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

Abstract

This photosensitive colored resin composition is used for a cured film that is formed on an organic light-emitting element. The photosensitive colored resin composition contains a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent. The coloring material includes a first coloring material having a maximum absorption wavelength of 480-520 nm and a second coloring material having a maximum absorption wavelength of 560-600 nm. The transmittances at 460 nm, 530 nm, and 620 nm of the cured film with a thickness of 3.0 μm formed using the photosensitive colored resin composition are all 45-85%, the transmittance at a transmission minimum wavelength of 480-520 nm is 50% or less, and the transmittance at a transmission minimum wavelength of 560-600 nm is 25% or less.

Description

Photosensitive colored resin composition, display device, and method for manufacturing laminate of organic light-emitting element and external light anti-reflection film

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

[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 response to this, efforts have been made to suppress external light reflection by forming color filters, which can replace polarizing plates, directly on the organic light-emitting element substrate (for example, Patent Document 1). However, if three color filter layers, which can replace polarizing plates, are formed corresponding to the RGB of the organic light-emitting element, the number of steps increases, resulting in an increase in manufacturing costs.

[0005] A known technology uses a colored layer that absorbs specific wavelengths instead of a color filter, which can replace a polarizing plate, to improve color purity in the display area and suppress degradation of display quality due to external light reflection (Patent Document 2). Patent Document 2 discloses a colored layer-forming composition containing an active energy ray-curable resin, a photopolymerization initiator, a dye, and a solvent, wherein the dye comprises a first coloring material having a maximum absorption wavelength in the range of 470 nm to 530 nm and a half-width of an absorption spectrum of 15 nm to 45 nm, a second coloring material having a maximum absorption wavelength in the range of 560 nm to 620 nm and a half-width of an absorption spectrum of 15 nm to 55 nm, and a third coloring material having a wavelength of 400 to 780 nm with the lowest transmittance in the range of 650 nm to 780 nm, and the colored layer-forming composition has a thickness of 5 μm formed on the second surface side of a transparent substrate having one or more functional layers formed on the first surface side, and the colored layer-forming composition has hue values ​​a* and b* defined by specific formulas each in the range of −5 to +5.

[0006] JP 2017-173828 A JP 2022-140434 A

[0007] Using a colored layer that absorbs specific wavelengths to improve color purity in the display area and suppress degradation of display quality due to external light reflection can reduce the number of manufacturing steps for an organic light-emitting element panel that suppresses external light reflection and lower manufacturing costs compared to forming a three-color color filter layer instead of a polarizing plate. As methods for manufacturing organic light-emitting element panels, a manufacturing method in which a colored layer that absorbs specific wavelengths is patterned panel by panel from a large substrate, and a manufacturing method in which a colored layer that absorbs specific wavelengths is patterned pixel by pixel corresponding to the RGB of the organic light-emitting element are considered to be efficient and preferable. Therefore, compositions for forming colored layers that absorb specific wavelengths are required to be designed to enable pattern formation. However, the colored layer in Patent Document 2 is designed to be incapable of being patterned.

[0008] The present invention has been made in view of the above-mentioned circumstances, and aims to provide a photosensitive colored resin composition that can be patterned to form a colored cured film that suppresses external light reflection and improves the display quality of an organic light-emitting device. The present invention also aims to provide a display device containing a colored cured film of the photosensitive colored resin composition, and a method for producing a laminate of an organic light-emitting device and an external light anti-reflection film using the photosensitive colored resin composition.

[0009] That is, the present invention relates to the following [1] to

[10] . [1] A photosensitive colored resin composition used for a cured film formed on an organic light-emitting device, comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, wherein the colorant comprises a first colorant having a maximum absorption wavelength of 480 nm to 520 nm and a second colorant having a maximum absorption wavelength of 560 nm to 600 nm, and wherein a 3.0 μm-thick cured film formed using the photosensitive colored resin composition has transmittances of 45% to 85% at 460 nm, 530 nm, and 620 nm, transmittances of 50% or less at a minimum transmission wavelength of 480 nm to 520 nm, and transmittances of 25% or less at a minimum transmission wavelength of 560 nm to 600 nm. [2] The colorant further comprises a third colorant selected from C.I. The photosensitive colored resin composition according to [1], which contains at least one green pigment selected from the group consisting of Citral Pigment Green 7, 36, 58, and 59. [3] The photosensitive colored resin composition according to [1] or [2], wherein the colorant further contains a fourth colorant having a maximum absorption wavelength of 370 nm to 450 nm. [4] The photosensitive colored resin composition according to any one of [1] to [3], wherein the photoinitiator contains at least one of a compound represented by the following general formula (A) and a compound represented by the following general formula (B):

[0010] (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 １２and 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 , 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 The hydrogen atom of the group represented by R may be further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, or a carboxy group, 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 ２４may contain 1 to 5 oxygen atoms of -, -SCO-, -COS-, -OCS- or -CSO-, provided that the oxygen atoms are not adjacent to each other; 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 R may have a branched side chain or may be a cyclic alkyl, 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 , 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 , C.O.R. １５ R １６ , N.R. １２ COR １１ , O.C.O.R. 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 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 , CSOR １１ , a hydroxyl group, CN or a halogen atom, and k represents 0 or 1.

[0011] (In formula (B), X １ , X ３ and X ６ are each independently R ４１ , OR ４１ , C.O.R. ４１ , S.R. ４１ , C.O.R. ４２ R ４３or CN, and X ２ represents 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; X ４ and X ５ are each independently R ４１ , OR ４１ , S.R. ４１ , C.O.R. ４１ , C.O.R. ４２ R ４３ , N.R. ４２ COR ４１ , O.C.O.R. ４１ , COOR ４１ , SCOR ４１ , OCSR ４１ , COSR ４１ , CSOR ４１ , CN, a halogen atom or a hydroxyl group. ４１ , R ４２ and R ４３ 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 ４１ , R ４２ and R ４３ , and X ２ The hydrogen atoms of the group represented by ５１ , OR ５１ , C.O.R. ５１ , S.R. ５１ , N.R. ５２ R ５３ , C.O.R. ５２ R ５３ , -NR ５２ -OR ５３ , -NCOR ５２ -OCOR ５３ , N.R. ５２ COR ５１ , O.C.O.R. ５１ , COOR ５１ , SCOR ５１ , OCSR ５１ , COSR ５１ , CSOR ５１ , optionally substituted with a hydroxyl group, a nitro group, CN, or a halogen atom, R ５１ , R ５２ and R ５３each 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 ５１ , R ５２ and R ５３ The hydrogen atom of the group represented by R may be further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, or a carboxy group, ４１ , R ４２ , R ４３ , X ２ , R ５１ , R ５２ and R ５３ The alkylene portion of the group represented by the formula: ５４ -, -NR ５４ CO-, -NR ５４ COO-,-OCONR ５４ may contain 1 to 5 oxygen atoms of -, -SCO-, -COS-, -OCS- or -CSO-, provided that the oxygen atoms are not adjacent to each other; ５４ 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 ４１ , R ４２ , R ４３ , R ５１ , R ５２ , R ５３ and R ５４ The alkyl portion of the group represented by the formula (I) may have a branched side chain or may be a cyclic alkyl. a and b are each independently an integer of 0 to 3.

[0012] [5] The photosensitive colored resin composition according to any one of [1] to [4], wherein the alkali-soluble resin has an ethylenically unsaturated bond equivalent of 500 or less and an acid value of 30 mgKOH / g to 90 mgKOH / g. [6] The photosensitive colored resin composition according to any one of [1] to [5], wherein the photopolymerizable compound comprises a mixture of glycerin diacrylate and glycerin triacrylate. [7] The photosensitive colored resin composition according to any one of [1] to [6], further comprising at least one inorganic particle having an average particle size of 100 nm or less selected from the group consisting of zirconium oxide, barium titanate, and titanium oxide, and a dispersant, wherein the dispersant comprises at least one dispersant selected from the group consisting of a phosphate ester dispersant, a phosphonic acid dispersant, and a phosphonic acid ester dispersant, and wherein the photoinitiator comprises an oxime photoinitiator. [8] A display device having, on an organic light-emitting element, a cured film of the photosensitive colored resin composition described in any one of [1] to [7] above. [9] A method for producing a laminate of an organic light-emitting element and an external light antireflection film, the method comprising the steps of forming a cured film of the photosensitive colored resin composition described in any one of [1] to [7] above on an organic light-emitting element by applying the photosensitive colored resin composition described in any one of [1] to [7] above to form a coating film, irradiating the coating film with light, post-baking the film after light irradiation, and developing the film after light irradiation.

[10] A method for producing a laminate of an organic light-emitting element and an external light antireflection film described in [9] above, in which the heating temperature in the post-baking step is 130°C or less.

[0013] According to the present invention, it is possible to provide a photosensitive colored resin composition that can be patterned to form a colored cured film that suppresses external light reflection and improves the display quality of an organic light-emitting device. The present invention also provides a display device containing a colored cured film of the photosensitive colored resin composition, and a method for producing a laminate of an organic light-emitting device and an external light anti-reflection film using the photosensitive colored resin composition.

[0014] 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, and Fig. 2 is a schematic cross-sectional view showing another example of a display device including an organic light-emitting element according to the present invention.

[0015] Hereinafter, embodiments and examples of the present invention will be described with reference to the drawings. However, the present invention can be embodied in many different forms, and should not be construed as being limited to the following embodiments and examples. Furthermore, for clarity of explanation, the drawings may schematically depict the width, thickness, shape, etc. of each part compared to the actual form. However, 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 may be denoted by the same reference numerals, and detailed descriptions may be omitted as appropriate. For convenience of explanation, the terms "above" and "below" may be used in some cases, but the up-down direction may be reversed. In this specification, when a certain component, such as a certain member or region, is described as being "above (or below)" another component, such as another member or region, unless otherwise specified, this includes not only the case where the component is directly above (or below) the other component, but also the case where the component is above (or below) the other component, i.e., the case where another component is present above (or below) the other component. In the present invention, light includes electromagnetic waves with wavelengths in the visible and invisible regions, as well as radiation, and examples of radiation include microwaves and electron beams. Specifically, this refers to electromagnetic waves with wavelengths of 5 μm or less and electron beams. In the present invention, (meth)acryloyl refers to acryloyl and methacryloyl, (meth)acrylic refers to acrylic and methacrylic, and (meth)acrylate refers to acrylate and methacrylate. Furthermore, in this specification, the term "to" indicating a numerical range is used to mean that the numerical values ​​before and after it are included as the upper and lower limits. For example, "1 to 100" is equivalent to "1 or more and 100 or less." Furthermore, in this specification, any combination of the upper and lower limits indicating a numerical range can be used. Furthermore, in this specification, a patterned cured film formed by patterning using a photosensitive colored resin composition may simply be referred to as a colored pattern. Below, the photosensitive colored resin composition, display device, and method for producing a laminate of an organic light-emitting element and an external light anti-reflection film according to the present invention will be described in detail.

[0016] I. Photosensitive Colored Resin Composition The photosensitive colored resin composition according to the present invention is a photosensitive colored resin composition used for a cured film formed on an organic light-emitting device, and contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, wherein the colorant comprises a first colorant having a maximum absorption wavelength of 480 nm to 520 nm and a second colorant having a maximum absorption wavelength of 560 nm to 600 nm, and the cured film having a thickness of 3.0 μm formed using the photosensitive colored resin composition has transmittances of 460 nm, 530 nm, and 620 nm of 45% to 85%, a transmittance of 50% or less at a minimum transmission wavelength of 480 nm to 520 nm, and a transmittance of 25% or less at a minimum transmission wavelength of 560 nm to 600 nm.

[0017] The photosensitive colored resin composition according to the present invention is characterized in that it is used for a cured film formed on an organic light-emitting element. That is, the photosensitive colored resin composition according to the present invention is used for a cured film formed directly on an element substrate equipped with an organic light-emitting element. Since the photosensitive colored resin composition according to the present invention is a photosensitive colored resin composition used for a cured film formed adjacent to or via at least one layer on an organic light-emitting element, it is possible to manufacture a display device that is thinner and more flexible than a display device in which a colored layer formed on a substrate such as a glass substrate is bonded to an organic light-emitting element.

[0018] In the photosensitive colored resin composition according to the present invention, the colorant comprises a first colorant having a maximum absorption wavelength of 480 nm to 520 nm and a second colorant having a maximum absorption wavelength of 560 nm to 600 nm, and the transmittance of 460 nm, 530 nm, and 620 nm of a 3.0 μm thick cured film formed using the photosensitive colored resin composition is 45% to 85%. The transmittance of the minimum transmission wavelength of 480 nm to 520 nm is 50% or less, and the transmittance of the minimum transmission wavelength of 560 nm to 600 nm is 25% or less. Therefore, the colored cured film formed using the photosensitive colored resin composition transmits most of the red light, green light, and blue light emitted from the organic light-emitting element side, and reduces the amount of transmitted light of the wavelength components between the maximum wavelengths of the red light and green light, and the wavelength components between the maximum wavelengths of the green light and blue light. Therefore, for example, wavelength components of reflected external light that reduce the color purity of the display light are absorbed by the cured film. This makes it possible to form a colored cured film that suppresses external light reflection and improves the display quality of the organic light-emitting device. The photosensitive colored resin composition according to the present invention contains an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator, so that it is possible to form a colored cured film that suppresses external light reflection and improves the display quality of the organic light-emitting device by performing patterning using an alkali development treatment.

[0019] When a colored cured film that suppresses external light reflection and improves the display quality of an organic light-emitting element is formed on an organic light-emitting element by patterning, it is further required that the cured film of the colored pattern have good solvent resistance. It is also required that the colored pattern have good adhesion and linearity after development. Because organic light-emitting elements have low heat resistance, it is considered preferable to use low-temperature heating at 130°C or less, and even 100°C or less, during the process of producing a colored cured film formed on an organic light-emitting element substrate. In a typical color filter production process, a cured film is cured by performing a heat treatment on a glass substrate at about 230°C, whereas a low-temperature heating treatment at 130°C or less, even 100°C or less, makes it difficult for the cured film to be cured by heat. Therefore, it is required that the cured film of the formed colored pattern have the solvent resistance required for subsequent processes. Furthermore, in the photosensitive colored resin composition according to the present invention, since the first coloring material having a maximum absorption wavelength of 480 nm to 520 nm and the second coloring material having a maximum absorption wavelength of 560 nm to 600 nm are contained, curing inhibition is likely to occur, and it is therefore difficult to improve the solvent resistance, adhesion, and linearity of the colored pattern, but it is also required to improve these.

[0020] The photosensitive coloring resin composition of the present invention contains at least coloring material, alkali-soluble resin, photopolymerizable compound, photoinitiator and solvent, and may further contain other components within the range that does not impair the effect of the present invention. Below, each component of the photosensitive coloring resin composition of the present invention will be explained in detail in order.

[0021] <Colorant> In the photosensitive colored resin composition according to the present invention, the colorant comprises a first colorant having a maximum absorption wavelength of 480 nm to 520 nm and a second colorant having a maximum absorption wavelength of 560 nm to 600 nm. In this specification, the maximum absorption wavelength means the wavelength that gives the maximum of the maximum values ​​of light absorptance in the spectrum of light absorptance (absorption spectrum). In the spectrum of light transmittance, it means the wavelength that gives the minimum of the minimum values, and is also called the minimum transmission wavelength. The first coloring material having a maximum absorption wavelength of 480 nm to 520 nm and the second coloring material having a maximum absorption wavelength of 560 nm to 600 nm may each be a coloring material having a maximum absorption wavelength in the above wavelength range, and may be appropriately selected from at least one compound selected from the group consisting of compounds having any of a porphyrin structure, a merocyanine structure, a phthalocyanine structure, an azo structure, a cyanine structure, a squarylium structure, a coumarin structure, a polyene structure, a quinone structure, a tetraazaporphyrin structure, a pyrromethene structure, an oxazine structure, and an indigo structure, and metal complexes thereof. In particular, from the viewpoint of durability, it is preferable to use at least one compound selected from the group consisting of compounds having any of a tetraazaporphyrin structure, a pyrromethene structure, a phthalocyanine structure, and a squarylium structure in the molecule.

[0022] The first colorant having a maximum absorption wavelength of 480 nm to 520 nm may have a peak width at half maximum (full width at half maximum) of 15 nm to 55 nm inclusive, from the viewpoint of suppressing external light reflection while suppressing a decrease in the brightness of the display device. Furthermore, the second colorant having a maximum absorption wavelength of 560 nm to 600 nm may have a peak width at half maximum (full width at half maximum) of 15 nm to 70 nm inclusive, from the viewpoint of suppressing external light reflection while suppressing a decrease in the brightness of the display device. Furthermore, in order to achieve such peak characteristics, the first colorant and the second colorant are preferably dyes. Note that, in this specification, "dye" refers to a coloring compound that dissolves in a solvent (an aqueous solvent containing water or an organic solvent). The dye used in the present invention preferably dissolves in an amount of 0.01 g or more, more preferably 0.05 g or more, and even more preferably 0.10 g or more, in 100 g of propylene glycol monomethyl ether acetate at 25°C.

