Colored resin composition, film, color filter, solid-state imaging element, and image display device

Abstract

The present invention provides a colored resin composition, a film, a color filter, a solid-state imaging element and an image display device, wherein the colored resin composition comprises a resin, a colorant and an organic solvent, wherein the resin comprises at least one repeating unit selected from the repeating units represented by any one of the following formulas (1-1) to (1-5), the total amount of the repeating units represented by any one of the following formulas (1-1) to (1-5) exceeds 60 mol% relative to the total molar amount of all repeating units contained in the resin, and the content of the colorant is 30% by mass or more relative to the total solid content of the composition.

Description

Technical Field

[0001] The present invention relates to a colored resin composition, a film, a color filter, a solid-state imaging element, and an image display device. Background Art

[0002] In recent years, due to the popularity of digital cameras, mobile phones with cameras, etc., the demand for solid-state imaging elements such as charge coupled devices (CCD) image sensors has increased significantly. Films containing pigments such as color filters are used in solid-state imaging elements. Films containing pigments such as color filters are manufactured using a colored resin composition containing a colorant, a resin, and a solvent.

[0003] For example, Patent Document 1 describes an alkali-soluble resin having specific structural units and a photosensitive resin composition for a color filter containing the resin. The alkali-soluble resin is characterized in that each structural unit is contained in a specific content.

[0004] Patent Document 2 describes a water-soluble colored photosensitive resin composition, which is characterized by comprising: a water-soluble resin having a polymer using at least one monomer selected from acrylamide-based monomers selected from α-substituted acrylamide, N-monosubstituted acrylamide, N,N-disubstituted acrylamide, and N-monosubstituted methacrylamide; a crosslinking agent having a water-soluble azide compound; and a colorant.

[0005] Previous technical literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2019-031627

[0008] Patent Document 2: Japanese Patent Application Laid-Open No. 7-311461 Summary of the invention

[0009] Technical issues to be solved by the invention

[0010] In recent years, in the manufacturing process of solid-state imaging devices, after forming a film such as a color filter using a colored resin composition containing a colorant, a resin and a solvent, a step of subjecting the film to a heat treatment requiring a high temperature (eg, 300° C. or higher) has been reviewed.

[0011] Therefore, an object of the present invention is to provide a novel colored resin composition, film, color filter, solid-state imaging element, and image display device capable of expanding the process window of steps after film production.

[0012] Means for solving technical problems

[0013] Representative embodiments of the present invention are described below.

[0014] <1> A colored resin composition comprising:

[0015] Resin;

[0016] Colours; and

[0017] Organic solvents,

[0018] The resin contains at least one repeating unit selected from the repeating units represented by any one of the following formulae (1-1) to (1-5),

[0019] The total amount of the repeating units represented by any one of the following formulae (1-1) to (1-5) exceeds 60 mol% relative to the total molar amount of all the repeating units contained in the above resin.

[0020] The content of the coloring material is 30% by mass or more based on the total solid content of the composition.

[0021] [Chemical formula 1]

[0022]

[0023] In formula (1-1), R 11 , R 12 and R 13 Each independently represents a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, Ar represents an aromatic group having 5 to 30 ring members,

[0024] In formula (1-2), R 21 , R 22 and R 23 Each independently represents a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and R 24 and R 25 Each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, and R 24 and R 25 can bond to form a ring structure,

[0025] In formula (1-3), R 31 , R 32 and R 33 Each independently represents a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and R 34 and R 35 Each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, and R 34 and R 35 can bond to form a ring structure,

[0026] In formula (1-4), R 41 and R 42Each independently represents a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and R 43 represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms,

[0027] In formula (1-5), R 51 ~R 54 Each independently represents a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and R 55 It represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0028] <2> The colored resin composition according to <1>, wherein the content of the repeating unit derived from (meth)acrylic acid or a (meth)acrylate compound in the resin is 0 to 20 mol % based on the total molar amount of all repeating units contained in the resin.

[0029] <3> The colored resin composition according to <1> or <2>, wherein the resin has at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfone group, a phosphoric acid group, and an amino group.

[0030] <4> The colored resin composition according to any one of <1> to <3>, wherein the resin has an acid value of 20 to 150 mgKOH / g.

[0031] <5> The colored resin composition according to any one of <1> to <4>, wherein the resin has an ethylenically unsaturated bond.

[0032] <6> The colored resin composition according to any one of <1> to <5>, wherein the resin has a C=C value of 0.1 to 3 mmol / g.

[0033] <7> The colored resin composition according to any one of <1> to <6>, wherein the resin is a graft polymer or a star polymer.

[0034] <8> The colored resin composition according to any one of <1> to <7>, wherein the resin has a molecular weight of 1,000 to 10,000 and has a molecular chain containing no acid group or basic group.

[0035] <9> The colored resin composition according to <8>, wherein the molecular chain includes at least one selected from a repeating unit derived from a (meth)acrylate compound, a repeating unit derived from a (meth)acrylamide compound, a repeating unit derived from an aromatic vinyl compound, and a polyester structure.

[0036] <10> The colored resin composition according to any one of <1> to <9>, comprising the following resin 1 and the following resin 2 as the resin,

[0037] Resin 1: is the above resin, and contains an acid group and a group having an ethylenically unsaturated bond,

[0038] Resin 2: The above resin having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic group, a phosphoric acid group, and an amino group, and a molecular chain having a molecular weight of 1,000 to 10,000 and no acid group.

[0039] <11> The colored resin composition according to any one of <1> to <10>, wherein the colorant includes at least one colorant selected from chromatic colorants and near infrared absorbing colorants.

[0040] <12> The colored resin composition according to any one of <1> to <11>, wherein the colorant includes a chromatic colorant and a near infrared absorbing colorant.

[0041] <13> The colored resin composition according to any one of <1> to <12>, wherein the colorant includes a black colorant.

[0042] <14> The colored resin composition according to any one of <1> to <13>, wherein the colorant includes at least one colorant selected from the group consisting of a red colorant, a yellow colorant, a blue colorant, and a violet colorant.

[0043] <15> The colored resin composition according to any one of <1> to <14>, further comprising a photopolymerization initiator.

[0044] <16> The colored resin composition according to <15>, wherein the photopolymerization initiator is an oxime compound.

[0045] <17> The colored resin composition according to any one of <1> to <16>, which is used for pattern formation by photolithography.

[0046] <18> The colored resin composition according to any one of <1> to <17>, which is used for a solid-state imaging element.

[0047] <19> A film obtained from the colored resin composition according to any one of <1> to <18>.

[0048] <20> A color filter comprising the film according to <19>.

[0049] <21> A solid-state imaging element including the film according to <19>.

[0050] <22> An image display device comprising the film according to <19>.

[0051] Effects of the Invention

[0052] According to the present invention, there can be provided a novel colored resin composition, film, color filter, solid-state imaging element, and image display device capable of expanding the process window of steps after film production. DETAILED DESCRIPTION

[0053] Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the embodiments shown.

[0054] In this specification, "to" is used to mean that the numerical values ​​described before and after it are included as a lower limit and an upper limit.

[0055] In the marking of groups (atomic groups) in this specification, the marking not indicating substituted or unsubstituted includes groups (atomic groups) without substitution and also includes groups (atomic groups) with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups).

[0056] The term "exposure" in this specification includes not only exposure using light, but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. In addition, examples of light used for exposure include bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), actinic rays or radiation such as X-rays and electron beams.

[0057] In the present specification, a (meth)allyl group represents both or either an allyl group and a methallyl group, a (meth)acrylate group represents both or either an acrylate group and a methacrylate group, a (meth)acrylic acid group represents both or either an acrylic acid group and a methacrylic acid group, and a (meth)acryloyl group represents both or either an acryloyl group and a methacryloyl group.

[0058] In this specification, the weight average molecular weight and the number average molecular weight are polystyrene conversion values ​​measured by GPC (gel permeation chromatography) method.

[0059] In this specification, near infrared rays refer to light with a wavelength of 700 to 2500 nm.

[0060] In this specification, the total solid content refers to the total mass of the components excluding the solvent from all the components of the composition.

[0061] In this specification, the term "step" refers not only to an independent step but also to a step that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved.

[0062] In the present specification, a combination of preferred embodiments is a more preferred embodiment.

[0063] (Colored resin composition)

[0064] The colored resin composition of the present invention comprises a resin, a colorant and an organic solvent.

[0065] The resin comprises at least one repeating unit selected from the repeating units represented by any one of formulas (1-1) to (1-5),

[0066] The ratio of the total amount of the repeating units represented by any one of the formulae (1-1) to (1-5) to the total molar amount of all the repeating units contained in the above resin is more than 60 mol%,

[0067] The content of the coloring material is 30% by mass or more based on the total solid content of the composition.

[0068] In the present invention, the following resin is referred to as a "specific resin", which resin contains at least one repeating unit selected from the repeating units represented by any one of the formulas (1-1) to (1-5), and the total amount of the repeating units represented by any one of the formulas (1-1) to (1-5) is greater than 60 mol% relative to the total molar amount of all repeating units contained in the above-mentioned resin.

[0069] [Chemical formula 2]

[0070]

[0071] In formula (1-1), R 11 , R 12 and R 13 Each independently represents a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, Ar represents an aromatic group having 5 to 30 ring members,

[0072] In formula (1-2), R 21 , R 22 and R 23 Each independently represents a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and R 24 and R 25 Each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, and R 24 and R 25 can bond to form a ring structure,

[0073] In formula (1-3), R 31 , R 32 and R 33 Each independently represents a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and R 34 and R 35 Each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, and R 34 and R35 can bond to form a ring structure,

[0074] In formula (1-4), R 41 and R 42 Each independently represents a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and R 43 represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms,

[0075] In formula (1-5), R 51 ~R 54 Each independently represents a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and R 55 It represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0076] The colored resin composition of the present invention contains a colorant, a resin, and an organic solvent at a high concentration (30% by mass or more).

[0077] As a result of intensive studies, the present inventors have found that, in a colored resin composition containing such a high concentration of a colorant, a resin, and an organic solvent, when a conventionally used acrylic resin is used as a resin, when a process requiring a high temperature (e.g., 300° C. or higher) heat treatment is performed, the film shrinkage of the obtained composition film becomes high, cracks occur in other films (e.g., inorganic films) formed on the obtained composition film, and the process window of the subsequent steps of film production becomes narrow.

[0078] This is presumably because the acrylic resin decomposes due to high temperatures.

[0079] Therefore, as a result of in-depth research conducted by the present inventors, it was found that by using a resin in which the total amount of repeating units represented by any one of the above formulas (1-1) to (1-5) exceeds 60 mol%, the occurrence of the above-mentioned cracks can be suppressed, and the process window of the subsequent steps of manufacturing the film can be expanded.

[0080] Although the mechanism for obtaining the above effect is unclear, it is believed that the film obtained by the colored resin composition containing the resin having a content of the above specific repeating unit exceeding 60 mol% also suppresses the decomposition of the above resin in the process requiring high temperature heating treatment. Therefore, it is presumed that the shrinkage of the above film caused by heating is suppressed, and cracking is not easy to occur, so that the applicable range of the heating temperature in the process after the film is manufactured using the colored resin composition is expanded to a higher temperature (for example, 300°C or more), thereby expanding the process window of the process after the film is manufactured.

[0081] When a film having a thickness of 0.60 μm is formed by heating the colored resin composition of the present invention at 200° C. for 30 minutes, the thickness of the film after heat treatment at 300° C. for 5 hours in a nitrogen atmosphere is preferably 70% or more of the thickness of the film before the heat treatment, more preferably 80% or more, and even more preferably 90% or more.

[0082] Furthermore, the thickness of the film after heat treatment at 350° C. for 5 hours in a nitrogen environment is preferably 70% or more of the thickness of the film before heat treatment, more preferably 80% or more, and even more preferably 90% or more.

[0083] Furthermore, the thickness of the film after heat treatment at 400° C. for 5 hours in a nitrogen environment is preferably 70% or more of the thickness of the film before heat treatment, more preferably 80% or more, and even more preferably 90% or more.

[0084] The above-mentioned physical properties can be achieved by adjusting the type and content of the specific resin or other resins used.

[0085] Furthermore, when the colored resin composition of the present invention is heated at 200°C for 30 minutes to form a film having a thickness of 0.60 μm, and the film is heat-treated at 300°C for 5 hours under a nitrogen atmosphere, the rate of change ΔA of the absorbance represented by the following formula (1) of the film after the heat treatment is preferably 50% or less, more preferably 45% or less, further preferably 40% or less, and particularly preferably 35% or less.

[0086] ΔA(%)=|100-(A2 / A1)×100|······(1)

[0087] ΔA is the rate of change of absorbance of the film after heating treatment,

[0088] A1 is the maximum absorbance of the film before heat treatment in the wavelength range of 400 to 1100 nm.

[0089] A2 is the absorbance of the film after the heat treatment, and is the absorbance at a wavelength showing the maximum value of the absorbance of the film before the heat treatment within the wavelength range of 400 to 1100 nm.

[0090] The above-mentioned physical properties can be achieved by adjusting the type and content of the specific resin or other resins used.

[0091] Furthermore, when the colored resin composition of the present invention is heated at 200°C for 30 minutes to form a film having a thickness of 0.60 μm, the absolute value of the difference between the wavelength λ1 indicating the maximum absorbance of the film in the wavelength range of 400 to 1100 nm and the wavelength λ2 indicating the maximum absorbance of the film after heat treatment at 300°C for 5 hours under a nitrogen environment is preferably 50 nm or less, more preferably 45 nm or less, and even more preferably 40 nm or less.

[0092] The above-mentioned physical properties can be achieved by adjusting the type and content of the specific resin or other resins used.

[0093] Furthermore, when a film having a thickness of 0.60 μm is formed by heating the colored resin composition of the present invention at 200° C. for 30 minutes, and the film is heat-treated at 300° C. for 5 hours in a nitrogen atmosphere, the rate of change ΔA of the absorbance of the film after the heat treatment in the wavelength range of 400 to 1100 nm is λ The maximum value of is preferably 30% or less, more preferably 27% or less, and further preferably 25% or less. The rate of change in absorbance is a value calculated according to the following formula (2).

[0094] ΔA λ =|100-(A2 λ / A1 λ )×100|……(2)

[0095] ΔA λ is the rate of change of absorbance of the film at wavelength λ after heating,

[0096] A1 λ is the absorbance of the film at wavelength λ before heat treatment,

[0097] A2 λ is the absorbance of the film after heat treatment at wavelength λ.

[0098] The above-mentioned physical properties can be achieved by adjusting the type and content of the specific resin or other resins used.

[0099] Furthermore, the colored resin composition of the present invention is preferably a composition that, when applied to a glass substrate and heated at 100° C. for 120 seconds to form a film having a thickness of 0.6 μm, has a transmittance of 80% or more at a wavelength of 400 nm. Furthermore, the transmittance of the film at a wavelength of 450 nm is preferably 90% or more. More preferably, the transmittance of the film at a wavelength of 400 nm is 90% or more, and the transmittance at a wavelength of 450 nm is 95% or more.

[0100] The colored resin composition of the present invention can be used for a color filter, a near infrared transmission filter, a near infrared cut filter, a black matrix, a light shielding film, and the like.

[0101] As the color filter, there can be mentioned a filter having colored pixels that transmit light of a specific wavelength, preferably a filter having at least one colored pixel selected from red pixels, blue pixels, green pixels, yellow pixels, cyan pixels, and magenta pixels. The color filter can be formed using a colored resin composition containing a colorant.

[0102] As a near infrared cut filter, a filter having a maximum absorption wavelength in the range of wavelengths of 700 to 1800 nm can be cited. The near infrared cut filter is preferably a filter having a maximum absorption wavelength in the range of wavelengths of 700 to 1300 nm, and more preferably a filter having a maximum absorption wavelength in the range of wavelengths of 700 to 1100 nm. In addition, the transmittance of the near infrared cut filter in the entire range of wavelengths of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. In addition, the transmittance at at least one point in the range of wavelengths of 700 to 1800 nm is preferably 20% or less. In addition, the ratio of the absorbance Amax at the maximum absorption wavelength of the near infrared cut filter to the absorbance A550 at a wavelength of 550 nm, i.e., absorbance Amax / absorbance A550, is preferably 20 to 500, more preferably 50 to 500, further preferably 70 to 450, and particularly preferably 100 to 400. The near infrared cut filter can be formed using a colored resin composition containing a near infrared absorbing coloring material.

[0103] The near-infrared transmission filter is a filter that transmits at least a portion of near-infrared rays. The near-infrared transmission filter may be a filter (transparent film) that transmits any one of visible light and near-infrared rays, or may be a filter that shields at least a portion of visible light and transmits at least a portion of near-infrared rays. As a near-infrared transmission filter, preferably, there may be cited a filter that satisfies the spectral characteristics that the maximum value of the transmittance within the wavelength range of 400 to 640 nm is less than 20% (preferably less than 15%, more preferably less than 10%), and the minimum value of the transmittance within the wavelength range of 1100 to 1300 nm is more than 70% (preferably more than 75%, more preferably more than 80%). The near-infrared transmission filter is preferably a filter that satisfies any one of the following spectral characteristics (1) to (4).

[0104] (1): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 800 to 1300 nm.

[0105] (2): A filter whose maximum transmittance within the wavelength range of 400 to 750 nm is less than 20% (preferably less than 15%, more preferably less than 10%) and whose minimum transmittance within the wavelength range of 900 to 1300 nm is greater than 70% (preferably greater than 75%, more preferably greater than 80%).

[0106] (3): A filter having a maximum transmittance of less than 20% (preferably less than 15%, more preferably less than 10%) in the wavelength range of 400 to 830 nm and a minimum transmittance of more than 70% (preferably more than 75%, more preferably more than 80%) in the wavelength range of 1000 to 1300 nm.

[0107] (4): A filter whose maximum transmittance in the wavelength range of 400 to 950 nm is less than 20% (preferably less than 15%, more preferably less than 10%) and whose minimum transmittance in the wavelength range of 1100 to 1300 nm is greater than 70% (preferably greater than 75%, more preferably greater than 80%).

[0108] The colored resin composition of the present invention can be preferably used as a colored resin composition for a color filter. Specifically, it can be preferably used as a colored resin composition for forming pixels of a color filter, and can more preferably be used as a colored resin composition for forming red or blue pixels of a color filter. In addition, the colored resin composition of the present invention can be preferably used as a colored resin composition for forming pixels of a color filter for a solid-state imaging element.

[0109] When the colored resin composition of the present invention is applied to a glass substrate and heated at 100°C for 120 seconds to form a film having a thickness of 0.6 μm, the maximum transmittance of the film within a wavelength of 400 to 1100 nm is preferably 70% or more (preferably 75% or more, more preferably 80% or more, and further preferably 85% or more), and the minimum value is 30% or less (preferably 25% or less, more preferably 20% or less, and further preferably 15% or less). The colored resin composition capable of forming a film satisfying the above spectral characteristics can be particularly preferably used as a colored resin composition for forming a color filter, a near infrared transmission filter, or a near infrared cut filter.

[0110] Furthermore, the colored resin composition of the present invention is also preferably a colored resin composition for pattern formation based on photolithography. According to this method, pixels of fine size can be easily formed. Therefore, it can be particularly preferably used as a colored resin composition for pixel formation of a color filter for a solid-state imaging element. For example, a colored resin composition containing a component having a polymerizable group (for example, a resin or a polymerizable compound having a polymerizable group) and a photopolymerization initiator can be preferably used as a colored resin composition for pattern formation based on photolithography. The colored resin composition for pattern formation based on photolithography also preferably contains an alkali-soluble resin (for example, resin 1 described later or an alkali-developable resin described later).

[0111] Hereinafter, each component used for the colored resin composition of this invention is demonstrated.

[0112] <Color>

[0113] The colored resin composition of the present invention contains a colorant. Examples of the colorant include white colorants, black colorants, color colorants, and near infrared absorbing colorants. In the present invention, the white colorant includes not only pure white but also bright gray colorants (e.g., off-white, light gray, etc.) close to white.

[0114] Furthermore, the colorant preferably includes at least one colorant selected from color colorants, black colorants and near-infrared absorbing colorants, more preferably includes at least one colorant selected from color colorants and near-infrared absorbing colorants, further preferably includes color colorants, and further preferably includes at least one colorant selected from red colorants, yellow colorants, blue colorants and purple colorants.

[0115] Furthermore, the colorant preferably includes a black colorant.

[0116] Furthermore, the colorant preferably includes a chromatic colorant and a near-infrared absorbing colorant, and more preferably includes two or more chromatic colorants and near-infrared absorbing colorants.

[0117] Furthermore, the colorant preferably includes a black colorant and a near infrared absorbing colorant.

[0118] According to this embodiment, the colored resin composition of the present invention can be preferably used as a colored resin composition for forming a near infrared transmission filter.

[0119] Regarding the combination of these coloring materials, reference can be made to Japanese Patent Application Laid-Open No. 2013-77009, Japanese Patent Application Laid-Open No. 2014-130338, International Publication No. 2015 / 166779, and the like.

[0120] As the colorant, dyes and pigments can be cited, and from the viewpoint of heat resistance, pigments are preferred. Furthermore, the pigment may be any of an inorganic pigment and an organic pigment, but from the viewpoints of the diversity of color changes, ease of dispersion, safety, etc., an organic pigment is preferred. Furthermore, the pigment preferably contains at least one selected from a color pigment and a near infrared absorbing pigment, and more preferably contains a color pigment.

