as a dispersant can be measured.

[0137] The content (mol %) of each structural unit in the copolymer of the dispersant can be determined from the amount of raw materials charged during production, and can also be measured using an analytical device such as NMR. The structure of the dispersant can also be measured using NMR, various mass spectrometry, etc. Alternatively, the dispersant can be decomposed by pyrolysis or the like as needed, and the resulting decomposition products can be analyzed using high-performance liquid chromatography, gas chromatograph mass spectrometry, NMR, elemental analysis, XPS / ESCA, TOF-SIMS, etc.

[0138] In the photocurable green resin composition according to the present invention, the content of the dispersant is not particularly limited as long as it is selected so as to provide excellent dispersibility and dispersion stability of the colorant. For example, it is preferably in the range of 2% to 30% by mass, more preferably 3% to 25% by mass, based on the total solid content of the photocurable green resin composition. If the content is equal to or greater than the lower limit, the dispersibility and dispersion stability of the colorant are excellent, and the storage stability of the photocurable green resin composition is also excellent. Furthermore, if the content is equal to or less than the upper limit, the developability is good. In particular, when a cured film with a high colorant concentration is to be formed, the content of the dispersant is preferably in the range of 2% to 25% by mass, more preferably 3% to 20% by mass, based on the total solid content of the photocurable green resin composition.

[0139] <Thiol compounds> The photocurable green resin composition of the present invention preferably further contains a thiol compound from the viewpoint of improving solvent resistance and substrate adhesion after low-temperature heat treatment. The thiol compound may be a monofunctional thiol compound having one thiol group or a polyfunctional thiol compound having two or more thiol groups. From the viewpoint of suppressing line width shift and improving substrate adhesion, it is more preferable to use a monofunctional thiol compound having one thiol group. Examples of monofunctional thiol compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, and octyl 3-mercaptopropionate. Examples of polyfunctional thiol compounds include 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate). The thiol compounds may be used alone or in combination of two or more kinds. Among them, 2-mercaptobenzoxazole or 2-mercaptobenzothiazole is preferred from the viewpoint of improving solvent resistance and substrate adhesion after low-temperature heat treatment. The content of the thiol compound is usually 0.5% by mass to 10% by mass, preferably 1% by mass to 5% by mass, based on the total solid content of the photocurable green resin composition. If the content is equal to or greater than the lower limit, the solvent resistance and substrate adhesion after low-temperature heat treatment are likely to be improved. On the other hand, if the content is equal to or less than the upper limit, the photocurable green resin composition of the present invention is likely to have good developability and suppressed line width shift.

[0140] <Other ingredients> The photocurable green resin composition of the present invention may further contain various additives as needed, such as antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet absorbers, and adhesion promoters. Specific examples of surfactants and plasticizers include those described in JP-A-2013-029832.

[0141] The photocurable green resin composition of the present invention preferably further contains an antioxidant in order to suppress line width shifts in the cured film. For example, by including an antioxidant in combination with the compound represented by general formula (A), the photocurable green resin composition of the present invention can control excessive radical chain reactions without impairing curability when forming a cured film, thereby improving linearity when forming a fine line pattern and improving the ability to form a fine line pattern according to the designed mask line width. Furthermore, heat resistance can be improved, and brightness reduction after exposure and post-baking can be suppressed, thereby improving brightness. 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 hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and hydrazine-based antioxidants. Ma From the viewpoints of improving the ability to form a fine line pattern according to the designed line width and heat resistance, it is preferable to use a hindered phenol-based antioxidant, and a latent antioxidant such as that described in WO 2014 / 021023 may also be used.

[0142] Examples of hindered phenol-based antioxidants include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name :Examples of such products include 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris(4-hydroxy-3,5-di-tert-butylbenzyl)mesitylene (trade name: Irganox 1330, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (trade name: Sumilizer MDP-S, manufactured by Sumitomo Chemical), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), and 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester (trade name: Irgamod 195, manufactured by BASF). Among these, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name) is preferred from the viewpoint of heat resistance and light resistance. : IRGANOX1010 (manufactured by BASF) is preferred.

[0143] The content of the antioxidant is usually within a range of 0.1% by mass to 10.0% by mass, and preferably 0.5% by mass to 5.0% by mass, based on the total solid content of the photocurable green resin composition. If the content is equal to or greater than the lower limit, the ability to form a fine line pattern according to the designed mask line width is improved, and heat resistance is excellent. On the other hand, if the content is equal to or less than the upper limit, the photocurable green resin composition of the present invention is likely to be a highly sensitive photocurable green resin composition.

[0144] Examples of silane coupling agents include 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, and X-12-967C (manufactured by Shin-Etsu Silicones Co., Ltd.). Among these, KBM-502, KBM-503, KBE-502, KBE-503, and KBM-5103, which have methacrylic groups or acrylic groups, are preferred in terms of adhesion to SiN substrates.

[0145] The content of the silane coupling agent is usually within a range of 0.05% by mass to 10.0% by mass, and preferably 0.1% by mass to 5.0% by mass, based on the total solid content of the photocurable green resin composition. When the content is equal to or greater than the lower limit and equal to or less than the upper limit, the effect of improving substrate adhesion tends to be good.