[0023] These coloring materials may be appropriately selected from commercially available products. Examples of first coloring materials having a maximum absorption wavelength of 480 nm to 520 nm include, but are not limited to, FDB-022 and FDB-007 (all trade names, manufactured by Yamada Chemical Co., Ltd.). Examples of second coloring materials having a maximum absorption wavelength of 560 nm to 600 nm include, but are not limited to, FDG-005, FDG-006, FDG-007, and FDG-024 (all trade names, manufactured by Yamada Chemical Co., Ltd.).

[0024] When a composition contains a first colorant having a maximum absorption wavelength of 480 nm to 520 nm and a second colorant having a maximum absorption wavelength of 560 nm to 600 nm, curing inhibition is likely to occur due to the radical trapping effect of the dye colorant, making it difficult to improve the solvent resistance, adhesion, and linearity of the colored pattern. To suppress such curing inhibition, it is preferable to further include at least one green pigment selected from the group consisting of C.I. Pigment Green 7, 36, 58, and 59 as a third colorant. When at least one green pigment selected from the group consisting of C.I. Pigment Green 7, 36, 58, and 59 is included as the third colorant, the transmittance at 620 nm can be reduced to 85% or less with a small amount of green pigment. Therefore, the content of the first colorant having a maximum absorption wavelength of 480 nm to 520 nm and the content of the second colorant having a maximum absorption wavelength of 560 nm to 600 nm can be reduced, and the total amount of colorant contained in the solid content of the photosensitive colored resin composition can be reduced. This makes it possible to relatively increase the amount of patterning components such as alkali-soluble resins, photopolymerizable compounds, and photoinitiators contained in the solid content of the photosensitive colored resin composition of the present invention, which makes it easier to improve the solvent resistance, adhesion, and linearity of the colored pattern, and also makes it easier to improve solvent resistance, which is particularly problematic. The green pigment used as the third colorant is preferably at least one green pigment selected from the group consisting of C.I. Pigment Green 36, 58, and 59, and C.I. Pigment Green 58 or 59 is preferred, as it can efficiently reduce the transmittance at 620 nm without reducing the transmittance at 530 nm.

[0025] Furthermore, in order to suppress the reflectance of external light in the 380 nm to 450 nm region, it is preferable that the coloring material further contains a fourth coloring material having a maximum absorption wavelength of 370 nm to 450 nm. When a fourth coloring material having a maximum absorption wavelength of 370 nm to 450 nm is contained, external light in that region is absorbed, thereby further improving visibility. The fourth coloring material may have a maximum absorption wavelength of 370 nm to 430 nm.

[0026] Examples of the fourth coloring material having a maximum absorption wavelength of 370 nm to 450 nm include compounds having at least one structure selected from the group consisting of a benzophenone structure, a benzotriazole structure, a triazine structure, a benzoxazinone structure, an anthracene structure, an indole structure, a metalloporphyrin structure, and a methine structure. Among these, compounds having at least one structure selected from the group consisting of a benzotriazole structure and a metalloporphyrin structure are preferred because they have a broader absorption peak in the visible light region.

[0027] As the fourth coloring material having a maximum absorption wavelength of 370 nm to 450 nm, a commercially available product may be appropriately selected and used. Examples of the fourth coloring material having a maximum absorption wavelength of 370 nm to 450 nm include, but are not limited to, Tinuvin 970 (trade name, manufactured by BASF Japan Ltd.) and FDB-001 (trade name, manufactured by Yamada Chemical Co., Ltd.).

[0028] Other coloring materials may be contained as long as the transmittance characteristics of the cured film described below are satisfied. As other coloring materials, various dyes, lake coloring materials, pigments, etc. can be appropriately selected and used. As other coloring materials, for example, yellow pigments can be used to adjust the transmittance at 460 nm, and blue pigments can be used to adjust the transmittance at 620 nm. As yellow pigments, for example, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185, and derivative pigments of C.I. Pigment Yellow 150. Examples of blue pigments include, for example, C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60, etc.

[0029] In the photosensitive colored resin composition according to the present invention, the transmittance of a 3.0 μm thick cured film formed using the photosensitive colored resin composition at 460 nm, 530 nm, and 620 nm is all 45% to 85%, the transmittance at the minimum transmission wavelength of 480 nm to 520 nm is 50% or less, and the transmittance at the minimum transmission wavelength of 560 nm to 600 nm is 25% or less. The colorant is contained so as to satisfy these conditions. The transmittance at 460 nm of a 3.0 μm thick cured film formed using the photosensitive colored resin composition may be 47% or more, 50% or more, 55% or more, 83% or less, or 80% or less, from the viewpoint of being able to suppress external light reflection while suppressing a decrease in the brightness of a display device. The transmittance at 530 nm of a 3.0 μm thick cured film formed using the photosensitive colored resin composition may be 47% or more, 50% or more, 55% or more, 83% or less, or 80% or less, from the viewpoint that it is possible to suppress a decrease in the brightness of a display device while suppressing external light reflection. The transmittance at 620 nm of a 3.0 μm thick cured film formed using the photosensitive colored resin composition may be 47% or more, 50% or more, 55% or more, 83% or less, or 80% or less, from the viewpoint that it is possible to suppress a decrease in the brightness of a display device while suppressing external light reflection.

[0030] The transmittance of a 3.0 μm thick cured film formed using the photosensitive colored resin composition at a minimum transmission wavelength of 480 nm to 520 nm may be 48% or less, 45% or less, or even 40% or less, from the viewpoint of suppressing external light reflection. The lower limit is not limited, but is usually 0.1% or more. Furthermore, the transmittance of a 3.0 μm thick cured film formed using the photosensitive colored resin composition at a minimum transmission wavelength of 560 nm to 600 nm may be 23% or less, or even 20% or less, from the viewpoint of suppressing external light reflection. The lower limit is not limited, but is usually 0.1% or more.

[0031] In the photosensitive colored resin composition according to the present invention, the content of each colorant is not particularly limited as long as the transmittance of the cured film is satisfied. In the photosensitive colored resin composition according to the present invention, the content of the first colorant may be generally 1% by mass or more and 30% by mass or less, preferably 2% by mass or more, more preferably 3% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, based on the total amount of colorants. In the photosensitive colored resin composition according to the present invention, the content of the second colorant may be generally 5% by mass or more and 70% by mass or less, preferably 7% by mass or more, more preferably 10% by mass or more, preferably 65% ​​by mass or less, more preferably 60% by mass or less, based on the total amount of colorants. In the photosensitive colored resin composition according to the present invention, the content of the first coloring material is 5 parts by mass or more and 50 parts by mass or less, preferably 7 parts by mass or more, more preferably 10 parts by mass or more, and preferably 45 parts by mass or less, more preferably 40 parts by mass or less, relative to 100 parts by mass of the total content of the first coloring material and the second coloring material.

[0032] In the photosensitive colored resin composition according to the present invention, the content of the green pigment as the third colorant may be 0% by mass or more and 50% by mass or less, preferably 3% by mass or more, more preferably 5% by mass or more, preferably 45% by mass or less, more preferably 40% by mass or less, relative to the total amount of the colorants. In the photosensitive colored resin composition according to the present invention, the content of the third colorant may be 0 parts by mass or more and 130 parts by mass or less, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, preferably 120 parts by mass or less, more preferably 110 parts by mass or less, relative to 100 parts by mass of the total content of the first colorant and the second colorant.

[0033] In the photosensitive colored resin composition according to the present invention, the content of the fourth colorant may be 0% by mass or more and 85% by mass or less, preferably 30% by mass or more, more preferably 40% by mass or more, preferably 80% by mass or less, more preferably 75% by mass or less, relative to the total amount of the colorants. In the photosensitive colored resin composition according to the present invention, the content of the fourth colorant may be 0 parts by mass or more and 500 parts by mass or less, preferably 50 parts by mass or more, more preferably 100 parts by mass or more, and preferably 450 parts by mass or less, more preferably 400 parts by mass or less, relative to 100 parts by mass of the total content of the first colorant and the second colorant.

[0034] In the photosensitive colored resin composition according to the present invention, the content of the other coloring material may be 0% by mass or more and 20% by mass or less, preferably 1% by mass or more, more preferably 2% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, relative to the total amount of the coloring material. In the photosensitive colored resin composition according to the present invention, the content of the other coloring material may be 0 parts by mass or more and 50 parts by mass or less, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and preferably 45 parts by mass or less, more preferably 40 parts by mass or less, relative to 100 parts by mass of the total content of the first coloring material and the second coloring material.

[0035] In the photosensitive color resin composition according to the present invention, the content of the colorant is not particularly limited. From the viewpoint of the transmittance of the cured film, the total content of the colorant is, for example, preferably in the range of 1% by mass to 25% by mass, more preferably 2% by mass to 20% by mass, relative to the total solid content of the photosensitive color resin composition. The upper limit may be 15% by mass or less. If the content is equal to or greater than the lower limit, the photosensitive color resin composition is more likely to satisfy the transmittance characteristics of the cured film, and the external light reflection suppression effect is more likely to be good. Furthermore, if the content is equal to or less than the upper limit, the storage stability is excellent, sufficient hardness is more likely to be obtained, and good solvent resistance, adhesion after development of the color pattern, and linearity are more likely to be obtained. In the present invention, the solid content refers to everything other than the solvent described below, including monomers dissolved in the solvent.

[0036] <Alkali-Soluble Resin> The alkali-soluble resin used in the present invention has an acidic group, and can be appropriately selected from those that act as a binder resin and are soluble in an alkaline developer used in pattern formation. In the present invention, the alkali-soluble resin has an acid value of 25 mgKOH / g or more.

[0037] Specific examples of preferred alkali-soluble resins in the present invention include (meth)acrylic resins such as (meth)acrylic copolymers having a carboxy group and styrene-(meth)acrylic copolymers having a carboxy group, and epoxy (meth)acrylate resins having a carboxy group. Among these, particularly preferred are reactive alkali-soluble resins having a carboxy group on a side chain and a reactive group on the side chain. This is because the inclusion of a reactive group improves the film strength and solvent resistance of the cured film formed. The reactive group may be at least one selected from the group consisting of an ethylenically unsaturated bond-containing group, an epoxy group, an oxetane group, and a blocked isocyanate group.

[0038] (Meth)acrylic resins, such as (meth)acrylic copolymers having structural units with carboxy groups and styrene-(meth)acrylic copolymers with carboxy groups, are (co)polymers obtained by (co)polymerizing, for example, carboxy group-containing ethylenically unsaturated monomers and, if necessary, other copolymerizable monomers, using known methods. Examples of carboxy group-containing ethylenically unsaturated 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 polybasic acid anhydrides, such as maleic anhydride, succinic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, and ω-carboxy-polycaprolactone mono(meth)acrylate. Furthermore, anhydride-containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, may also be used as carboxy group precursors. Furthermore, a (meth)acrylic copolymer or the like having a structural unit having a carboxy group may be obtained, for example, by producing a polymer having a hydroxy group, and then subjecting the hydroxy group of the polymer to an addition reaction with a polybasic acid anhydride such as maleic anhydride or succinic anhydride to introduce a carboxy group.

[0039] The alkali-soluble resin used in the present invention is preferably a reactive alkali-soluble resin having an ethylenically unsaturated bond-containing group in its side chain. When the alkali-soluble resin has an ethylenically unsaturated bond-containing group, crosslinking can occur between the alkali-soluble resins themselves or between the alkali-soluble resin and a photopolymerizable compound or the like during the curing process of the resin composition. Therefore, when a reactive alkali-soluble resin having an ethylenically unsaturated bond-containing group in its side chain is used, the film strength of the cured film is further improved due to a synergistic effect. Therefore, even when a low-temperature heat treatment is performed and the first and second coloring materials are further included, the solvent resistance of the colored cured film can be further improved. Furthermore, development resistance is improved, and thermal shrinkage of the cured film is suppressed, resulting in excellent adhesion to the substrate. The method for introducing an ethylenically unsaturated bond-containing group into the alkali-soluble resin may be appropriately selected from conventionally known methods. Examples of such methods include a method in which a compound having both an epoxy group and an ethylenically unsaturated bond in the molecule, such as glycidyl (meth)acrylate, is added to a carboxy group of an alkali-soluble resin, thereby introducing the ethylenically unsaturated bond into the side chain; a method in which a structural unit having a hydroxyl group is introduced into a polymer, and a compound having an isocyanate group and an ethylenically unsaturated bond in the molecule is added, thereby introducing the ethylenically unsaturated bond into the side chain; and a method in which a structural unit having an epoxy group is introduced into a polymer, and a compound having a carboxy group and an ethylenically unsaturated bond in the molecule is added, thereby introducing the ethylenically unsaturated bond into the side chain.

[0040] The alkali-soluble resin may further have a hydrocarbon ring in order to improve the adhesion of the colored cured film and solvent resistance, such as suppressing swelling caused by solvents. A (meth)acrylic copolymer having a structural unit having a carboxy group and the above-mentioned hydrocarbon ring can be prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the aforementioned "other copolymerizable monomer." Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and styrene. Cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and styrene are preferred in terms of their significant effect of maintaining the cross-sectional shape of the colored pattern after development even during heat treatment.

[0041] The alkali-soluble resin used in the present invention may further contain other structural units such as structural units having an ester group, such as methyl (meth)acrylate, ethyl (meth)acrylate, etc. The structural unit having an ester group not only functions as a component that suppresses the alkali solubility of the photosensitive color resin composition, but also functions as a component that improves the solubility in a solvent and further the resolubility in a solvent.

[0042] The alkali-soluble resin can be made to have the desired properties by appropriately adjusting the amount of each constituent unit charged.

[0043] The amount of the carboxyl group-containing ethylenically unsaturated monomer charged is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total amount of monomers, from the viewpoint of obtaining a good pattern. On the other hand, from the viewpoint of suppressing film roughness on the pattern surface after development, the amount of the carboxyl group-containing ethylenically unsaturated monomer charged is preferably 50% by mass or less, more preferably 40% by mass or less, based on the total amount of monomers. When the proportion of the carboxyl group-containing ethylenically unsaturated monomer is equal to or greater than the above-mentioned lower limit, the resulting coating film has sufficient solubility in an alkaline developer. When the proportion of the carboxyl group-containing ethylenically unsaturated monomer is equal to or less than the above-mentioned upper limit, the formed pattern tends to be less likely to fall off from the substrate or to have film roughness on the pattern surface during development with an alkaline developer.

[0044] Furthermore, in (meth)acrylic resins such as (meth)acrylic copolymers and styrene-(meth)acrylic copolymers having a structural unit having an ethylenically unsaturated bond in a side chain, which are more preferably used as alkali-soluble resins, the amount of the compound having both an epoxy group and an ethylenically unsaturated bond is preferably 50% by mass to 150% by mass, and more preferably 70% by mass to 140% by mass, relative to the amount of the carboxy group-containing ethylenically unsaturated monomer charged.

[0045] The weight average molecular weight (Mw) of the alkali-soluble resin such as a carboxy group-containing copolymer is preferably 3,000 or more, more preferably 5,000 or more, from the viewpoint of binder function after curing, and is preferably 30,000 or less, more preferably 20,000 or less, from the viewpoint of pattern formability during development with an alkaline developer. The weight average molecular weight (Mw) in the present invention can be measured with a Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent.