[0121] Furthermore, the pigment preferably contains at least one selected from phthalocyanine pigments, dioxazine pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, azo pigments, diketopyrrolopyrrole pigments, pyrrolopyrrole pigments, isoindoline pigments, and quinophthalone pigments, more preferably contains at least one selected from phthalocyanine pigments, diketopyrrolopyrrole pigments, and pyrrolopyrrole pigments, and further preferably contains phthalocyanine pigments or diketopyrrolopyrrole pigments. Furthermore, the phthalocyanine pigment is preferably a phthalocyanine pigment without a central metal, or a phthalocyanine pigment having copper or zinc as a central metal, because it is easy to form a film whose spectral characteristics are not easily changed even after heating to a high temperature (for example, 300° C. or more).

[0122] Furthermore, since it is easy to form a film whose spectral characteristics are not easily changed even after the colorant contained in the colored resin composition is heated to a high temperature (for example, 300° C. or higher), it is preferred to contain at least one selected from a red pigment, a yellow pigment, and a blue pigment, more preferably at least one selected from a red pigment and a blue pigment, and even more preferably a blue pigment.

[0123] The colorant contained in the colored resin composition preferably contains the pigment A of condition 1 shown below. By using a colorant with such characteristics, a film whose spectral characteristics are not easily changed even after heating to a high temperature (for example, 300° C. or more) can be formed. The ratio of the pigment A in the total amount of the pigment contained in the colored resin composition is preferably 20 to 100% by mass, more preferably 30 to 100% by mass, and further preferably 40 to 100% by mass.

[0124] Condition 1)

[0125] When a composition containing 6 mass % of pigment A, 10 mass % of resin B-5, and 84 mass % of propylene glycol monomethyl ether acetate is heated at 200° C. for 30 minutes to form a film having a thickness of 0.60 μm, and the film is heat-treated at 300° C. for 5 hours in a nitrogen atmosphere, the rate of change ΔA10 of the absorbance of the film after the heat treatment represented by the following formula (10) is 50% or less,

[0126] ΔA10=|100-(A12 / A11)×100|……(10)

[0127] ΔA10 is the change rate of the absorbance of the film after heating treatment,

[0128] A11 is the maximum absorbance of the film before heat treatment in the wavelength range of 400 to 1100 nm.

[0129] A12 is the absorbance of the film after the heat treatment, which is the absorbance of the film before the heat treatment at a wavelength showing the maximum absorbance in the range of wavelengths from 400 to 1100 nm,

[0130] Resin B-5 is a resin having the following structure. The numerical value indicated on the main chain is a molar ratio. The weight average molecular weight is 11,000 and the acid value is 32 mgKOH / g.

[0131] [Chemical formula 3]

[0132]

[0133] Examples of the pigment A satisfying condition 1 include CI Pigment Red 254, CI Pigment Red 264, Pigment Red 272, Pigment Red 122, Pigment Red 177, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, and CI Pigment Blue 16.

[0134] The average primary particle size of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and further preferably 100 nm or less. As long as the average primary particle size of the pigment is within the above range, the dispersion stability of the pigment in the colored resin composition is good. In addition, in the present invention, the primary particles of the pigment can be observed by a transmission electron microscope, and the primary particle size of the pigment can be obtained based on the obtained photographs. Specifically, the projected area of ​​the primary particles of the pigment is obtained, and the corresponding circle equivalent diameter is calculated as the primary particle size of the pigment. In addition, the average primary particle size in the present invention is set to the arithmetic mean of the primary particle sizes of 400 primary particles of the pigment. In addition, the primary particles of the pigment refer to independent particles that are not agglomerated.

[0135] 〔Color pigment〕

[0136] As the color pigment, there can be mentioned a color pigment having a maximum absorption wavelength in the range of 400 to 700 nm. For example, yellow color pigment, orange color pigment, red color pigment, green color pigment, purple color pigment, blue color pigment, etc. can be mentioned. From the viewpoint of heat resistance, the color pigment is preferably a pigment (color pigment), more preferably a red pigment, a yellow pigment and a blue pigment, and further preferably a red pigment and a blue pigment. As a specific example of the color pigment, for example, the color pigment shown below can be mentioned.

[0137] Color Index (CI) Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,1 37, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232 (methine series), 233 (quinoline series), 234 (aminoketone series), 235 (aminoketone series), 236 (aminoketone series), etc. (the above are yellow pigments),

[0138] CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (the above are orange pigments),

[0139] CIPigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52: 2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 14 9, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, 294 (xanthene series, Organo Ultramarine, Bluish Red), 295 (monoazo series), 296 (diazo series), 297 (aminoketone series), etc. (the above are red pigments),

[0140] CI Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64 (phthalocyanine), 65 (phthalocyanine), 66 (phthalocyanine), etc. (the above are green pigments),

[0141] CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane series), 61 (xanthene series), etc. (the above are purple pigments),

[0142] CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87 (monoazo series), 88 (methine series), etc. (the above are blue pigments).

[0143] Among these color pigments, CI Pigment Red 254, CI Pigment Red 264, Pigment Red 272, Pigment Red 122, and Pigment Red 177 are preferred as red pigments because they can easily form a film whose spectral characteristics are not easily changed even after heating to a high temperature (e.g., 300° C. or higher). Furthermore, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, and CI Pigment Blue 16 are preferred as blue pigments.

[0144] Furthermore, as a green colorant, a zinc phthalocyanine halogenated pigment having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule can also be used. As a specific example, the compounds described in International Publication No. 2015 / 118720 can be cited. Furthermore, as a green pigment, the compounds described in the specification of Chinese Patent Application Publication No. 106909027, the phthalocyanine compounds having a phosphate ester as a ligand described in International Publication No. 2012 / 102395, the phthalocyanine compounds described in Japanese Patent Publication No. 2019-008014, the phthalocyanine compounds described in Japanese Patent Publication No. 2018-180023, the compounds described in Japanese Patent Publication No. 2019-038958, etc. can also be used.

[0145] Furthermore, an aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue colorant, and specific examples thereof include compounds described in paragraphs 0022 to 0030 of JP-A-2012-247591 and paragraph 0047 of JP-A-2011-157478.

[0146] In addition, as yellow colorants, compounds described in Japanese Patent Application Laid-Open No. 2017-201003, compounds described in Japanese Patent Application Laid-Open No. 2017-197719, compounds described in paragraphs 0011 to 0062 and paragraphs 0137 to 0276 of Japanese Patent Application Laid-Open No. 2017-171912, compounds described in paragraphs 0010 to 0062 and paragraphs 0138 to 0295 of Japanese Patent Application Laid-Open No. 2017-171913, compounds described in paragraphs 0011 to 0062 and paragraphs 0139 to 0190 of Japanese Patent Application Laid-Open No. 2017-171914, compounds described in paragraphs 0010 to 0062 and paragraphs 0139 to 0190 of Japanese Patent Application Laid-Open No. 2017-171915, The compounds described in paragraphs 0142 to 0222, the quinophthalone compounds described in paragraphs 0011 to 0034 of Japanese Patent Application Publication No. 2013-054339, the quinophthalone compounds described in paragraphs 0013 to 0058 of Japanese Patent Application Publication No. 2014-026228, the isoindoline compounds described in Japanese Patent Application Publication No. 2018-062644, the quinophthalone compounds described in Japanese Patent Application Publication No. 2018-203798, the quinophthalone compounds described in Japanese Patent Application Publication No. 2018-062578, the quinophthalone compounds described in Japanese Patent No. 6432077, the quinophthalone compounds described in Japanese Patent No. 6432076 Quinophthalone compounds, quinophthalone compounds described in Japanese Patent Laid-Open No. 2018-155881, quinophthalone compounds described in Japanese Patent Laid-Open No. 2018-111757, quinophthalone compounds described in Japanese Patent Laid-Open No. 2018-040835, quinophthalone compounds described in Japanese Patent Laid-Open No. 2017-197640, quinophthalone compounds described in Japanese Patent Laid-Open No. 2016-145282, quinophthalone compounds described in Japanese Patent Laid-Open No. 2014-085565, quinophthalone compounds described in Japanese Patent Laid-Open No. 2014-021139, quinophthalone compounds described in Japanese Patent Laid-Open No. 2013-209614 Quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2013-209435, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2013-181015, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2013-061622, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2013-054339, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2013-032486, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2012-226110, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2008-074987, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2008-081565,Quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2008-074986, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2008-074985, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2008-050420, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2008-031281, quinophthalone compounds described in Japanese Patent Publication No. 48-032765, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2019-008014, compounds represented by the following formula (QP1), compounds represented by the following formula (QP2).

[0147] [Chemical formula 4]

[0148]

[0149] In formula (QP1), X 1 ~X 16 Each independently represents a hydrogen atom or a halogen atom, and Z 1 represents an alkylene group having 1 to 3 carbon atoms. Specific examples of the compound represented by the formula (QP1) include compounds described in paragraph 0016 of Japanese Patent No. 6443711.

[0150] [Chemical formula 5]

[0151]

[0152] In formula (QP2), Y 1 ~Y 3 Each independently represents a halogen atom. n and m represent integers of 0 to 6, and p represents an integer of 0 to 5. (n+m) is 1 or more. Specific examples of the compound represented by formula (QP2) include compounds described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077.

[0153] As red colorants, diketopyrrolopyrrole compounds in which at least one bromine atom is substituted in the structure described in Japanese Patent Application Laid-Open No. 2017-201384, diketopyrrolopyrrole compounds described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838, diketopyrrolopyrrole compounds described in International Publication No. 2012 / 102399, diketopyrrolopyrrole compounds described in International Publication No. 2012 / 117965, naphthol azo compounds described in Japanese Patent Application Laid-Open No. 2012-229344, compounds described in Japanese Patent No. 6516119, compounds described in Japanese Patent No. 6525101, etc. can also be used. In addition, as red pigments, compounds having a structure in which an aromatic ring group having a group bonded to an oxygen atom, a sulfur atom or a nitrogen atom introduced into the aromatic ring is bonded to a diketopyrrolopyrrole skeleton can also be used. As such a compound, a compound represented by formula (DPP1) is preferred, and a compound represented by formula (DPP2) is more preferred.

[0154] [Chemical formula 6]

[0155]

[0156] In the above formula, R 11 and R 13 Each independently represents a substituent, R 12 and R 14 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, n11 and n13 each independently represent an integer of 0 to 4, and X 12 and X 14 Each independently represents an oxygen atom, a sulfur atom or a nitrogen atom, and X 12 When it is an oxygen atom or a sulfur atom, m12 represents 1, X 12 When it is a nitrogen atom, m12 represents 2, X 14 When it is an oxygen atom or a sulfur atom, m14 represents 1, X 14 When it is a nitrogen atom, m14 represents 2. 11 and R 13 Preferred specific examples of the substituent represented by include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an amide group, a cyano group, a nitro group, a trifluoromethyl group, a sulfoxide group, and a sulfone group.

[0157] Examples of color dyes include pyrazole azo compounds, aniline azo compounds, triarylmethane compounds, anthraquinone compounds, anthrapyridone compounds, benzal compounds, oxocyanine compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azo methine compounds, xanthene compounds, phthalocyanine compounds, benzopyran compounds, indigo compounds, and pyrromethene compounds.

[0158] The coloring material may be used in combination of two or more. Furthermore, when two or more coloring materials are used in combination, black may be formed by the combination of two or more coloring materials. As such a combination, for example, the following modes (1) to (7) may be cited. When the coloring resin composition contains two or more coloring materials and the combination of two or more coloring materials presents black, the coloring resin composition of the present invention can be preferably used as a near-infrared transmission filter.

[0159] (1) A method containing red pigment and blue pigment.

[0160] (2) A method containing red, blue and yellow pigments.

[0161] (3) A method containing red colorant, blue colorant, yellow colorant and purple colorant.

[0162] (4) A method containing red colorant, blue colorant, yellow colorant, purple colorant and green colorant.

[0163] (5) A method containing red colorant, blue colorant, yellow colorant and green colorant.

[0164] (6) A method containing red pigment, blue pigment and green pigment.

[0165] (7) A method containing yellow colorant and purple colorant.

[0166] 〔White pigment〕

[0167] As white coloring materials, inorganic pigments (white pigments) such as titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silicon dioxide, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, and zinc sulfide can be cited. The white pigment is preferably a particle having a titanium atom, and titanium oxide is more preferred. In addition, the white pigment is preferably a particle having a refractive index of 2.10 or more relative to light of a wavelength of 589 nm. The above refractive index is preferably 2.10 to 3.00, and more preferably 2.50 to 2.75.

[0168] Furthermore, as the white pigment, titanium oxide described in "Physical Properties and Applications of Titanium Oxide, Manabu Seino, pp. 13-45, published on June 25, 1991, published by Gihodo Publishing" can also be used.

[0169] White pigment can use not only the particle made of single inorganic substance, but also the particle synthesized with other materials. For example, it is preferred to use the particle with vacancy or other materials inside, the particle with multiple inorganic particles attached to the core particle, the core particle made of polymer particles and the core-shell composite particle made of the shell made of inorganic nanoparticles. As the core particle made of the above-mentioned polymer particles and the core-shell composite particle made of the shell made of inorganic nanoparticles, for example, it is possible to refer to the record of paragraphs 0012 to 0042 of Japanese Patent Publication No. 2015-047520, and the content is incorporated in this specification.

[0170] White pigment can also use hollow inorganic particles.Hollow inorganic particles refer to inorganic particles with a hollow structure inside, and they have hollow inorganic particles surrounded by an outer shell.As hollow inorganic particles, hollow inorganic particles described in Japanese Unexamined Patent Publication No. 2011-075786, International Publication No. 2013 / 061621, Japanese Unexamined Patent Publication No. 2015-164881, etc. can be enumerated, and these contents are incorporated in this specification.

[0171] 〔Black Pigment〕

[0172] As black colorant, there is no particular limitation, and known black colorants can be used. For example, inorganic pigments (black pigments) such as carbon black, titanium black, and graphite can be cited, preferably carbon black and titanium black, and more preferably titanium black. Titanium black refers to black particles containing titanium atoms, preferably low-order titanium oxide or titanium oxynitride. Titanium black can modify the surface as needed for the purpose of improving dispersibility, inhibiting cohesion, etc. For example, the surface of titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. In addition, it can also be treated with a water-repellent substance as shown in Japanese Patent Gazette No. 2007-302836. As black pigments, color index (CI) Pigment Black 1, 7, etc. can be cited. Titanium black preferably has a small primary particle size and an average primary particle size per particle. Specifically, the average primary particle size is preferably 10 to 45 nm. Titanium black can also be used as a dispersed material. For example, a dispersion containing titanium black particles and silicon dioxide particles, wherein the ratio of Si atoms to Ti atoms in the dispersion is adjusted within the range of 0.20 to 0.50, etc. can be cited. For the above-mentioned dispersion, reference can be made to the records of paragraphs 0020 to 0105 of Japanese Patent Publication No. 2012-169556, and the contents are incorporated into this specification. Examples of commercially available products of titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R-N, 13M-T (trade name: Mitsubishi Materials Corporation), Tilack D (trade name: Ako Kasei Co., Ltd.), etc.

[0173] In addition, as a black colorant, organic black colorants such as bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds can also be used. As bisbenzofuranone compounds, compounds described in Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, and Japanese Patent Publication No. 2012-515234 can be cited, and for example, "Irgaphor Black" manufactured by BASF SE can be used. As perylene compounds, compounds described in paragraphs 0016 to 0020 of Japanese Patent Publication No. 2017-226821, CI Pigment Black 31, 32, etc. can be cited. Examples of the azomethine compound include compounds described in JP-A-01-170601 and JP-A-02-034664. For example, “Chromo Fine Black A1103” manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. can be used.

[0174] The colorant used in the composition of the present invention may be only the above-mentioned black colorant, or may also include a colorant. According to this mode, it is easy to obtain a composition that can form a film with high light-shielding properties in the visible region. When a black colorant and a colorant are used as a colorant, the mass ratio of the two is preferably black colorant: colorant=100:10~300, more preferably 100:20~200. In addition, a black pigment is preferably used as the above-mentioned black colorant, and a color pigment is preferably used as the above-mentioned colorant.

[0175] Examples of the color pigment include red pigment, green pigment, blue pigment, yellow pigment, violet pigment, and orange pigment.

[0176] As the color colorant, a color pigment is preferred, and examples of the color pigment include a red pigment, a green pigment, a blue pigment, a yellow pigment, a violet pigment, and an orange pigment.

[0177] Furthermore, as a color pigment, a material that replaces an organic chromophore in an inorganic pigment or an organic-inorganic pigment can also be used. By replacing an inorganic pigment or an organic-inorganic pigment with an organic chromophore, a hue can be easily designed. Regarding pigment A, it is preferred to use at least one pigment selected from a red pigment, a blue pigment and a yellow pigment, more preferably to use at least one pigment selected from a blue pigment and a yellow pigment, and further preferably to use a pigment comprising a blue pigment. According to this mode, a film having excellent light-shielding properties in a visible region can be easily formed. Furthermore, by using a blue pigment, a film having excellent light resistance can be formed. Furthermore, by using a yellow pigment, the uniformity of the visible transmittance of the obtained film can be achieved.

[0178] The blue pigment is preferably a phthalocyanine compound because it is easy to form a film with excellent light resistance. In addition, the blue pigment includes color index (CI) pigment blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87 (monoazo system), 88 (methine / polymethine system), preferably at least one selected from CI pigment blue 15:3, CI pigment blue 15:6 and CI pigment blue 16, and more preferably CI pigment blue 15:6.

[0179] Furthermore, as a blue pigment, an aluminum phthalocyanine compound having a phosphorus atom can also be used. Examples of such a compound include an aluminum phthalocyanine compound whose ligand is a phosphoric acid ester. Specific examples of aluminum phthalocyanine compounds having a phosphorus atom include compounds described in paragraphs 0022 to 0030 of Japanese Patent Application Publication No. 2012-247591 and paragraph 0047 of Japanese Patent Application Publication No. 2011-157478.

[0180] Examples of yellow pigments include azo compounds, quinophthalone compounds, isoindolinone compounds, isoindolinone compounds, anthraquinone compounds, and the like, preferably isoindolinone compounds. Examples of yellow pigments include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 231, 232 (methine / polymethine series) and the like.

[0181] Furthermore, as yellow pigments, pigments described in Japanese Patent Publication No. 2017-201003 and pigments described in Japanese Patent Publication No. 2017-197719 can be used. Furthermore, as yellow pigments, metal azo pigments can also be used, which contain at least one anion selected from azo compounds represented by the following formula (I) and azo compounds of tautomeric structures thereof, two or more metal ions, and melamine compounds.

[0182] [Chemical formula 7]

[0183]

[0184] In the formula, R 1 and R 2 are independently -OH or -NR 5 R 6 , R 3 and R 4 are independently =O or =NR 7 , R 5 ~R 7 are independently a hydrogen atom or an alkyl group. 5 ~R 7The number of carbon atoms of the alkyl group represented is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4. The alkyl group may be any of linear, branched, and cyclic, preferably linear or branched, and more preferably linear. The alkyl group may have a substituent. The substituent is preferably a halogen atom, a hydroxyl group, an alkoxy group, a cyano group, and an amino group.

[0185] Regarding the above-mentioned metal azo pigments, reference can be made to paragraphs 0011 to 0062 and 0137 to 0276 of JP-A-2017-171912, paragraphs 0010 to 0062 and 0138 to 0295 of JP-A-2017-171913, paragraphs 0011 to 0062 and 0139 to 0190 of JP-A-2017-171914, and paragraphs 0010 to 0065 and 0142 to 0222 of JP-A-2017-171915, and these contents are incorporated into the present specification.

[0186] Examples of red pigments include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, and quinacridone compounds, and diketopyrrolopyrrole compounds are preferred. In addition, examples of red pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 1 44, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, 294 (Xanton series, Organo Ultramarine, Bluish Red), etc.

[0187] Furthermore, as a red pigment, a diketopyrrolopyrrole pigment in which at least one bromine atom is substituted in the structure described in Japanese Patent Application Laid-Open No. 2017-201384, a diketopyrrolopyrrole pigment described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838, etc. can also be used. Furthermore, as a red pigment, a compound having a structure in which an aromatic ring group having a group bonded to an oxygen atom, a sulfur atom or a nitrogen atom introduced into the aromatic ring is bonded to a diketopyrrolopyrrole skeleton can also be used.

[0188] As orange pigments, CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. can be cited. As purple pigments, CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane series), 61 (xanthene series) and the like can be cited. As green pigments, CI Pigment Green 7, 10, 36, 37, 58, 59, 62, 63 and the like can be cited. In addition, as green pigments, halogenated zinc phthalocyanine pigments having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule can also be used. As specific examples, compounds described in International Publication No. 2015 / 118720 can be cited.

[0189] Preferred combinations of organic black colorants and chromatic colorants include the following, for example.

[0190] (A-1) A method of containing an organic black colorant and a blue colorant.

[0191] (A-2) An embodiment containing an organic black colorant, a blue colorant, and a yellow colorant.

[0192] (A-3) An embodiment containing organic black colorant, blue colorant, yellow colorant and red colorant.

[0193] (A-4) An embodiment containing organic black colorant, blue colorant, yellow colorant and violet colorant.