[0146] <Method for producing photocurable green resin composition> In the method for producing the photocurable green resin composition of the present invention, the photocurable green resin composition can be prepared by mixing a colorant, a photopolymerizable compound, a photoinitiator, and various optional additive components using a known mixing means. When the photocurable green resin composition of the present invention contains a colorant, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, and various optional additives, methods for preparing the resin composition include, for example, (1) a method of first adding a colorant and a dispersant to a solvent to prepare a colorant dispersion, and then mixing the alkali-soluble resin, the photopolymerizable compound, the photoinitiator, and various optional additives with the dispersion; (2) a method of first adding a colorant, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various optional additives with a solvent to prepare a colorant dispersion; (3) a method in which a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various optional additive components are simultaneously added and mixed in a solvent, and then a colorant is added and dispersed; (4) a method in which a colorant, a dispersant, and an alkali-soluble resin are added in a solvent to prepare a colorant dispersion, and then an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, and various optional additive components are added to the dispersion, and then mixed; etc. Among these methods, the above methods (1) and (4) are preferred because they can effectively prevent aggregation of the coloring material and allow it to be dispersed uniformly.

[0147] The method for preparing the colorant dispersion liquid can be appropriately selected from conventionally known dispersion methods. For example, (1) a method in which a dispersant is mixed in a solvent and stirred to prepare a dispersant solution, and then an organic acid compound is added as needed to form a salt between the amino group of the dispersant and the organic acid compound, and then the resulting solution is mixed with a colorant and other components as needed, and dispersed using a known stirrer or disperser; (2) a method in which a dispersant is mixed in a solvent and stirred to prepare a dispersant solution, and then a colorant, an organic acid compound as needed, and other components as needed are added, and then dispersed using a known stirrer or disperser; (3) a method in which a dispersant is mixed in a solvent and stirred to prepare a dispersant solution, and then a dispersant is mixed in a solvent and stirred to prepare a dispersant solution. Made Then, a coloring material and, if necessary, other components are mixed, and a dispersion is prepared using a known stirrer or disperser, and an organic acid compound is added if necessary.

[0148] Examples of dispersing machines for carrying out the dispersion treatment include roll mills such as two-roll and three-roll mills, ball mills such as ball mills and vibration ball mills, paint conditioners, and bead mills such as continuous disk bead mills and continuous annular bead mills. As a preferred dispersion condition for the bead mill, the diameter of the beads used is preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.

[0149] <Application> The photocurable green resin composition according to the present invention is preferably used for forming a colored cured film that replaces a circular polarizing plate, since the cured film has an effect of suppressing external light reflection. When a cured film of the photocurable green resin composition according to the present invention is used in place of a circular polarizing plate, a display device that does not include a polarizing plate can be obtained, and therefore the photocurable green resin composition according to the present invention is preferably used for display devices that do not include a polarizing plate. Furthermore, the photocurable green resin composition according to the present invention is a photocurable green resin composition used for a cured film formed on an organic light-emitting element, and is therefore suitably used for display devices that do not include an external color filter substrate, and for thin-film organic light-emitting display devices with improved flexibility. Furthermore, by appropriately selecting the components as described above, the photocurable green resin composition of the present invention can form a cured film that has good solvent resistance and excellent substrate adhesion even when heated at a low temperature. Therefore, the photocurable green resin composition of the present invention can be suitably used for forming a cured film on a substrate on which a heat-resistant element has been formed by heating at a low temperature of 130°C or less, further 100°C or less, or 90°C or less.

[0150] II.Display device The display device according to the present invention is characterized by having a cured film of the photocurable green resin composition according to the present invention on an organic light-emitting element. In the display device of the present invention, a cured film of the photocurable green resin composition used in the cured film formed on the organic light-emitting element of the present invention is formed on the organic light-emitting element, and therefore an external circular polarizer or an external color filter substrate is not required, and the display device may not have these. In the display device according to the present invention, a cured film is formed on an organic light-emitting element using the photocurable green resin composition used in the cured film formed on the organic light-emitting element according to the present invention. Therefore, there is no substrate such as that used in an external color filter substrate between the organic light-emitting element and the cured film, and therefore the display device has improved thinning and flexibility.

[0151] An organic light-emitting display device including such an organic light-emitting element 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 display device including an organic light-emitting element according to the present invention. As shown in Fig. 1, a display device 100 according to the present invention includes an element substrate 30 including an organic light-emitting element, an external light antireflection film 20 including colored cured films (9R, 9G, 9B) on the element substrate 30, and a sealing film 11 thereon. The element substrate 30 equipped with the organic light-emitting elements has thin film transistors (TFTs) 2 serving as driving elements arranged on a substrate 1 so as to correspond to each subpixel, a sealing film 3 thereon, electrodes 4 (anodes) corresponding to each subpixel and partition walls 5 dividing each subpixel on the sealing film 3, organic light-emitting elements (6R, 6G, 6B) constituting subpixels of three colors R, G, and B are arranged within the divisions, and an electrode 7 (cathode) is further provided on the organic light-emitting elements (6R, 6G, 6B). The element substrate 30 equipped with the organic light-emitting elements further has a sealing layer 8 covering the organic light-emitting elements from above. On the sealing layer 8 on the organic EL elements (6R, 6G, 6B) in the element substrate 30, there is provided an external light antireflection film 20 including three colored cured films (9R, 9G, 9B) corresponding to each organic EL element formed using a photocurable colored resin composition and a light-shielding portion 10, and there is further provided a sealing film 11 thereon. The display device 100 according to the present invention shown in FIG. 1 further includes a cover material 13 on a sealing film 11 with a transparent adhesive layer 12 interposed therebetween. Although not shown, the display device 100 according to the present invention may further include, for example, a touch sensor layer consisting of an insulating film and a transparent electrode layer on the sealing film 11, and may further include a known configuration such as a hard coat layer on the touch sensor layer as appropriate. As described above, the layer of the colored cured film (9R, 9G, 9B) and the light-shielding portion 10 provided on the element substrate 30 including the organic light-emitting element is used as the external light antireflection film 20. Therefore, the external light antireflection film used in the present invention does not include a separate substrate such as an external circular polarizer or an external color filter substrate, and can be made thinner and more flexible.