[0046] The epoxy (meth)acrylate resin having a carboxy group is not particularly limited, but an epoxy (meth)acrylate compound obtained by reacting a reaction product of an epoxy compound and an ethylenically unsaturated bond-containing monocarboxylic acid with an acid anhydride is suitable. The epoxy compound, ethylenically unsaturated bond-containing monocarboxylic acid, and acid anhydride can be appropriately selected from known compounds and used. For example, they can be appropriately used by referring to the descriptions in paragraphs 0226 to 0240 of Japanese Patent No. 6911365. For the epoxy (meth)acrylate resin having a carboxy group, when a large number of reactive groups are to be contained in the side chain, for example, by reducing the ethylenically unsaturated bond equivalent as described below, a polymer of an epoxy group-containing (meth)acrylate such as glycidyl (meth)acrylate or a copolymer of an epoxy group-containing (meth)acrylate and another ethylenically unsaturated monomer may be subjected to an addition reaction of an ethylenically unsaturated bond-containing monocarboxylic acid such as (meth)acrylic acid with at least a portion of the epoxy groups to introduce ethylenic unsaturated bonds, and then a polybasic acid anhydride such as maleic anhydride or succinic anhydride may be subjected to an addition reaction of at least a portion of the hydroxyl groups generated by the addition reaction to introduce carboxy groups into the polymer. Examples of other ethylenically unsaturated monomers include, but are not limited to, the ethylenically unsaturated monomers having a hydrocarbon ring and alkyl (meth)acrylates. The amount of epoxy group-containing (meth)acrylate charged is preferably 10% to 80% by mass, more preferably 20% to 70% by mass, based on the total amount of monomers. The amount of the ethylenically unsaturated bond-containing monocarboxylic acid charged is preferably 5% by mass to 50% by mass, and more preferably 10% by mass to 40% by mass, based on the total amount of monomers. The amount of the polybasic acid anhydride charged is preferably 1% by mass to 50% by mass, and more preferably 2% by mass to 40% by mass, based on the total amount of monomers. The amount of the other ethylenically unsaturated monomer charged may be 55% by mass or less, or 50% by mass or less, based on the total amount of monomers, with the lower limit being 0% by mass. The epoxy (meth)acrylate resins having a carboxy group may be used alone or in combination of two or more types.

[0047] The alkali-soluble resin is selected from those having an acid value of 25 mgKOH / g or more in terms of developability (solubility) in the alkaline aqueous solution used in the developer. The alkali-soluble resin preferably has an acid value of 30 mgKOH / g or more and 100 mgKOH / g or less, more preferably 30 mgKOH / g or more and 90 mgKOH / g or less, in terms of developability in the alkaline aqueous solution used in the developer and adhesion to the substrate. The upper limit of the acid value may be 80 mgKOH / g or less, 70 mgKOH / g or less, or 60 mgKOH / g or less. The acid value in the present invention can be measured according to JIS K 0070:1992.

[0048] When the alkali-soluble resin has an ethylenically unsaturated bond in its side chain, the ethylenically unsaturated bond equivalent may be in the range of 100 to 1000, from the viewpoint of obtaining effects such as improved film strength of the cured film, improved solvent resistance and development resistance, and excellent adhesion to the substrate. In particular, since the photosensitive colored resin composition of the present invention is used in a cured film formed on an organic light-emitting device and therefore requires low-temperature heat treatment, and curing is likely to be inhibited by the first color material and the second color material, it is preferable that the ethylenically unsaturated bond equivalent of the alkali-soluble resin be 500 or less, from the viewpoint of improving the solvent resistance of the cured film. The ethylenically unsaturated bond equivalent of the alkali-soluble resin may be 400 or less, or may be 300 or less. Here, the ethylenically unsaturated bond equivalent refers to the weight-average molecular weight per mole of ethylenically unsaturated bonds in the alkali-soluble resin, and is represented by the following mathematical formula (1):

[0049] Ethylenically unsaturated bond equivalent (g / mol)=W(g) / M(mol) Formula (1) (In formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of ethylenically unsaturated bonds contained in the alkali-soluble resin W (g).)

[0050] The ethylenically unsaturated bond equivalent may be calculated by measuring the number of ethylenically unsaturated bonds contained in 1 g of the alkali-soluble resin in accordance with the iodine value testing method described in JIS K 0070:1992, for example.

[0051] The alkali-soluble resin preferably has an ethylenically unsaturated bond equivalent of 500 or less and an acid value of 30 mgKOH / g to 90 mgKOH / g, from the viewpoints of improving the solvent resistance of the cured film, and improving the development adhesion and linearity of the pattern.

[0052] The alkali-soluble resin used in the photosensitive coloring 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 20% to 80% by mass, more preferably 30% to 70% by mass, based on the total solid content of the photosensitive coloring resin composition. When the content of the alkali-soluble resin is equal to or greater than the above lower limit, sufficient alkali developability is obtained and solvent resistance is also likely to be improved. Furthermore, when the content of the alkali-soluble resin is equal to or less than the above upper limit, film roughness and pattern chipping during development can be suppressed, and a pattern with good linearity is likely to be obtained.

[0053] <Photopolymerizable Compound> The photopolymerizable compound used in the photosensitive colored resin composition includes a compound having a photopolymerizable group in the molecule. The photopolymerizable group may be any group that can be polymerized by a photoinitiator, and is not particularly limited, but includes an ethylenically unsaturated bond, such as a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group. As the photopolymerizable group, from the viewpoint of ultraviolet curability, an acryloyl group or a methacryloyl group is preferably used. As the photopolymerizable compound, from the viewpoint of curability, it is preferable to contain a compound having two or more photopolymerizable groups in one molecule, and it is more preferable to contain a compound having three or more photopolymerizable groups in one molecule.

[0054] As the photopolymerizable compound, a compound having two or more ethylenically unsaturated 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. Specific examples include those described in JP 2013-029832 A.

[0055] These polyfunctional (meth)acrylates may be used alone or in combination of two or more. Further, when the photosensitive colored resin composition of the present invention is required to have excellent photocurability (high sensitivity), it is preferable that the polyfunctional (meth)acrylate contains one having three (trifunctional) or more polymerizable ethylenically unsaturated bonds, and poly(meth)acrylates of trivalent or higher polyhydric alcohols or their dicarboxylic acid modified products are preferred, specifically, glycerin tri(meth)acrylate, 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.

[0056] Among these, it is preferable that the photopolymerizable compound contains a mixture of glycerin diacrylate and glycerin triacrylate from the viewpoint of linearity of the pattern.

[0057] The content of the photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited, but is, for example, preferably in the range of 5% by mass to 60% by mass, more preferably 10% by mass to 40% by mass, based on the total solid content of the photosensitive colored 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 is easily suppressed. Furthermore, when the content of the photopolymerizable compound is equal to or less than the upper limit, alkaline developability is likely to be sufficient. From the viewpoint of solvent resistance, the content of the photopolymerizable compound is preferably 15% by mass or more, and may be more than 20% by mass, based on the total solid content of the photosensitive colored resin composition.

[0058] <Photoinitiator> The photoinitiator used in the photosensitive colored resin composition of the present invention is not particularly limited, and one or a combination of two or more of various conventionally known photoinitiators can be used. Examples of the photoinitiator include polymerization initiators such as photopolymerization initiators, and specific examples include those described in JP-A-2013-029832.

[0059] 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. Examples of the photoinitiator include the photoinitiators described in WO 2018 / 062105, and other conventionally known photoinitiators can be appropriately selected and used.

[0060] In the present invention, it is preferable to use a highly sensitive oxime photoinitiator from the viewpoint of improving the solvent resistance of the cured film and improving development adhesion and pattern linearity. When the photoinitiator contains an oxime photoinitiator, photocuring reactivity is enhanced, and when a cured film is formed on an element substrate as in the present invention, the solvent resistance of the cured film is likely to be good even if heating is performed in the production process at a low temperature of 130°C or less, or even 100°C or less.

[0061] The oxime-based photoinitiator used in the present invention can be appropriately selected from oxime ester-based 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.

[0062] From the viewpoint of improving the solvent resistance of the cured film and improving the development adhesion and linearity of the pattern, it is particularly preferred that the photoinitiator contains at least one of a compound represented by the following general formula (A) and a compound represented by the following general formula (B):

[0063] (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 , 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 ２２and R ２３ The hydrogen atom of the group represented by R may be further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, or a carboxy group, 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 oxygen atoms of -, -SCO-, -COS-, -OCS- or -CSO-, provided that the oxygen atoms are not adjacent to each other; 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 R may have a branched side chain or may be a cyclic alkyl, 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 , 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 , C.O.R. １５ R １６ , N.R. １２ COR １１ , O.C.O.R. 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 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 , OCSR１１ , COSR １１ , CSOR １１ , a hydroxyl group, CN or a halogen atom, and k represents 0 or 1.

[0064] (In formula (B), X １ , X ３ and X ６ are each independently R ４１ , OR ４１ , C.O.R. ４１ , S.R. ４１ , C.O.R. ４２ R ４３ or CN, and X ２ represents 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; X ４ and X ５ are each independently R ４１ , OR ４１ , S.R. ４１ , C.O.R. ４１ , C.O.R. ４２ R ４３ , N.R. ４２ COR ４１ , O.C.O.R. ４１ , COOR ４１ , SCOR ４１ , OCSR ４１ , COSR ４１ , CSOR ４１ , CN, a halogen atom or a hydroxyl group. ４１ , R ４２ and R ４３ 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 ４１ , R ４２ and R ４３ , and X ２ The hydrogen atoms of the group represented by ５１ , OR ５１ , C.O.R. ５１ , S.R. ５１ , N.R. ５２ R ５３ , C.O.R. ５２ R ５３ , -NR５２ -OR ５３ , -NCOR ５２ -OCOR ５３ , N.R. ５２ COR ５１ , O.C.O.R. ５１ , COOR ５１ , SCOR ５１ , OCSR ５１ , COSR ５１ , CSOR ５１ , optionally substituted with a hydroxyl group, a nitro group, CN, or a halogen atom, R ５１ , R ５２ and R ５３ 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 ５１ , R ５２ and R ５３ The hydrogen atom of the group represented by R may be further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, or a carboxy group, ４１ , R ４２ , R ４３ , X ２ , R ５１ , R ５２ and R ５３ The alkylene portion of the group represented by the formula: ５４ -, -NR ５４ CO-, -NR ５４ COO-,-OCONR ５４ may contain 1 to 5 oxygen atoms of -, -SCO-, -COS-, -OCS- or -CSO-, provided that the oxygen atoms are not adjacent to each other; ５４ 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 ４１ , R ４２ , R ４３ , R ５１ , R ５２ , R ５３ and R ５４ The alkyl portion of the group represented by the formula (I) may have a branched side chain or may be a cyclic alkyl. a and b are each independently an integer of 0 to 3.

[0065] (Compound Represented by General Formula (A)) 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.

[0066] 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 ２４ Examples 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.

[0067] 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-mentioned alkyl groups, biphenylyl, naphthyl, anthryl, and the like.

[0068] In the above general formula (A), R３ , 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, phenylethyl, and the like.

[0069] 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 heterocyclic group having 2 to 20 carbon atoms represented by the formula (A) 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. 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 these rings 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.

[0070] 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 , R２１ , R ２２ and R ２３ Examples of halogen atoms which may substitute include fluorine, chlorine, bromine and iodine.

[0071] 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-,-OCONR ２４ It may contain 1 to 5 -, -SCO-, -COS-, -OCS- or -CSO- provided that the oxygen atoms are not adjacent to each other, and the divalent group contained may be one type or two or more types, and in the case of groups that can be contained consecutively, two or more of them may be contained consecutively.

[0072] 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 (A) may have a branched side chain or may be a cyclic alkyl. ３ The compounds represented by the following general formula (A') are preferred because they have high sensitivity and are easy to produce.

[0073] (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 , C.O.R. １５ R １６ , N.R. １２ COR １１ , O.C.O.R. １１ , COOR １４ , SCOR １１ , OCSR １１ , COSR １４ , CSOR １１ , 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.)

[0074] R ３１ and R ３２ , R ３２ and R ３３ , R ３３ and R ３４ and R ３４ and R ３５ Examples of rings formed by combining are 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 Examples of the ring that can be formed by combining with each other include the same rings as those listed above.

[0075] 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 ７is 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 of ease of synthesis, and k is preferably 1 because of high sensitivity. ３１ ~R ３５ At least one of the following is a nitro group, CN, a halogen atom, or COR １１ and R １１ is 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.

[0076] Specific preferred examples of the compound represented by the general formula (A) include the following compounds: Further, compounds No. 1 to No. 212 described in WO 2015 / 152153 are also included.

[0077]

[0078] The compound represented by the general formula (A) can be synthesized by appropriately selecting a 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.

[0079] (Compounds Represented by General Formula (B)) The oxime ester compounds represented by the general formula (B) also have geometric isomers due to the double bond of the oxime, but these are not distinguished from each other. That is, in this specification, the compounds represented by the general formula (B) and their exemplified compounds represent a mixture of both or either one of them, and are not limited to the structures representing the isomers.

[0080] In the above general formula (B), X ２ , R ４１ , R ４２ , R ４３ , R ５１ , R ５２ , R ５３and R ５４ Examples of the alkyl group having 1 to 20 carbon atoms represented by the formula (B) include the same alkyl groups having 1 to 20 carbon atoms as those in the formula (A). ２ , R ４１ , R ４２ , R ４３ , R ５１ , R ５２ , R ５３ and R ５４ Examples of the aryl group having 6 to 30 carbon atoms represented by the formula (B) include the same aryl groups as those represented by the formula (A) having 6 to 30 carbon atoms. ２ , R ４１ , R ４２ , R ４３ , R ５１ , R ５２ , R ５３ and R ５４ Examples of the arylalkyl group having 7 to 30 carbon atoms represented by the formula (B) include the same arylalkyl groups as those in the formula (A) having 7 to 30 carbon atoms. ２ , R ４１ , R ４２ , R ４３ , R ５１ , R ５２ , R ５３ and R ５４ Examples of the heterocyclic group having 2 to 20 carbon atoms represented by the formula (B) include the same as the heterocyclic group having 2 to 20 carbon atoms in the general formula (A). Examples of the halogen atom in the general formula (B) include the same as the halogen atom in the general formula (A).

[0081] In the above general formula (B), R ４１ , R ４２ , R ４３ , X ２ , R ５１ , R ５２ and R ５３ The alkylene portion of the group represented by the formula: ５４ -, -NR ５４ CO-, -NR ５４ COO-,-OCONR ５４It may contain 1 to 5 -, -SCO-, -COS-, -OCS- or -CSO- provided that the oxygen atoms 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.

[0082] In the above general formula (B), X １ From the viewpoints of sensitivity, solubility, and compatibility, is more preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group, n-hexyl group, or 2-ethylhexyl group; a cyclic alkyl group having 5 to 10 carbon atoms, which may have a side chain, such as a cyclopentyl group or cyclohexyl group; or an alkyl group having 2 to 10 carbon atoms and one ether bond in a methylene chain, such as a methoxymethyl group, ethoxymethyl group, ethoxyethyl group, 2-(1-methoxypropyl) group, or 2-(1-ethoxypropyl) group; and even more preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, ethyl group, or 2-ethylhexyl group.

[0083] In the above general formula (B), X ２ , X ３ and X ６ are each independently particularly preferably, from the viewpoints of sensitivity, solubility, and compatibility, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-amyl group, an isoamyl group, a t-amyl group, or an n-hexyl group, a cyclic alkyl group having 5 to 6 carbon atoms such as a cyclopentyl group or a cyclohexyl group, or an alkyl group having 2 to 6 carbon atoms and one ether bond in the methylene chain such as a methoxymethyl group, an ethoxymethyl group, an ethoxyethyl group, a 2-(1-methoxypropyl) group, or a 2-(1-ethoxypropyl) group, and more preferably an alkyl group having 1 to 6 carbon atoms or an alkyl group having 2 to 6 carbon atoms and one ether bond in the methylene chain. ３ , and X ６ are each independently more preferably an alkyl group having 1 to 6 carbon atoms in terms of sensitivity, solubility, and compatibility. ２From the viewpoint of sensitivity, solubility and compatibility, more preferably is an alkyl group having 2 to 6 carbon atoms and one ether bond in the methylene chain.

[0084] In the above general formula (B), X ４ , and X ５ are each independently particularly preferably hydrogen or an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-amyl group, an isoamyl group, a t-amyl group, or an n-hexyl group, from the viewpoints of sensitivity, solubility, and compatibility.

[0085] Preferable specific examples of the compound represented by the above general formula (B) include the following compounds.

[0086]

[0087]

[0088] The compound represented by the general formula (B) 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 JP-A-2010-256891. Alternatively, a commercially available product may be obtained and used as appropriate.

[0089] The total content of one or more photoinitiators used in the photosensitive colored 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 within the range of 0.1% by mass to 15.0% by mass, more preferably 1.0% by mass to 10.0% by mass, relative to the total solid content of the photosensitive colored resin composition. If this content is above the lower limit, photocuring is easily carried out, and solvent resistance and substrate adhesion are easily improved, while if it is below the upper limit, line width shift is suppressed, and it is easy to form a high-resolution pattern.

[0090] The total content of at least one of the compound represented by the general formula (A) and the compound represented by the general formula (B) is preferably 30.0% by mass or more, more preferably 50.0% by mass or more, and even more preferably 70.0% by mass or more, relative to the total amount of the photoinitiator, from the viewpoint that a cured film having good development adhesion and solvent resistance can be formed even by low-temperature heat treatment.