[0194] In the above embodiment (A-1), the mass ratio of the organic black colorant to the blue colorant is preferably organic black colorant:blue colorant=100:1-70, more preferably 100:5-60, and even more preferably 100:10-50.

[0195] In the above embodiment (A-2), the mass ratio of the organic black colorant, the blue colorant and the yellow colorant is preferably organic black colorant: blue colorant: yellow colorant = 100:10 to 90:10 to 90, more preferably 100:15 to 85:15 to 80, and even more preferably 100:20 to 80:20 to 70.

[0196] In the above-mentioned embodiment (A-3), the mass ratio of the organic black colorant, the blue colorant, the yellow colorant and the red colorant is preferably organic black colorant: blue colorant: yellow colorant: red colorant = 100:20~150:1~60:10~100, more preferably 100:30~130:5~50:20~90, and further preferably 100:40~120:10~40:30~80.

[0197] In the above-mentioned embodiment (A-4), the mass ratio of the organic black colorant, the blue colorant, the yellow colorant and the purple colorant is preferably organic black colorant: blue colorant: yellow colorant: purple colorant = 100:20~150:1~60:10~100, more preferably 100:30~130:5~50:20~90, and further preferably 100:40~120:10~40:30~80.

[0198] The colorant used in the composition of the present invention can also use a colorant having a maximum absorption wavelength in a range of more than 700nm and less than 800nm. Such a colorant is used as a near-infrared absorbing pigment. By using a colorant containing a pigment having such a spectral characteristic as a colorant, the wavelength of light transmitted through the obtained film can be shifted to the long wavelength side. Among the pigments having a maximum absorption wavelength in a range of more than 700nm and less than 800nm, the absorbance A at a wavelength of 500nm is 1 and the absorbance A at the maximum absorption wavelength 2 Ratio A 1 / A 2 A pigment having a molecular weight of 0.08 or less is preferred, and a pigment having a molecular weight of 0.04 or less is more preferred.

[0199] Examples of pigments having a maximum absorption wavelength in a range exceeding 700 nm and below 800 nm include pyrrolopyrrole compounds, cyanine compounds, squaric acid compounds, phthalocyanine compounds, naphthalocyanine compounds, quartacene compounds, merocyanine compounds, crotonium compounds, oxocyanine compounds, imine compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds, azomethine compounds, anthraquinone compounds, and dibenzofuranone compounds.

[0200] The content of the colorant in the total solid content of the composition of the present invention is preferably 10 to 60% by mass, and the lower limit is preferably 20% by mass or more, and more preferably 30% by mass or more.

[0201] Furthermore, the content of the above-mentioned organic black colorant in the colorant is 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, further preferably 50% by mass or more, and further preferably 60% by mass or more. Conventional compositions tend to be prone to contamination in the piping hose as the content of the organic black colorant increases, but the composition of the present invention is not prone to contamination in the piping hose even if the content of the organic black colorant is increased, so the more the content of the organic black colorant, the more significant the effect of the present invention.

[0202] Furthermore, the content of the lactam pigment as the organic black colorant in the colorant is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, even more preferably 30% by mass or more, further more preferably 40% by mass or more, and particularly preferably 50% by mass or more.

[0203] Furthermore, the content of the organic black colorant in the total solid content of the composition of the present invention is preferably 5 to 70% by mass. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more. The upper limit is preferably 65% ​​by mass or less, more preferably 60% by mass or less.

[0204] 〔Near infrared absorbing pigment〕

[0205] The near infrared absorbing colorant is preferably a pigment, more preferably an organic pigment. Furthermore, the near infrared absorbing colorant preferably has a maximum absorption wavelength in the range of more than 700 nm and less than 1400 nm. Furthermore, the maximum absorption wavelength of the near infrared absorbing colorant is preferably less than 1200 nm, more preferably less than 1000 nm, and further preferably less than 950 nm. Furthermore, the absorbance A of the near infrared absorbing colorant at a wavelength of 550 nm is preferably less than 1200 nm. 550 and the absorbance A at the maximum absorption wavelength max Ratio A 550 / A max It is preferably less than 0.1, more preferably less than 0.05, further preferably less than 0.03, and particularly preferably less than 0.02. The lower limit is not particularly limited, for example, it can be set to more than 0.0001, and it can also be set to more than 0.0005. As long as the above absorbance ratio is within the above range, it can be set to a near-infrared absorbing colorant with excellent visible light transparency and near-infrared shielding properties. In addition, in the present invention, the maximum absorption wavelength of the near-infrared absorbing colorant and the absorbance value at each wavelength are values ​​obtained based on the absorption spectrum of the film formed using the colored resin composition containing the near-infrared absorbing colorant.

[0206] As the near infrared absorbing colorant, there are no particular limitations, and examples thereof include pyrrolopyrrole compounds, cyanine compounds, squaryl compounds, phthalocyanine compounds, naphthalocyanine compounds, quartacene compounds, merocyanine compounds, crotonium compounds, oxonol compounds, imine compounds, dithiol compounds, triarylmethane compounds, pyrromethio compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiol-ene metal complexes, etc. Examples of the pyrrolopyrrole compound include compounds described in paragraphs 0016 to 0058 of Japanese Unexamined Patent Application Publication No. 2009-263614, compounds described in paragraphs 0037 to 0052 of Japanese Unexamined Patent Application Publication No. 2011-068731, and compounds described in paragraphs 0010 to 0033 of International Publication No. 2015 / 166873. Examples of the squaric acid compound include compounds described in paragraphs 0044 to 0049 of Japanese Patent Publication No. 2011-208101, compounds described in paragraphs 0060 to 0061 of Japanese Patent Publication No. 6065169, compounds described in paragraph 0040 of International Publication No. 2016 / 181987, compounds described in Japanese Patent Publication No. 2015-176046, and compounds described in paragraph 0072 of International Publication No. 2016 / 190162. , the compounds described in paragraphs 0196 to 0228 of Japanese Patent Application Publication No. 2016-074649, the compounds described in paragraph 0124 of Japanese Patent Application Publication No. 2017-067963, the compounds described in International Publication No. 2017 / 135359, the compounds described in Japanese Patent Application Publication No. 2017-114956, the compounds described in Japanese Patent No. 6197940, the compounds described in International Publication No. 2016 / 120166, etc. Examples of cyanine compounds include compounds described in paragraphs 0044 to 0045 of Japanese Patent Application Laid-Open No. 2009-108267, compounds described in paragraphs 0026 to 0030 of Japanese Patent Application Laid-Open No. 2002-194040, compounds described in Japanese Patent Application Laid-Open No. 2015-172004, compounds described in Japanese Patent Application Laid-Open No. 2015-172102, compounds described in Japanese Patent Application Laid-Open No. 2008-088426, compounds described in paragraph 0090 of International Publication No. 2016 / 190162, compounds described in Japanese Patent Application Laid-Open No. 2017-031394, etc. Examples of crotonium compounds include compounds described in Japanese Patent Application Laid-Open No. 2017-082029.Examples of imine compounds include compounds described in JP-A-2008-528706, compounds described in JP-A-2012-012399, compounds described in JP-A-2007-092060, and compounds described in paragraphs 0048 to 0063 of International Publication No. 2018 / 043564. Examples of phthalocyanine compounds include compounds described in paragraph 0093 of JP-A-2012-077153, titanyl phthalocyanine described in JP-A-2006-343631, compounds described in paragraphs 0013 to 0029 of JP-A-2013-195480, and vanadium phthalocyanine compounds described in Japanese Patent No. 6081771. Examples of the naphthalocyanine compound include compounds described in paragraph 0093 of JP-A-2012-077153. Examples of the dithiol-ene metal complex include compounds described in JP-A-5733804.

[0207] As the near infrared absorbing colorant, the squaric acid compounds described in Japanese Patent Publication No. 2017-197437, the squaric acid compounds described in Japanese Patent Publication No. 2017-025311, the squaric acid compounds described in International Publication No. 2016 / 154782, the squaric acid compounds described in Japanese Patent No. 5884953, the squaric acid compounds described in Japanese Patent No. 6036689, the squaric acid compounds described in Japanese Patent No. 5810604, and the squaric acid compounds described in Japanese Patent No. 6036689 can also be used. The squaric acid compound described in paragraphs 0090 to 0107 of International Publication No. 2017 / 213047, the pyrrole ring-containing compound described in paragraphs 0019 to 0075 of Japanese Patent Publication No. 2018-054760, the pyrrole ring-containing compound described in paragraphs 0078 to 0082 of Japanese Patent Publication No. 2018-040955, and the pyrrole ring-containing compound described in paragraphs 0043 to 0069 of Japanese Patent Publication No. 2018-002773 , a squaryl acid compound having an aromatic ring at the amide α position as described in paragraphs 0024 to 0086 of Japanese Patent Application Laid-Open No. 2018-041047, an amide-linked squaryl acid compound as described in Japanese Patent Application Laid-Open No. 2017-179131, a compound having a pyrrole bis-type squaryl acid skeleton or a crotonium skeleton as described in Japanese Patent Application Laid-Open No. 2017-141215, a dihydrocarbazole bis-type squaryl acid compound as described in Japanese Patent Application Laid-Open No. 2017-082029, a -The asymmetric compounds described in paragraphs 0027 to 0114 of Japanese Patent Publication No. 068120, the pyrrole ring-containing compounds (carbazole type) described in Japanese Patent Publication No. 2017-067963, the phthalocyanine compounds described in Japanese Patent Publication No. 6251530, the colorants described in Japanese Patent Publication No. 2013-77009, Japanese Patent Publication No. 2014-130338, and International Publication No. 2015 / 166779, or a combination of the colorants described in these documents, etc.

[0208] The content of the colorant in the total solid content of the colored resin composition is 30% by mass or more, preferably 30 to 90% by mass, more preferably 30 to 80% by mass, and even more preferably 30 to 70% by mass.

[0209] Furthermore, the content of the pigment in the total solid content of the colored resin composition is preferably 30% by mass or more, preferably 30 to 90% by mass, more preferably 30 to 80% by mass, and further preferably 30 to 70% by mass.

[0210] Furthermore, the content of the dye in the coloring material is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.

[0211] In addition, the colored resin composition of the present invention also preferably contains substantially no dye for the reason that the change in film thickness when the obtained film is heated to a high temperature is more easily and effectively suppressed. When the colored resin composition of the present invention contains substantially no dye, the content of the dye in the total solid content of the colored resin composition of the present invention is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and particularly preferably no dye.

[0212] <Specified resin>

[0213] The colored resin composition of the present invention contains a resin (specific resin) containing at least one repeating unit selected from the repeating units represented by any one of formulas (1-1) to (1-5), and the total amount of the repeating units represented by any one of formulas (1-1) to (1-5) relative to the total molar amount of all repeating units contained in the above resin exceeds 60 mol%.

[0214] The ratio of the total amount of the repeating units represented by any one of the formula (1-1) to the following formula (1-5) relative to the total molar amount of all the repeating units contained in the specific resin is measured by the following method.

[0215] The specific resin is thermally decomposed and mass analyzed by thermal decomposition GC-MS to confirm the structure of the decomposed repeating unit. The molar amount of the repeating unit in the specific resin can be confirmed from the molar mass of the confirmed structure.

[0216] The ratio of the total amount is preferably 70 mol% or more, more preferably 80 mol% or more. The upper limit is not particularly limited, but may be 100 mol% or less.

[0217] [Formula (1-1)]

[0218] -R 11 , R 12 and R 13 -

[0219] In formula (1-1), R 11 , R 12 and R 13 Each independently represents a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.

[0220] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group.

[0221] In the present specification, unless otherwise specified, the term "alkyl group" or "aliphatic hydrocarbon group" includes all alkyl groups or aliphatic hydrocarbon groups having a linear, branched or cyclic structure.

[0222] The aromatic hydrocarbon group is preferably an aromatic hydrocarbon ring having 6 to 20 carbon atoms, and more preferably a phenyl group.

[0223] The alkyl group or the aromatic hydrocarbon group may have a substituent as long as the effects of the present invention are obtained.

[0224] Furthermore, the aromatic hydrocarbon group may be bonded to another aromatic hydrocarbon ring or another aromatic heterocyclic ring within the scope of obtaining the effects of the present invention. Examples of the bonding form include a condensed ring, a crosslinked ring, and a spiro ring.

[0225] -Ar-

[0226] In formula (1-1), Ar represents an aromatic group having 5 to 30 ring members, preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms or an aromatic heterocyclic group having 5 to 20 ring members, and more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms.

[0227] As the aromatic hydrocarbon group, a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred.

[0228] The aromatic heterocyclic group is preferably an aromatic heterocyclic group containing a nitrogen atom, a sulfur atom or an oxygen atom as a heteroatom. The aromatic heterocyclic group may contain only one heteroatom or two or more heteroatoms. When there are two or more heteroatoms in the aromatic heterocyclic group, the heteroatoms may be the same or different. Examples of the aromatic heterocyclic group include thienyl, pyridyl, 1-imidazolyl and the like.

[0229] The aromatic group may have a substituent within the scope of obtaining the effect of the present invention. Examples of the substituent include a hydroxyl group, a carboxyl group, a sulfo group, a phosphoric acid group, a phosphonic acid group, an active imide group (substituted sulfonamide group, -S(=O)2NHC(=O)R, -S(=O)2NHS(=O)2R, -C(=O)NHS(=O)2R, R is a hydrocarbon group which may have a substituent), or a sulfonamide group (-S(=O)2NR S1 2 or R S2 -S(=O)2-NR S3 -、R S1 represents a hydrogen atom or a hydrocarbon group which may have a substituent, preferably R S1 At least one of them is a hydrogen atom, and more preferably R S1 Two of the above R are hydrogen atoms. S2 represents a monovalent substituent, preferably a hydrocarbon group. S3 represents a hydrogen atom or a hydrocarbon group, preferably a hydrocarbon group. ) and the like, an amino group, an alkyl group, an aromatic hydrocarbon group, an aromatic heterocyclic group, a halogen atom, and the like.

[0230] Furthermore, these substituents may be bonded to the above aromatic groups via a linking group. Examples of the linking group include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, -O-, -C(=O)-, -S-, -S(=O)2-, -NR N - or a group formed by bonding two or more of these. N represents a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom. Furthermore, two or more of the above substituents may be bonded to the above linking group.

[0231] As a preferred embodiment of the present invention, there is mentioned an embodiment in which the substituent is directly bonded to the aromatic group without being linked via the linking group.

[0232] From the viewpoint of imparting alkali developability to the colored resin composition, Ar preferably has an acid group such as the above-mentioned hydroxyl group, carboxyl group, sulfone group, phosphoric acid group, phosphonic acid group, active imide group or sulfonamide group.

[0233] Furthermore, the acid group may form an ester bond with other structures. Examples of the other structures include structures containing alkyl groups (e.g., methyl groups, ethyl groups, etc.), polymer chains, and groups having ethylenically unsaturated bonds. Examples of the polymer chain include molecular chains having a molecular weight of 1,000 to 10,000 and having no acid group or basic group, as described later.

[0234] Furthermore, the amino group may form an amide bond, a urethane bond or a urea bond with another structure. The other structure is the same as the other structure described as the object of the acid group to form an ester bond.

[0235] [Formula (1-1-1), Formula (1-1-2), Formula (1-1-3)]

[0236] The repeating unit represented by the formula (1-1) is preferably a repeating unit represented by the following formula (1-1-1), a repeating unit represented by the following formula (1-1-2), or a repeating unit represented by the following formula (1-1-3).

[0237] Furthermore, the specific resin preferably contains a repeating unit represented by formula (1-1-2) as the repeating unit represented by formula (1-1), and more preferably contains a repeating unit represented by formula (1-1-2) and a repeating unit represented by formula (1-1-3).

[0238] [Chemical formula 8]

[0239]

[0240] In formula (1-1-1), formula (1-1-2) and formula (1-1-3), R 11 , R 12 and R13 Each independently represents a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, Ar 1 represents an aromatic group having 5 to 30 ring members, X 11 represents a group consisting of at least one group selected from an alkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms and -C(=O)O- or -C(=O)NR N -, n1 represents 0 or more and Ar 1 An integer below the maximum number of substitutions, Ar 2 represents an aromatic group having 5 to 30 ring members, X 12 Each independently represents a hydroxyl group, a carboxyl group, a sulfo group, a phosphoric acid group, a phosphonic acid group, an active imide group or a sulfonamide group, n2 represents 1 or more, and Ar 2 An integer below the maximum number of substitutions, Ar 3 represents an aromatic group having 5 to 30 ring members, X 13 Each independently represents a group represented by any one of the following formulae (E-1) to (E-11), n3 represents 1 or more, and Ar 3 An integer less than the maximum number of substitutions. N represents a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

[0241] [Chemical formula 9]

[0242]

[0243] In formula (E-1) to formula (E-11), R E1 ~R E3 , R E13 , R E15 , R E17 and R E19 Each independently represents a monovalent substituent, R E4 ~R E12 , R E14 , R E16 and R E18 Each independently represents a hydrogen atom or a monovalent substituent, and R E4 and R E5 At least one of them is a monovalent substituent, R E6 and R E7 At least one of them is a monovalent substituent, R E8 and R E9 At least one of them is a monovalent substituent, R E10 and R E11 At least one of them is a monovalent substituent, and * represents the same as Ar in formula (1-1-3).3 bonding position.

[0244] -R 11 , R 12 and R 13 -

[0245] In formula (1-1-1), formula (1-1-2) and formula (1-1-3), R 11 , R 12 and R 13 Respectively with R in formula (1-1) 11 , R 12 and R 13 The meanings are the same and the preferred aspects are also the same.

[0246] -Ar 1 -

[0247] In formula (1-1-1), Ar 1 It has the same meaning as Ar in formula (1-1), and preferred aspects are also the same.

[0248] -X 11 -

[0249] In formula (1-1-1), X 11 represents a group consisting of at least one group selected from an alkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkyl group having 1 to 30 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms and -C(=O)O- or -C(=O)NR N The group represented by the combination of - is preferably composed of at least one group selected from a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms and -C(=O)O- or -C(=O)NR N - represents a group in combination.

[0250] The alkyl group having 1 to 30 carbon atoms is more preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms.

[0251] The aromatic hydrocarbon group having 6 to 20 carbon atoms is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.

[0252] The saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms is more preferably a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and still more preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms.

[0253] as a group consisting of at least one group selected from a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms and -C(=O)O- or -C(=O)NR N -, from the viewpoint of heat resistance and affinity with organic solvents, preferably the group represented by the combination of Ar in formula (1-1-1) 1 The bonding position is *-C(=O)O- or *-C(=O)NR N -group. The above * represents 1 bonding position.

[0254] In addition, at least one group selected from a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms and -C(=O)O- or -C(=O)NR N - is preferably a group represented by the following formula (D-1) or the following formula (D-2), and more preferably a group represented by the following formula (D-1).

[0255] [Chemical formula 10]

[0256]

[0257] In formula (D-1) or formula (D-2), * independently represents the same group as Ar in formula (1-1-1). 1 The bonding position, R D1 represents a substituent D, R described below D2 and R D3 Each independently represents a hydrogen atom or a substituent D described below.

[0258] The substituent D is a group selected from an alkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an aliphatic saturated hydrocarbon group having 1 to 30 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms, and -C(=O)O- or -C(=O)NR N - represents a group in combination.

[0259] Preferred embodiments of the alkyl group having 1 to 30 carbon atoms, the aromatic hydrocarbon group having 6 to 20 carbon atoms, or the aliphatic saturated hydrocarbon group having 1 to 30 carbon atoms in the substituent D are the same as those described above. 11 The preferred manner of these groups is the same as in .

[0260] From the viewpoint of heat resistance and affinity with organic solvents, R D1 The substituent D in is preferably an alkyl group having 1 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an alkyl group having 1 to 30 carbon atoms, further preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group.

[0261] R D2 and R D3 Both may be hydrogen atoms, but preferably at least one is the above-mentioned substituent D, and more preferably one is a hydrogen atom and the other is the above-mentioned substituent D.

[0262] R D2 and R D3 The substituent D in is preferably an alkyl group having 1 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an alkyl group having 1 to 30 carbon atoms, further preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

[0263] -n1-

[0264] In formula (1-1-1), n1 represents 0 or more and Ar 1 It is an integer less than the maximum number of substitutions, preferably 0 or 1, more preferably 0.

[0265] Ar 1 The maximum number of substitutions is the number of substitutions by Ar 1 The maximum number of substituents that an aromatic group having 5 to 30 ring members can have is 1 In the case of a benzene ring structure, the maximum number of substitutions is 5. Hereinafter, the above contents are the same in the explanation of the maximum number of substitutions.

[0266] -Ar 2 -

[0267] In formula (1-1-2), Ar 2 It has the same meaning as Ar in formula (1-1), and preferred aspects are also the same.

[0268] -X 12 -

[0269] In formula (1-1-2), X 12 represents a hydroxyl group, a carboxyl group, a sulfo group, a phosphoric acid group or a phosphonic acid group, preferably a hydroxyl group or a carboxyl group, more preferably a carboxyl group.

[0270] -n2-

[0271] In formula (1-1-2), n2 represents 1 or more and Ar 2 It is an integer less than the maximum number of substitutions, preferably 1 or 2, more preferably 1.

[0272] -Ar 3 -

[0273] In formula (1-1-3), Ar 3 It has the same meaning as Ar in formula (1-1), and preferred aspects are also the same.