[0152] In the display device according to the present invention, it is preferable to adjust the colors of the subpixels (6R, 6G, 6B) of the organic light-emitting element to be the same as the colors of the colored cured film (9R, 9G, 9B) directly above it via at least one layer such as the sealing layer 8. The colored cured film provided on this organic light-emitting element blocks external light except for the color originally emitted by the organic light-emitting element, while not blocking the light emitted by the organic light-emitting element, making it possible to suppress external light reflection without reducing light utilization efficiency. The cured film of the photocurable green resin composition according to the present invention may be the green cured film (9G) of the three colored cured films (9R, 9G, 9B).

[0153] The substrate 1, thin film transistor (TFT) 2 as a driving element, sealing film 3, electrode 4 (anode), partition wall 5 that separates each subpixel, organic light-emitting elements (6R, 6G, 6B) that constitute the subpixel, electrode 7 (cathode), and the like used in the display device according to the present invention can be appropriately selected from known configurations. The organic light-emitting element may have known configurations such as a hole injection layer, a hole transport layer, and an electron injection layer in addition to the light-emitting layer.

[0154] The sealing layer 8 on the organic EL element used in the display device according to the present invention is made of an inorganic film, an organic film, or a multilayer film formed by laminating them. It is preferable to use a multilayer film because it is highly effective in suppressing the penetration of moisture and oxygen. Specifically, examples include a metal film, a metal oxide film, and a multilayer film in which an inorganic film such as SiOx or SiNx and an organic film are laminated.

[0155] At least one of the colored cured films used in the display device according to the present invention is a cured film of the photocurable green resin composition according to the present invention. The colored cured film is usually formed in the opening of the light-shielding part (described later) on the sealing layer 8 on the organic light-emitting element, and usually has a colored pattern of three or more colors. These may be the same colored patterns as the subpixels (6R, 6G, 6B) of the organic light-emitting element. The arrangement of the colored cured films (9R, 9G, 9B) can be, for example, a common arrangement such as a stripe type, a mosaic type, a triangle type, a four-pixel arrangement type, etc. The width, area, etc. of the colored layer can be appropriately set so as to match the subpixels (6R, 6G, 6B) of the organic light-emitting element. The thickness of the colored cured film can be appropriately controlled by adjusting the coating method, the solids concentration and viscosity of the photocurable green resin composition, etc., but is usually in the range of 1 μm to 5 μm.

[0156] The light-shielding portion 10 used in the display device of the present invention is usually formed in a pattern on the sealing layer 8 above the organic light-emitting element, and can be similar to 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 stripe and matrix shapes. The light-shielding portion may be a thin metal film such as chromium 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, or organic pigments in a resin binder. In the case of a resin layer containing light-shielding particles, methods include patterning by development using a photosensitive resist, patterning using an inkjet ink containing light-shielding particles, and thermal transfer of a photosensitive resist.

[0157] The film thickness of the light-shielding portion is set to about 0.2 μm to 0.4 μm in the case of a metal thin film, and to about 0.5 μm to 2 μm in the case of a black pigment dispersed or dissolved in a binder resin.

[0158] The sealing film 11 provided on the colored cured films (9R, 9G, 9B) and the light-shielding portion 10 can be made of any known material. Also, known materials can be appropriately selected and used for the transparent adhesive layer 12 provided on the sealing film 11 and the cover material 13. In the present invention, even when glass is used as the cover material, the weather resistance of the green cured film is good and a decrease in transmittance is suppressed, so that glass can be used as the cover material.

[0159] The display device according to the present invention is not limited to the configuration shown in FIG. 1, and may further include the configuration of a display device equipped with a known organic light-emitting element.

[0160] III. Method for manufacturing a laminate of an organic light-emitting element and an external light anti-reflection film The method for producing a laminate of an organic light-emitting element and an external light antireflection film according to the present invention comprises the steps of: a step of forming a coating film by applying the photocurable green resin composition according to the present invention onto an organic light-emitting element; a step of irradiating the coating film with light; a post-baking step of heating the film after the light irradiation; and By including a step of developing the film after the light irradiation, The method includes a step of forming a cured film of the photocurable green resin composition according to the present invention on an organic light-emitting element. Each step will be explained below.

[0161] In the step of applying the photocurable green resin composition according to the present invention to an organic light-emitting element, the photocurable green resin composition does not have to be applied adjacent to the organic light-emitting element, but may be applied via at least one layer. As shown in Fig. 1, in an element substrate 30 equipped with an organic light-emitting element, an electrode 7 and a sealing layer 8 for suppressing the penetration of moisture and oxygen are usually further provided on the subpixels (6R, 6G, 6B) of the organic light-emitting element, so the photocurable green resin composition may be applied onto the organic light-emitting element via these electrodes and sealing layers.

[0162] For example, the light-shielding portion 10 may be provided in advance on the sealing layer 8 by a known method such as those exemplified above, and the colored cured films (9R, 9G, 9B) may be applied to the openings of the light-shielding portion 10 so as to be formed therein.