[0091] <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 each component in the photosensitive color resin composition and can dissolve or disperse them. The solvent can be used alone or in combination of two or more kinds.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, which are preferred in terms of the solubility of other components and coating suitability. Furthermore, in the solvent used in the present invention, from the viewpoints of colorant dispersibility, the solubility of other components, and coating suitability, the content of propylene glycol monomethyl ether acetate may be 50% by mass or more, 70% by mass or more, 80% by mass or more, or even 100% by mass, relative to the total amount of solvent in the photosensitive color resin composition. The solvent used in the present invention is one or more selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol methyl ethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate, and the content of propylene glycol monomethyl ether acetate may be 50% by mass or more, or 70% by mass or more, based on the total amount of the solvent.

[0092] In the photosensitive colored resin composition according to the present invention, the content of the solvent may be appropriately set within a range that allows for the accurate formation of a colored layer (coating film). The content of the solvent is usually preferably within the 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 photosensitive colored resin composition containing the solvent. By having the content of the solvent within the above range, excellent coating properties can be achieved.

[0093] Moreover, the photosensitive colored resin composition according to the present invention, from the viewpoint of being able to form a colored cured film that improves light extraction efficiency, further contains at least one type of inorganic particles selected from the group consisting of zirconium oxide, barium titanate, and titanium oxide and having an average particle size of 100 nm or less, and a dispersant, wherein the dispersant contains at least one type of dispersant selected from the group consisting of a phosphate ester-based dispersant, a phosphonic acid-based dispersant, and a phosphonic acid ester-based dispersant, and the photoinitiator preferably contains an oxime-based photoinitiator.

[0094] In organic light-emitting devices, the refractive index of the light-emitting layer (refractive index 1.7 to 2.0), transparent conductive layer, and sealing material (refractive index 1.9 to 2.3) is significantly higher than the refractive index of the transparent cover material (refractive index 1.5) on the light extraction side, so that a portion of the light emitted by the light-emitting layer undergoes total reflection at the interface between the transparent conductive layer and the transparent substrate or the interface between the transparent substrate and the air layer, resulting in the phenomenon of being trapped inside the element, and there is a problem that not all of the emitted light can be extracted to the outside. On the other hand, when the photosensitive colored resin composition according to the present invention further contains at least one inorganic particle having an average particle size of 100 nm or less selected from the group consisting of zirconium oxide, barium titanate, and titanium oxide, the refractive index of the cured film can be increased by the at least one inorganic particle selected from the group consisting of zirconium oxide, barium titanate, and titanium oxide, and the light extraction efficiency can be improved. (Hereinafter, at least one type of inorganic particle selected from the group consisting of zirconium oxide, barium titanate, and titanium oxide may be simply referred to as "high refractive index inorganic particles.") Furthermore, when high refractive index inorganic particles having an average particle size of 100 nm or less are used in combination with at least one type of dispersant selected from the group consisting of phosphate ester-based dispersants, phosphonic acid-based dispersants, and phosphonic acid ester-based dispersants (hereinafter, in this specification, may be simply referred to as "phosphate-based dispersant"), the high refractive index inorganic particles can be stably dispersed throughout the colored cured film by the phosphate-based dispersant, thereby improving the refractive index of the colored cured film from about 1.6 to 1.7 or more. Here, reflection occurs when light enters a medium having a refractive index n2 from a medium having a refractive index n1, and the reflectance is calculated by the following formula: R=(n1-n2)２ / (n1+n2) ２ From this formula, for example, when the refractive index of the sealant on the light-emitting layer is 2.0, the refractive index of the colored cured film provided on the sealant is 1.7, and the refractive index of the glass serving as the transparent cover material on the light extraction side is 1.5, the reflectance between the sealant and the colored cured film is 0.66%, and the reflectance between the colored cured film and the glass is 0.39%, for a total of 1.05%. On the other hand, in the above example, when the refractive index of the colored cured film is 1.56, the reflectance between the sealant and the colored cured film is 1.53%, and the reflectance between the colored cured film and the glass is 0.04%, for a total of 1.57%. In this way, by setting the refractive index of the colored cured film to 1.7, the reflectance between the layers is reduced, thereby improving the light extraction efficiency. Furthermore, in the photosensitive colored resin composition according to the present invention, when high-refractive-index inorganic particles having an average particle size of 100 nm or less are dispersed using a phosphate-based dispersant, development residues caused by the addition of high-refractive-index inorganic particles can be suppressed. Furthermore, when high refractive index inorganic particles and a phosphate-based dispersant are contained, the addition of an oxime-based photoinitiator facilitates the progress of the curing reaction, and improves solvent resistance even with low-temperature heat treatment.

[0095] <High-Refractive Index Inorganic Particles Having an Average Particle Size of 100 nm or Less> In the present invention, at least one type of inorganic particles (high-refractive index inorganic particles) selected from the group consisting of zirconium oxide, barium titanate, and titanium oxide is preferably selected and used with an average particle size of 100 nm or less in order to suppress sedimentation and improve stability in the photosensitive color resin composition. The average particle size of the high-refractive index inorganic particles is preferably smaller, and the lower limit is not particularly limited, but it may be 1 nm or more, or 10 nm or more. On the other hand, the average particle size of the high-refractive index inorganic particles may be 90 nm or less, or 70 nm or less, in terms of transparency and resist stability. In the present invention, the average particle size of the high-refractive index inorganic particles can be determined as follows. The powdered inorganic particles are observed with a transmission electron microscope (TEM) to observe primary particles that are not aggregated, thereby determining the primary particle size. Regarding the particle size distribution of the inorganic particles, a TEM image of the powdered inorganic particles, which are primary particles, is taken, and the particle size distribution is measured from the TEM image using an image processing device. The average primary particle diameter of the inorganic particles is the arithmetic mean diameter based on the number calculated from the particle size distribution. For example, a transmission electron microscope (H-7000) manufactured by Hitachi, Ltd. can be used, and a Luzex AP manufactured by Nireco Corporation can be used as the image processing device.

[0096] The inorganic particles used in the present invention to impart a high refractive index are at least one selected from the group consisting of zirconium oxide, barium titanate, and titanium oxide, from the viewpoint of availability, and among these, titanium oxide may be used.

[0097] In the photosensitive color resin composition according to the present invention, the content of the high refractive index inorganic particles having an average particle size of 100 nm or less may be appropriately adjusted according to the required refractive index. The amount is preferably such that the refractive index of the photosensitive color resin composition is 0.03 or more higher than the refractive index of the state in which the high refractive index inorganic particles are not contained, and more preferably such that the refractive index is 0.05 or more higher.

[0098] In the photosensitive colored resin composition according to the present invention, the content of high refractive index inorganic particles having an average particle size of 100 nm or less may be appropriately adjusted according to the desired refractive index, and is not particularly limited. From the viewpoint of dispersibility and dispersion stability, the content of high refractive index inorganic particles having an average particle size of 100 nm or less is, for example, preferably in the range of 1% by mass to 50% by mass, more preferably 3% by mass to 45% by mass, relative to the total solid content of the photosensitive colored resin composition. If the content is above the lower limit, the photosensitive colored resin composition is cured to a predetermined film thickness (usually 1.0 μm to 5.0 μm, for example, 3.0 μm) and has a sufficient refractive index, which tends to improve the light extraction efficiency. Furthermore, if the content is below the upper limit, it is easy to obtain a cured film that has excellent storage stability, sufficient hardness, and adhesion to the substrate. The content of high refractive index inorganic particles having an average particle size of 100 nm or less is, in terms of solvent resistance and development residue, preferably 1% by mass to 30% by mass, more preferably 2% by mass to 28% by mass, and even more preferably 3% by mass to 25% by mass, relative to the total solid content of the photosensitive colored resin composition.

[0099] <Dispersant> In the photosensitive color resin composition of the present invention, when a pigment such as a green pigment is used as the colorant or when the high refractive index inorganic particles are used, a dispersant may be used from the viewpoint of dispersibility and dispersion stability of the pigment or the high refractive index inorganic particles. When the high refractive index inorganic particles are used, it is preferable to contain a dispersant containing a phosphate-based dispersant (at least one dispersant selected from the group consisting of phosphate ester-based dispersants, phosphonic acid-based dispersants, and phosphonic acid ester-based dispersants).

[0100] (Phosphate-Based Dispersant) The phosphate-based dispersant used in the present invention is at least one dispersant selected from the group consisting of phosphate ester-based dispersants, phosphonic acid-based dispersants, and phosphonate ester-based dispersants, and may include a phosphate ester-based compound, a phosphonic acid-based compound, or a phosphonate ester-based compound. The phosphate ester-based compound is phosphoric acid (O=P(OH) ３ ) in which at least one of the three hydrogen atoms is substituted with an organic group containing hydrocarbon, and phosphonic acid compounds include phosphoric acid (O=P(OH) ３) in which one of the three hydroxyl groups is substituted with an organic group containing hydrocarbon, and phosphonate ester compounds include phosphoric acid (O=P(OH) ３ ) one of the three hydroxyl groups contained in the hydroxyl group is substituted with an organic group containing hydrocarbon, and at least one of the hydrogen atoms of the remaining hydroxyl groups is substituted with an organic group containing hydrocarbon. The phosphoric acid-based dispersant used in the present invention may be one containing a phosphate ester compound, a phosphonic acid compound, or a phosphonic acid ester compound in the side chain of the polymer, and for example, a polymer having at least one selected from the structural units represented by the general formula (I) described in WO 2020 / 071041 can also be used.

[0101] The phosphoric acid dispersant used in the present invention preferably has a weight-average molecular weight of 5,000 or less, from the viewpoint of the effect of suppressing development residue, but may also have a weight-average molecular weight of 4,000 or less, or may have a weight-average molecular weight of 3,000 or less. On the other hand, from the viewpoint of dispersibility, the phosphoric acid dispersant may have a weight-average molecular weight of 100 or more. Here, the weight-average molecular weight of the phosphoric acid dispersant is a value measured by GPC (gel permeation chromatography). Measurements can be performed using a Tosoh HLC-8220GPC, using N-methylpyrrolidone containing 0.01 mol / L of lithium bromide as the elution solvent, and two TSK-GEL ALPHA-M measurement columns (Tosoh).

[0102] The phosphoric acid-based dispersant used in the present invention may be a compound represented by the following general formula (1) from the viewpoint of dispersibility and developability.

[0103] (In the formula, R ａ each independently represents a (poly)ethylene glycol residue, a (poly)propylene glycol residue, or a (poly)caprolactone residue; R ｂ each independently represents an alkyl group which may be substituted with a phenyl group, an aryl group which may be substituted with an alkyl group, a (meth)acryloyl group, or a hydrogen atom, m represents 0 to 3, n represents 1 to 3, and o represents 0 to 1. However, when m is 0, R ｂrepresents an alkyl group which may be substituted with a phenyl group, an aryl group which may be substituted with an alkyl group, or a (meth)acryloyl group.

[0104] R ａ The (poly)ethylene glycol residue in ２ CH ２ -O) ｐ１ -CH ２ CH ２ -, and p1 may be 0 to 30, may be 0 to 25, may be 1 to 25, or may be 3 to 20. R ａ The (poly)propylene glycol residue in ２ CH (CH ３ )-O) ｐ２ -CH ２ CH (CH ３ )-, and p2 may be 0 to 30, may be 0 to 25, may be 1 to 25, or may be 3 to 20. R ａ The (poly)caprolactone residue in ２ ) ５ CO-O) ｐ３ - (CH ２ ) ５ CO-, and p3 may be 0 to 30, 0 to 25, 1 to 25, or 3 to 20. Thus, in the present invention, the (poly)ethylene glycol residue represents each of an ethylene glycol residue and a polyethylene glycol residue, the (poly)propylene glycol residue represents each of a propylene glycol residue and a polypropylene glycol residue, and the (poly)caprolactone residue represents each of a caprolactone residue and a polycaprolactone residue.

[0105] m represents 0 to 3, and when m is 0, P is directly connected to -(O) ｏ -R ｂ When m is 1, it means that one of a (poly)ethylene glycol residue (PEG), a (poly)propylene glycol residue (PPG), or a (poly)caprolactone residue (PCL) is bonded to P via —O—. When m is 2, it means that —(O—R ａ)- are two types (here R ａ represents that two types selected from PEG, PPG, and PCL are linked together, and examples thereof include P-O-PEG-O-PCL, P-O-PEG-O-PPG, P-O-PCL-O-PEG, and P-O-PPG-O-PCL. When m is 3, P is linked to -(O-R ａ )- are two or three types (where R ａ represents two or three selected from PEG, PPG, and PCL) linked together, and examples include P-O-PEG-O-PCL-O-PEG, P-O-PEG-O-PPG-O-PEG, P-O-PCL-O-PEG-O-PCL, and P-O-PEG-O-PPG-O-PCL.

[0106] In particular, the phosphoric acid-based dispersant used in the present invention preferably contains a (poly)ethylene glycol residue in its structure, and more preferably contains a (poly)ethylene glycol residue and a (poly)caprolactone residue in its structure, in order to further improve developability and the effect of suppressing development residues.

[0107] o represents 0 to 1, but when m is 0, o may be 0 to 1, when m is not 0, o does not have to be 0, and when m is 1 or more, o may be 1.

[0108] R ｂ The alkyl group in R may be an alkyl group having 1 to 35 carbon atoms which may be substituted with a phenyl group, or an alkyl group having 3 to 30 carbon atoms which may be substituted with a phenyl group. ｂ The aryl group optionally substituted with an alkyl group in R may be a phenyl group optionally substituted with an alkyl group having 1 to 35 carbon atoms, or may be a phenyl group optionally substituted with an alkyl group having 3 to 30 carbon atoms. ｂ is preferably an alkyl group having 8 to 23 carbon atoms or a phenyl group substituted with an alkyl group having 8 to 23 carbon atoms. ｂExamples of the alkyl group include a nonylphenyl group, an octylphenyl group, a dodecyl group, a tridecyl group, a lauryl group, a 2-ethylhexyl group, an octadecyl group, an oleyl group, and a dodecylphenyl group.

[0109] Suitable examples of the compound represented by the general formula (1) include R ａ p1 contains a (poly)ethylene glycol residue of 0 to 25, and R ｂ is an alkyl group having 1 to 23 carbon atoms or a (meth)acryloyl group, particularly a methyl group, a dodecyl group, a tridecyl group, or a (meth)acryloyl group; ａ p1 contains a (poly)ethylene glycol residue of 0 to 25 and p3 contains a (poly)caprolactone residue of 0 to 20, ｂ is an alkyl group having 1 to 23 carbon atoms or a (meth)acryloyl group, particularly a methyl group, a dodecyl group, a tridecyl group, or a (meth)acryloyl group; ｂ is a dodecyl group or a tridecyl group, and the like.

[0110] n represents a number from 1 to 3, and may be a number from 1 to 2. Commercially available phosphate dispersants are usually mixtures of esters, for example, a mixture of a phosphate monoester and a phosphate diester. That is, n may be an average value determined from a mixture of a phosphate monoester, a phosphate diester, etc.

[0111] The phosphate dispersant used in the present invention may also be reacted with a tertiary amine to form a phosphate. The phosphate dispersant is preferably a phosphate salt with a tertiary amine, as this improves storage stability. Examples of the tertiary amine used in the phosphate salt include tertiary amines substituted with hydrocarbon groups. Examples of the hydrocarbon group 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 groups having 1 to 18 carbon atoms may be linear, branched, or cyclic, and examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, n-nonyl, n-lauryl, n-stearyl, cyclopentyl, cyclohexyl, bornyl, isobornyl, dicyclopentanyl, adamantyl, and lower alkyl-substituted adamantyl groups. The alkyl group preferably has 1 to 12 carbon atoms, and more preferably 1 to 6 carbon atoms. The alkenyl group having 2 to 18 carbon atoms may be linear, branched, or cyclic. Examples of such alkenyl groups include vinyl, allyl, and propenyl groups. While there are no limitations on the position of the double bond in the alkenyl group, from the viewpoint of the reactivity of the resulting polymer, it is preferable for the double bond to be located at the terminal of the alkenyl group. The alkenyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms. Examples of aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl groups. The aryl group preferably has 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms. Examples of aralkyl groups include benzyl, phenethyl, naphthylmethyl, and biphenylmethyl groups, and may further have a substituent. The aralkyl group preferably has 7 to 20 carbon atoms, more preferably 7 to 14 carbon atoms. 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.

[0112] Specific examples of the tertiary amine used in the phosphate salt of the present invention include at least one selected from the group consisting of dimethylbenzylamine, diethylbenzylamine, triethylamine, N,N-diisopropylethylamine, quinuclidine, pyridine, diazabicycloundecene, and diazabicyclononene, and at least one selected from the group consisting of dimethylbenzylamine and diethylbenzylamine is preferably used from the viewpoints of safety and ease of handling.