[0274] -X 13 -

[0275] In formula (1-1-3), X 13 It represents a group represented by any one of formula (E-1) to formula (E-11), preferably a group represented by formula (E-1) or formula (E-2), and more preferably a group represented by formula (E-2).

[0276] In formula (E-1) to formula (E-11), R E1 ~R E19 Each of the above groups is preferably independently selected from an aliphatic hydrocarbon group, an aromatic group, or an aliphatic hydrocarbon group, an aromatic group, -O-, -C(=O)-, -S-, -S(=O)2-, -C(=O)O-, -C(=O)NR N -、-OC(=O)NR N -、-NR N C(=O)NR N -, -CH2CH(OH)CH2-, a group having an ethylenically unsaturated bond, and a group represented by at least two bonds in the polymer chain.

[0277] The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and more preferably an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms.

[0278] As the aromatic group, the same group as Ar in formula (1-1) is preferred.

[0279] Examples of the group having an ethylenically unsaturated bond include an acryloyl group, an acryloyloxy group, an acrylamide group, a vinylphenyl group, and an allyl group. From the viewpoint of reactivity, an acryloyloxy group is preferred.

[0280] The above-mentioned polymer chain is preferably a polymer chain containing at least one repeating unit selected from the group consisting of repeating units represented by formula (1-1) to formula (1-5), repeating units derived from (meth)acrylic acid, and repeating units derived from (meth)acrylate compounds. A polymer chain containing at least one repeating unit selected from the group consisting of repeating units represented by formula (1-1) to formula (1-5) and repeating units derived from (meth)acrylate compounds is more preferred.

[0281] The repeating units represented by formula (1-1) to formula (1-5) contained in the above-mentioned polymer chain are preferably repeating units that do not have the above-mentioned polymer chain, preferably repeating units represented by formula (1-1-1), repeating units represented by formula (1-2-1) described later, repeating units represented by formula (1-3), repeating units represented by formula (1-4) or repeating units represented by formula (1-5), and more preferably repeating units represented by formula (1-1-1) or repeating units represented by formula (1-2-1) described later.

[0282] The repeating unit derived from (meth)acrylic acid in the above polymer chain is preferably a repeating unit represented by the formula (1-6) described below, and the repeating unit derived from the (meth)acrylate compound is preferably a repeating unit represented by the formula (1-7) described below (more preferably, a repeating unit represented by the formula (1-7), wherein R in the formula (1-7) is A2 is a repeating unit of formula (F-1)).

[0283] Furthermore, the repeating units included in the above-mentioned polymer chain are included in the total molar amount of all the repeating units included in the specific resin.

[0284] Among these, R E1 ~R E7 , preferably a group represented by any one of the following formulae (F-1) to (F-5). In the following formulae, * each independently represents a bonding position to another structure.

[0285] [Chemical formula 11]

[0286]

[0287] In formula (F-1), R F1 It represents an alkyl group or an aromatic hydrocarbon group, preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.

[0288] In formula (F-2), R F2 each independently represents an alkylene group, a divalent aromatic hydrocarbon group, -C(=O)NR N -、-OC(=O)NR N -、-NR N C(=O)NR N - or a group formed by bonding two or more of these, preferably an alkylene group. N As mentioned above.

[0289] In this specification, it is simply described as -C(=O)NR N -、-OC(=O)NR N -、-NR N C(=O)NR N -, the bonding directions of these in the structure are not particularly limited.

[0290] The alkylene group is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and still more preferably an ethylene group or a propylene group.

[0291] As the divalent aromatic hydrocarbon group, a phenylene group is preferred.

[0292] In formula (F-2), n represents an integer of 0 or greater, preferably an integer of 0 to 20, more preferably an integer of 0 to 10, further preferably 0, 1 or 2, and particularly preferably 0 or 1.

[0293] In formula (F-2), R F3 represents a hydrogen atom or a methyl group.

[0294] In formula (F-3), R F4 represents an alkylene group, a divalent aromatic hydrocarbon group, -C(=O)NR N -、-OC(=O)NR N -、-NR N C(=O)NR N - or a group formed by bonding two or more of these, preferably an alkylene group. N As mentioned above.

[0295] The alkylene group is preferably an alkylene group having 2 to 10 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

[0296] As the divalent aromatic hydrocarbon group, a phenylene group is preferred.

[0297] In formula (F-3), R F5 represents a hydrogen atom or a methyl group.

[0298] In formula (F-4), R F6 represents an alkylene group, an arylene group, -C(=O)NR N -、-OC(=O)NR N -、-NR N C(=O)NR N - or a group formed by bonding two or more of these groups, preferably an alkylene group or two or more alkylene groups using -OC(=O)NR N -bonded group. N As mentioned above.

[0299] The alkylene group is preferably an alkylene group having 2 to 20 carbon atoms, and more preferably an alkylene group having 2 to 10 carbon atoms.

[0300] In formula (F-4), Polymer represents the above R E1 ~R E7 The same applies to the polymer chains in the description of .

[0301] In formula (F-5), R F7 represents a single bond, an alkylene group or a divalent aromatic hydrocarbon group, and a single bond is preferred.

[0302] The alkylene group is preferably an alkylene group having 2 to 20 carbon atoms, and more preferably an alkylene group having 2 to 10 carbon atoms.

[0303] As the divalent aromatic hydrocarbon group, a phenylene group is preferred.

[0304] In formula (F-5), R F8 represents an alkylene group or a divalent aromatic hydrocarbon group, and an alkylene group is preferred.

[0305] The alkylene group is preferably an alkylene group having 2 to 20 carbon atoms, and more preferably an alkylene group having 2 to 10 carbon atoms.

[0306] As the divalent aromatic hydrocarbon group, a phenylene group is preferred.

[0307] In the formula (F-5), m represents an integer of 1 or more, preferably an integer of 2-50, and more preferably an integer of 2-30.

[0308] In formula (F-5), R F9 It represents an alkyl group or a monovalent aromatic hydrocarbon group, and an alkyl group is more preferable.

[0309] The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.

[0310] The monovalent aromatic hydrocarbon group is preferably a phenyl group.

[0311] -n3-

[0312] In formula (1-1-3), n3 represents 1 or more and Ar 3 It is an integer less than the maximum number of substitutions, preferably 1 or 2, more preferably 1.

[0313] The repeating unit represented by formula (1-1) is preferably a repeating unit derived from a vinyl aromatic hydrocarbon compound which may have a substituent (such as styrene, vinyl naphthalene, etc.) or a vinyl aromatic compound which may have a substituent (such as vinylthiophene, vinylpyridine, vinylimidazole, etc.).

[0314] [Repeating unit represented by formula (1-2)]

[0315] -R 21 , R 22 and R 23 -

[0316] In formula (1-2), R 21 , R 22 and R 23 Respectively with R in formula (1-1) 11 , R 12 and R 13 The meanings are the same and the preferred aspects are also the same.

[0317] -R 24 and R 25 -

[0318] R 24 and R 25 Each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, and R 24 and R 25 They may be bonded to form a ring structure.

[0319] Preferred R 24 and R 25 At least one of them represents an alkyl group having 1 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 30 carbon atoms, or R 24 and R 25 bonded to form a ring structure.

[0320] R 24 and R 25 Each independently is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms.

[0321] As R 24 and R 25 The aromatic hydrocarbon group having 6 to 30 carbon atoms is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.

[0322] As R 24 and R 25 Examples of the ring structure formed by bonding include aliphatic heterocyclic structures such as a piperidine ring, a piperazine ring, and a morpholine ring.

[0323] In the range of obtaining the effect of the present invention, R 24 and R 25 An alkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or R 24 and R 25 The ring structure formed by bonding may have a substituent. Examples of the substituent include acid groups such as carboxyl groups, sulfo groups, phosphoric acid groups, phosphonic acid groups, active imide groups, and sulfonamide groups, amino groups, alkyl groups, aryl groups, and halogen atoms. 24 and R 25 The aromatic hydrocarbon group having 6 to 30 carbon atoms may have a hydroxyl group as a substituent.

[0324] From the viewpoint of imparting alkali developability to the colored resin composition, an alkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or R 24 and R 25 The ring structure formed by bonding has an acid group such as the above-mentioned carboxyl group, sulfo group, phosphoric acid group, phosphonic acid group, active imide group, sulfonamide group, etc. 24 and R 25When at least one of the aromatic hydrocarbon groups is an aromatic hydrocarbon group having 6 to 30 carbon atoms, the aromatic hydrocarbon group may have a hydroxyl group as an acid group.

[0325] Furthermore, the acid group may form an ester bond with another structure. Examples of the other structure include a polymer chain and a structure having an ethylenically unsaturated bond. Examples of the polymer chain include a molecular chain having a molecular weight of 1,000 to 10,000 and having no acid group or basic group, as described below.

[0326] Furthermore, the amino group may form an amide bond, a urethane bond or a urea bond with another structure. The other structure is the same as the other structure described as the object of the acid group to form an ester bond.

[0327] [Formula (1-2-1), Formula (1-2-2), Formula (1-2-3)]

[0328] The repeating unit represented by the formula (1-2) is preferably a repeating unit represented by the following formula (1-2-1), a repeating unit represented by the following formula (1-2-2), or a repeating unit represented by the following formula (1-2-3).

[0329] Furthermore, in the specific resin, as the repeating unit represented by the formula (1-2), it is preferred that the repeating unit be represented by the formula (1-2-2), and it is more preferred that the repeating unit be represented by the formula (1-2-2) and the repeating unit be represented by the formula (1-2-3).

[0330] [Chemical formula 12]

[0331]

[0332] In formula (1-2-1), formula (1-2-2) and formula (1-2-3), R 21 , R 22 and R 23 Each independently represents a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and R 26 and R 27 Each independently represents an alkyl group having 1 to 30 carbon atoms, and R 28 represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group, X 21 Each independently represents a hydroxyl group, a carboxyl group, a sulfo group, a phosphoric acid group, a phosphonic acid group, an active imide group or a sulfonamide group, n1 is 1 or 2, n2 is 0 or 1, n1+n2 is 2, n3 is an integer greater than 1, R 29 represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group, X 22 Each independently represents a group represented by any one of the above formulae (E-1) to (E-11), m1 is 1 or 2, m2 is 0 or 1, m1+m2 is 2, and m3 is an integer of 1 or more.

[0333] In formula (1-2-1), formula (1-2-2) and formula (1-2-3), R 21 , R 22 and R 23 Respectively with R in formula (1-2) 21 , R 22 and R 23 The meanings are the same and the preferred aspects are also the same.

[0334] -R 26 and R 27 -

[0335] In formula (1-2-1), R 26 and R 27 Each independently represents an alkyl group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

[0336] -R 28 -

[0337] In formula (1-2-2), R 28 represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group, preferably an aliphatic hydrocarbon group, more preferably an aliphatic saturated hydrocarbon group.

[0338] The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 2 to 30 carbon atoms, and more preferably an aliphatic hydrocarbon group having 2 to 20 carbon atoms.

[0339] As the aromatic hydrocarbon group, a group obtained by removing 1+n3 hydrogen atoms from a benzene ring is preferred.

[0340] -X 21 -

[0341] In formula (1-2-2), R 28 When X is an aliphatic hydrocarbon group, 21 Each of them is independently preferably a carboxyl group, a sulfo group, a phosphoric acid group, a phosphonic acid group, an active imide group or a sulfonamide group, and more preferably a carboxyl group.

[0342] In formula (1-2-2), R 28 When X is an aromatic hydrocarbon group, 21 Each independently preferably is a hydroxyl group or a carboxyl group, and more preferably is a carboxyl group.

[0343] -n1, n2, n3-

[0344] In formula (1-2-2), it is preferred that n1 is 1 and n2 is 1.

[0345] In formula (1-2-2), n3 is an integer of 1 or more, preferably 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1.

[0346] -R29 -

[0347] In formula (1-2-3), R 29 represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group, preferably an aliphatic hydrocarbon group, more preferably an aliphatic saturated hydrocarbon group.

[0348] The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 2 to 30 carbon atoms, and more preferably an aliphatic hydrocarbon group having 2 to 20 carbon atoms.

[0349] As the aromatic hydrocarbon group, a group obtained by removing 1+m3 hydrogen atoms from a benzene ring is preferred.

[0350] -X 22 -

[0351] In formula (1-2-3), R 29 When X is an aliphatic hydrocarbon group, 22 The groups represented by any one of formula (E-2), formula (E-3), formula (E-4) and formula (E-5) are respectively independently preferred, and the groups represented by formula (E-2) are more preferred.

[0352] In formula (1-2-3), R 29 When X is an aromatic hydrocarbon group, 22 The groups represented by either formula (E-1) or formula (E-2) are respectively independently preferred, and the groups represented by formula (E-2) are more preferred.

[0353] -m1, m2, m3-

[0354] In formula (1-2-3), preferably, m1 is 1 and m2 is 1.

[0355] In the formula (1-2-3), m3 is an integer of 1 or more, preferably 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1.

[0356] The repeating unit represented by the formula (1-2) is preferably a repeating unit derived from an acrylamide compound which may have a substituent.

[0357] [Repeating unit represented by formula (1-3)]

[0358] -R 31 , R 32 and R 33 -

[0359] In formula (1-3), R 31 , R 32 and R 33 Respectively with R in formula (1-1) 11 , R 12 and R 13The meanings are the same and the preferred aspects are also the same.

[0360] -R 34 and R 35 -

[0361] In formula (1-3), R 34 and R 35 Each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, and is preferably an alkyl group having 1 to 30 carbon atoms.

[0362] The alkyl group having 1 to 30 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

[0363] The aromatic hydrocarbon group having 6 to 30 carbon atoms is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.

[0364] The alkyl group having 1 to 30 carbon atoms and the aromatic hydrocarbon group having 6 to 30 carbon atoms may have a substituent within a range in which the effects of the present invention are obtained.

[0365] In formula (1-3), R 34 and R 35 At least one of them preferably represents an alkyl group having 1 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0366] And, preferably R 34 and R 35 The ring structure to be formed is preferably a lactam ring structure having 5 to 20 ring members, and more preferably a lactam ring structure having 5 to 10 ring members.

[0367] The repeating unit represented by formula (1-3) is preferably a repeating unit derived from an N-vinyl-N-acyl compound (N-vinylacetamide, etc.) or an N-vinyllactam compound (N-vinyl 2-pyrrolidone, N-vinyl-ε-caprolactam, etc.).

[0368] [Repeating unit represented by formula (1-4)]

[0369] -R 41 and R 42 -

[0370] In formula (1-4), R 41 and R 42 Respectively with R in formula (1-1) 11 and R 13 The meanings are the same and the preferred aspects are also the same.

[0371] -R 43 -

[0372] In formula (1-4), R 43 It represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an alkyl group having 1 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 30 carbon atoms, and preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0373] The alkyl group having 1 to 30 carbon atoms is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.

[0374] The aromatic hydrocarbon group having 6 to 30 carbon atoms is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and further preferably a phenyl group.

[0375] The alkyl group having 1 to 30 carbon atoms or the aromatic hydrocarbon group having 6 to 30 carbon atoms may have a substituent within a range in which the effects of the present invention are obtained.

[0376] The repeating unit represented by the formula (1-4) is preferably a repeating unit derived from a maleimide compound (maleimide, N-alkylmaleimide, N-phenylmaleimide, etc.).

[0377] [Repeating unit represented by formula (1-5)]

[0378] -R 51 and R 52 -

[0379] In formula (1-5), R 51 and R 52 Respectively with R in formula (1-1) 11 and R 12 The meanings are the same and the preferred aspects are also the same.

[0380] -R 53 and R 54 -

[0381] In formula (1-5), R 53 and R 54 Each independently represents a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.

[0382] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group.

[0383] The aromatic hydrocarbon group is preferably an aromatic hydrocarbon ring having 6 to 20 carbon atoms, and more preferably a phenyl group.

[0384] The alkyl group or the aromatic hydrocarbon group may have a substituent as long as the effects of the present invention are obtained.

[0385] Furthermore, the aromatic hydrocarbon group may be bonded to another aromatic hydrocarbon ring or another aromatic heterocyclic ring within the scope of obtaining the effects of the present invention. Examples of the bonding form include a condensed ring, a crosslinked ring, and a spiro ring.

[0386] -R 55 -

[0387] In formula (1-5), R 55 It represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an alkyl group having 1 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 30 carbon atoms, and preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0388] The alkyl group having 1 to 30 carbon atoms is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.

[0389] The aromatic hydrocarbon group having 6 to 30 carbon atoms is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and further preferably a phenyl group.

[0390] The alkyl group having 1 to 30 carbon atoms or the aromatic hydrocarbon group having 6 to 30 carbon atoms may have a substituent within a range in which the effects of the present invention are obtained.

[0391] The repeating unit represented by the formula (1-5) is preferably a repeating unit derived from an itaconimide compound (itaconimide, N-alkylitaconimide, N-phenylitaconimide, etc.).

[0392] From the viewpoint of widening the process window, the content of the repeating unit derived from (meth)acrylic acid or a (meth)acrylate compound in the specific resin is preferably 0 to 20 mol % based on the total molar amount of all repeating units contained in the specific resin.

[0393] The above content is preferably 0 to 15 mol %, more preferably 0 to 10 mol %.

[0394] Furthermore, in the present invention, an embodiment in which the content is 0 to 1 mol % (preferably 0 to 0.5 mol %, more preferably 0 to 0.1 mol %) is also a preferred embodiment.

[0395] The repeating unit derived from (meth)acrylic acid which may be contained in the specific resin is preferably a repeating unit represented by the following formula (1-6).

[0396] Furthermore, the repeating unit derived from the (meth)acrylate compound which may be contained in the specific resin is preferably a repeating unit represented by the following formula (1-7).

[0397] [Chemical formula 13]

[0398]

[0399] In formula (1-6), R A1 It represents a hydrogen atom or a methyl group, and is more preferably a hydrogen atom.

[0400] In formula (1-7), R A1 It represents a hydrogen atom or a methyl group, and is more preferably a hydrogen atom.

[0401] In formula (1-7), R A2 It is a group represented by any one of the above formulae (F-1) to (F-5), and preferred embodiments of these groups are as described above.

[0402] 〔Specific substituent〕

[0403] The specific resin preferably has at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfo group, a phosphoric acid group, and an amino group, and more preferably has a hydroxyl group or a carboxyl group. The hydroxyl group is preferably a phenolic hydroxyl group.

[0404] For example, by introducing a repeating unit represented by the above formula (1-1-2) or a repeating unit represented by the above formula (1-2-2) into the specific resin, these groups are introduced into the specific resin.

[0405] 〔Acid group〕

[0406] From the viewpoint of improving alkali developability, the specific resin preferably has an acid group. Examples of the acid group include a phenolic hydroxyl group, a carboxyl group, a sulfone group, a phosphoric acid group, an active imide group, and a sulfonamide group.

[0407] From the viewpoint of improving film forming properties and alkali developability, the acid value in the specific resin is preferably 0 to 500 mgKOH / g.

[0408] The lower limit of the acid value is preferably 20 mgKOH / g or more, more preferably 30 mgKOH / g or more, and even more preferably 50 mgKOH / g or more.

[0409] The upper limit of the acid value is preferably 300 mgKOH / g or less, more preferably 200 mgKOH / g or less, and further preferably 150 mgKOH / g or less.

[0410] The acid value of the specific resin is calculated by the same method as the measurement method in Examples described later.

[0411] 〔Ethylenically unsaturated bond〕

[0412] The specific resin preferably has an ethylenically unsaturated bond.

[0413] Furthermore, the specific resin preferably includes a group having an ethylenically unsaturated bond.

[0414] Examples of the group having an ethylenically unsaturated bond include an acryloyl group, an acryloyloxy group, an acrylamide group, a vinylphenyl group, and an allyl group. From the viewpoint of reactivity, an acryloyloxy group is preferred.

[0415] For example, a group having an ethylenically unsaturated bond can be introduced into a specific resin by introducing into the specific resin a repeating unit represented by the above formula (1-1-2) or a repeating unit represented by the above formula (1-2-2), and a repeating unit having a group represented by the above formula (F-2) or formula (F-3).

[0416] From the viewpoint of storage stability and curability, the C=C value of the specific resin is preferably 0 to 5 mmol / g.

[0417] The lower limit of the C=C value is preferably 0.01 mmol / g or more, more preferably 0.03 mmol / g or more, further preferably 0.05 mmol / g or more, and particularly preferably 0.1 mmol / g or more.

[0418] The upper limit of the C=C value is preferably 3 mmol / g or less, more preferably 2 mmol / g or less, further preferably 1.5 mmol / g or less, and particularly preferably 1 mmol / g or less.

[0419] In the present invention, the C=C value of a specific resin refers to the number of ethylenically unsaturated bonds contained in 1 g of the specific resin, and is a value measured by the method in Examples described later.

[0420] 〔Grafted polymer, star-shaped polymer〕

[0421] The specific resin may be any of a linear polymer, a star polymer, and a graft polymer compound, and may be a star polymer having multiple branch points and a specific terminal group described in JP-A-2007-277514, etc., but is preferably a graft polymer or a star polymer.

[0422] -Grafted polymer-

[0423] When the specific resin is a graft polymer, the specific resin preferably has a molecular chain having a molecular weight of 1,000 to 10,000 as described below and containing no acid group or basic group as a graft chain.