[0163] For example, the photocurable green resin composition of the present invention is applied onto the organic light-emitting element by a coating method such as spray coating, dip coating, bar coating, roll coating, spin coating, die coating, etc. Of these, spin coating and die coating are preferably used as the coating method. Next, the wet coating film is dried using a hot plate, an oven, or the like to form a coating film.

[0164] The resulting coating film is irradiated (exposed) with light through a mask having a predetermined pattern to photopolymerize the photopolymerizable compound and, if necessary, the alkali-soluble resin, etc. Examples of light sources used for exposure include ultraviolet light from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, electron beams, etc. The exposure dose is adjusted appropriately depending on the light source used, the thickness of the coating film, etc.

[0165] Next, in order to promote the polymerization reaction after the exposure, a post-baking step of heating the film after the light exposure may be performed. The heating conditions may be appropriately selected depending on the blending ratio of each component in the photocurable green resin composition used, the thickness of the coating film, etc. The post-baking step may be performed on the film after the light irradiation before the development step described below, after the development step, or before or after the development step.

[0166] In the present invention, since a colored cured film is formed directly on an element substrate equipped with an organic light-emitting element, the heating temperature in the post-baking step is preferably 130° C. or lower. The heating temperature is more preferably 100° C. or lower, and even more preferably 90° C. or lower. The heating temperature may also be 30° C. or higher, 35° C. or higher, or 40° C. or higher.

[0167] Next, the film after the light irradiation is developed. The film after the light irradiation to be developed may be a film after post-baking. In the development step, the coating is developed using a developer to dissolve and remove the unexposed portions, thereby forming a coating film in a desired pattern. The developer is usually a solution in which an alkali is dissolved in water or a water-soluble solvent. A suitable amount of a surfactant or the like may be added to this alkaline solution. A conventional development method can be used.

[0168] After the development treatment, the developer is usually washed away and the cured film of the photocurable green resin composition is dried to form a colored cured film. After the development treatment, a heat treatment may be carried out to sufficiently cure the coating film. In the present invention, since a colored cured film is formed directly on an element substrate equipped with an organic light-emitting element, the heating temperature in this post-baking step is also preferably 130° C. or lower, more preferably 100° C. or lower, and even more preferably 90° C. or lower. The heating temperature may be 30° C. or higher, 35° C. or higher, or 40° C. or higher.

[0169] In addition, in order to further harden the film after development or post-baking, additional light irradiation (exposure) may be performed. [Example]

[0170] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The mass average molecular weight (Mw) of the copolymer before salt formation was determined as a standard polystyrene equivalent value by GPC (gel permeation chromatography) according to the measurement method described in the above specification of the present invention.

[0171] (Synthesis Example 1: Synthesis of Block Copolymer 1) A 500 mL round-bottom, four-neck separable flask equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 250 parts by mass of THF and 0.6 parts by mass of lithium chloride, and the atmosphere was thoroughly purged with nitrogen. After cooling the reaction flask to -60°C, 4.9 parts by mass of butyllithium (15% by mass in hexane), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isobutyrate were added using a syringe. The B block monomers, 2.2 parts by weight of 1-ethoxyethyl methacrylate (EEMA), 29.1 parts by weight of 2-(trimethylsilyloxy)ethyl methacrylate (TMSMA), 12.8 parts by weight of 2-ethylhexyl methacrylate (EHMA), 13.7 parts by weight of n-butyl methacrylate (BMA), 9.5 parts by weight of benzyl methacrylate (BzMA), and 17.5 parts by weight of methyl methacrylate (MMA), were added dropwise over 60 minutes using an addition funnel. After 30 minutes, 26.7 parts by weight of the A block monomer, dimethylaminoethyl methacrylate (DMMA), was added dropwise over 20 minutes. After 30 minutes of reaction, 1.5 parts by weight of methanol was added to terminate the reaction. The resulting precursor block copolymer THF solution was reprecipitated in hexane, filtered, purified by vacuum drying, and diluted with PGMEA to obtain a 30% solids solution. 32.5 parts by mass of water was added, the temperature was raised to 100°C, and the reaction was carried out for 7 hours. The EEMA-derived structural units were deprotected to form structural units derived from methacrylic acid (MAA), and the TMSMA-derived structural units were deprotected to form structural units derived from 2-hydroxyethyl methacrylate (HEMA). The resulting block copolymer PGMEA solution was reprecipitated in hexane, filtered, and purified by vacuum drying to obtain block copolymer 1 (amine value 95 mg KOH / g, acid value 8 mg KOH / g, Tg 38°C) containing structural units represented by the general formula (I). quality The weight average molecular weight Mw was 7,730.

[0172] (Synthesis Example 2: Synthesis of oxime ester photoinitiator represented by formula (A-2)) The oxime ester photoinitiator represented by the formula (A-2) was synthesized in the same manner as in the production of compound No. 73 in paragraphs 0114 to 0117 of WO 2015 / 152153.

[0173] (Preparation Example 1: Preparation of Alkali-Soluble Resin A) A polymerization vessel was charged with 300 parts by mass of PGMEA and heated to 100°C under a nitrogen atmosphere, after which 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 Perbutyl O (NOF Corporation), and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. The reaction was then continued while maintaining the temperature at 100°C, and 2 hours after the completion of the dropwise addition of the main chain formation mixture, 0.1 parts by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization. Next, while blowing air into the mixture, 20 parts by mass of glycidyl methacrylate (GMA) was added as an epoxy group-containing compound, and the mixture was heated to 110°C. After that, 0.8 parts by mass of triethylamine was added and subjected to an addition reaction at 110°C for 15 hours to obtain an alkali-soluble resin A solution ( quality The weight-average molecular weight (Mw) was 8,500, the acid value was 75 mg KOH / g, and the solid content was 40% by mass. In addition, the above quality The weight average molecular weight was measured using a Shodex GPC System-21H with polystyrene as the standard substance and THF as the eluent. quality The weight average molecular weight was measured, and the acid value was measured according to JIS K 0070.