[0113] Furthermore, in a phosphoric acid dispersant used in a state in which it is reacted with a tertiary amine to form a phosphate, the content of the tertiary amine 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 phosphorus moiety of the phosphoric acid dispersant. When the content is above the above lower limit, the effect of improving stability by salt formation is easily obtained. Similarly, it 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 it is below the above upper limit, excellent dispersion stability can be achieved. The tertiary amine may be used alone, or two or more types may be combined. When two or more types are combined, it is preferable that the total content is within the above range.

[0114] From the viewpoints of dispersibility and developability, the phosphate dispersant used in the present invention preferably has an acid value of 10 mgKOH / g or more, more preferably 50 mgKOH / g or more, and may be 1000 mgKOH / g or less, or may be 500 mgKOH / g or less. The acid value can be measured in accordance with JIS K0070:1992.

[0115] The phosphoric acid-based dispersant used in the present invention is preferably used to disperse the high refractive index inorganic particles having an average particle size of 100 nm or less. That is, in the photosensitive color resin composition of the present invention, it is preferable that the high refractive index inorganic particles are dispersed in a phosphoric acid-based dispersant.

[0116] The content of the phosphoric acid-based dispersant used in the present invention is in the range of 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, relative to 100 parts by mass of the high refractive index inorganic particles. If the content is equal to or greater than the lower limit, the dispersibility and dispersion stability of the high refractive index inorganic particles are excellent, and the storage stability of the photosensitive colored resin composition is also excellent. Furthermore, if the content is equal to or less than the upper limit, the solvent resistance of the resist is good.

[0117] (Other dispersants) When dispersing a colorant such as a pigment in the photosensitive color resin composition of the present invention, other dispersants may be further contained in terms of colorant dispersibility and colorant dispersion stability. The other dispersants for dispersing the colorant can be appropriately selected from conventionally known dispersants and used. As the dispersant, for example, cationic, anionic, nonionic, amphoteric, silicone, fluorine-based surfactants can be used. Among the surfactants, polymer dispersants are preferred because they can be dispersed uniformly and finely.

[0118] Examples of polymer dispersants include (meth)acrylate copolymer dispersants; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamidophosphates; polyethyleneimine derivatives (amides obtained by reacting poly(lower alkyleneimine) with a polyester containing a free carboxy group, 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 a free carboxy group, polyamides, or co-condensates of esters and amides (polyesteramides)).

[0119] In the present invention, it is preferable to use a (meth)acrylate copolymer dispersant as the dispersant, since it is likely to have good solvent resistance even in low-temperature heat treatment.The (meth)acrylate copolymer dispersant has good compatibility with the photopolymerizable compound, the oxime photoinitiator, and at least one photoinitiator of the compound represented by general formula (A) and the compound represented by general formula (B), so that the photoinitiator is likely to be uniformly present in the colored layer (coating film), and the colored layer is uniformly cured, so that the unreacted components are reduced, and the internal stress of the colored cured film is also reduced, so that it is presumed that the change of the colored cured film when immersed in a solvent is reduced.

[0120] In the present invention, the (meth)acrylate copolymer dispersant refers to a copolymer dispersant containing at least a (meth)acrylate-derived structural unit. 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 the structural unit that functions as a solvent affinity site preferably contains at least a (meth)acrylate-derived structural unit.

[0121] 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 structural unit derived from a basic group-containing ethylenically unsaturated monomer, a structural unit represented by the following general formula (I) is preferred because of its excellent dispersibility.

[0122] (In general formula (I), R ７１ is a hydrogen atom or a methyl group, A １ represents 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.

[0123] For an explanation of each symbol in the general formula (I) and copolymers and salt-type copolymers having a constitutional unit represented by the general formula (I), JP-A-2016-224447 and WO 2016 / 104493 can be appropriately referenced.

[0124] The content (mol%) of each structural unit in the dispersant can be determined from the amount of raw materials charged during production, and can be measured using an analytical device such as NMR. The structure of the dispersant can be measured using NMR, various mass spectrometry, etc. Alternatively, the dispersant can be decomposed by pyrolysis or the like as necessary, and the obtained decomposition product can be determined using high performance liquid chromatography, a gas chromatograph mass spectrometer, NMR, elemental analysis, XPS / ESCA, TOF-SIMS, etc.

[0125] In the photosensitive color 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 high refractive index inorganic particles and colorant. The dispersant containing the phosphoric acid-based dispersant and optionally other dispersants is, for example, preferably in the range of 2% by mass to 30% by mass, more preferably 3% by mass to 25% by mass, based on the total amount of solids in the photosensitive color resin composition. If the content is equal to or greater than the above lower limit, the dispersibility and dispersion stability of the high refractive index inorganic particles and colorant are excellent, and the storage stability of the photosensitive color resin composition is also excellent. Furthermore, if the content is equal to or less than the above upper limit, the developability is good.

[0126] <Thiol Compound> The photosensitive colored resin composition of the present invention may further contain a thiol compound in order to improve solvent resistance and substrate adhesion after low-temperature heat treatment. Examples of the thiol compound include monofunctional thiol compounds having one thiol group and polyfunctional thiol compounds having two or more thiol groups. In terms 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. 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 photosensitive colored resin composition. If it is equal to or greater than the lower limit, the solvent resistance after low-temperature heat treatment and the substrate adhesion are likely to be excellent. On the other hand, if it is equal to or less than the upper limit, the photosensitive colored resin composition of the present invention is likely to have good developability and suppressed line width shift.

[0127] <Other Components> The photosensitive colored resin composition of the present invention may further contain various additives as necessary. Examples of the additives include antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, UV absorbers, and adhesion promoters. Specific examples of surfactants and plasticizers include those described in JP 2013-029832 A.

[0128] The photosensitive colored resin composition of the present invention preferably further contains an antioxidant in order to suppress the line width shift of the cured film. The photosensitive colored resin composition of the present invention, for example, contains an antioxidant in combination with the compound represented by the general formula (A). This allows for the control of 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, this composition can improve heat resistance and suppress a decrease in brightness after exposure and post-baking, 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 antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and hydrazine-based antioxidants. From the viewpoints of improving the ability to form a fine line pattern according to the designed mask line width and heat resistance, it is preferable to use a hindered phenol-based antioxidant. It may also be a latent antioxidant such as those described in WO 2014 / 021023.

[0129] Examples of the hindered phenol-based antioxidant include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate (trade name: IRGANOX 3114, manufactured by BASF), and 2,4,6-tris(4-hydroxy-3,5-di-tert-butylbenzyl). Examples of suitable esters include 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (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: Irganox 1010, manufactured by BASF) is preferred from the viewpoints of heat resistance and light resistance.

[0130] The content of the antioxidant is usually within the range of 0.1% by mass to 10.0% by mass, preferably 0.5% by mass to 5.0% by mass, based on the total solid content of the photosensitive color resin composition. If it 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 it is equal to or less than the upper limit, the photosensitive color resin composition of the present invention is easily made into a highly sensitive photosensitive color resin composition.

[0131] 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 a methacrylic group or an acrylic group, are preferred from the viewpoint of adhesion to SiN substrates.

[0132] The content of the silane coupling agent is usually within a range of 0.05% by mass to 10.0% by mass, preferably 0.1% by mass to 5.0% by mass, based on the total amount of solids in the photosensitive color 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.

[0133] <Production method of photosensitive colored resin composition> The production method of the photosensitive colored resin composition of the present invention can be prepared by using known mixing means to mix essential components and various additive components that are used as needed.As the preparation method of the photosensitive colored resin composition of the present invention, for example, (1) in a solvent, colorant, alkali-soluble resin, photopolymerizable compound, photoinitiator and various additive components that are used as needed are simultaneously added and mixed; (2) in a solvent, dispersant, alkali-soluble resin, photopolymerizable compound, photoinitiator and various additive components that are used as needed are added and mixed, and then colorant and, if necessary, high refractive index inorganic particles are added and dispersed; (3) in a solvent, first, colorant and dispersant are added to prepare a colorant dispersion, and if necessary, high refractive index inorganic particles and dispersant are added to prepare a high refractive index inorganic particle dispersion. (4) a method in which a colorant dispersion is prepared by adding a colorant, a dispersant, and an alkali-soluble resin to a solvent, and if necessary, high-refractive-index inorganic particles and a dispersant are added to the solvent to prepare a high-refractive-index inorganic particle dispersion, and then the colorant dispersion, the high-refractive-index inorganic particle dispersion, the colorant that is not to be dispersed, an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, and various additive components that are used as desired are added and mixed; and

[0134] The method for preparing the colorant dispersion liquid and the high refractive index inorganic particle dispersion liquid can be appropriately selected from conventionally known dispersion methods. 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.

[0135] <Applications> The photosensitive colored resin composition according to the present invention is formed on an organic light-emitting element and is used for a cured film having a specific transmittance, so it is suitable for use in forming a colored cured film that replaces a circular polarizer. When the cured film of the photosensitive colored resin composition according to the present invention is used in place of a circular polarizer, it can be used to form a display device that does not include a polarizer, so the photosensitive colored resin composition according to the present invention is suitable for use in a display device that does not include a polarizer. In addition, since the photosensitive colored resin composition according to the present invention is a photosensitive colored resin composition used for a cured film formed on an organic light-emitting element, it is suitable for use in a display device that does not include an external color filter substrate, and in an organic light-emitting display device that is thin and has improved flexibility.

[0136] The cured film of the photosensitive color resin composition according to the present invention may have a refractive index of 1.65 or more, or 1.70 or more, when containing the high refractive index inorganic particles. The refractive index here can be measured by the method described in the examples below.

[0137] II. Display Device The display device according to the present invention is characterized by having a cured film of the photosensitive colored resin composition according to the present invention on an organic light-emitting element. In the display device according to the present invention, a cured film of the photosensitive colored resin composition used in the cured film formed on the organic light-emitting element according to the present invention is formed on the organic light-emitting element, so an external circular polarizer or an external color filter substrate is not required, and the display device may be free of these. In the display device according to the present invention, a cured film is formed on the organic light-emitting element using the photosensitive colored resin composition used in the cured film formed on the organic light-emitting element according to the present invention, so there is no substrate such as that used in an external color filter substrate between the organic light-emitting element and the cured film, resulting in improved thinning and flexibility.

[0138] 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 illustrated in FIG. 1, the display device 100 according to the present invention includes an element substrate 30 including an organic light-emitting element, an external light anti-reflection film 20 including a colored cured film 9 on the element substrate 30, and an overcoat layer 11, a transparent adhesive layer 12, and a transparent cover material 13, in this order. The element substrate 30 including the organic light-emitting element includes a substrate 1 on which thin-film transistors (TFTs) 2 serving as driving elements are arranged to correspond to each subpixel, a sealing film 3 is provided thereon, and on the sealing film 3, electrodes 4 (anodes, reflective electrodes) corresponding to each subpixel and partition walls 5 that partition each subpixel are provided. Organic light-emitting elements (6R, 6G, 6B) constituting subpixels of three colors R, G, and B are arranged within the partitions, and an electrode 7 (cathode, transparent electrode) is provided on the organic light-emitting elements (6R, 6G, 6B). The element substrate 30 including the organic light-emitting element further includes a sealing film 8 that covers the organic light-emitting elements from above. An external light antireflection film 20 including a colored cured film 9 and a light-shielding portion 10 formed using the photosensitive colored resin composition of the present invention is provided on a sealing film 8 on an organic EL element (6R, 6G, 6B) on an element substrate 30, and further provided thereon in this order is an overcoat layer 11, a transparent adhesive layer 12, and a transparent cover material 13. In the example of FIG. 1, the colored cured film 9 is patterned pixel by pixel in the opening of the light-shielding portion 10 corresponding to the pixels of the organic EL element (6R, 6G, 6B). FIG. 2 is a schematic cross-sectional view showing another example of a display device including an organic light-emitting element according to the present invention. As illustrated in FIG. 2, a display device 100 according to the present invention includes an element substrate 30 including an organic light-emitting element, and an external light antireflection film 20 including a colored cured film 9 on the element substrate 30, and further provided thereon in this order is an overcoat layer 11, a transparent adhesive layer 12, and a transparent cover material 13. In the example of FIG. 2, the colored cured film 9 is provided over the entire organic EL element panel so as to cover the light-shielding portion 10. Even in the layer structure shown in FIG. 2, a pattern of the colored cured film 9 is formed for each panel, so it is necessary to impart developability to the photosensitive colored resin composition that forms the colored cured film 9 .

[0139] Although not shown, the display device 100 according to the present invention may further include a touch sensor layer made of an insulating film and a transparent electrode layer on the overcoat layer 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 9 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.

[0140] The display device according to the present invention includes a colored cured film formed on an organic light-emitting element using the photosensitive colored resin composition of the present invention. When a 3.0 μm-thick cured film is formed from the photosensitive colored resin composition of the present invention, the transmittance at 460 nm, 530 nm, and 620 nm is 45% to 85%, the transmittance at the minimum transmission wavelength of 480 nm to 520 nm is 50% or less, and the transmittance at the minimum transmission wavelength of 560 nm to 600 nm is 25% or less. The colored cured film formed on the organic light-emitting element absorbs external light except for the color originally emitted by the organic light-emitting element, while transmitting the light emitted by the organic light-emitting element, thereby suppressing external light reflection without reducing light utilization efficiency.

[0141] The substrate 1, thin film transistors (TFTs) 2 serving as driving elements, sealing film 3, electrodes 4 (anodes), partition walls 5 defining the subpixels, organic light-emitting elements (6R, 6G, 6B) constituting the subpixels, electrodes 7 (cathodes), 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.

[0142] Examples of the sealing film 8 on the organic EL element used in the display device according to the present invention include inorganic films, organic films, and multilayer films formed by laminating these. Multilayer films are preferred because they are highly effective in suppressing the intrusion of moisture and oxygen. Specific examples include multilayer films formed by laminating inorganic and organic films such as metal films, metal oxide films, SiOx, and SiNx.

[0143] The colored cured film 9 used in the display device according to the present invention is a cured film of the photosensitive colored resin composition according to the present invention. The colored cured film may usually be formed in the opening of the light-shielding part (described later) on the sealing film 8 on the organic light-emitting element, or may be formed so as to cover the light-shielding part. The thickness of the colored cured film is appropriately controlled by adjusting the coating method, the solids concentration and viscosity of the photosensitive colored resin composition, etc., but is usually in the range of 1 μm to 5 μm.

[0144] The light-shielding portion 10 used in the display device according to the present invention is typically formed in a pattern on the sealing film 8 on the organic light-emitting element, and may be similar to the light-shielding portion used in a general color filter. The pattern shape of the light-shielding portion may be appropriately selected to match the shape of the colored cured film, and may be, for example, a stripe shape, a matrix shape, or the like. The light-shielding portion may be a thin metal film such as chromium formed by a sputtering method, a vacuum deposition method, 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 such as patterning by development using a photosensitive resist, patterning using an inkjet ink containing light-shielding particles, and thermal transfer of a photosensitive resist are available.

[0145] The thickness of the light-shielding portion is set to about 0.2 μm to 0.4 μm in the case of a thin metal film, and to about 0.5 μm to 2 μm in the case of a black pigment dispersed or dissolved in a binder resin.

[0146] Known materials can be appropriately selected and used for the overcoat layer 11, transparent adhesive layer 12, and transparent cover material 13 provided on the colored cured film 9 and the light-shielding portion 10. The overcoat layer 11 may be the same as the sealing film, but may also be a resin film formed using a solvent. As described above, examples of the transparent cover material 13 include glass and PET film.

[0147] 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.

[0148] III. Method for manufacturing a laminate of an organic light-emitting element and an external light anti-reflection film The method for manufacturing a laminate of an organic light-emitting element and an external light anti-reflection film according to the present invention comprises the steps of forming a coating film by applying the photosensitive colored resin composition according to the present invention onto an organic light-emitting element, irradiating the coating film with light, post-baking the film after the light irradiation (post-baking), and developing the film after the light irradiation, thereby forming a cured film of the photosensitive colored resin composition according to the present invention on the organic light-emitting element. Each step will be described below.

[0149] In the step of applying the photosensitive color resin composition according to the present invention to an organic light-emitting element, the photosensitive color resin composition does not need to be applied adjacent to the organic light-emitting element, and may be applied via at least one layer. As shown in Fig. 1, in an element substrate 30 including an organic light-emitting element, an electrode 7 and a sealing film 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 photosensitive color resin composition may be applied onto the organic light-emitting element via these electrodes, sealing layers, etc.