[0424] Furthermore, when the specific resin is a graft polymer, the specific resin preferably has a repeating unit represented by the above formula (1-1-3) and having a group represented by the above formula (F-4) or formula (F-5) or a repeating unit represented by the above formula (1-2-3) and having a group represented by the above formula (F-4) or formula (F-5) in the main chain. In this case, the group represented by formula (F-4) or formula (F-5) preferably becomes a graft chain in the graft polymer.

[0425] -Star-shaped polymer-

[0426] When the specific resin is a star-shaped polymer, the specific resin is preferably a resin represented by the following formula (S-1).

[0427] [Chemical formula 14]

[0428]

[0429] In formula (S-1), R 1 represents an (m+n1)-valent organic linking group, R 2 Each independently represents a single bond or an n2+1 valent linking group, A 1 Each independently represents at least one group selected from hydroxyl, carboxyl, sulfonyl, phosphoric acid and amino, R 3 Each independently represents a single bond or an n2+1 valent linking group, P 1 Each independently represents a polymer chain, m represents an integer from 1 to 8, n1 represents an integer from 2 to 9, m+n1 is 3 to 10, n2 is an integer greater than 1, and the total amount of repeating units represented by any one of formulas (1-1) to (1-5) relative to the total molar amount of all repeating units contained in the resin represented by formula (S-1) exceeds 60 mol%.

[0430] -R 1 -

[0431] In formula (S-1), R 1 Preferably, it is a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms and 0 to 20 sulfur atoms; preferably, it is a group consisting of 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms and 0 to 10 sulfur atoms; more preferably, it is a group consisting of 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 hydrogen atoms and 0 to 7 sulfur atoms; and particularly preferably, it is a group consisting of 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, 1 to 80 hydrogen atoms and 0 to 5 sulfur atoms.

[0432] -R 2 -

[0433] In formula (S-1), R 2 Preferred is a divalent organic linking group consisting of a single bond, or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 10 sulfur atoms; more preferred is a divalent organic linking group consisting of a single bond, or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms; and particularly preferred is a divalent organic linking group consisting of a single bond, or 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms.

[0434] -R 3 -

[0435] In formula (S-1), R 3 Preferably, each independently represents a single bond, -S- or the above R 2 The same group is more preferably a single bond or -S-, and particularly preferably -S-.

[0436] -P 1 -

[0437] In formula (S-1), P 1 The polymer chain preferably contains at least one repeating unit selected from the repeating units represented by formula (1-1) to formula (1-7), and more preferably contains at least one repeating unit selected from the repeating units represented by formula (1-1) to formula (1-5) and formula (1-7).

[0438] And, P 1 It preferably contains a repeating unit represented by formula (1-1-1), a repeating unit represented by formula (1-2-1), a repeating unit represented by formula (1-3), a repeating unit represented by formula (1-4) or a repeating unit represented by formula (1-5), and more preferably contains a repeating unit represented by formula (1-1-1) or a repeating unit represented by formula (1-2-1).

[0439] -m, n1, n2-

[0440] In the formula (S-1), m represents an integer of 1 to 8, preferably 1 to 5, more preferably 1 to 4, and particularly preferably 2 to 4.

[0441] In the formula (S-1), n1 represents an integer of 2 to 9, preferably 2 to 8, more preferably 2 to 7, and particularly preferably 2 to 6.

[0442] In formula (S-1), n2 represents an integer of 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0443] -Formula (S-2)-

[0444] The star-shaped polymer represented by the formula (S-1) is preferably a star-shaped polymer represented by the formula (S-2).

[0445] [Chemical formula 15]

[0446]

[0447] In formula (S-2), R 1 , A 1 , P 1 、n 1 、n 2 , and m are respectively the same as R in formula (S-1) 1 , A 1 , P 1 、n 1 、n 2 , and m have the same meanings and the preferred aspects are also the same.

[0448] In formula (S-2), R 4 -S-Except when using 1 The bonding position of includes other than sulfur atom, and R in formula (S-1) 2 The meanings are the same and the preferred aspects are also the same.

[0449] 〔Molecular chain〕

[0450] The specific resin preferably has a molecular weight of 1,000 to 10,000 and has a molecular chain without an acid group or a basic group.

[0451] The specific resin preferably has the above-mentioned molecular chain as a branch chain.

[0452] When the specific resin is a grafted polymer, the above-mentioned molecular chain is preferably a grafted chain, and the above-mentioned molecular chain is more preferably included as the following groups, namely, the group represented by the above-mentioned formula (F-4) or formula (F-5) contained in the repeating unit represented by the above-mentioned formula (1-1-3) or the group represented by the above-mentioned formula (F-4) or formula (F-5) contained in the repeating unit represented by the above-mentioned formula (1-2-3).

[0453] When the specific resin is a star-shaped polymer, the molecular chain is preferably as P in the above formula (S-1). 1 And included.

[0454] The molecular chain preferably includes at least one selected from the group consisting of a repeating unit derived from a (meth)acrylate compound, a repeating unit derived from a (meth)acrylamide compound, a repeating unit derived from an aromatic vinyl compound, and a polyester structure.

[0455] As the repeating unit derived from the (meth)acrylate compound, a repeating unit represented by the above formula (1-7) is preferred, and a repeating unit represented by the above formula (1-7) is more preferred, wherein R A2 is a repeating unit of a group represented by formula (F-1), formula (F-2) or formula (F-3), and is further preferably represented by the above formula (1-7), and R A2 is a repeating unit of the group represented by formula (F-1).

[0456] As the repeating unit derived from the (meth)acrylamide compound, a repeating unit represented by the above formula (1-2) is preferred, and a repeating unit represented by the above formula (1-2-1) is more preferred.

[0457] The repeating unit derived from the aromatic vinyl compound is preferably a repeating unit represented by the formula (1-1), and more preferably a repeating unit represented by the formula (1-1-1).

[0458] The polyester structure is preferably a polyester structure represented by the above formula (F-5). The polyester structure is preferably contained in the specific resin as a repeating unit represented by the above formula (1-1-3) and having a group represented by the formula (F-5), or a repeating unit represented by the above formula (1-2-3) and having a group represented by the formula (F-5).

[0459] The colored resin composition of the present invention preferably contains at least one resin selected from the following resin 1 and the following resin 2 as a specific resin, and preferably contains the following resin 1 and the following resin 2.

[0460] By including the resin 1, the developability of the colored resin composition is improved.

[0461] By including the resin 2, the storage stability of the colored resin composition is improved.

[0462] Resin 1: a specific resin containing an acid group and a group having an ethylenically unsaturated bond

[0463] Resin 2: is a specific resin having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic group, a phosphoric acid group, and an amino group, and a molecular chain having a molecular weight of 1,000 to 10,000 and no acid group.

[0464] The at least one group selected from the group consisting of an acid group, a group having an ethylenically unsaturated bond, a hydroxyl group, a carboxyl group, a sulfonic group, a phosphoric acid group and an amino group in the above-mentioned resin 1 and the above-mentioned resin 2, and the molecular chain having a molecular weight of 1,000 to 10,000 and having no acid group are as described above.

[0465] The resin 1 may also have the above-mentioned molecular chain.

[0466] Furthermore, the resin 2 may further have the above-mentioned group having an ethylenically unsaturated bond.

[0467] 〔Molecular weight〕

[0468] The weight average molecular weight (Mw) of the specific resin is preferably 5,000 to 100,000, more preferably 10,000 to 50,000.

[0469] 〔Molar absorptivity〕

[0470] The maximum value of the molar absorption coefficient of the specific resin at a wavelength of 400 to 1100 nm is preferably 0 to 1,000 l / (mol·cm), more preferably 0 to 100 l / (mol·cm).

[0471] [Heat resistance]

[0472] In the specific resin, the 5% mass reduction temperature based on TG / DTA (thermal mass measurement / differential thermal measurement) under a nitrogen environment is preferably 280°C or higher, more preferably 300°C or higher, and further preferably 320°C or higher. The upper limit of the 5% mass reduction temperature is not particularly limited, and for example, it can be 1,000°C or lower. The 5% mass reduction temperature is a temperature at which the mass reduction rate becomes 5% when the resin is left at a specific temperature for 5 hours under a nitrogen environment, and can be obtained by a known TG / DTA measurement method.

[0473] Furthermore, the specific resin preferably has a mass reduction rate of 10% or less, more preferably 5% or less, and even more preferably 2% or less when left at 300°C for 5 hours in a nitrogen environment. The lower limit of the mass reduction rate is not particularly limited as long as it is 0% or more.

[0474] The mass reduction rate is a value calculated as a ratio of mass reduction in a specific resin before and after being left to stand at 300° C. for 5 hours in a nitrogen atmosphere.

[0475] [Synthesis method]

[0476] The synthesis method of the specific resin is not particularly limited, and the specific resin can be synthesized by a known method, for example, by a method described in Examples described later.

[0477] [Specific example]

[0478] Although specific examples of the specific resin are shown below, the present invention is not limited thereto.

[0479] In the following table, the "Item 1" column records the ratio (mol %) of the total amount of repeating units represented by any one of the above formulas (1-1) to (1-5) relative to the total molar amount of all repeating units contained in the specific resin, the "Item 2" column records the content (mol %) of repeating units derived from (meth)acrylic acid or (meth)acrylate compounds, and the "Acid Value" column records the acid value (mgKOH / g) of the specific resin, and the "C=C Value" column records the C=C value (mmol / g) of the specific resin.

[0480] In the following chemical formula, x, y, z, and w represent the content ratio (mol %) of each repeating unit, and can be appropriately set within the range satisfying item 1, item 2, acid value, and C=C value.

[0481] In the following chemical formula, for example, the term "polymer" in (A-22) indicates that a polymer chain is bonded to the sulfur atom described in (A-22), and the polymer chain is formed by randomly bonding repeating units derived from diethylacrylamide and repeating units derived from styrene at the content ratio (molar ratio) indicated by the suffix in the parentheses. The molar ratio can be appropriately set within the range satisfying item 1, item 2, acid value, and C=C value.

[0482] Furthermore, for example, in (A-34), any two of the six *s in R are bonded to the structure represented by the square brackets on the left, and any four of them are bonded to the structure represented by the square brackets on the right. Furthermore, the description in the square brackets on the right indicates a polymer chain in which repeating units derived from methyl vinyl benzoate and repeating units derived from butyl acrylate are randomly bonded.

[0483] [Table 1]

[0484]

[0485] [Table 2]

[0486]

[0487] [Table 3]

[0488]

[0489] [Table 4]

[0490]

[0491] [Table 5]

[0492]

[0493] [Table 6]

[0494]

[0495] [Table 7]

[0496]

[0497] [Table 8]

[0498]

[0499] [Table 9]

[0500]

[0501] [Table 10]

[0502]

[0503] [Table 11]

[0504]

[0505] 〔content〕

[0506] The content of the specific resin in the colored resin composition of the present invention is preferably 10 to 95% by mass relative to the total solid content of the colored resin composition. The lower limit is more preferably 20% by mass or more, and further preferably 30% by mass or more. The upper limit is more preferably 90% by mass or less, and further preferably 85% by mass or less.

[0507] The colored resin composition of the present invention may contain one specific resin alone or two or more specific resins in combination. When two or more specific resins are used in combination, the total amount is preferably within the above range.

[0508] When the colored resin composition of the present invention contains the above-mentioned resin 1 as a specific resin, the content of the resin 1 is preferably 1 to 30% by mass relative to the total solid content of the colored resin composition. The lower limit is more preferably 3% by mass or more, and further preferably 5% by mass or more. The upper limit is more preferably 25% by mass or less, and further preferably 20% by mass or less.

[0509] Furthermore, when the colored resin composition of the present invention contains the above-mentioned resin 2 as a specific resin, the content of the resin 2 is preferably 10 to 60% by mass relative to the total solid content of the colored resin composition. The lower limit is more preferably 15% by mass or more, and further preferably 20% by mass or more. The upper limit is more preferably 55% by mass or less, and further preferably 50% by mass or less.

[0510] Furthermore, when the colored resin composition of the present invention contains the above-mentioned resin 2 as a specific resin and contains a pigment as a colorant, the content of the resin 2 is preferably 25 to 85% by mass relative to the total mass of the pigment contained in the colored resin composition. The lower limit is more preferably 28% by mass or more, and further preferably 30% by mass or more. The upper limit is more preferably 80% by mass or less, and further preferably 50% by mass or less.

[0511] Furthermore, in the present invention, it is preferred that more than 20% by mass of a specific resin is contained in the component removing the colorant from the total solid content of the colored resin composition, more preferably more than 30% by mass, and further preferably more than 40% by mass. The upper limit can be set to 100% by mass, can also be set to less than 90% by mass, and can also be set to less than 85% by mass. As long as the content of the specific resin is within the above range, it is easy to form a film with excellent heat resistance, and it is easier to suppress the shrinkage of the film after heating. Moreover, when an inorganic film is formed on the surface of the film obtained using the colored resin composition of the present invention, even if the laminate is exposed to high temperature, cracking on the inorganic film can be suppressed.

[0512] The total content of the colorant and the resin A in the total solid content of the colored resin composition is preferably 25 to 100% by mass. The lower limit is more preferably 30% by mass or more, and further preferably 40% by mass or more. The upper limit is more preferably 90% by mass or less, and further preferably 80% by mass or less.

[0513] <Other resins>

[0514] The colored resin composition of the present invention may contain other resins.

[0515] The compound corresponding to the specific resin does not correspond to the above-mentioned other resins.

[0516] When the colored resin composition of the present invention contains other resins, the total amount of repeating units represented by any one of formula (1-1) to formula (1-5) relative to the total molar amount of all repeating units contained in all resin components contained in the colored resin composition of the present invention is preferably more than 60 mol%. The ratio of the total amount is preferably 70 mol% or more, more preferably 80 mol% or more. The upper limit is not particularly limited, and it can be 100 mol% or less.

[0517] As another resin, a resin which has alkali developability, a resin which functions as a dispersant, etc. are mentioned, for example.

[0518] However, when the colored resin composition of the present invention contains other resins, it is also preferable to adopt a mode shown in, for example, the following (1) or the following (2).

[0519] (1) The above-mentioned resin 1 and a resin as a dispersant are included.

[0520] (2) Contains a resin having alkali developability and the above-mentioned resin 2.

[0521] Furthermore, in the above-mentioned aspect (1), the above-mentioned resin 2 may be further contained, and in the above-mentioned aspect (2), the above-mentioned resin 1 may be further contained.

[0522] [Alkali-developable resin]

[0523] The weight average molecular weight (Mw) of the alkali-developable resin is preferably 3,000 to 2,000,000. The upper limit is more preferably 1,000,000 or less, and further preferably 500,000 or less. The lower limit is more preferably 4,000 or more, and further preferably 5,000 or more.

[0524] As the resin with alkali developability, (meth) acrylic resin, polyimide resin, polyether resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, etc. can be cited, preferably (meth) acrylic resin and polyimide resin, more preferably (meth) acrylic resin. And, as other resins, the resins recorded in paragraphs 0041 to 0060 of Japanese Patent Publication No. 2017-206689, the resins recorded in paragraphs 0022 to 0071 of Japanese Patent Publication No. 2018-010856, the resins recorded in Japanese Patent Publication No. 2017-057265, the resins recorded in Japanese Patent Publication No. 2017-032685, the resins recorded in Japanese Patent Publication No. 2017-075248, and the resins recorded in Japanese Patent Publication No. 2017-066240 can also be used.

[0525] In addition, as the resin having alkali developability, a resin having an acid group is preferably used. According to this embodiment, the developability of the colored resin composition can be further improved. As the acid group, phenolic hydroxyl group, carboxyl group, sulfonic group, phosphoric acid group, phosphonic acid group, active imide group, sulfonamide group, etc. can be cited, and carboxyl group is preferred. The resin having an acid group can be used as an alkali-soluble resin, for example.

[0526] The resin having an acid group preferably contains a repeating unit having an acid group in a side chain, and more preferably contains 1 to 70 mol% of a repeating unit having an acid group in a side chain in the total repeating units of the resin. The upper limit of the content of the repeating unit having an acid group in the side chain is preferably 50 mol% or less, more preferably 40 mol% or less. The lower limit of the content of the repeating unit having an acid group in the side chain is preferably 2 mol% or more, more preferably 5 mol% or more.

[0527] The acid value of the resin having an acid group is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, further preferably 120 mgKOH / g or less, and particularly preferably 100 mgKOH / g or less. Furthermore, the acid value of the resin having an acid group is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and further preferably 20 mgKOH / g or more.

[0528] The resin having an acid group also preferably further has a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, and a (meth)acryloyl group. An allyl group and a (meth)acryloyl group are preferred, and a (meth)acryloyl group is more preferred.

[0529] The resin having a group containing an ethylenically unsaturated bond preferably contains a repeating unit having a group containing an ethylenically unsaturated bond in the side chain, and more preferably contains 5 to 80 mol% of a repeating unit having a group containing an ethylenically unsaturated bond in the side chain in the total repeating units of the resin. The upper limit of the content of the repeating unit having a group containing an ethylenically unsaturated bond in the side chain is preferably 60 mol% or less, more preferably 40 mol% or less. The lower limit of the content of the repeating unit having a group containing an ethylenically unsaturated bond in the side chain is preferably 10 mol% or more, more preferably 15 mol% or more.

[0530] The alkali-developable resin also preferably includes a repeating unit derived from a monomer component including a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds are also referred to as “ether dimers”).

[0531] [Chemical formula 16]

[0532]

[0533] In formula (ED1), R 1 and R 2 Each independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 25 carbon atoms.

[0534] [Chemical formula 17]

[0535]

[0536] In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For formula (ED2), reference can be made to the description of Japanese Unexamined Patent Publication No. 2010-168539, and the contents are incorporated herein.

[0537] As specific examples of the ether dimer, for example, paragraph 0317 of JP-A-2013-029760 can be referred to, and the contents are incorporated into the present specification.

[0538] It is also preferred that the alkali-developable resin include a repeating unit derived from a compound represented by the following formula (X).

[0539] [Chemical formula 18]

[0540]

[0541] In formula (X), R1 represents a hydrogen atom or a methyl group, R2 represents an alkylene group having 2 to 10 carbon atoms, and R3 represents an alkyl group having 1 to 20 carbon atoms which may contain a hydrogen atom or a benzene ring. n represents an integer of 1 to 15.

[0542] Examples of the resin having an acid group include resins having the following structures. In the following structural formula, Me represents a methyl group.

[0543] [Chemical formula 19]

[0544]

[0545] 〔Dispersant〕

[0546] The colored resin composition of the present invention may also contain a resin as a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and an alkaline dispersant (alkaline resin). Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of alkaline groups. When the total amount of the acid groups and the amount of alkaline groups is set to 100 mol%, it is preferred that the amount of acid groups in the acidic dispersant (acidic resin) accounts for 70 mol% or more, and more preferably a resin substantially containing only acid groups. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and further preferably 60 to 105 mgKOH / g. Furthermore, the alkaline dispersant (alkaline resin) refers to a resin in which the amount of alkaline groups is greater than the amount of acid groups. When the total amount of the acid group and the basic group is 100 mol %, the basic dispersant (basic resin) preferably has a basic group amount exceeding 50 mol %. The basic group of the basic dispersant is preferably an amino group.

[0547] The resin used as the dispersant preferably contains a repeating unit having an acid group.

[0548] The resin used as the dispersant is also preferably a grafted resin. Examples of the grafted resin include the resins described in paragraphs 0025 to 0094 of JP-A-2012-255128, and the contents are incorporated into the present specification.

[0549] The resin used as a dispersant is also preferably a polyimine-based (polyimine resin) dispersant in which at least one of the main chain and the side chain contains a nitrogen atom. As a polyimine-based dispersant, it is preferred to have a main chain with a partial structure and a side chain with an atomic number of 40 to 10,000, and at least one of the main chain and the side chain has a basic nitrogen atom, wherein the partial structure has a functional group with a pKa of less than 14. As long as the basic nitrogen atom is a nitrogen atom that shows alkalinity, there is no particular limitation. As a polyimine-based dispersant, the resins described in paragraphs 0102 to 0166 of Japanese Patent Publication No. 2012-255128 can be cited, and the content is incorporated into this specification.

[0550] The resin used as the dispersant is also preferably a resin having a structure in which a plurality of polymer chains are bonded in the core. Examples of such resins include dendritic polymers (including star polymers). Specific examples of dendritic polymers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of Japanese Patent Application Publication No. 2013-043962.

[0551] The dispersant can be a commercial product, and specific examples thereof include DISPERBYK series (e.g., DISPERBYK-111, 161, etc.) manufactured by BYK Chemie GmbH, Solsperse series (e.g., Solsperse 36000, etc.) manufactured by Lubrizol, etc. In addition, the pigment dispersants described in paragraphs 0041 to 0130 of Japanese Unexamined Patent Publication No. 2014-130338 can also be used, and the contents are incorporated into this specification. Furthermore, as the dispersant, compounds described in JP-A-2018-150498, JP-A-2017-100116, JP-A-2017-100115, JP-A-2016-108520, JP-A-2016-108519, and JP-A-2015-232105 can be used.

[0552] Furthermore, the resin described as the dispersant can also be used for purposes other than the dispersant, for example, it can also be used as a binder.