[0174] Example 1: Preparation of photocurable green resin composition G-1 (1) Preparation of colorant dispersion B(1) A 225 mL mayonnaise bottle was charged with 64.9 parts by mass of PGMEA, 13.5 parts by mass of the alkali-soluble resin A solution (solid content 40% by mass) from Preparation Example 1, and 9.2 parts by mass of the PGMEA solution (solid content 35% by mass) of block copolymer 1 from Synthesis Example 1, and stirred. 0.39 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Industries, Ltd.) was added thereto, and the mixture was stirred at room temperature for 30 minutes. To this was added 12.0 parts by mass of CI Pigment Blue 15:4 (B15:4) as a blue pigment and 100 parts by mass of zirconia beads with a particle size of 2.0 mm, and the mixture was shaken for 1 hour in a paint shaker (manufactured by Asada Iron Works) as a preliminary crushing. Then, the mixture was changed to 200 parts of zirconia beads with a particle size of 0.1 mm, and the mixture was dispersed for 4 hours in a paint shaker as a main crushing, to obtain colorant dispersion B(1). Note that block copolymer 1 was salt-formed with phenylphosphonic acid to form salt-type block copolymer 1.

[0175] (2) Preparation of colorant dispersion Y(1) A colorant dispersion Y(1) was obtained in the same manner as in the production of colorant dispersion B(1), except that CI Pigment Blue 15:4 (B15:4) was changed to CI Pigment Yellow 139 (Y139).

[0176] (3) Preparation of colorant dispersion Y(2) A colorant dispersion Y(2) was obtained in the same manner as in the production of colorant dispersion B(1), except that CI Pigment Blue 15:4 (B15:4) was changed to CI Pigment Yellow 150 (Y150).

[0177] (4) Preparation of colorant dispersion Y (3) A colorant dispersion Y(3) was obtained in the same manner as in the production of colorant dispersion B(1), except that CI Pigment Blue 15:4 (B15:4) was changed to CI Pigment Yellow 138 (Y138).

[0178] (5) Preparation of Photocurable Green Resin Composition G-1 A photocurable green resin composition G-1 was obtained by adding 6.4 parts by mass of the colorant dispersion B(1) obtained above, 5.2 parts by mass of the colorant dispersion Y(1), 9.0 parts by mass of the colorant dispersion Y(2), 15.0 parts by mass of the colorant dispersion 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 Aronix M-305, manufactured by Toagosei Co., Ltd.), 0.5 parts by mass of the oxime ester photoinitiator represented by the formula (A-2), 0.03 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), and 54.6 parts by mass of PGMEA.

[0179] Examples 2 to 5: Production of Photocurable Green Resin Compositions G-2 to G-5 In Example 1, the types and / or mass ratios of the blue pigment, yellow pigment, and green pigment were changed as shown in Table 1, and the ratios of the alkali-soluble resin A solution, the polyfunctional monomer, and the oxime ester photoinitiator represented by formula (A-2) were kept the same as in Example 1. Except for this, the pigment concentrations were changed to the values ​​shown in Table 1. Photocurable green resin compositions G-2 to G-5 were obtained in the same manner as in Example 1 for photocurable green resin composition G-1. The colorant dispersions of CI Pigment Blue 15:6 (B15:6), CI Pigment Green 59 (G59), and CI Pigment Green 7 (G7) were obtained as colorant dispersions B(2), G(1), and G(2), respectively, in the same manner as in the production of colorant dispersion B(1), except that CI Pigment Blue 15:4 (B15:4) was changed to CI Pigment Blue 15:6 (B15:6), G(59), or G(2).

[0180] Comparative Examples 1 and 2: Preparation of Comparative Photocurable Green Resin Compositions CG-1 and CG-2 Comparative photocurable green resin compositions CG-1 to CG-2 were obtained in the same manner as in photocurable green resin composition G-4 or G-5, except that in Examples 4 and 5, the green pigment (halogenated phthalocyanine pigment) was used in an amount exceeding 10 mass% of the total amount of coloring materials, as shown in Table 1.

[0181] Comparative Examples 3 and 4: Preparation of Comparative Photocurable Green Resin Compositions CG-3 and CG-4 Comparative photocurable green resin compositions CG-3 to CG-4 were obtained in the same manner as photocurable green resin composition G-1, except that in Example 1, the types and / or mass ratio of the blue pigment and the yellow pigment, and the type of initiator (Irgacure 907 (907, manufactured by BASF) and Kayacure DETX-S (DETX, manufactured by Nippon Kayaku) in a mass ratio of 2:1) were changed to be similar to Examples 1 and 2 of Patent Document 2 (JP 2011-242568 A), as shown in Table 1, and the amounts of components other than the pigments were changed to achieve the pigment concentrations shown in Table 1. The colorant dispersion liquid of CI Pigment Blue 16 (B16) or CI Pigment Blue 15:3 (B15:3) was obtained as colorant dispersion liquid B(3) or colorant dispersion liquid B(4) in the same manner as in the production of colorant dispersion liquid B(1), except that CI Pigment Blue 15:4 (B15:4) was changed to CI Pigment Blue 16 (B16) or CI Pigment Blue 15:3 (B15:3).