[0150] For example, the light-shielding portion 10 may be provided in advance on the sealing film 8 by a known method such as those exemplified above, and the colored cured film 9 may be applied so as to be formed in the openings of the light-shielding portion 10. Alternatively, the colored cured film 9 may be applied to the sealing film 8 so as to be formed over the entire surface of one display panel so as to cover the light-shielding portion 10.

[0151] For example, the photosensitive colored resin composition of the present invention is applied to the organic light-emitting element by a coating method such as spray coating, dip coating, bar coating, roll coating, spin coating, die coating, or inkjet coating. As the coating method, spin coating and die coating are preferably used. Then, the wet coating film is dried using a hot plate or oven to form a coating film.

[0152] 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. Alternatively, the patterned coating film is irradiated (exposed) with light to photopolymerize the photopolymerizable compound. Examples of light sources used for exposure include low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, ultraviolet light such as UV-LEDs, and electron beams. The exposure dose is adjusted as appropriate depending on the light source used, the thickness of the coating film, etc.

[0153] Next, in order to promote the polymerization reaction after exposure, a post-baking step of heating the film after the light irradiation may be performed. The heating conditions may be appropriately selected depending on the blending ratio of each component in the photosensitive color 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.

[0154] In the present invention, since a colored cured film is formed directly on an element substrate including 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 be 30° C. or higher, 35° C. or higher, or 40° C. or higher.

[0155] 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, a developer is used to perform a development treatment, and the unexposed portions are dissolved and removed, thereby forming a coating film in a desired pattern. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. A suitable amount of a surfactant or the like may be added to this alkaline solution. Furthermore, a general method can be used as the development method.

[0156] After the development treatment, the developer is usually washed away and the cured film of the photosensitive colored resin composition is dried to form a colored cured film. After the development treatment, a heat treatment may be performed to sufficiently cure the coating film. In the present invention, since the colored cured film is formed directly on the element substrate equipped with the organic light-emitting element, the heating temperature in this post-baking step is preferably 130° C. or less, more preferably 100° C. or less, and even more preferably 90° C. or less. Furthermore, the heating temperature may be 30° C. or more, 35° C. or more, or 40° C. or more.

[0157] In addition, in order to further harden the film after development or post-baking, additional light irradiation (exposure) may be performed.

[0158] The present invention will be specifically described below with reference to examples. The present invention is not limited to these examples. The weight-average molecular weight of the alkali-soluble resin was measured using a Shodex GPC System-21H with polystyrene as the standard and THF as the eluent. The acid value was measured in accordance with JIS K 0070:1992.

[0159] (Synthesis Example 1: Preparation of Alkali-Soluble Resin I) A polymerization vessel was charged with 300 parts by mass of PGMEA, and the temperature was raised to 100 ° C. under a nitrogen atmosphere. Then, 122.5 parts by mass of glycidyl methacrylate (GMA), 6 parts by mass of Perbutyl O (manufactured by 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-forming mixture, 0.1 parts by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization. Next, while blowing in air, 59.6 parts by mass of acrylic acid (AA) was added, and the temperature was raised to 110 ° C., and 0.8 parts by mass of triethylamine was added and the addition reaction was carried out at 110 ° C. for 15 hours. Next, while blowing air into the mixture, 17.9 parts by mass of succinic anhydride was added, and an addition reaction was carried out at 110°C for 5 hours to obtain an alkali-soluble resin I solution (weight average molecular weight (Mw) 9,500, ethylenically unsaturated bond equivalent 242, acid value 30 mgKOH / g, solid content 40% by mass).

[0160] (Synthesis Example 2: Preparation of Alkali-Soluble Resin II) A polymerization vessel was charged with 300 parts by mass of PGMEA, and the temperature was raised to 100 ° C. under a nitrogen atmosphere. Then, 59.2 parts by mass of glycidyl methacrylate (GMA), 94.2 parts by mass of benzyl methacrylate (BzMA), 6 parts by mass of Perbutyl O (manufactured by NOF Corporation), and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. Thereafter, the reaction was continued while maintaining 100 ° C., and 2 hours after the end of the dropwise addition of the main chain forming mixture, 0.1 parts by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization. Next, while blowing air, 28.8 parts by mass of acrylic acid (AA) was added, and the temperature was raised to 110 ° C., and 0.8 parts by mass of triethylamine was added and the addition reaction was carried out at 110 ° C. for 15 hours. Next, while blowing air into the mixture, 17.8 parts by mass of succinic anhydride was added, and an addition reaction was carried out at 110°C for 5 hours to obtain an alkali-soluble resin II solution (weight average molecular weight (Mw) 9,500, ethylenically unsaturated bond equivalent 500, acid value 30 mgKOH / g, solid content 40% by mass).

[0161] (Synthesis Example 3: Preparation of Alkali-Soluble Resin III) A polymerization vessel was charged with 300 parts by mass of PGMEA, and the temperature was raised to 100 ° C. under a nitrogen atmosphere. Then, 49.3 parts by mass of glycidyl methacrylate (GMA), 108.8 parts by mass of benzyl methacrylate (BzMA), 6 parts by mass of Perbutyl O (manufactured by NOF Corporation), and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. Thereafter, the reaction was continued while maintaining the temperature at 100 ° C., and 2 hours after the end of the dropwise addition of the main chain forming mixture, 0.1 parts by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization. Next, while blowing in air, 24.0 parts by mass of acrylic acid (AA) was added, and the temperature was raised to 110 ° C., and 0.8 parts by mass of triethylamine was added and the addition reaction was carried out at 110 ° C. for 15 hours. Next, 17.9 parts by mass of succinic anhydride was added while blowing air into the mixture, and an addition reaction was carried out at 110°C for 5 hours to obtain an alkali-soluble resin III solution (weight average molecular weight (Mw) 9,500, ethylenically unsaturated bond equivalent 600, acid value 30 mgKOH / g, solid content 40% by mass).

[0162] (Synthesis Example 4: Preparation of Alkali-Soluble Resin IV) A polymerization vessel was charged with 300 parts by mass of PGMEA, and the temperature was raised to 100 ° C. under a nitrogen atmosphere. Then, 127.3 parts by mass of glycidyl methacrylate (GMA), 6 parts by mass of Perbutyl O (manufactured by 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 forming mixture, 0.1 parts by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization. Next, while blowing in air, 62.0 parts by mass of acrylic acid (AA) was added, and the temperature was raised to 110 ° C., and 0.8 parts by mass of triethylamine was added and the addition reaction was carried out at 110 ° C. for 15 hours. Next, 10.7 parts by mass of succinic anhydride was added while blowing air into the mixture, and an addition reaction was carried out at 110°C for 5 hours to obtain an alkali-soluble resin IV solution (weight average molecular weight (Mw) 9,200, ethylenically unsaturated bond equivalent 233, acid value 30 mgKOH / g, solid content 40% by mass).

[0163] (Synthesis Example 5: Preparation of Alkali-Soluble Resin V) A polymerization vessel was charged with 300 parts by mass of PGMEA, and the temperature was raised to 100 ° C. under a nitrogen atmosphere. Then, 112.9 parts by mass of glycidyl methacrylate (GMA), 6 parts by mass of Perbutyl O (manufactured by 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 forming mixture, 0.1 parts by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization. Next, while blowing in air, 54.9 parts by mass of acrylic acid (AA) was added, and the temperature was raised to 110 ° C., and 0.8 parts by mass of triethylamine was added and the addition reaction was carried out at 110 ° C. for 15 hours. Next, 32.2 parts by mass of succinic anhydride was added while blowing air into the mixture, and an addition reaction was carried out at 110°C for 5 hours to obtain an alkali-soluble resin V solution (weight average molecular weight (Mw) 9,700, ethylenically unsaturated bond equivalent 262, acid value 90 mgKOH / g, solid content 40% by mass).

[0164] (Synthesis Example 6: Preparation of Alkali-Soluble Resin VI) A polymerization vessel was charged with 300 parts by mass of PGMEA, and the temperature was raised to 100°C under a nitrogen atmosphere. Then, 128.6 parts by mass of glycidyl methacrylate (GMA), 6 parts by mass of Perbutyl O (manufactured by 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. Two hours after the completion of the dropwise addition of the main chain-forming 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, 62.6 parts by mass of acrylic acid (AA) was added, and the mixture was heated to 110°C. Then, 0.8 parts by mass of triethylamine was added and the mixture was subjected to an addition reaction at 110°C for 15 hours. Next, 8.9 parts by mass of succinic anhydride was added while blowing air into the mixture, and an addition reaction was carried out at 110°C for 5 hours to obtain an alkali-soluble resin VI solution (weight average molecular weight (Mw) 9,200, ethylenically unsaturated bond equivalent 230, acid value 25 mgKOH / g, solid content 40% by mass).

[0165] Synthesis Example 7: Preparation of Alkali-Soluble Resin VII A polymerization vessel was charged with 300 parts by mass of PGMEA, and the temperature was raised to 100°C under a nitrogen atmosphere. Then, 111.7 parts by mass of glycidyl methacrylate (GMA), 6 parts by mass of Perbutyl O (manufactured by 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. Two hours after the completion of the dropwise addition of the main chain-forming 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, 54.4 parts by mass of acrylic acid (AA) was added, and the mixture was heated to 110°C. Then, 0.8 parts by mass of triethylamine was added, and the mixture was subjected to an addition reaction at 110°C for 15 hours. Next, 34.0 parts by mass of succinic anhydride was added while blowing air into the mixture, and an addition reaction was carried out at 110°C for 5 hours to obtain an alkali-soluble resin VII solution (weight average molecular weight (Mw) 9,800, ethylenically unsaturated bond equivalent 265, acid value 95 mgKOH / g, solid content 40% by mass).

[0166] Synthesis Example 8 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 the reaction flask was cooled to −60° C., 3.8 parts by mass of butyllithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isobutyrate were injected using a syringe. B block monomers, 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA), 29.1 parts by mass of 2-(trimethylsilyloxy)ethyl methacrylate (TMSMA), 12.8 parts by mass of 2-ethylhexyl methacrylate (EHMA), 13.7 parts by mass of n-butyl methacrylate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), and 17.5 parts by mass of methyl methacrylate (MMA), were added dropwise over 60 minutes using an addition funnel. After 30 minutes, 26.7 parts by mass of A block monomer, dimethylaminoethyl methacrylate (DMMA), was added dropwise over 20 minutes. After reacting for 30 minutes, the reaction was terminated by adding 1.5 parts by mass of methanol. The resulting precursor block copolymer THF solution was reprecipitated in hexane, filtered, purified by vacuum drying, and diluted with PGMEA to obtain a solution with a solids content of 30% by mass. 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 general formula (I). The weight-average molecular weight Mw was 10,000.

[0167] Synthesis Example 9 Preparation of Alkali-Soluble Resin A A polymerization tank was charged with 300 parts by mass of PGMEA and heated to 100°C under a nitrogen atmosphere. Then, 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 (manufactured by 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. Two hours after the completion of the dropwise addition of the main chain-forming 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 an addition reaction was carried out at 110°C for 15 hours to obtain an alkali-soluble resin A solution (weight average molecular weight (Mw) 8,500, ethylenically unsaturated bond equivalent 1,400, acid value 75 mgKOH / g, solid content 40% by mass).

[0168] Synthesis Example 10: Synthesis of oxime ester photoinitiator represented by formula (A-2) The oxime ester photoinitiator represented by 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.

[0169] Synthesis Example 11: Synthesis of oxime ester photoinitiator represented by formula (B-1) The oxime ester photoinitiator represented by formula (B-1) was synthesized in the same manner as in the production of photopolymerization initiator W (photopolymerization initiator represented by formula (3)) described in paragraph 0080 of JP2010-256891A.

[0170] Synthesis Example 12 Preparation of Phosphoric Acid Dispersant A1 A flask was charged with 618 parts by mass of methoxypolyethylene glycol having an average molecular weight of 1000, 353 parts by mass of caprolactone, and 1 part by mass of dibutyltin dilaurate, and the mixture was heated to 160°C and stirred at this temperature until the solids content reached 98%, yielding a monohydroxy compound. 29 parts by mass of phosphorus pentoxide was added thereto, and the mixture was stirred at 80°C for 5 hours while removing moisture, yielding a phosphoric acid dispersant A1 (molecular weight 2000, a mixture of general formula (1) containing a polycaprolactone residue in which m=2 in Ra and p3 is 5 and a polyethylene glycol residue in which p1 is 22, Rb is an alkyl group having 1 carbon atom, and n is 1 or 2).

[0171] (Preparation Example 1: Preparation of Colorant Dispersion G1) In a 225 mL mayonnaise bottle, 72.1 parts by mass of PGMEA, 15 parts by mass of the alkali-soluble resin A solution (solid content 40% by mass), and 10.2 parts by mass of the PGMEA solution of block copolymer 1 (solid content 35% by mass) were added and stirred. 0.4 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Industries, Ltd.) was added, and the mixture was stirred at room temperature for 30 minutes. 13.3 parts by mass of C.I. Pigment Green 58 (G58, maximum absorption wavelength 663 nm) as a green pigment and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were added, and the mixture was shaken for 1 hour using a paint shaker (manufactured by Asada Iron Works Co., Ltd.) as a pre-crushing agent. 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 using a paint shaker to obtain colorant dispersion G1. The block copolymer 1 is salt-formed with phenylphosphonic acid to form a salt-type block copolymer 1.

[0172] (Preparation Example 2: Preparation of Colorant Dispersion Liquid G2) A colorant dispersion liquid G2 was obtained in the same manner as in Preparation Example 1, except that C.I. Pigment Green 7 (G7, maximum absorption wavelength 642 nm) was used instead of the green pigment C.I. Pigment Green 58 (G58).

[0173] (Preparation Example 3: Preparation of Colorant Dispersion Liquid G3) A colorant dispersion liquid G3 was obtained in the same manner as in Preparation Example 1, except that C.I. Pigment Green 36 (G36, maximum absorption wavelength 656 nm) was used instead of the green pigment C.I. Pigment Green 58 (G58).

[0174] (Preparation Example 4: Preparation of Colorant Dispersion Liquid G4) A colorant dispersion liquid G4 was obtained in the same manner as in Preparation Example 1, except that C.I. Pigment Green 59 (G59, maximum absorption wavelength 645 nm) was used instead of the green pigment C.I. Pigment Green 58 (G58).

[0175] (Preparation Example 5: Preparation of Colorant Dispersion Liquid Y1) A colorant dispersion liquid Y1 was obtained in the same manner as in Preparation Example 1, except that C.I. Pigment Yellow 150 (Y150) was used instead of the green pigment C.I. Pigment Green 58 (G58).

[0176] (Preparation Example 6: Preparation of Colorant Dispersion Liquid B1) A colorant dispersion liquid B1 was obtained in the same manner as in Preparation Example 1, except that C.I. Pigment Blue 15:6 (B15:6) was used instead of the green pigment C.I. Pigment Green 58 (G58).

[0177] [Preparation of High-Refractive Index Inorganic Particle Dispersion] (Preparation Example 5: Preparation of High-Refractive Index Inorganic Particle Dispersion a) 81.25 parts by mass of PGMEA and 3.75 parts by mass of a phosphate-based dispersant with a molecular weight of 2000 (solid content 100% by mass, the phosphate-based dispersant A1) were added to a 225 mL mayonnaise bottle and stirred at room temperature for 30 minutes. 15 parts by mass of zirconia oxide particles with a particle size of 15 nm and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were added thereto, and the mixture was shaken for 1 hour using a paint shaker (manufactured by Asada Iron Works Co., Ltd.) as a pre-crushing solution. Subsequently, the mixture was changed to 200 parts of zirconia beads with a particle size of 0.1 mm and dispersed for 4 hours using the paint shaker as a main crushing solution, thereby obtaining a high-refractive index inorganic particle dispersion a.

[0178] Preparation Example 6: Preparation of high refractive index inorganic particle dispersion liquid b A high refractive index inorganic particle dispersion liquid b was obtained in the same manner as in Preparation Example 5, except that barium titanate particles having a particle diameter of 15 nm were used instead of the zirconia particles having a particle diameter of 15 nm in Preparation Example 5.

[0179] Preparation Example 7 Preparation of High-Refractive-Index Inorganic Particle Dispersion Liquid c A high-refractive-index inorganic particle dispersion liquid c was obtained in the same manner as in Preparation Example 5, except that titanium oxide particles having a particle diameter of 15 nm were used instead of the zirconia particles having a particle diameter of 15 nm in Preparation Example 5.