[0553] The content of the total resin component in the total solid content of the colored resin composition is preferably 10 to 95% by mass. The lower limit is more preferably 20% by mass or more, and further preferably 30% by mass or more. The upper limit is more preferably 90% by mass or less, and further preferably 85% by mass or less.

[0554] Furthermore, in the colored resin composition, the content of the above-mentioned other resins is preferably 230 parts by mass or less, more preferably 200 parts by mass or less, and further preferably 150 parts by mass or less relative to 100 parts by mass of the above-mentioned specific resin. The lower limit can be 0 parts by mass, can be set to 5 parts by mass or more, and can also be set to 10 parts by mass or more. Furthermore, the colored resin composition is also preferably substantially free of the above-mentioned other resins. According to this mode, it is easier to form a film with excellent heat resistance. The situation where substantially no other resins are contained refers to that the content of other resins in the total solid content of the resin composition is 0.1% by mass or less, preferably 0.05% by mass or less, and more preferably not contained.

[0555] <Organic solvents>

[0556] The colored resin composition of the present invention contains an organic solvent. As an organic solvent, there is basically no particular restriction as long as the solubility of each component and the coating property of the colored resin composition are satisfied. As organic solvents, ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents, etc. can be cited. Regarding these, specific reference can be made to paragraph 0223 of International Publication No. 2015 / 166779, and the content is incorporated into this specification. In addition, ester solvents substituted by cyclic alkyl groups and ketone solvents substituted by cyclic alkyl groups can also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, methylene chloride, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, γ-butyrolactone, N-methyl-2-pyrrolidone, etc. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may be preferably reduced in amount (for example, it can be set to 50 mass ppm (parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less relative to the total amount of the organic solvent) for reasons such as environmental considerations.

[0557] In the present invention, it is preferred to use an organic solvent with a low metal content, for example, the metal content of the organic solvent is preferably 10 mass ppb (parts per billion) or less. If necessary, an organic solvent of mass ppt (parts per trillion) level can also be used, such as provided by TOYO Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015). As a method for removing impurities such as metals from an organic solvent, for example, distillation (molecular distillation and thin film distillation, etc.) or filtration using a filter can be cited. The filter pore size of the filter used in the filtration is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

[0558] The organic solvent may contain isomers (compounds having the same number of atoms but different structures). Furthermore, the isomers may contain only one type or multiple types.

[0559] The content of the peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially no peroxide is contained.

[0560] The content of the organic solvent in the colored resin composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and still more preferably 30 to 90% by mass.

[0561] <Pigment derivatives>

[0562] The colored resin composition of the present invention can contain a pigment derivative. As a pigment derivative, a compound having a structure in which a part of the chromophore is substituted with an acid group, a basic group or a phthalimide methyl group can be cited. As the chromophore constituting the pigment derivative, a quinoline skeleton, a benzimidazolone skeleton, a diketopyrrolopyrrole skeleton, an azo skeleton, a phthalocyanine skeleton, an anthraquinone skeleton, a quinacridone skeleton, a dioxazine skeleton, a perylene skeleton, a thioindigo skeleton, an isoindoline skeleton, an isoindolinone skeleton, a quinophthalone skeleton, a styrene skeleton, a metal complex skeleton, etc. are cited, preferably a quinoline skeleton, a benzimidazolone skeleton, a diketopyrrolopyrrole skeleton, an azo skeleton, a quinophthalone skeleton, an isoindoline skeleton and a phthalocyanine skeleton, more preferably an azo skeleton and a benzimidazolone skeleton. As the acid group possessed by the pigment derivative, a sulfonic group and a carboxyl group are preferred, and a sulfonic group is more preferred. As the basic group possessed by the pigment derivative, an amino group is preferred, and a tertiary amino group is more preferred.

[0563] As the pigment derivative, a pigment derivative having excellent visible light transparency (hereinafter also referred to as a transparent pigment derivative) can also be used. The maximum value (εmax) of the molar absorption coefficient of the transparent pigment derivative in the wavelength region of 400 to 700 nm is preferably 3000 L·mol -1 cm -1 Below, more preferably 1000 L·mol -1 cm -1 Below, more preferably 100 L·mol -1 cm -1 Below. The lower limit of εmax is, for example, 1 L·mol -1 cm -1 Above, it can also be 10L·mol -1 cm -1 above.

[0564] Specific examples of the pigment derivatives include Japanese Patent Application Laid-Open Nos. 56-118462, 63-264674, 01-217077, 03-009961, 03-026767, 03-153780, 03-0456 62, Japanese Patent Application Laid-Open No. 04-285669, Japanese Patent Application Laid-Open No. 06-145546, Japanese Patent Application Laid-Open No. 06-212088, Japanese Patent Application Laid-Open No. 06-240158, Japanese Patent Application Laid-Open No. 10-030063, Japanese Patent Application Laid-Open No. 10-195326, International Publication No. 2011 / 024896, No. 0086 to 0098, paragraphs 0063 to 0094 of International Publication No. 2012 / 102399, paragraph 0082 of International Publication No. 2017 / 038252, paragraph 0171 of Japanese Patent Application Publication No. 2015-151530, paragraphs 0162 to 0183 of Japanese Patent Application Publication No. 2011-252065, Japanese Patent Application Publication No. 2003-081972, Japan Compounds described in Japanese Patent No. 5299151, Japanese Patent Application Publication No. 2015-172732, Japanese Patent Application Publication No. 2014-199308, Japanese Patent Application Publication No. 2014-085562, Japanese Patent Application Publication No. 2014-035351, Japanese Patent Application Publication No. 2008-081565, and Japanese Patent Application Publication No. 2019-109512.

[0565] The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, based on 100 parts by mass of the pigment. The pigment derivative may be used alone or in combination of two or more.

[0566] <Polymerizable compounds>

[0567] The colored resin composition of the present invention can contain a polymerizable compound. The polymerizable compound is preferably a compound having a group containing an ethylenically unsaturated bond, for example. As the group containing an ethylenically unsaturated bond, vinyl, (meth)allyl, (meth)acryloyl, etc. can be cited. The polymerizable compound used in the present invention is preferably a free radical polymerizable compound.

[0568] The polymerizable compound may be any of the chemical forms such as monomer, prepolymer, oligomer, etc., preferably a monomer. The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is more preferably 2000 or less, and further preferably 1500 or less. The lower limit is more preferably 150 or more, and further preferably 250 or more.

[0569] The polymerizable compound is preferably a compound containing 3 or more groups containing ethylenically unsaturated bonds, more preferably a compound containing 3 to 15 groups containing ethylenically unsaturated bonds, and further preferably a compound containing 3 to 6 groups containing ethylenically unsaturated bonds. Furthermore, the polymerizable compound is preferably a tri- to penta-functional (meth)acrylate compound, more preferably a tri- to hexa-functional (meth)acrylate compound. Specific examples of the polymerizable compound include compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-029760, paragraphs 0254 to 0257 of JP-A-2008-292970, paragraphs 0034 to 0038 of JP-A-2013-253224, paragraph 0477 of JP-A-2012-208494, JP-A-2017-048367, Japanese Patent No. 6057891, Japanese Patent No. 6031807, and Japanese Patent No. 2017-194662, and the contents thereof are incorporated into the present specification.

[0570] Preferred polymerizable compounds include dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by NIPPON KAYAKU CO., LTD.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by NIPPON KAYAKU CO., LTD.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by NIPPON KAYAKU CO., LTD.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by NIPPON KAYAKU CO., LTD., NK ester A-DPH-12E; manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), and compounds having a structure in which (meth)acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues (for example, SARTOMER Company, Inc. (SR454, SR499). As the polymerizable compound, diglycerol EO (ethylene oxide)-modified (meth)acrylate (commercially available as M-460; manufactured by TOAGOSEI CO., LTD.), pentaerythritol tetraacrylate (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD., NK ester A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.), NK Oligo UA-7200 (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), Lightacrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), Co., Ltd.), etc.

[0571] Furthermore, as the polymerizable compound, trifunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide-modified tri(meth)acrylate, trimethylolpropane ethylene oxide-modified tri(meth)acrylate, isocyanuric acid ethylene oxide-modified tri(meth)acrylate, and pentaerythritol tri(meth)acrylate are also preferably used. Commercially available products of the trifunctional (meth)acrylate compound include ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M-452, and M-450 (manufactured by TOAGOSEI CO., LTD.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, and TMPT (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, and PET-30 (manufactured by Nippon Kayaku Co., Ltd.).

[0572] The polymerizable compound may also be a compound having an acid group. By using a polymerizable compound having an acid group, it is easy to remove the polymerizable compound in the unexposed part during development, and the generation of development residues can be suppressed. Examples of the acid group include a carboxyl group, a sulfonic group, a phosphoric acid group, and the like, preferably a carboxyl group. Commercially available products of polymerizable compounds having an acid group include ARONIX M-305, M-510, M-520, ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.), and the like. The preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the solubility in the developer is good, and if it is 40 mgKOH / g or less, it is advantageous for manufacturing or handling.

[0573] It is also a preferred embodiment that the polymerizable compound is a compound having a caprolactone structure. The polymerizable compound having a caprolactone structure is commercially available, for example, from NIPPON KAYAKU CO., Ltd. as KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, and DPCA-120.

[0574] The polymerizable compound may also be a polymerizable compound having an alkyleneoxy group. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and further preferably a tri- to hexa-functional (meth)acrylate compound having 4 to 20 ethyleneoxy groups. Commercially available polymerizable compounds having an alkyleneoxy group include, for example, SR-494, a tetrafunctional (meth)acrylate having 4 ethyleneoxy groups, and KAYARADTPA-330, a trifunctional (meth)acrylate having 3 isobutyleneoxy groups, manufactured by Sartomer Company.

[0575] The polymerizable compound may also be a polymerizable compound having a fluorene skeleton. Examples of commercially available polymerizable compounds having a fluorene skeleton include OGSOL EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., a (meth)acrylate monomer having a fluorene skeleton).

[0576] As the polymerizable compound, it is also preferable to use a compound that does not substantially contain environmentally regulated substances such as toluene. Examples of commercially available products of such a compound include KAYARAD DPHA LT and KAYARAD DPEA-12LT (manufactured by Nippon Kayaku Co., Ltd.).

[0577] As the polymerizable compound, polyurethane acrylates as described in JP-48-041708, JP-51-037193, JP-02-032293, JP-02-016765, and carbamate compounds having an ethylene oxide skeleton as described in JP-58-049860, JP-56-017654, JP-62-039417, JP-62-039418 are also preferred. In addition, polymerizable compounds having an amino structure or a thioether structure in the molecule as described in JP-63-277653, JP-63-260909, JP-01-105238 are also preferably used. Furthermore, commercially available products such as UA-7200 (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, and LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) can be used as the polymerizable compound.

[0578] When a polymerizable compound is contained, the content of the polymerizable compound in the total solid content of the colored resin composition is preferably 0.1 to 50% by mass. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 45% by mass or less, and further preferably 40% by mass or less. The polymerizable compound may be used alone or in combination of two or more.

[0579] <Photopolymerization initiator>

[0580] The colored resin composition of the present invention may contain a photopolymerization initiator. There is no particular limitation on the photopolymerization initiator, and it can be appropriately selected from known photopolymerization initiators. For example, a compound that is photosensitized to light in the ultraviolet region to the visible region is preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

[0581] Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having an imidazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, and the like. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably a trihalomethyl triazine compound, a biimidazole compound, a benzyl dimethyl ketal compound, an α-hydroxy ketone compound, an α-amino ketone compound, an acyl phosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl imidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyl oxadiazole compound, and a 3-aryl substituted coumarin compound, more preferably a compound selected from a biimidazole compound, an oxime compound, an α-hydroxy ketone compound, an α-amino ketone compound, and an acyl phosphine compound, and further preferably an oxime compound. As the photopolymerization initiator, the compounds described in paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173 and Japanese Patent Publication No. 6301489 can be cited, and the contents are incorporated into this specification.

[0582] Examples of the biimidazole compound include 2,2-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5-tetrakis(3,4,5-trimethoxyphenyl)-1,2'-biimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(o-chlorophenyl)-4,4,5,5'-tetraphenyl-1,2'-biimidazole. Examples of commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins BV), Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (all manufactured by BASF SE), etc. Examples of commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins BV), Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (all manufactured by BASF SE), etc. Examples of commercially available products of the acylphosphine compound include Omnirad 819 and Omnirad TPO (both manufactured by IGM Resins BV), Irgacure 819 and Irgacure TPO (both manufactured by BASF SE), and the like.

[0583] Examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in Journal of Photopolymer Science and Technology. The compounds described in Japanese Unexamined Patent Application (1995, pp. 202-232), the compounds described in Japanese Unexamined Patent Application No. 2000-066385, the compounds described in Japanese Unexamined Patent Application No. 2000-080068, the compounds described in Japanese Unexamined Patent Application No. 2004-534797, the compounds described in Japanese Unexamined Patent Application No. 2006-342166, the compounds described in Japanese Unexamined Patent Application No. 2017-019766 Compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Unexamined Publication No. 2017-198865, compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, compounds described in International Publication No. 2013 / 167515, etc. Specific examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, and Irgacure OXE04 (all manufactured by BASF SE), TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), and Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, a photopolymerization initiator 2 described in Japanese Patent Application Publication No. 2012-014052). In addition, as the oxime compound, a non-coloring compound or a compound that is highly transparent and does not easily change color is preferably used.Examples of commercially available products include ADEKA ARKLS NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA CORPORATION).

[0584] As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466.

[0585] Furthermore, as the photopolymerization initiator, an oxime compound having a carbazole ring and a skeleton in which at least one benzene ring is a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013 / 083505.

[0586] As the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and compound (C-3) described in JP-A-2013-164471.

[0587] As the photopolymerization initiator, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton can also be used.

[0588] Examples of such a photopolymerization initiator include compounds described in International Publication No. 2019 / 088055.

[0589] As the photopolymerization initiator, an oxime compound having a nitro group can also be used. The oxime compound having a nitro group is also preferably a dimer. As specific examples of the oxime compound having a nitro group, there can be cited the compounds described in paragraphs 0031 to 0047 of Japanese Patent Publication No. 2013-114249, paragraphs 0008 to 0012, paragraphs 0070 to 0079 of Japanese Patent Publication No. 2014-137466, and the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, and ADEKA ARKLS NCI-831 (made by ADEKA CORPORATION).

[0590] As the photopolymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples thereof include OE-01 to OE-75 described in International Publication No. 2015 / 036910.

[0591] Specific examples of the oxime compound are shown below, but the present invention is not limited to these.

[0592] [Chemical formula 20]

[0593]

[0594] [Chemical formula 21]

[0595]

[0596] The oxime compound is preferably a compound having a maximum absorption wavelength in the range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the range of 360 to 480 nm. In addition, from the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably higher, more preferably 1000 to 300000, further preferably 2000 to 300000, and particularly preferably 5000 to 200000. The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferably measured by a spectrophotometer (Varian Medical Systems, Inc. Cary-5 spectrophotometer) using ethyl acetate at a concentration of 0.01 g / L.

[0597] As the photopolymerization initiator, a difunctional or trifunctional or higher photoradical polymerization initiator may also be used. By using such a photoradical polymerization initiator, two or more free radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained. In addition, when using a compound with an asymmetric structure, the solubility in a solvent or the like is improved due to the decrease in crystallinity, so that it is not easy to precipitate over time, thereby being able to improve the stability over time of the colored resin composition. Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include dimers of oxime compounds described in paragraphs 0407 to 0412 of Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015 / 004565, Japanese Patent Publication No. 2016-532675, and International Publication No. 2017 / 033680, and compounds described in paragraphs 0039 to 0055, Japanese Patent Publication No. 2013-522445 ( E) and compound (G), Cmpd1 to 7 described in International Publication No. 2016 / 034963, the oxime ester photoinitiator described in paragraph 0007 of Japanese Unexamined Patent Application Publication No. 2017-523465, the photoinitiator described in paragraphs 0020 to 0033 of Japanese Unexamined Patent Application Publication No. 2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Unexamined Patent Application Publication No. 2017-151342, and the oxime compound described in Japanese Patent No. 6469669.

[0598] When a photopolymerization initiator is contained, the content of the photopolymerization initiator in the total solid content of the colored resin composition is preferably 0.1 to 30% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, and more preferably 15% by mass or less. Only one type of photopolymerization initiator may be used, or two or more types may be used.

[0599] <Silane coupling agent>

[0600] The colored resin composition of the present invention can contain a silane coupling agent. In the present invention, a silane coupling agent refers to a silane compound having a hydrolyzable group and other functional groups. In addition, a hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and forms a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. As a hydrolyzable group, for example, a halogen atom, an alkoxy group, an acyloxy group, etc., preferably an alkoxy group. That is, the silane coupling agent preferably has a compound of an alkoxysilyl group. In addition, as a functional group other than a hydrolyzable group, for example, a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetane group, an amino group, a urea group, a thioether group, an isocyanate group, a phenyl group, etc., preferably an amino group, a (meth) acryloyl group and an epoxy group. Specific examples of the silane coupling agent include compounds described in paragraphs 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraphs 0056 to 0066 of JP-A-2009-242604, and the contents thereof are incorporated into the present specification.

[0601] The content of the silane coupling agent in the total solid content of the colored resin composition is preferably 0.1 to 5% by mass. The upper limit is preferably 3% by mass or less, and more preferably 2% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The silane coupling agent may be only one or more.

[0602] <Curing accelerator>

[0603] The colored resin composition of the present invention may further contain a curing accelerator for the purpose of promoting the reaction of the resin or polymerizable compound or lowering the curing temperature. The curing accelerator may include hydroxymethyl compounds (for example, compounds exemplified as crosslinking agents in paragraph 0246 of Japanese Patent Application Laid-Open No. 2015-034963), amines, phosphonium salts, amidine salts, amide compounds (for example, curing agents described in paragraph 0186 of Japanese Patent Application Laid-Open No. 2013-041165), base generators (for example, ionic compounds described in Japanese Patent Application Laid-Open No. 2014-055114), cyanate compounds (for example, For example, compounds described in paragraph 0071 of Japanese Patent Publication No. 2012-150180), alkoxysilane compounds (for example, alkoxysilane compounds having an epoxy group described in Japanese Patent Publication No. 2011-253054), onium salt compounds (for example, compounds exemplified as acid generators in paragraph 0216 of Japanese Patent Publication No. 2015-034963, compounds described in Japanese Patent Publication No. 2009-180949), etc.

[0604] When the colored resin composition of the present invention contains a curing accelerator, the content of the curing accelerator is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass, based on the total solid content of the colored resin composition.

[0605] <Polymerization inhibitor>

[0606] The colored resin composition of the present invention may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and N-nitrosophenylhydroxylamine salts (ammonium salts, cerium salts, etc.). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the colored resin composition is preferably 0.0001 to 5% by mass.

[0607] <Surfactant>

[0608] The colored resin composition of the present invention may contain a surfactant. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, silicone-based surfactants, etc. can be used. As for the surfactant, the surfactants described in paragraphs 0238 to 0245 of International Publication No. 2015 / 166779 can be cited, and the contents are incorporated into this specification.

[0609] The surfactant is preferably a fluorine-based surfactant. By including a fluorine-based surfactant in the colored resin composition, liquid properties (especially fluidity) can be further improved, and liquid saving can be further improved. In addition, a film with less uneven thickness can be formed.

[0610] The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorine-based surfactants having a fluorine content within this range are effective in terms of thickness uniformity and liquid saving of the coating film, and also have good solubility in the colored resin composition.

[0611] Examples of the fluorine-based surfactant include the surfactants described in paragraphs 0060 to 0064 of JP-A-2014-041318 (paragraphs 0060 to 0064 of the corresponding International Publication No. 2014 / 017669), and the surfactants described in paragraphs 0117 to 0132 of JP-A-2011-132503, and these contents are incorporated into the present specification. Examples of commercially available fluorine-based surfactants include Megaface F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS-330 (all manufactured by DICCORPORATION), Fluorad FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA SOLUTIONS INC.), etc.

[0612] In addition, the fluorine-based surfactant is preferably a polymer of a fluorine-containing vinyl ether compound having a fluorinated alkyl or fluorinated alkylene ether group and a hydrophilic vinyl ether compound. Such a fluorine-based surfactant can be described in Japanese Unexamined Patent Publication No. 2016-216602, and the content is incorporated into this specification.

[0613] The fluorine-based surfactant can also use block polymers. For example, the compounds described in Japanese Patent Publication No. 2011-089090 can be cited. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound, which contains: a repeating unit derived from a (meth)acrylate compound having a fluorine atom; and a repeating unit derived from a (meth)acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy, propyleneoxy). As the fluorine-based surfactant used in the present invention, the following compounds are also exemplified.

[0614] [Chemical formula 22]

[0615]

[0616] The weight average molecular weight of the above compound is preferably 3000 to 50000, for example, 14000. In the above compound, % indicating the ratio of the repeating unit is mol %.

[0617] In addition, the fluorine-based surfactant can also use a fluorine-containing polymer having a group containing an ethylenically unsaturated bond in the side chain. As a specific example, the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese Patent Publication No. 2010-164965, such as Megaface RS-101, RS-102, RS-718K, RS-72-K manufactured by DIC CORPORATION, etc. The fluorine-based surfactant can also use the compounds described in paragraphs 0015 to 0158 of Japanese Patent Publication No. 2015-117327.