[0182] Comparative Examples 5 to 7: Preparation of Comparative Photocurable Green Resin Compositions CG-5 to CG-7 In Example 1, as shown in Table 1, the types and / or mass ratios of the blue pigment and yellow pigment, and the type of initiator (Irgacure OXE02 (OXE02, manufactured by BASF)) were changed to be similar to Examples 2, 5, and 1 of Patent Document 3 (WO 2020 / 196393), and the amounts of components other than the pigments were changed to achieve the pigment concentrations shown in Table 1. Comparative photocurable green resin compositions CG-5 to CG-7 were obtained in the same manner as photocurable green resin composition G-1.

[0183] Comparative Example 8: Preparation of Comparative Photocurable Green Resin Composition CG-8 In Example 1, as shown in Table 1, the types and / or mass ratios of the yellow pigment, green pigment, and black pigment were changed to the same as in Example 1 of Patent Document 1 (JP 2017-182067 A), the types of initiator (Irgacure 907 (907, manufactured by BASF) and Irgacure OXE01 (OXE01, manufactured by BASF)) and the amounts of components other than the pigments were changed to the pigment concentrations shown in Table 1. A comparative photocurable green resin composition CG-8 was obtained in the same manner as in Photocurable Green Resin Composition G-1. A colorant dispersion of black pigment (carbon black) was obtained as colorant dispersion BK(1) in the same manner as in the production of colorant dispersion B(1), except that CI Pigment Blue 15:4 (B15:4) was changed to carbon black (MA77, manufactured by Mitsubishi Chemical Corporation).

[0184] [Evaluation method] The photocurable green resin compositions obtained in each Example and Comparative Example were applied to a glass substrate ("NA35" manufactured by NH Technoglass Co., Ltd.) using a spin coater so that the final cured film would be 3.0 μm thick, and then dried on a hot plate at 80°C for 3 minutes to form a coating film on the substrate. This coating film was then irradiated with 70 mJ / cm using an ultra-high pressure mercury lamp through a photomask (chrome mask) having a pattern with openings of 2 μm to 100 μm in size for forming isolated fine lines. 2 The coated film was exposed to ultraviolet light at 1000 Wt. Hz to form a post-exposure coating film. The film was then spin-developed using a 0.05 wt. % potassium hydroxide aqueous solution as the developer, and developed by immersing the film in the developer for 60 seconds and then rinsing with pure water, yielding a coating film with a pattern of independent fine lines. This was then post-baked in a clean oven at 90°C for 30 minutes to form a cured film with a pattern of independent fine lines (green cured film). The cured films thus obtained were subjected to transmittance measurement, weather resistance evaluation, solvent resistance evaluation, and external light reflection suppression evaluation.

[0185] <Transmittance> The transmission spectrum of the cured film from 380 nm to 780 nm was measured using a microspectrophotometer (OSP-SP200, manufactured by Olympus), and the half-value width was calculated by calculating the maximum transmittance from 380 nm to 480 nm, the maximum and minimum transmittances from 510 nm to 550 nm, and the maximum transmittance from 580 nm to 700 nm, as well as the difference between the wavelengths at two points where the transmittance was half the maximum transmittance at the peak showing the maximum transmittance in the wavelength range of 380 nm to 700 nm.

[0186] <Weather resistance evaluation> A sample was prepared by attaching a glass substrate to the cured film formed on the glass substrate via a transparent adhesive layer. The sample was then subjected to a weathering test using a weathering tester (ATLAS Ci4000) with a light intensity of 0.63 W / m at 340 nm. 2 A weather resistance test was carried out for 48 hours under the conditions of a temperature inside the chamber of 60°C and a humidity of 50%RH. For each cured film for weather resistance evaluation before and after the weather resistance test, the chromaticity (L0, a0, b0) before the weather resistance test and the chromaticity (L1, a1, b1) after the weather resistance test were measured using an Olympus microspectrophotometer OSP-SP200. The change in chromaticity of the cured film before and after the weather resistance test was evaluated using the following formula. The results are shown in the table. ΔEab={(L1-L0)2+(a1-a0)2+(b1-b0) 2} 1 / 2 The smaller the ΔEab value, the more excellent the heat resistance is evaluated to be. (Evaluation criteria for weather resistance evaluation) A: ΔEab value is less than 3 B: ΔEab value is 3 or more and less than 5 C: ΔEab value is 5 or more If the evaluation result is B, the weather resistance is good, and if the evaluation result is A, the weather resistance is excellent.

[0187] <Solvent resistance (PGME resistance) evaluation> The thickness of the resulting cured film was measured, then immersed in propylene glycol monomethyl ether (PGME) for 10 minutes, air-dried, and the thickness was measured again. A stylus-type step film thickness meter "P-15 Tencor" (manufactured by Instruments) was used for film thickness measurement. The remaining film ratio was calculated by multiplying the film thickness after solvent immersion by the film thickness before solvent immersion × 100. (Evaluation criteria for solvent resistance) A: Remaining film rate after solvent immersion is 98% or more B: The remaining film rate after solvent immersion is 96% or more but less than 98% C: Remaining film rate after solvent immersion is 94% or more but less than 96% D: The remaining film rate after solvent immersion is less than 94% If the evaluation result is B, the solvent resistance is good, and if the evaluation result is A, the solvent resistance is excellent.