[0180] (Example 1: Production of Photosensitive Colored Resin Composition 1) 0.10 parts by mass of FDB-022 (manufactured by Yamada Chemical Co., Ltd., hereinafter referred to as "Dye-1", maximum absorption wavelength 493 nm) as a first colorant, 0.34 parts by mass of FDG-005 (manufactured by Yamada Chemical Co., Ltd., hereinafter referred to as "Dye-2-1", maximum absorption wavelength 583 nm) as a second colorant, 1.99 parts by mass of Colorant Dispersion G1 as a green pigment third colorant, 1.12 parts by mass of Tinuvin 970 (manufactured by BASF, hereinafter referred to as "Dye-4", maximum absorption wavelength 380 nm) as a fourth colorant, 18.75 parts by mass of the obtained alkali-soluble resin I, 4.86 parts by mass of photopolymerizable compound (i) (trade name Aronix M-930, manufactured by Toagosei Co., Ltd., a mixture of glycerin diacrylate and glycerin triacrylate), 0.60 parts by mass of the oxime ester photoinitiator represented by the formula (A-1), 0.04 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), and 72.17 parts by mass of PGMEA were added to obtain a photosensitive colored resin composition 1.

[0181] (Example 2: Production of photosensitive colored resin composition 2) Dye-1 as the first colorant 0.09 parts by mass, FDG-006 (manufactured by Yamada Chemical Co., Ltd., hereinafter "Dye-2-2", maximum absorption wavelength 585 nm) as the second colorant 0.52 parts by mass, 1.62 parts by mass of colorant dispersion G1 as a green pigment of the third colorant, 1.08 parts by mass of Dye-4 as a fourth colorant, 18.75 parts by mass of the alkali-soluble resin I obtained in Synthesis Example 1, 4.82 parts by mass of photopolymerizable compound (i), 0.60 parts by mass of the oxime ester photoinitiator represented by the formula (A-1), 0.04 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), 72.47 parts by mass of PGMEA was added to obtain a photosensitive colored resin composition 2.

[0182] (Example 3: Production of photosensitive colored resin composition 3) 0.10 parts by mass of Dye-1 as the first colorant, 0.34 parts by mass of FDG-007 (manufactured by Yamada Chemical Co., Ltd., hereinafter "Dye-2-3", maximum absorption wavelength 594 nm) as the second colorant, 1.38 parts by mass of colorant dispersion G1 as a green pigment of the third colorant, 1.14 parts by mass of Dye-4 as a fourth colorant, 18.75 parts by mass of the alkali-soluble resin I obtained in Synthesis Example 1, 4.98 parts by mass of photopolymerizable compound (i), 0.60 parts by mass of the oxime ester photoinitiator represented by the formula (A-1), 0.04 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), 72.66 parts by mass of PGMEA was added to obtain a photosensitive colored resin composition 3.

[0183] (Example 4: Production of photosensitive colored resin composition 4) 0.10 parts by mass of Dye-1 as the first colorant, 0.34 parts by mass of Dye-2-1 as the second colorant, 1.87 parts by mass of colorant dispersion G1 as a green pigment of the third colorant, 18.75 parts by mass of the alkali-soluble resin I obtained in Synthesis Example 1, 6.01 parts by mass of photopolymerizable compound (i), 0.60 parts by mass of the oxime ester photoinitiator represented by the formula (A-1), 0.04 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), and 72.27 parts by mass of PGMEA were added to obtain a photosensitive colored resin composition 4.

[0184] (Example 5: Production of photosensitive colored resin composition 5) 0.07 parts by mass of Dye-1 as the first colorant, 0.30 parts by mass of Dye-2-1 as the second colorant, 2.00 parts by mass of colorant dispersion G1 as a green pigment of the third colorant, 1.12 parts by mass of Dye-4 as a fourth colorant, 18.75 parts by mass of the alkali-soluble resin I obtained in Synthesis Example 1, 4.94 parts by mass of photopolymerizable compound (i), 0.60 parts by mass of the oxime ester photoinitiator represented by the formula (A-1), 0.04 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), 72.17 parts by mass of PGMEA was added to obtain a photosensitive colored resin composition 5.

[0185] (Example 6: Production of photosensitive colored resin composition 6) 0.10 parts by mass of Dye-1 as the first colorant, 0.22 parts by mass of Dye-2-1 as the second colorant, 2.13 parts by mass of colorant dispersion G1 as a green pigment of the third colorant, 1.12 parts by mass of Dye-4 as a fourth colorant, 18.75 parts by mass of the alkali-soluble resin I obtained in Synthesis Example 1, 4.95 parts by mass of photopolymerizable compound (i), 0.60 parts by mass of the oxime ester photoinitiator represented by the formula (A-1), 0.04 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), 72.07 parts by mass of PGMEA was added to obtain a photosensitive colored resin composition 6.

[0186] (Example 7: Production of photosensitive colored resin composition 7) 0.18 parts by mass of Dye-1 as the first colorant, 0.34 parts by mass of Dye-2-1 as the second colorant, 1.95 parts by mass of colorant dispersion G1 as a green pigment of the third colorant, 1.01 parts by mass of Dye-4 as the fourth colorant, 0.91 parts by mass of colorant dispersion Y1 as another colorant (fifth colorant), 18.75 parts by mass of the alkali-soluble resin I obtained in Synthesis Example 1, 4.73 parts by mass of photopolymerizable compound (i), 0.60 parts by mass of the oxime ester photoinitiator represented by the formula (A-1), 0.04 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), 71.49 parts by mass of PGMEA was added to obtain a photosensitive colored resin composition 7.

[0187] (Example 8: Production of photosensitive colored resin composition 8) 0.07 parts by mass of Dye-1 as the first colorant, 0.24 parts by mass of Dye-2-1 as the second colorant, 1.02 parts by mass of colorant dispersion G4 as a green pigment of the third colorant, 18.75 parts by mass of the alkali-soluble resin I obtained in Synthesis Example 1, 6.33 parts by mass of photopolymerizable compound (i), 0.60 parts by mass of the oxime ester photoinitiator represented by the formula (A-1), 0.04 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), and 72.94 parts by mass of PGMEA were added to obtain a photosensitive colored resin composition 8.

[0188] (Example 9: Production of photosensitive colored resin composition 9) 0.13 parts by mass of Dye-1 as the first colorant, 0.66 parts by mass of Dye-2-1 as the second colorant, 1.51 parts by mass of colorant dispersion G1 as a green pigment of the third colorant, 0.86 parts by mass of Dye-4 as a fourth colorant, 18.75 parts by mass of the alkali-soluble resin I obtained in Synthesis Example 1, 4.89 parts by mass of photopolymerizable compound (i), 0.60 parts by mass of the oxime ester photoinitiator represented by the formula (A-1), 0.04 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), 72.56 parts by mass of PGMEA was added to obtain a photosensitive colored resin composition 9.

[0189] (Example 10: Production of photosensitive colored resin composition 10) 0.09 parts by mass of Dye-1 as the first colorant, 0.30 parts by mass of Dye-2-3 as the second colorant, 1.50 parts by mass of colorant dispersion G1 as a green pigment of the third colorant, 1.20 parts by mass of Dye-4 as a fourth colorant, 18.75 parts by mass of the alkali-soluble resin I obtained in Synthesis Example 1, 4.95 parts by mass of photopolymerizable compound (i), 0.60 parts by mass of the oxime ester photoinitiator represented by the formula (A-1), 0.04 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), 72.57 parts by mass of PGMEA was added to obtain a photosensitive colored resin composition 10.

[0190] (Example 11: Production of photosensitive colored resin composition 11) 0.10 parts by mass of Dye-1 as the first colorant, 0.32 parts by mass of Dye-2-1 as the second colorant, 1.00 parts by mass of colorant dispersion G1 as a green pigment of the third colorant, 1.07 parts by mass of Dye-4 as the fourth colorant, 1.69 parts by mass of colorant dispersion B1 as another colorant (fifth colorant), 18.75 parts by mass of the alkali-soluble resin I obtained in Synthesis Example 1, 4.80 parts by mass of photopolymerizable compound (i), 0.60 parts by mass of the oxime ester photoinitiator represented by the formula (A-1), 0.04 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), 71.63 parts by mass of PGMEA was added to obtain a photosensitive colored resin composition 11.

[0191] (Example 12: Production of photosensitive colored resin composition 12) 0.10 parts by mass of Dye-1 as the first colorant, 0.34 parts by mass of Dye-2-1 as the second colorant, 1.12 parts by mass of colorant dispersion G1 as a green pigment of the third colorant, 1.17 parts by mass of Dye-4 as a fourth colorant, 18.75 parts by mass of the alkali-soluble resin I obtained in Synthesis Example 1, 5.00 parts by mass of photopolymerizable compound (i), 0.60 parts by mass of the oxime ester photoinitiator represented by the formula (A-1), 0.04 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), 72.86 parts by mass of PGMEA was added to obtain a photosensitive colored resin composition 12.

[0192] (Example 13: Production of photosensitive colored resin composition 13) 0.10 parts by mass of Dye-1 as the first colorant, 0.34 parts by mass of Dye-2-1 as the second colorant, 1.25 parts by mass of colorant dispersion G2 as a green pigment of the third colorant, 1.14 parts by mass of Dye-4 as a fourth colorant, 18.75 parts by mass of the alkali-soluble resin I obtained in Synthesis Example 1, 5.00 parts by mass of photopolymerizable compound (i), 0.60 parts by mass of the oxime ester photoinitiator represented by the formula (A-1), 0.04 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), 72.76 parts by mass of PGMEA was added to obtain a photosensitive colored resin composition 13.

[0193] (Example 14: Production of photosensitive colored resin composition 14) 0.10 parts by mass of Dye-1 as the first colorant, 0.34 parts by mass of Dye-2-1 as the second colorant, 2.00 parts by mass of colorant dispersion G3 as a green pigment of the third colorant, 1.11 parts by mass of Dye-4 as a fourth colorant, 18.75 parts by mass of the alkali-soluble resin I obtained in Synthesis Example 1, 4.88 parts by mass of photopolymerizable compound (i), 0.60 parts by mass of the oxime ester photoinitiator represented by the formula (A-1), 0.04 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), 72.17 parts by mass of PGMEA was added to obtain a photosensitive colored resin composition 14.

[0194] (Example 15: Production of photosensitive colored resin composition 15) 0.10 parts by mass of Dye-1 as the first colorant, 0.34 parts by mass of Dye-2-1 as the second colorant, 1.50 parts by mass of colorant dispersion G4 as a green pigment of the third colorant, 1.15 parts by mass of Dye-4 as a fourth colorant, 18.75 parts by mass of the alkali-soluble resin I obtained in Synthesis Example 1, 4.93 parts by mass of photopolymerizable compound (i), 0.60 parts by mass of the oxime ester photoinitiator represented by the formula (A-1), 0.04 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), 72.57 parts by mass of PGMEA was added to obtain a photosensitive colored resin composition 15.

[0195] (Example 16: Production of photosensitive colored resin composition 16) 0.15 parts by mass of Dye-1 as the first colorant, 0.69 parts by mass of Dye-2-3 as the second colorant, 18.75 parts by mass of the alkali-soluble resin I obtained in Synthesis Example 1, 1.14 parts by mass of Dye-4 as the fourth colorant, 4.87 parts by mass of photopolymerizable compound (i), 0.60 parts by mass of the oxime ester photoinitiator represented by the formula (A-1), 0.04 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), and 73.75 parts by mass of PGMEA were added to obtain a photosensitive colored resin composition 16.

[0196] (Example 17: Production of photosensitive colored resin composition 17) In Example 1, except that in place of the alkali-soluble resin I, alkali-soluble resin II is used, the same procedure as in Example 1 is carried out to obtain photosensitive colored resin composition 17.

[0197] (Example 18: production of photosensitive colored resin composition 18) In Example 1, except that in place of the alkali-soluble resin I, alkali-soluble resin III is used, the same procedure as in Example 1 is carried out to obtain photosensitive colored resin composition 18.

[0198] (Example 19: Production of photosensitive colored resin composition 19) In Example 1, except that in place of the alkali-soluble resin I, alkali-soluble resin IV is used, the same procedure as in Example 1 is carried out to obtain photosensitive colored resin composition 19.

[0199] (Example 20: production of photosensitive colored resin composition 20) In Example 1, except that in Example 1, instead of the alkali-soluble resin I, alkali-soluble resin V is used, the same procedure as in Example 1 is carried out to obtain photosensitive colored resin composition 20.

[0200] (Example 21: production of photosensitive colored resin composition 21) In Example 1, except that in place of the alkali-soluble resin I, alkali-soluble resin VI is used, the same procedure as in Example 1 is carried out to obtain photosensitive colored resin composition 21.

[0201] (Example 22: Production of photosensitive colored resin composition 22) In Example 1, except that in place of the alkali-soluble resin I, alkali-soluble resin VII is used, the same procedure as in Example 1 is carried out to obtain photosensitive colored resin composition 22.

[0202] (Example 23: Production of photosensitive colored resin composition 23) In Example 1, the photopolymerizable compound (i) was replaced with a photopolymerizable compound (ii) (trade name Aronix M-305, manufactured by Toa Gosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate), except that the same procedure as in Example 1 was used to obtain a photosensitive colored resin composition 23.

[0203] (Example 24: Production of photosensitive colored resin composition 24) In Example 1, the photopolymerizable compound (i) was replaced with a photopolymerizable compound (iii) (trade name Aronix M-403, manufactured by Toa Gosei Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), except that the same procedure as in Example 1 was used to obtain a photosensitive colored resin composition 24.

[0204] (Example 25: Production of photosensitive colored resin composition 25) In Example 1, instead of the oxime ester photoinitiator represented by the formula (A-1), the oxime ester photoinitiator represented by the formula (B-1) was used, except that the same procedure as in Example 1 was used to obtain a photosensitive colored resin composition 25.

[0205] (Example 26: Production of photosensitive colored resin composition 26) In Example 1, instead of the photoinitiator A-1, photoinitiator C-1 (Omnirad369, manufactured by IGM Resins BV) was used, except that a photosensitive colored resin composition 26 was obtained in the same manner as in Example 1.

[0206] (Example 27: Production of photosensitive colored resin composition 27) 0.10 parts by mass of Dye-1 as the first colorant, 0.34 parts by mass of Dye-2-1 as the second colorant, 1.99 parts by mass of colorant dispersion G1 as a green pigment of the third colorant, 1.12 parts by mass of Dye-4 as a fourth colorant, 25.00 parts by mass of high refractive index inorganic particle dispersion a, 12.00 parts by mass of the alkali-soluble resin I obtained in Synthesis Example 1, 2.86 parts by mass of photopolymerizable compound (i), 0.60 parts by mass of the oxime ester photoinitiator represented by the formula (A-1), 0.04 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), and 55.92 parts by mass of PGMEA were added to obtain a photosensitive colored resin composition 27.

[0207] (Example 28: Production of photosensitive colored resin composition 28) In Example 27, in place of the high refractive index inorganic particle dispersion liquid a, high refractive index inorganic particle dispersion liquid b was used, except for the same procedure as in Example 27, photosensitive colored resin composition 28 was obtained.

[0208] (Example 29: Production of photosensitive colored resin composition 29) In Example 27, in place of the high refractive index inorganic particle dispersion liquid a, high refractive index inorganic particle dispersion liquid c was used, except for the same procedure as in Example 27, photosensitive colored resin composition 29 was obtained.

[0209] (Comparative Example 1: Production of photosensitive colored resin composition C1) 0.12 parts by mass of Dye-1, 1.50 parts by mass of colorant dispersion G1, 18.75 parts by mass of the alkali-soluble resin I obtained in Synthesis Example 1, 6.42 parts by mass of photopolymerizable compound (i), 0.60 parts by mass of the oxime ester photoinitiator represented by the formula (A-1), 0.04 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), and 72.57 parts by mass of PGMEA were added to obtain a photosensitive colored resin composition C1.

[0210] (Comparative Example 2: Production of photosensitive colored resin composition C2) Dye-2-1 0.34 parts by mass, colorant dispersion G1 1.80 parts by mass, Dye-4 1.80 parts by mass, 18.75 parts by mass of the alkali-soluble resin I obtained in Synthesis Example 1, 6.13 parts by mass of photopolymerizable compound (i), 0.60 parts by mass of the oxime ester photoinitiator represented by the formula (A-1), 0.04 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), and 72.33 parts by mass of PGMEA were added to obtain a photosensitive colored resin composition C2.

[0211] (Comparative Example 3: Production of Photosensitive Colored Resin Composition C3) 0.10 parts by mass of Dye-1, 0.34 parts by mass of Dye-2-1, 1.99 parts by mass of colorant dispersion G1, 1.12 parts by mass of Dye-4, 8.60 parts by mass of urethane acrylate (UA) (trade name UA-306H, manufactured by Kyoeisha Chemical Co., Ltd., pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer) as a photopolymerizable compound, 2.46 parts by mass of photopolymerizable compound (ii), 1.23 parts by mass of photopolymerizable compound (iii), photoinitiator C-2 (Omnirad TPO, IGM Resins 0.68 parts by mass of a fluororesin (manufactured by BV), 0.04 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), and 83.42 parts by mass of PGMEA were added to obtain a photosensitive colored resin composition C3.