[0618] The content of the surfactant in the total solid content of the colored resin composition is preferably 0.001% to 5.0% by mass, and more preferably 0.005% to 3.0% by mass. The surfactant may be one or more. When two or more are present, the total amount is preferably within the above range.

[0619] <Ultraviolet light absorber>

[0620] The colored resin composition of the present invention can contain an ultraviolet absorber. The ultraviolet absorber can use a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyl triazine compound, an indole compound, a triazine compound, etc. For these, specifically, reference can be made to paragraphs 0052 to 0072 of Japanese Patent Publication No. 2012-208374, paragraphs 0317 to 0334 of Japanese Patent Publication No. 2013-068814, and paragraphs 0061 to 0080 of Japanese Patent Publication No. 2016-162946, and these contents are incorporated into this specification. As a commercially available product of the ultraviolet absorber, for example, UV-503 (manufactured by DAITO CHEMICAL CO., LTD.) can be cited. In addition, as benzotriazole compounds, MYUA series manufactured by MIYOSHI & FAT CO., LTD. can be cited (Chemical Industry Daily, February 1, 2016). In addition, the ultraviolet absorber can also use the compounds described in paragraphs 0049 to 0059 of Japanese Patent Gazette No. 6268967. The content of the ultraviolet absorber in the total solid content of the colored resin composition is preferably 0.01 to 10% by mass, and more preferably 0.01 to 5% by mass. The ultraviolet absorber can be used alone or in combination of two or more. When two or more are used, the total amount is preferably within the above range.

[0621] <Antioxidants>

[0622] The colored resin composition of the present invention can contain an antioxidant. As the antioxidant, phenolic compounds, phosphite compounds, thioether compounds, etc. can be mentioned. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferred phenolic compound, a hindered phenolic compound can be mentioned. Preferably, a compound having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position). As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. In addition, the antioxidant is also preferably a compound having a phenolic group and a phosphite group in the same molecule. In addition, the antioxidant can also preferably use a phosphorus antioxidant. The content of the antioxidant in the total solid content of the colored resin composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass. The antioxidant can be used alone or in combination of two or more. When two or more are used, the total amount is preferably within the above range.

[0623] <Other ingredients>

[0624] The colored resin composition of the present invention may contain a sensitizer, a filler (Japanese: フィラー), a thermosetting accelerator, a plasticizer and other auxiliary agents (for example, conductive particles, fillers (Japanese: filling agent), defoamers, flame retardants, leveling agents, peeling accelerators, fragrances, surface tension adjusters, chain transfer agents, etc.) as needed. By appropriately containing these components, the properties such as the physical properties of the film can be adjusted. For example, these components can refer to the description of paragraphs 0183 and later of Japanese Unexamined Patent Application No. 2012-003225 (paragraph 0237 of the corresponding U.S. Patent Application Publication No. 2013 / 0034812), paragraphs 0101 to 0104, 0107 to 0109 of Japanese Unexamined Patent Application No. 2008-250074, and the contents are incorporated into this specification. In addition, the colored resin composition may contain a potential antioxidant as needed. As potential antioxidants, compounds in which the sites acting as antioxidants are protected by protective groups can be cited, and the protective groups are heated at 100 to 250 ° C or heated at 80 to 200 ° C in the presence of an acid / base catalyst to dissociate the compounds acting as antioxidants. As potential antioxidants, compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Publication No. 2017-008219 can be cited. As commercially available products, ADEKAARKLS GPA-5001 (made by ADEKA CORPORATION) can be cited. In addition, CI Pigment Yellow 129 can be added for the purpose of improving weather resistance, as described in Japanese Patent Publication No. 2018-155881.

[0625] The colored resin composition of the present invention may also contain a metal oxide in order to adjust the refractive index of the obtained film. Examples of the metal oxide include TiO2, ZrO2, Al2O3, SiO2, etc. The primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, and further preferably 5 to 50 nm. The metal oxide may also have a core-shell structure. In addition, the core may also be hollow.

[0626] The colored resin composition of the present invention may contain a light resistance improver. Examples of the light resistance improver include compounds described in paragraphs 0036 to 0037 of Japanese Patent Application Laid-Open No. 2017-198787, compounds described in paragraphs 0029 to 0034 of Japanese Patent Application Laid-Open No. 2017-146350, compounds described in paragraphs 0036 to 0037 and 0049 to 0052 of Japanese Patent Application Laid-Open No. 2017-129774, and compounds described in paragraphs 0049 to 0052 of Japanese Patent Application Laid-Open No. 201 The compounds described in paragraphs 0031 to 0034 and 0058 to 0059 of 7-129674, the compounds described in paragraphs 0036 to 0037 and 0051 to 0054 of JP-A-2017-122803, the compounds described in paragraphs 0025 to 0039 of International Publication No. 2017 / 164127, and JP-A-2017-186546 The compounds described in paragraphs 0034 to 0047 of the publication, the compounds described in paragraphs 0019 to 0041 of Japanese Patent Application Laid-Open No. 2015-025116, the compounds described in paragraphs 0101 to 0125 of Japanese Patent Application Laid-Open No. 2012-145604, the compounds described in paragraphs 0018 to 0021 of Japanese Patent Application Laid-Open No. 2012-103475, the compounds described in paragraphs 0019 to 0041 of Japanese Patent Application Laid-Open No. 2011 The compounds described in paragraphs 0015 to 0018 of JP-A-257591, the compounds described in paragraphs 0017 to 0021 of JP-A-2011-191483, the compounds described in paragraphs 0108 to 0116 of JP-A-2011-145668, the compounds described in paragraphs 0103 to 0153 of JP-A-2011-253174, and the like.

[0627] The content of free metals bonded to or uncoordinated with the pigment or the like in the colored resin composition of the present invention is preferably 100 ppm or less, more preferably 50 ppm or less, further preferably 10 ppm or less, and particularly preferably substantially free. According to this embodiment, it is expected that the dispersibility of the pigment is stabilized (agglomeration is suppressed), the spectral characteristics are improved with the improvement of dispersibility, the curing component is stabilized, the conductivity change with the dissolution of metal atoms / metal ions is suppressed, and the display characteristics are improved. Furthermore, the effects described in Japanese Patent Publication No. 2012-153796, Japanese Patent Publication No. 2000-345085, Japanese Patent Publication No. 2005-200560, Japanese Patent Publication No. 08-043620, Japanese Patent Publication No. 2004-145078, Japanese Patent Publication No. 2014-119487, Japanese Patent Publication No. 2010-083997, Japanese Patent Publication No. 2017-090930, Japanese Patent Publication No. 2018-025612, Japanese Patent Publication No. 2018-025797, Japanese Patent Publication No. 2017-155228, Japanese Patent Publication No. 2018-036521, etc. can also be obtained. As the types of the above-mentioned free metals, Na, K, Ca, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Co, Mg, Al, Sn, Zr, Ga, Ge, Ag, Au, Pt, Cs, Ni, Cd, Pb, Bi, etc. can be cited. In addition, the content of free halogens bonded to or uncoordinated with pigments, etc. in the colored resin composition of the present invention is preferably 100 ppm or less, more preferably 50 ppm or less, further preferably 10 ppm or less, and particularly preferably substantially free. As halogens, F, Cl, Br, I and their anions can be cited. As methods for reducing free metals or halogens in colored resin compositions, methods such as washing, filtration, ultrafiltration, and purification based on ion exchange resins based on ion exchange water can be cited.

[0628] The colored resin composition of the present invention also preferably contains substantially no terephthalate. Here, “substantially contains” means that the content of terephthalate is 1000 ppb by mass or less, more preferably 100 ppb by mass or less, and particularly preferably zero, based on the total amount of the colored resin composition.

[0629] <Storage container>

[0630] The storage container of the colored resin composition of the present invention is not particularly limited, and a known storage container can be used. In addition, as a storage container, for the purpose of suppressing the mixing of impurities into the raw materials or the colored resin composition, it is also preferred to use a multilayer bottle in which the inner wall of the container is composed of 6 kinds of 6 layers of resin or a bottle with 6 kinds of resins as a 7-layer structure. As such a container, for example, the container described in Japanese Patent Publication No. 2015-123351 can be cited. In addition, in order to prevent the metal from dissolving from the inner wall of the container and improve the storage stability of the colored resin composition or suppress the deterioration of the components, it is also preferred to make the inner wall of the container glass or stainless steel.

[0631] <Method for preparing colored resin composition>

[0632] The colored resin composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the colored resin composition, all the components can be dissolved and / or dispersed in an organic solvent at the same time to prepare the colored resin composition, or each component can be appropriately prepared as two or more solutions or dispersions in advance as needed and mixed during use (during coating) to prepare the colored resin composition.

[0633] And, when preparing the colored resin composition, it is preferred to include a process for dispersing pigments. In the process for dispersing pigments, compression, squeezing, impact, shearing, cavitation, etc. can be cited as mechanical forces for the dispersion of pigments. As specific examples of these processes, bead mills, sand mixers (sand mill), roller mills, ball mills, paint shakers (paint shaker), microfluidizers (microfluidizer), high-speed impellers, sand mills, jet mixers (flowjet mixer), high-pressure wet micronization, ultrasonic dispersion, etc. can be cited. And, in the crushing of the pigment in the sand mixer (bead mill), it is preferably processed under the conditions of improving the crushing efficiency by using beads with a small diameter, increasing the filling rate of beads, etc. And, after the crushing process, it is preferably removed by filtering, centrifugation, etc. And, the process and dispersion work of the dispersed pigment can preferably use "Dispersion Technology Encyclopedia, JOHOKIKO CO., LTD. Issue, July 15, 2005" or "Dispersion Technology and Industrial Application Actual Comprehensive Data Collection Center, Business Development Center Publishing Department Issue, October 10, 1978", Japanese Patent Publication No. 2015-157893 Communique 0022 and the process and dispersion machine recorded in it. And, in the process of dispersed pigment, the micronization of particles can be carried out by salt milling (salt milling) process. The materials, equipment, treatment conditions used in the salt milling process, for example, can refer to the records of Japanese Patent Publication No. 2015-194521 and Japanese Patent Publication No. 2012-046629.

[0634] When preparing a colored resin composition, it is preferred to filter the colored resin composition using a filter for the purpose of removing foreign matter or reducing defects. As a filter, as long as it is a filter that has been used for filtering purposes, it can be used without particular limitation. For example, filters using materials such as fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (such as nylon-6, nylon-6,6), polyethylene, polypropylene (PP) and polyolefin resins (including high-density, ultra-high molecular weight polyolefin resins) can be cited. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

[0635] The pore size of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and further preferably 0.05 to 0.5 μm. As long as the pore size of the filter is within the above range, fine foreign matter can be removed more reliably. Regarding the pore size value of the filter, the rated value of the filter manufacturer can be referred to. The filter can use various filters provided by NIHON PALL LTD. (DFA4201NIEY, etc.), Advantec Toyo Kaisha, Ltd., Nihon Entegris KK (formerly Nipponmicro squirrel Co., Ltd.) and KITZMICROFILTER CORPORATION.

[0636] Furthermore, it is also preferable to use a fibrous filter material as the filter. Examples of the fibrous filter material include polypropylene fibers, nylon fibers, and glass fibers. Examples of commercially available products include SBP series (SBP008, etc.), TPR series (TPR002, TPR005, etc.), and SHPX series (SHPX003, etc.) manufactured by ROKI TECHNO CO., LTD.

[0637] When using filters, different filters (e.g., a first filter and a second filter, etc.) may be combined. In this case, filtering based on each filter may be performed only once or twice or more. In addition, filters with different pore sizes may be combined within the above range. In addition, filtering based on the first filter may be performed only on the dispersion, and filtering with the second filter may be performed after mixing other components.

[0638] (membrane)

[0639] The film of the present invention is a film obtained from the above-mentioned colored resin composition of the present invention. The film of the present invention can be used for color filters, near infrared transmission filters, near infrared cut filters, black matrices, light shielding films, etc. For example, it can be preferably used as a coloring layer of a color filter.

[0640] The film thickness of the film of the present invention can be appropriately adjusted according to the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.

[0641] The thickness of the film of the present invention after heat treatment at 300° C. for 5 hours in a nitrogen atmosphere is preferably 70% or more of the thickness of the film before heat treatment, more preferably 80% or more, and even more preferably 90% or more.

[0642] Furthermore, the thickness of the film after heat treatment at 350° C. for 5 hours in a nitrogen environment is preferably 70% or more of the thickness of the film before heat treatment, more preferably 80% or more, and even more preferably 90% or more.

[0643] Furthermore, the thickness of the film after heat treatment at 400° C. for 5 hours in a nitrogen environment is preferably 70% or more of the thickness of the film before heat treatment, more preferably 80% or more, and even more preferably 90% or more.

[0644] The film of the present invention preferably has a maximum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more, and further preferably 85% or more) and a minimum transmittance of 30% or less (preferably 25% or less, more preferably 20% or less, and further preferably 15% or less) within a wavelength range of 400 to 1100 nm.

[0645] (Method for producing film)

[0646] The film of the present invention can be produced by applying the colored resin composition of the present invention on a support. In the method for producing the film of the present invention, it is further preferred to include a step of forming a pattern (pixel). As a method for forming a pattern (pixel), photolithography and dry etching can be cited, and photolithography is preferred.

[0647] <Photolithography>

[0648] First, the case of forming a pattern by photolithography to manufacture a film is described. The pattern formation based on photolithography preferably includes a process of forming a colored resin composition layer on a support using the colored resin composition of the present invention, a process of exposing the colored resin composition layer to a pattern, and a process of developing and removing the unexposed portion of the colored resin composition layer to form a pattern (pixel). It is also possible to set a process (pre-baking process) of baking the colored resin composition layer and a process (post-baking process) of baking the developed pattern (pixel) as needed.

[0649] In the process of forming a colored resin composition layer, a colored resin composition layer is formed on a support using the colored resin composition of the present invention. As a support, it is not particularly limited and can be appropriately selected according to the purpose. For example, a glass substrate, a silicon substrate, etc. can be cited, preferably a silicon substrate. In addition, a charge coupled device (CCD), a complementary metal oxide film semiconductor (CMOS), a transparent conductive film, etc. can also be formed on the silicon substrate. In addition, there will also be a situation where a black matrix is ​​formed on the silicon substrate to isolate each pixel. In addition, in order to improve the adhesion with the upper layer, prevent the diffusion of the substance or the flattening of the substrate surface, a primer layer can also be provided on the silicon substrate.

[0650] As a coating method of the colored resin composition, a known method can be used. For example, a drop method (drop casting), a slit coating method, a spray coating method, a roll coating method, a spin coating method (spin coating method), a cast coating method, a slit spin coating method, a pre-wetting method (for example, the method described in Japanese Patent Application Publication No. 2009-145395), an inkjet (for example, a press-on method, a piezoelectric method, a thermal method), a nozzle jet and other ejection system printing, flexographic printing, screen printing, gravure printing, reverse offset printing and metal mask printing methods and other printing methods, a transfer method using a mold, etc., a nanoimprint method, etc. can be cited. The application method by inkjet is not particularly limited, and examples thereof include the method described in "Expanded / usable inkjet - Infinite possibilities seen in patents -, published in February 2005, SBRESEARCH CO., LTD." (particularly pages 115 to 133) or Japanese Patent Application Publication No. 2003-262716, Japanese Patent Application Publication No. 2003-185831, Japanese Patent Application Publication No. 2003-261827, Japanese Patent Application Publication No. 2012-126830, Japanese Patent Application Publication No. 2006-169325, etc. In addition, the coating method of the colored resin composition can also adopt the method described in International Publication No. 2017 / 030174 and International Publication No. 2017 / 018419, and these contents are incorporated into this specification.

[0651] The colored resin composition layer formed on the support may also be dried (prebaked). When the film is manufactured by a low temperature process, prebaking may not be performed. When prebaking is performed, the prebaking temperature is preferably below 150°C, more preferably below 120°C, and further preferably below 110°C. The lower limit can be set to above 50°C, for example, and can also be set to above 80°C. The prebaking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and further preferably 80 to 220 seconds. Prebaking can be performed using a hot plate, an oven, or the like.

[0652] Next, the colored resin composition layer is exposed in a pattern (exposure step). For example, a stepper or a scanner is used to expose the colored resin composition layer through a mask having a predetermined mask pattern, thereby exposing the colored resin composition layer in a pattern. Thus, the exposed portion can be cured.

[0653] As radiation (light) that can be used during exposure, g-rays, i-rays, etc. can be cited. In addition, light with a wavelength of 300nm or less (preferably light with a wavelength of 180 to 300nm) can also be used. As light with a wavelength of 300nm or less, KrF rays (wavelength 248nm), ArF rays (wavelength 193nm), etc. can be cited, and KrF rays (wavelength 248nm) are preferred. In addition, long-wave light sources with a wavelength of 300nm or more can also be used.

[0654] Furthermore, during exposure, exposure can be performed by continuous irradiation of light or by pulse irradiation (pulse exposure). In addition, pulse exposure refers to an exposure method in which light irradiation and pause are repeated in a short cycle (for example, less than milliseconds) to perform exposure. During pulse exposure, the pulse width is preferably less than 100 nanoseconds (ns), more preferably less than 50 nanoseconds, and further preferably less than 30 nanoseconds. The lower limit of the pulse width is not particularly limited, and can be set to more than 1 femtosecond (fs), and can also be set to more than 10 femtoseconds. The frequency is preferably more than 1kHz, more preferably more than 2kHz, and further preferably more than 4kHz. The upper limit of the frequency is preferably less than 50kHz, more preferably less than 20kHz, and further preferably less than 10kHz. The maximum instantaneous illumination is preferably 50000000W / m 2 More preferably 100000000 W / m 2 More preferably, 200000000 W / m 2 Furthermore, the upper limit of the maximum instantaneous illuminance is preferably 1000000000 W / m 2 Below, more preferably 800000000 W / m 2 Below, more preferably 500000000 W / m 2 Below. In addition, pulse width refers to the time of irradiation of light in the pulse cycle. And, frequency refers to the number of pulse cycles per second. And, maximum instantaneous illuminance refers to the average illuminance during the time of irradiation of light in the pulse cycle. And, pulse cycle refers to the cycle in which the irradiation and pause of light in pulse exposure are regarded as one cycle.

[0655] The irradiation amount (exposure amount) is preferably, for example, 0.03 to 2.5 J / cm 2 , more preferably 0.05 to 1.0 J / cm 2The oxygen concentration during exposure can be appropriately selected. In addition to exposure under the atmosphere, exposure can also be performed in a low oxygen atmosphere with an oxygen concentration of 19% by volume or less (e.g., 15% by volume, 5% by volume, or substantially oxygen-free), or in a high oxygen atmosphere with an oxygen concentration exceeding 21% by volume (e.g., 22% by volume, 30% by volume, or 50% by volume). In addition, the exposure illuminance can be appropriately set, usually from 1000 W / m 2 ~100000W / m 2 (For example, 5000W / m 2 , 15000W / m 2 or 35000W / m 2 The oxygen concentration and exposure illuminance can be appropriately combined, for example, the oxygen concentration can be set to 10% by volume and the illuminance can be set to 10000 W / m 2 , set the oxygen concentration to 35 volume % and the illumination to 20000 W / m 2 wait.

[0656] Next, the unexposed portion of the colored resin composition layer is removed by development to form a pattern (pixel). The unexposed portion of the colored resin composition layer can be removed by development using a developer. As a result, the unexposed portion of the colored resin composition layer in the exposure step is dissolved in the developer, and only the photocured portion remains. The temperature of the developer is preferably 20 to 30° C., for example. The development time is preferably 20 to 180 seconds. In addition, in order to improve the removability of the residue, the following process can be repeated several times, that is, the developer is thrown off every 60 seconds and then the developer is re-supplied.

[0657] The developer can include organic solvents, alkaline developers, etc., and an alkaline developer can be preferably used. As an alkaline developer, an alkaline aqueous solution (alkaline developer) of an alkaline agent diluted with pure water is preferably used. As an alkaline agent, for example, organic alkaline compounds such as ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, or inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate can be mentioned. Regarding the alkaline agent, compounds with large molecular weight are preferred in terms of environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. In addition, the developer may further contain a surfactant. As the surfactant, the above-mentioned surfactants can be cited, and nonionic surfactants are preferred. From the viewpoint of convenience of transportation and storage, the developer can also be prepared as a concentrated solution first, and then diluted to the desired concentration when used. The dilution ratio is not particularly limited, for example, it can be set in the range of 1.5 to 100 times. In addition, it is also preferred to use pure water for cleaning (rinsing) after development. In addition, the rinsing is preferably carried out while rotating the support body on which the developed colored resin composition layer is formed, while supplying the rinsing liquid to the developed colored resin composition layer. In addition, it is also preferred to move the nozzle that spits out the rinsing liquid from the center of the support body to the peripheral portion of the support body. At this time, the moving speed of the nozzle can also be gradually reduced and moved when moving from the center of the support body to the peripheral portion of the nozzle. By rinsing as above, the in-plane deviation of the rinsing can be suppressed. In addition, the same effect can be obtained by gradually reducing the rotation speed of the support body while moving the nozzle from the center of the support body to the peripheral portion.