[0188] <External light reflection suppression evaluation of green cured film> (Luminance Y) The transmission spectrum of the resulting cured film from 380 nm to 780 nm was measured using a microspectrophotometer (OSP-SP200, manufactured by Olympus), the luminance Y was measured, and the transmittance of the green cured film was evaluated. (reflectance) When the transmittance of the obtained cured film at each wavelength from 380 nm to 780 nm is T(CF), the reflectance of the glass substrate is 50%, and the visual color matching function is y, the reflectance Rn at each wavelength was calculated by Rn = T(CF) × 0.5 × T(CF) × y, and the value obtained by integrating Rn at each wavelength was defined as the reflectance of the green cured film at 380 nm to 780 nm. If the brightness Y is 32 or more and the reflectance is less than 9%, the green cured film has high transmittance and low reflectance, and is judged to have a good effect of suppressing external light reflection.

[0189] [Table 1]

[0190] [Summary of results] In Comparative Examples 1 and 2, in which the green pigment (halogenated phthalocyanine pigment) was used in an amount exceeding 10% by mass of the total colorant, the spectral transmittance was 20% or less in the wavelength range of 380 to 480 nm, 30% or less in the wavelength range of 580 to 700 nm, and 40% to 80% in the wavelength range of 510 to 550 nm. However, the reflectance was low but the transmittance was also low, or the transmittance was high but the reflectance was also high, indicating a poor effect of suppressing external light reflection. Furthermore, the cured films of Comparative Examples 1 and 2 also had poor weather resistance. Comparative Examples 3 and 4, which used the same types and / or mass ratios of blue and yellow pigments as in Examples 1 and 2 of Patent Document 2 (JP 2011-242568 A), did not satisfy the specified spectral transmittance in the specified wavelength range, and either had low reflectance but low transmittance, or high reflectance but low transmittance, indicating poor external light reflection suppression effect. Furthermore, the cured films of Comparative Examples 3 and 4 also had poor solvent resistance. Furthermore, Comparative Examples 5, 6, and 7, which used the same types and / or mass ratios of blue and yellow pigments as Examples 2, 5, and 1 of Patent Document 3 (WO 2020 / 196393), also failed to meet the specified spectral transmittance in the specified wavelength range, resulting in low reflectance and low transmittance, and poor external light reflection suppression. Furthermore, the cured films of Comparative Examples 5 to 7 also had poor solvent resistance. Furthermore, the cured film of Comparative Example 8, in which the types and / or mass ratios of yellow, green, and black pigments and the type of initiator were changed to those of Example 1 of Patent Document 1 (JP 2017-182067 A), had high transmittance but also high reflectance, indicating a poor effect in suppressing external light reflection. The cured film of Comparative Example 8 also had poor weather resistance and solvent resistance. In contrast, in Examples 1 to 5, which are photocurable green resin compositions according to the present invention, cured films were formed by post-baking at a low temperature (90°C), which is preferable for forming on organic light-emitting devices. When a cured film with a thickness of 3.0 μm was formed, the spectral transmittance in the wavelength range of 380 nm to 480 nm was 20% or less, the spectral transmittance in the wavelength range of 580 nm to 700 nm was 30% or less, and the spectral transmittance in the wavelength range of 510 nm to 550 nm was 40% or more and 80% or less. This revealed high transmittance and low reflectance, and good external light reflection suppression effect. Furthermore, it was demonstrated that a cured film with excellent weather resistance and good solvent resistance could be formed even when bonded to glass via a transparent adhesive layer, even after low-temperature heat treatment. Therefore, it was demonstrated that the photocurable green resin composition according to the present invention is suitable for use in a cured film formed on an organic light-emitting device, and the cured film is thin and capable of suppressing external light reflection, making it possible to produce an organic light-emitting display device with improved flexibility. [Explanation of symbols]

[0191] 1 board 2 Thin-film transistor (TFT) 3. Sealing film 4 electrodes 5 Bulkhead 6R, 6G, 6B organic light-emitting elements 7 electrodes 8 Sealing Layer 9R, 9G, 9B colored cured film 10 Light blocking section 11 Sealing film 12 Transparent adhesive layer 13 Cover material 20. Anti-reflection coating for external light 30 Element substrate equipped with organic light-emitting element 100 display device

Claims

1. A photocurable green resin composition used for a cured film formed on an organic light-emitting device, comprising: the photocurable green resin composition contains a colorant, a photopolymerizable compound, and a photoinitiator; the coloring material contains a blue pigment and a yellow pigment, and the halogenated metal phthalocyanine pigment is contained in an amount of 10 mass % or less based on the total amount of the coloring material; The yellow pigment includes C.I. Pigment Yellow 139 and further includes 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, and the content of the yellow pigment is 50% by mass or more based on the total amount of coloring materials, A photocurable green resin composition which, when formed into a cured film having a film thickness of 3.0 μm, has a spectral transmittance of 20% or less in a wavelength range of 380 nm to 480 nm, a spectral transmittance of 30% or less in a wavelength range of 580 nm to 700 nm, and a spectral transmittance of 45% or more and 80% or less in a wavelength range of 510 nm to 550 nm.

2. 2. The photocurable 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.