[0212] In Table 1, the concentration of the coloring material indicates the content (% by mass) based on the total solid content.

[0213] [Evaluation Method] <Transmittance> The photosensitive color resin composition obtained in each Example and Comparative Example was applied to a glass substrate (manufactured by NH Technoglass Co., Ltd., "NA35") having a SiNx film formed thereon using a spin coater so that the cured film had a thickness of 3.0 μm, and then dried using a hot plate at 80° C. for 3 minutes to form a coating film on the substrate. This coating film was then irradiated with 100 mJ / cm using an ultra-high pressure mercury lamp. ２ Each SiNx film was exposed to ultraviolet light 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 incubating in the developer for 60 seconds and then rinsing with pure water to obtain a coating film. This was then post-baked in a clean oven at 90°C for 30 minutes to form a 3.0 μm thick cured film. Using the cured film thus obtained, transmittance measurements and light extraction efficiency evaluations were performed. The transmission spectrum of the 3.0 μm thick cured film was measured in the range of 380 nm to 780 nm using a microspectrophotometer OSP-SP200 (manufactured by Olympus), and the transmittances at 380 nm, 460 nm, 530 nm, and 620 nm, the transmittance at the minimum transmission wavelength of 480 nm to 520 nm, and the transmittance at the minimum transmission wavelength of 560 nm to 600 nm were determined.

[0214] <Solvent Resistance Evaluation> The photosensitive colored resin compositions obtained in each Example and Comparative Example were applied to a glass substrate (manufactured by NH Technoglass Co., Ltd., "NA35") having a SiNx film formed thereon using a spin coater so that the cured film had a thickness of 3.0 μm, and then dried at 80° C. for 3 minutes using a hot plate to form a coating film on the substrate. This coating film was irradiated with 100 mJ / cm using an ultra-high pressure mercury lamp through a photomask (chrome mask) having a pattern with opening dimensions of 2 μm to 100 μm for forming isolated thin lines. ２Each SiNx film was exposed to ultraviolet light at 1000 Wt. 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. The film was then exposed to the developer for 60 seconds, followed by rinsing with pure water for development, 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. The resulting cured film was evaluated for solvent resistance. The film thickness of the resulting cured film was measured, then immersed in propylene glycol monomethyl ether (PGME) for 10 minutes, air-dried, and the film 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 as film thickness after solvent immersion / film thickness before solvent immersion x 100. (Evaluation criteria for solvent resistance) AA: Residual film rate after solvent immersion is 98.5% or more A: Residual film rate after solvent immersion is 96% or more and less than 98.5% B: Residual film rate after solvent immersion is 94% or more and less than 96% C: Residual film rate after solvent immersion is less than 94% If the evaluation result is B, the film can be used for practical purposes, but if the evaluation result is A or even AA, the film has excellent solvent resistance.

[0215] <Evaluation of adhesion during development> The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were applied to a glass substrate (manufactured by NH Technoglass Co., Ltd., "NA35") having a SiNx film formed thereon using a spin coater in a thickness that would form a cured film with a thickness of 3.0 μm after post-baking, and then dried using a hot plate at 80° C. for 3 minutes to form a coating film. This coating film was then exposed to 100 mJ / cm 2 of light using an ultra-high pressure mercury lamp through a photomask (chrome mask) having a pattern with opening dimensions of 2 μm to 80 μm. ２The glass plate on which the exposed coating film was formed was shower-developed for 60 seconds using a 0.05% by mass aqueous potassium hydroxide solution as an alkaline developer. The developed substrate was observed under an optical microscope to check for the presence or absence of a colored cured film in the fine line pattern relative to the mask opening line width. The development adhesion was evaluated based on the minimum line width of the colored cured film in the remaining fine line pattern. (Development Adhesion Evaluation Criteria) AA: A colored cured film was observed in areas with a mask opening line width of less than 10 μm. A: A colored cured film was observed in areas with a mask opening line width of 10 μm or more but less than 20 μm. B: A colored cured film was observed in areas with a mask opening line width of 20 μm or more but less than 30 μm. C: A colored cured film was not observed in areas with a mask opening line width of 30 μm or less. A rating of B indicates practical use, while A is better, and AA is even better.

[0216] [Evaluation of Pattern Linearity] In the colored cured film used for evaluating development adhesion, the width of the fine line pattern of the colored cured film in a portion corresponding to the 35 μm opening width of the chrome mask was measured at five points using an optical microscope, and linearity was evaluated based on the variation in line width. AA: Variation within ±0.1 μm A: Variation exceeding ±0.1 μm to ±0.3 μm B: Variation exceeding ±0.3 μm to ±0.5 μm C: Variation exceeding ±0.5 μm An evaluation result of B indicates practical use, while an evaluation result of A or even AA indicates excellent linearity.

[0217] <Evaluation of Light Extraction Efficiency (Refractive Index)> The refractive index of the colored cured film used in the transmittance measurement was measured using a rotary compensator type high-speed spectroscopic ellipsometer M-2000UI (manufactured by J.A. Woollam Japan). The measurement wavelength range was 380 to 780 nm, and the n value was measured every 1 nm, and the average value was taken as the refractive index. When the refractive index of the colored cured film is 1.65 or more, it can be evaluated that the light extraction efficiency is sufficiently improved.

[0218]

[0219] [Summary of Results] The photosensitive colored resin compositions of Examples 1 to 29 comprise a first colorant having a maximum absorption wavelength of 480 nm to 520 nm and a second colorant having a maximum absorption wavelength of 560 nm to 600 nm, and the transmittance of the cured film having a thickness of 3.0 μm at 460 nm, 530 nm, and 620 nm is 45% to 85%. The transmittance of the minimum transmission wavelength of 480 nm to 520 nm is 50% or less, and the transmittance of the minimum transmission wavelength of 560 nm to 600 nm is 25% or less. It was shown that the photosensitive colored resin composition can form a colored cured film that suppresses external light reflection and improves the display quality of organic light-emitting devices. In contrast, the photosensitive colored resin composition of Comparative Example 1, which does not contain a second colorant having a maximum absorption wavelength of 560 nm to 600 nm, has a high transmittance at the minimum transmission wavelength of 560 nm to 600 nm, and shows insufficient suppression of external light reflection. Furthermore, the photosensitive colored resin composition of Comparative Example 2, which does not contain a first coloring material having a maximum absorption wavelength of 480 nm to 520 nm, had a high transmittance at a minimum transmission wavelength of 480 nm to 520 nm, and was shown to have insufficient suppression of external light reflection. Furthermore, the colored resin composition of Comparative Example 3, which does not contain an alkali-soluble resin as in Patent Document 2, could not be developed, and patterning could not be performed. Furthermore, the cured film of the colored resin composition of Comparative Example 3, which used the same photopolymerizable compound and photoinitiator as in Patent Document 2, also had poor solvent resistance.

[0220] Among the examples, when the colorant further contains at least one green pigment selected from the group consisting of C.I. Pigment Green 7, 36, 58, and 59 as a third colorant, it is possible to reduce the contents of the first colorant and the second colorant compared to when the green pigment is not included, suppressing curing inhibition and improving the solvent resistance, adhesion, and linearity of the colored pattern. Also, among the examples, when the colorant further contains a fourth colorant with a maximum absorption wavelength of 370 nm to 450 nm, it is possible to further suppress external light reflection.

[0221] Furthermore, among the examples, it was shown that when the photoinitiator contains at least one of a compound represented by the following general formula (A) and a compound represented by the following general formula (B), the solvent resistance and adhesion of the colored pattern are improved. Furthermore, among the examples, it was shown that when the alkali-soluble resin has an ethylenically unsaturated bond equivalent of 500 or less and an acid value of 30 mgKOH / g to 90 mgKOH / g, the solvent resistance of the colored pattern is improved and the adhesion and linearity are also good. Furthermore, among the examples, it was shown that when the photopolymerizable compound contains a mixture of glycerin diacrylate and glycerin triacrylate, the linearity of the colored pattern can be improved. Furthermore, among the examples, it was shown that when the composition further contains at least one type of inorganic particles having an average particle size of 100 nm or less selected from the group consisting of zirconium oxide, barium titanate, and titanium oxide, and a dispersant, wherein the dispersant includes at least one type of dispersant selected from the group consisting of phosphate ester-based dispersants, phosphonic acid-based dispersants, and phosphonic acid ester-based dispersants, and the photoinitiator includes an oxime-based photoinitiator, it is possible to form a colored cured film that has good solvent resistance, a refractive index of 1.65 or greater, and improves light extraction efficiency.

[0222] REFERENCE SIGNS LIST 1 Substrate 2 Thin film transistor (TFT) 3 Sealing film 4 Electrode 5 Partition 6R, 6G, 6B Organic light-emitting element 7 Electrode 8 Sealing film 9 Colored cured film 10 Light-shielding part 11 Overcoat layer 12 Transparent adhesive layer 13 Transparent cover material 20 External light anti-reflection film 30 Element substrate provided with organic light-emitting element 100 Display device

Claims

1. A photosensitive colored resin composition used for a cured film formed on an organic light-emitting element, comprising a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, wherein the coloring material includes a first coloring material having a maximum absorption wavelength of 480 nm to 520 nm and a second coloring material having a maximum absorption wavelength of 560 nm to 600 nm, and the transmittances of the cured film with a thickness of 3.0 μm formed using the photosensitive colored resin composition at 460 nm, 530 nm, and 620 nm are all 45% to 85%, the transmittance at the transmission minimum wavelength of 480 nm to 520 nm is 50% or less, and the transmittance at the transmission minimum wavelength of 560 nm to 600 nm is 25% or less.

2. The photosensitive colored resin composition according to claim 1, wherein the coloring material further includes at least one green pigment selected from the group consisting of C.I. Pigment Green 7, 36, 58, and 59 as a third coloring material.

3. The photosensitive colored resin composition according to claim 1 or 2, wherein the coloring material further includes a fourth coloring material having a maximum absorption wavelength of 370 nm to 450 nm.

4. The photosensitive coloring resin composition according to claim 1 or 2, wherein the photoinitiator contains at least one compound represented by the following general formula (A) and a compound represented by the following general formula (B). (In the formula, R １ and R ２ each independently represents R １１ , OR １１ , COR １１ , SR １１ , CONR １２ R １３ or CN, and 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. The hydrogen atom of the group represented by R １１ , R １２ and R １３ may be further substituted with R ２１ , OR ２１ , COR ２１ , SR ２１ , NR ２２ R ２３ , CONR ２２ R ２３ , -NR ２２ -OR ２３ , -NOCOR ２２ -O COR ２３ , NR ２２ COR ２１ , O COR ２１ , COOR ２１ , SCOR ２１ , OCSR ２１ , COR ２１ , CSOR ２１ , a hydroxyl group, a nitro group, CN, or a halogen atom, and 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 The hydrogen atom of the group represented by may be further substituted with a hydroxyl group, nitro group, CN, halogen atom, or carboxy group, and R １１ , R １２ , R １３ , R ２１ , R ２２ and R ２３ The alkylene moiety of the group represented by may contain 1 to 5 of -O-, -S-, -COO-, -OCO-, -NR ２４ -, -NR ２４ CO-, -NR ２４ COO-, -OCONR ２４ -,-SCO-,-COS-,-OCS- or -CSO- under the condition that oxygen atoms are not adjacent to each other, and 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, and R １１ , R １２ , R １３ , R ２１ , R ２２ , R ２３ and R ２４ The alkyl moiety of the group represented by may have a branched side chain or may be a cyclic alkyl, and 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, and R ３ The alkyl moiety of the group represented by may have a branched side chain or may be a cyclic alkyl. Also, R ３ and R ７ , and R ３ and R ８ may each together form a ring, and the hydrogen atom of the group represented by R ３ may be further R ２１ , OR ２１ , COR ２１ , SR ２１ , NR ２２ R ２３ , CONR ２２ R ２３ , -NR ２２ -OR ２３ , -NCOR ２２ -O COR ２３ , NR ２２ COR ２１ , OCOR ２１ , COOR ２１ , SCOR ２１ , OCSR ２１ , COSR ２１ , CSOR ２１ , may be substituted with a hydroxyl group, nitro group, CN, or halogen atom, and R ４ , R ５ , R ６ and R ７ are each independently R １１ , OR １１ , SR １１ , COR １４ , CONR １５ R １６ , NR １２ COR １１ , OCOR １１ , COOR １４ , SCOR １１ , OCSR １１ , COSR １４ , CSOR １１ , represent a hydroxyl group, CN, or halogen atom, and R ４ and R ５ , R ５ and R ６ , and R ６ and R ７ may together form a ring, and R １４ , R １５ and R １６ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R １４ , R １５ and R １６ in the group represented by may have a branched side chain or may be a cyclic alkyl, and R ８ is R １１ , OR １１ , SR １１ , COR １１ , CONR １２ R １３ , NR １２ COR １１ , OCOR １１ , COOR １１ , SCOR １１ , OCSR １１ , COSR １１ 、CSOR １１ represents a hydroxyl group, CN or a halogen atom, and k represents 0 or 1.) (In formula (B), X １ 、X ３ and X ６ are each independently R ４１ 、OR ４１ 、COR ４１ 、SR ４１ 、CONR ４２ R ４３ or CN, and X ２ represents 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, and X ４ and X ５ are each independently R ４１ 、OR ４１ 、SR ４１ 、COR ４１ 、CONR ４２ R ４３ 、NR ４２ COR ４１ 、O COR ４１ 、COOR ４１ 、SCOR ４１ 、OCSR ４１ 、COS R ４１ 、CSOR ４１ 、CN, a halogen atom or a hydroxyl group. R ４１ 、R ４２ and R ４３ are each independently 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, and the hydrogen atoms of the group represented by R ４１ 、R ４２ and R ４３ 、as well as the hydrogen atoms of the group represented by X ２ may further be R ５１ 、OR ５１ 、COR ５１ 、SR ５１ 、NR ５２ R ５３ 、CONR ５２ R ５３ 、-NR ５２ -OR ５３ 、-N COR ５２ -OCOR ５３ , NR ５２ COR ５１ , OCOR ５１ , COOR ５１ , SCOR ５１ , OCSR ５１ , COSR ５１ , CSOR ５１ , may be substituted with a hydroxyl group, nitro group, CN, or halogen atom, and R ５１ , R ５２ and R ５３ 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. The hydrogen atom of the group represented by R ５１ , R ５２ and R ５３ may be further substituted with a hydroxyl group, nitro group, CN, halogen atom, or carboxy group. The alkylene moiety of the group represented by R ４１ , R ４２ , R ４３ , X ２ , R ５１ , R ５２ and R ５３ may contain 1 to 5 of -O-, -S-, -COO-, -OCO-, -NR ５４ -, -NR ５４ CO-, -NR ５４ COO-, -OCONR ５４ -, -SCO-, -COS-, -OCS-, or -CSO- under the condition that oxygen atoms are not adjacent to each other. R ５４ 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. The alkyl moiety of the group represented by R ４１ , R ４２ , R ４３ , R ５１ , R ５２ , R ５３ and R ５４ may have a branched side chain or may be a cyclic alkyl. a and b are each independently an integer from 0 to 3.) 5. The photosensitive colored resin composition according to claim 1 or 2, wherein the alkali-soluble resin has an ethylenically unsaturated bond equivalent of 500 or less and an acid value of 30 mgKOH / g to 90 mgKOH / g.

6. The photosensitive colored resin composition according to claim 1 or 2, wherein the photopolymerizable compound includes a mixture of glycerin diacrylate and glycerin triacrylate.

7. Further, it contains at least one inorganic particle having an average particle size of 100 nm or less selected from the group consisting of zirconium oxide, barium titanate, and titanium oxide, and a dispersant, wherein the dispersant includes at least one dispersant selected from the group consisting of phosphate ester-based dispersants, phosphonic acid-based dispersants, and phosphonic acid ester-based dispersants, and the photoinitiator includes an oxime-based photoinitiator. The photosensitive colored resin composition according to claim 1 or 2.

8. A display device having a cured film of the photosensitive colored resin composition according to claim 1 or 2 on an organic light-emitting element.

9. A step of forming a coating film by applying the photosensitive colored resin composition according to claim 1 or 2 on an organic light-emitting element, a step of irradiating the coating film with light, a post-baking step of heating the film after the light irradiation, and a step of developing the film after the light irradiation, thereby forming a cured film of the photosensitive colored resin composition according to claim 1 or 2 on the organic light-emitting element. A method for manufacturing a laminate of an organic light-emitting element and an external light reflection preventing film, which comprises the step.

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