3. 3. The photocurable green resin composition according to claim 1, wherein the photoinitiator comprises at least one compound represented by the following general formula (A): 【Chemistry 1】 (In the formula, R １ and R ２ are each independently R １１ , OR １１ , C.O.R. １１ , S.R. １１ , C.O.R. １２ R １３ or CN, R １１ , R １２ and R １３ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms; R １１ , R １２ and R １３ The hydrogen atoms of the group represented by ２１ , OR ２１ , C.O.R. ２１ , S.R. ２１ , N.R. ２２ R ２３ , C.O.R. ２２ R ２３ , -NR ２２ -OR ２３ , -NCOR ２２ -OCOR ２３ , N.R. ２２ COR ２１ , O.C.O.R. ２１ , COOR ２１ , SCOR ２１ , OCSR ２１ , COSR ２１ , CSR ２１ , optionally substituted with a hydroxyl group, a nitro group, CN, or a halogen atom; R ２１ , R ２２ and R ２３ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms; R ２１ , R ２２ and R ２３ A hydrogen atom of the group represented by the formula (I) may be further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, or a carboxy group, R １１ , R １２ , R １３ , R ２１ , R ２２ and R ２３ The alkylene portion of the group represented by the formula: ２４ -, -NR ２４ CO-, -NR ２４ COO-,-OCONR ２４ may contain 1 to 5 -, -SCO-, -COS-, -OCS- or -CSO-, provided that the oxygen atoms are not adjacent to each other; 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 arylalkyl 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 ２４ The alkyl portion of the group represented by the formula (I) may have a branched side chain or may be a cyclic alkyl, 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 arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms; R ３ The alkyl portion of the group represented by R may have a branched side chain or may be a cyclic alkyl. ３ and R ７ , and R ３ and R ８ may be joined together to form a ring, R ３ The hydrogen atoms of the group represented by ２１ , OR ２１ , C.O.R. ２１ , S.R. ２１ , N.R. ２２ R ２３ , C.O.R. ２２ R ２３ , -NR ２２ -OR ２３ , -NCOR ２２ -OCOR ２３ , N.R. ２２ COR ２１ , O.C.O.R. ２１ , COOR ２１ , SCOR ２１ , OCSR ２１ , COSR ２１ , CSR ２１ , optionally substituted with a hydroxyl group, a nitro group, CN, or a halogen atom; R ４ , R ５ , R ６ and R ７ are each independently R １１ , OR １１ , S.R. １１ , C.O.R. １４ , C.O.R. １５ R １６ , N.R. １２ COR １１ , O.C.O.R. １１ , COOR １４ , SCOR １１ , OCSR １１ , COSR １４ , CSR １１ , a hydroxyl group, CN or a halogen atom; R ４ and R ５ , R ５ and R ６ , and R ６ and R ７ may be joined together to form a ring, R １４ , R １５ and R １６ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R １４ , R １５ and R １６ The alkyl portion of the group represented by R may have a branched side chain or may be a cyclic alkyl, ８ is R １１ , OR １１ , S.R. １１ , C.O.R. １１ , C.O.R. １２ R １３ , N.R. １２ COR １１ , O.C.O.R. １１ , COOR １１ , SCOR １１ , OCSR １１ , COSR １１ , CSR １１ , a hydroxyl group, CN or a halogen atom; k represents 0 or 1.

4. 4. The photocurable green resin composition according to claim 1, wherein, when a cured film having a thickness of 3.0 μm is formed, the half-value width of a peak exhibiting maximum transmittance in a wavelength range of 380 nm to 700 nm in a transmission spectrum is 70 nm or less.

5. 5. The photocurable green resin composition according to claim 1, wherein, when a cured film having a thickness of 3.0 μm is formed, the wavelength at which the maximum transmittance is exhibited within a wavelength range of 380 nm to 700 nm in the transmission spectrum is within a range of 525 nm to 545 nm.

6. A photocurable green resin composition according to any one of claims 1 to 5, further comprising a (meth)acrylate copolymer-based dispersant as a dispersant.

7. The photocurable green resin composition according to any one of claims 1 to 6, further comprising, as a dispersant, a block copolymer containing an A block including a constituent unit represented by the following general formula (I) and a B block including a constituent unit derived from a carboxy group-containing monomer and a constituent unit derived from a (meth)acrylate, and at least one salt-type block copolymer in which at least a portion of the nitrogen moieties of the constituent unit represented by the following general formula (I) of the block copolymer form a salt with at least one member selected from the group consisting of organic acid compounds and halogenated hydrocarbons, wherein the block copolymer and at least one of the salt-type block copolymers have an acid value of 1 mgKOH / g to 18 mgKOH / g and a glass transition temperature of 30°C or higher. 【Chemistry 2】 (In general formula (I), R 71 represents a hydrogen atom or a methyl group, A 1 represents a divalent linking group, R 72 and R 73 each independently represent a hydrogen atom or a hydrocarbon group which may contain a heteroatom, and R 72 and R 73 may be bonded to each other to form a ring structure.)

8. A display device having a cured film of the photocurable green resin composition according to any one of claims 1 to 7 on an organic light-emitting element.

9. A step of forming a coating film by applying the photocurable green resin composition according to any one of claims 1 to 7 onto an organic light-emitting element; a step of irradiating the coating film with light; a post-baking step of heating the film after the light irradiation; and By including a step of developing the film after the light irradiation, A method for producing a laminate of an organic light-emitting element and an external light antireflection film, comprising a step of forming a cured film of the photocurable green resin composition according to any one of claims 1 to 7 on an organic light-emitting element.

10. The method for producing a laminate of an organic light-emitting element and an external light antireflection film according to claim 9 , wherein the heating temperature in the post-baking step is 130° C. or less.

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