[0658] After development, it is preferred to perform additional exposure treatment or heating treatment (post-baking) after drying. Additional exposure treatment or post-baking is a curing treatment after development for completely curing it. The heating temperature in the post-baking is preferably 100 to 240°C, more preferably 200 to 240°C. The film after development can be post-baked in a continuous or intermittent manner using a heating mechanism such as a heating plate or a convection oven (hot air circulation dryer), a high-frequency heater, etc. to achieve the above conditions. In the case of performing additional exposure treatment, the light used in the exposure is preferably light with a wavelength of less than 400nm. In addition, the additional exposure treatment can also be performed by the method described in Korean Patent Gazette No. 10-2017-0122130.

[0659] <Dry Etching Method>

[0660] The pattern formation based on the dry etching method preferably includes the following steps: forming a colored resin composition layer on a support using the colored resin composition of the present invention, and curing the colored resin composition layer as a whole to form a cured layer; forming a photoresist layer on the cured layer; exposing the photoresist layer to a pattern, and then developing to form a resist pattern; and using the resist pattern as a mask, the cured layer is dry-etched using an etching gas. When forming the photoresist layer, it is preferred to further perform a pre-baking treatment. In particular, as a process for forming the photoresist layer, it is preferred to perform a heating treatment after exposure and a heating treatment after development (post-baking treatment). Regarding the pattern formation based on the dry etching method, reference can be made to the description of paragraphs 0010 to 0067 of Japanese Patent Publication No. 2013-064993, and the content is incorporated into this specification.

[0661] (Color Filter)

[0662] The color filter of the present invention has the above-mentioned film of the present invention. More preferably, the pixel of the color filter has the film of the present invention. The color filter of the present invention can be used in solid-state imaging elements such as CCD (charge coupled device) and CMOS (complementary metal oxide semiconductor) and image display devices.

[0663] In the color filter of the present invention, the thickness of the film of the present invention can be appropriately adjusted according to the purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.

[0664] In the color filter of the present invention, the width of the pixel is preferably 0.5 to 20.0 μm. The lower limit is preferably 1.0 μm or more, and more preferably 2.0 μm or more. The upper limit is preferably 15.0 μm or less, and more preferably 10.0 μm or less. In addition, the Young's modulus of the pixel is preferably 0.5 to 20 GPa, and more preferably 2.5 to 15 GPa.

[0665] Each pixel included in the color filter of the present invention preferably has high flatness. Specifically, the surface roughness Ra of the pixel is preferably less than 100 nm, more preferably less than 40 nm, and further preferably less than 15 nm. There is no regulation on the lower limit, for example, it is preferably more than 0.1 nm. The surface roughness of the pixel can be measured using, for example, AFM (atomic force microscope) Dimension 3100 manufactured by Veeco Instruments Inc. In addition, the contact angle of water on the pixel can be set to an appropriately preferred value, typically in the range of 50 to 110°. The contact angle can be measured using, for example, a contact angle meter CV-DT·A type (manufactured by Kyowa Interface Science Co., LTD.). In addition, the volume resistance value of the pixel is preferably high. Specifically, the volume resistance value of the pixel is preferably 10 9 Ω·cm or more, more preferably 10 11 Ω·cm or more. The upper limit is not specified, but is preferably 10 14 The volume resistance value of the pixel can be measured using an ultra-high resistance meter 5410 (manufactured by Advantest Corporation).

[0666] Furthermore, in the color filter of the present invention, a protective layer may also be provided on the surface of the film of the present invention. By providing a protective layer, various functions such as oxygen shielding, low reflection, hydrophilicity and hydrophobicity, and shielding of light of a specific wavelength (ultraviolet rays, near infrared rays, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, and more preferably 0.1 to 5 μm. As a method for forming the protective layer, a method of coating a protective layer-forming resin composition dissolved in an organic solvent, a chemical vapor deposition method, a method of attaching a formed resin using an adhesive material, etc. can be cited. As the components constituting the protective layer, (meth) acrylic resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenyl resin, polyarylether phosphine oxide resin, polyimide resin, polyamide-imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, carbamate resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluororesin, polycarbonate resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al2O3, Mo, SiO2, Si2N4, etc. can be cited, and two or more of these components can also be contained. For example, when it is a protective layer for the purpose of oxygen shielding, the protective layer preferably includes polyol resin, SiO2 and Si2N4. And, when it is a protective layer for the purpose of low reflection, the protective layer preferably includes (meth) acrylic resin and fluororesin.

[0667] When the protective layer is formed by coating the protective layer forming resin composition, as the coating method of the protective layer forming resin composition, known methods such as spin coating, casting, screen printing, inkjet method, etc. can be used. The organic solvent contained in the protective layer forming resin composition can use a known organic solvent (for example, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.). When the protective layer is formed by chemical vapor deposition, as the chemical vapor deposition method, a known chemical vapor deposition method (thermal chemical vapor deposition method, plasma chemical vapor deposition method, photochemical vapor deposition method) can be used.

[0668] The protective layer may also contain organic / inorganic particles, absorbents of light of a specific wavelength (e.g., ultraviolet rays, near infrared rays, etc.), refractive index adjusters, antioxidants, adhesives, surfactants and other additives as needed. Examples of organic / inorganic particles include polymer particles (e.g., silicone resin particles, polystyrene particles, melamine resin particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, acid titanium nitride, magnesium fluoride, hollow silica, silicon dioxide, calcium carbonate, barium sulfate, etc. The absorbent of light of a specific wavelength can use a known absorbent. The content of these additives can be appropriately adjusted, preferably 0.1 to 70% by mass, and more preferably 1 to 60% by mass relative to the total mass of the protective layer.

[0669] Furthermore, as the protective layer, the protective layer described in paragraphs 0073 to 0092 of Japanese Patent Application Laid-Open No. 2017-151176 can also be used.

[0670] The color filter may have an undercoat layer. The undercoat layer may be formed using, for example, a composition obtained by removing a colorant from the coloring resin composition of the present invention.

[0671] The preferred surface contact angle of the substrate is preferably 20 to 70° when measured in diiodomethane, and preferably 30 to 80° when measured in water.

[0672] When the surface contact angle is within the above range, the coating properties of the colored resin composition and the coating properties of the composition for forming a base are both excellent.

[0673] In order to adjust the surface contact angle to the above range, a method such as adding a surfactant may be mentioned.

[0674] Furthermore, in the green pixel of the color filter, green may be formed by a combination of CI Pigment Green 7, CI Pigment Green 36, CI Pigment Yellow 139, and CI Pigment Yellow 185, or may be formed by a combination of CI Pigment Green 58, CI Pigment Yellow 150, and CI Pigment Yellow 185.

[0675] The color filter may also have a structure in which each colored pixel is filled in a space divided into, for example, a grid shape by a partition wall. In addition, the colored resin composition of the present invention can also be preferably used in the pixel structure described in International Publication No. 2019 / 102887.

[0676] (Solid-state imaging device)

[0677] The solid-state imaging device of the present invention has the above-mentioned film of the present invention. The structure of the solid-state imaging device of the present invention is not particularly limited as long as it has the film of the present invention and functions as a solid-state imaging device, and examples thereof include the following structures.

[0678] The structure is as follows: a substrate has a plurality of photodiodes and transfer electrodes such as polysilicon that include a light-receiving area constituting a solid-state imaging element (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.), a light-shielding film with only the light-receiving portion of the photodiode opened on the photodiode and the transfer electrode, a device protection film including silicon nitride formed in a manner covering the entire surface of the light-shielding film and the light-receiving portion of the photodiode is provided on the light-shielding film, and a color filter is provided on the device protection film. Furthermore, it may also be a structure having a focusing mechanism (for example, a microlens, etc., the same below) on the device protection film and below the color filter (on the side close to the substrate) or a structure having a focusing mechanism on the color filter. Furthermore, the color filter may also have a structure in which each colored pixel is filled in a space divided into, for example, a grid shape by partition walls. In this case, the partition walls preferably have a lower refractive index than each colored pixel. As examples of imaging devices having such a structure, there can be cited the devices described in Japanese Patent Publication No. 2012-227478, Japanese Patent Publication No. 2014-179577, International Publication No. 2018 / 043654, and U.S. Patent Application Publication No. 2018 / 0040656. The imaging device having the solid-state imaging element of the present invention can be used as a vehicle-mounted camera or a surveillance camera in addition to a digital camera or an electronic device having an imaging function (such as a mobile phone).

[0679] Furthermore, in the solid-state imaging element incorporating the color filter of the present invention, other color filters, infrared cut filters, organic photoelectric conversion films, and the like may be further incorporated in addition to the color filter of the present invention.

[0680] (Image display device)

[0681] The image display device of the present invention has the above-mentioned film of the present invention. As the image display device, a liquid crystal display device or an organic electroluminescent display device can be cited. Regarding the definition of the image display device and each image display device, for example, it is recorded in "Electronic Display Device (written by Akio Sasaki, Kogyo Chosakai Publishing Co., Ltd., published in 1990)", "Display Device (written by Junaki Ibuki, Sangyo-Tosho Publishing Co., Ltd., published in 1989)" and the like. In addition, regarding the liquid crystal display device, for example, it is recorded in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosakai Publishing Co., Ltd., published in 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied, for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology".

[0682] Example

[0683] The present invention is further specifically described by enumerating examples below. The materials, usage, ratio, processing content, processing sequence, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the purpose of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are mass references.

[0684] <Measurement of weight average molecular weight (Mw) of sample>

[0685] The weight average molecular weight of the sample was measured by gel permeation chromatography (GPC) under the following conditions.

[0686] Column types: Columns that connect TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000

[0687] Developing solvent: tetrahydrofuran

[0688] Column temperature: 40℃

[0689] Flow rate (sample injection volume): 1.0 μL (sample concentration: 0.1 mass %)

[0690] Device name: HLC-8220GPC manufactured by Tosoh Corporation

[0691] Detector: RI (refractive index) detector

[0692] Calibration curve base resin: polystyrene resin

[0693] <Measurement of acid value of sample>

[0694] The acid value of the sample indicates the mass of potassium hydroxide required to neutralize the acidic components in each 1g of solid content. The acid value of the sample was measured as follows. That is, the test sample was dissolved in a mixed solvent of tetrahydrofuran / water = 9 / 1 (mass ratio), and the obtained solution was neutralized and titrated with a 0.1 mol / L sodium hydroxide aqueous solution at 25°C using a potentiometric titrator (product name: AT-510, manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD.). The inflection point of the titration pH curve was taken as the titration endpoint, and the acid value was calculated by the following formula.

[0695] A=56.11×Vs×0.5×f / w

[0696] A: Acid value (mgKOH / g)

[0697] Vs: The amount of 0.1 mol / L sodium hydroxide aqueous solution required for titration (mL)

[0698] f: titration of 0.1 mol / L sodium hydroxide aqueous solution

[0699] w: mass of sample (g) (converted into solid content)

[0700] <Measurement of C=C value of sample>

[0701] The low molecular weight component (a) at the ethylenically unsaturated bond site (for example, acrylic acid when the resin has an acryloyloxy group) is removed from the resin by alkali treatment, and its content is measured by high performance liquid chromatography (HPLC). The C=C value is calculated from the measured value by the following formula.

[0702] Specifically, 0.1 g of resin was dissolved in a tetrahydrofuran / methanol mixture (50 mL / 15 mL), 10 mL of a 4 mol / L sodium hydroxide aqueous solution was added, and the mixture was reacted at 40 ° C for 2 hours. The reaction solution was neutralized by 10.2 mL of a 4 mol / L methanesulfonic acid aqueous solution, and then the mixed solution to which 5 mL of ion exchange water and 2 mL of methanol were added was transferred to a 100 mL volumetric flask, and the HPLC assay sample was prepared by constant volume with methanol, and the assay was performed under the following conditions. In addition, the content of the low molecular weight component (a) was calculated from the calibration curve of the low molecular weight component (a) prepared separately, and the olefinic unsaturated bond value was calculated by the following formula.

[0703] [C = C value calculation formula]

[0704] C = C value (mmol / g) = (content of low molecular weight component (a) (ppm) / molecular weight of low molecular weight component (a) (g / mol)) / (weight value of polymer solution (g) × (solid content concentration of polymer solution (%) / 100) × 10)

[0705] -HPLC assay conditions-

[0706] Measurement equipment: Agilent-1200 (manufactured by Agilent Technologies Japan, Ltd.)

[0707] Column: Synergi 4u Polar-RP 80A, manufactured by Phenomenex, 250 mm × 4.60 mm (inner diameter) + guard column

[0708] Column temperature: 40℃

[0709] Analysis time: 15 minutes

[0710] Flow rate: 1.0 mL / min (maximum delivery pressure: 182 bar (18.2 MPa))

[0711] Injection volume: 5μl

[0712] Detection wavelength: 210nm

[0713] Eluent: tetrahydrofuran (for HPLC without stabilizer) / buffer solution (ion exchange aqueous solution containing 0.2 volume % phosphoric acid and 0.2 volume % triethylamine) = 55 / 45 (volume %)

[0714] In addition, in this specification, volume % is a value at 25°C.

[0715] <Synthesis Example 1: Synthesis of specific resin A-20>

[0716] 13.5 g of vinyl benzoic acid, 13.5 g of N,N-diethylacrylamide and 127 g of macromonomer M1 described in paragraphs 0180 to 0181 of Japanese Patent Publication No. 2011-89108 were dissolved in 320 g of propylene glycol monomethyl ether acetate. 2.3 g of V-601 was added thereto under a nitrogen stream and heated and stirred at 75° C. for 8 hours. The precipitate obtained by crystallizing the obtained polymer solution with hexane was dried to obtain a polymer (A-20). The obtained polymer had an Mw of 20,000 and an acid value of 46 mgKOH / g.

[0717] The other specific resins used in the present examples or comparative examples were synthesized by the same method as that of A-20 except that the types and amounts of monomers used were appropriately changed.

[0718] The details of the content ratio (molar ratio) of each repeating unit in the specific resins A-1 to A-40 used in the present examples or comparative examples, namely, x, y, z, and w are shown in the following table.

[0719] Furthermore, in A-22, A-25, and A-26, n:m was set to 50:50 (molar ratio).

[0720] [Table 12]

[0721]

[0722] <Production of dispersions R1 to R8, B1 to B5, G1 to G4, Y1 to Y2, I1 to I6, and Bk1 to Bk7>

[0723] The mixed solution obtained by mixing the raw materials listed in the following table was mixed and dispersed for 3 hours using a bead mill (zirconia beads with a diameter of 0.3 mm), and then further dispersed at a pressure of 2,000 MPa and a flow rate of 500 g / min using a high-pressure disperser NANO-3000-10 (manufactured by NipponBEE Co., Ltd.) with a decompression mechanism. This dispersion treatment was repeated 10 times to obtain each dispersion.

[0724]

[0725] The unit of the numerical values ​​described in the above table is part by mass. The raw materials represented by the abbreviations in the above table are as follows.

[0726] 〔Color〕

[0727] PR264: CI Pigment Red 264 (red pigment, diketopyrrolopyrrole pigment)

[0728] PR254: CI Pigment Red 254 (red pigment, diketopyrrolopyrrole pigment)

[0729] PR179:CI Pigment Red 179

[0730] PB15:4: CI Pigment Blue 15:4 (blue pigment, phthalocyanine pigment)

[0731] PB15:6: CI Pigment Blue 15:6 (blue pigment, phthalocyanine pigment)

[0732] PB16:CI Pigment Blue 16 (blue pigment, phthalocyanine pigment)

[0733] PG7:CI Pigment Green 7

[0734] PG36:CI Pigment Green 36

[0735] PY138:CI Pigment Yellow 138

[0736] PY215:CI Pigment Yellow 215

[0737] PV23:CI Pigment Violet 23

[0738] IR pigment: A compound having the following structure (near infrared absorbing pigment, in the structural formula, Me represents a methyl group and Ph represents a phenyl group)

[0739] [Chemical formula 23]

[0740]

[0741] IRGAPHORE: Irgaphor Black S 0100 CF (manufactured by BASF, a compound having the following structure, a lactam pigment)

[0742] [Chemical formula 24]

[0743]

[0744] PBk32: CI Pigment Black 32 (compound with the following structure, perylene pigment)

[0745] [Chemical formula 25]

[0746]

[0747] Derivative 1: Compound with the following structure

[0748] [Chemical formula 26]

[0749]

[0750] Derivative 2: Compound with the following structure

[0751] [Chemical formula 27]

[0752]

[0753] Derivative 3: Compounds with the following structure

[0754] [Chemical formula 28]

[0755]

[0756] 〔Resin〕

[0757] A-20, A-22, A-26, A-29 and A-40: Resins synthesized in the above synthesis examples

[0758] CA-1: a resin having the following structure (a (meth)acrylic resin, the numerical value indicated on the main chain indicates the molar ratio, and the numerical value indicated on the side chain indicates the number of repeating units. The weight average molecular weight is 20,000, and the acid value is 77 mgKOH / g. CA-1 is a resin that does not contain any repeating unit represented by any of the formulas (1-1) to (1-5).

[0759] [Chemical formula 29]

[0760]

[0761] CA-2: DISPERBYK-193 (manufactured by BYK Additives & Instruments, a nonionic polymer dispersant. CA-2 is a resin that does not contain any repeating unit represented by any of the formulas (1-1) to (1-5).

[0762] [Solvent (organic solvent)]

[0763] S-1: Propylene glycol monomethyl ether acetate

[0764] S-2: Propylene glycol monomethyl ether

[0765] S-3: Cyclohexanone

[0766] S-4: Cyclopentanone

[0767] <Manufacturing of resin composition>

[0768] In each example and comparative example, the raw materials described in the following table are mixed to prepare a colored resin composition or a comparative composition. The unit of the numerical value in the column of the amount of addition described in the following table is mass parts. The description in the column of "Colorant concentration in solid content (%)" indicates the content (mass %) of the colorant relative to the total solid content of the composition. In addition, the description in the column of "Ratio of the total amount of specific repeating units" indicates the total amount of the repeating units represented by any one of formulas (1-1) to (1-5) relative to the total molar amount of all repeating units contained in all resin components contained in the composition (mole %).

[0769] [Table 14]

[0770]

[0771] [Table 15]

[0772]

[0773] The raw materials represented by the abbreviations in the raw materials described in the above table are as follows.

[0774] 〔Dispersion liquid〕

[0775] Dispersions R1 to R8, B1 to B5, G1 to G4, Y1 to Y2, I1 to I6, Bk1 to Bk7: the above dispersions

[0776] 〔Resin〕

[0777] A-1 to A-40: Resins synthesized in the above synthesis examples

[0778] CA-3: A resin represented by the following formula. In the following formula, the numerical value indicated on the main chain is a molar ratio. CA-3 is a resin in which the ratio of the total amount of repeating units represented by any one of formulas (1-1) to (1-5) to the total molar amount of all repeating units contained in the resin is 20 mol%.

[0779] [Chemical formula 30]

[0780]

[0781] CA-4: A resin represented by the following formula. In the following formula, the numerical value indicated on the main chain is a molar ratio. CA-4 is a resin in which the ratio of the total amount of repeating units represented by any one of formulas (1-1) to (1-5) to the total molar amount of all repeating units contained in the resin is 40 mol%.

[0782] [Chemical formula 31]

[0783]

[0784] 〔Polymerizable compounds〕

[0785] D-1: KAYARAD DPHA (made by NIPPON KAYAKU Co., Ltd.)

[0786] D-2: NK Ester A-DPH-12E (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.)

[0787] D-3: ARONIX M-510 (manufactured by TOAGOSEI CO., LTD.)

[0788] 〔Photopolymerization initiator〕

[0789] E-1: IRGACURE 379 (aminoacetophenone-based photoradical initiator (manufactured by BASF))

[0790] E-2: IRGACURE OXE01 (oxime ester photoradical initiator (manufactured by BASF))

[0791] E-3: IRGACURE OXE03 (oxime ester photoradical initiator (manufactured by BASF))

[0792] [Solvent (organic solvent)]

[0793] S-1: Propylene glycol monomethyl ether acetate

[0794] S-3: Cyclohexanone

[0795] <Evaluation>

[0796] [Evaluation of exposure sensitivity]

[0797] In each of the Examples and Comparative Examples, the colored resin composition or the comparative composition was applied onto a silicon wafer using a spin coater, dried (prebaked) at 100° C. for 120 seconds using a hot plate, and then heated (postbaked) at 200° C. for 30 minutes using an oven to form a resin composition layer having a thickness of 0.60 μm.

[0798] Next, the resin composition layer was exposed to light of 365 nm wavelength at a specific exposure amount using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) via a mask pattern in which square non-mask portions with a side of 1.0 μm were arranged in an area of ​​4 mm×3 mm.

[0799] Next, the silicon wafer having the exposed resin composition layer formed thereon was placed on a horizontal rotating table of a spin / spray developer (DW-30 model, manufactured by CHEMITRONICS CO., LTD.), and a developer (CD-2000, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was used to perform spin immersion development at 23°C for 60 seconds. Next, while the silicon wafer was rotated at a rotation speed of 50 rpm, pure water was supplied from a nozzle in a spray state from above the rotation center for rinsing treatment, and then spray drying was performed to form a pattern (pixel).

[0800] The obtained pattern was observed while changing the above specific exposure amount, and the minimum exposure amount for distinguishing a square pattern with a side of 1.0 μm was determined, and the evaluation was performed according to the following evaluation criteria. The evaluation results are recorded in Table 16. It can be said that the smaller the above minimum exposure amount, the better the exposure sensitivity of the composition.

[0801] -Evaluation Criteria-

[0802] A: The above minimum exposure is less than 100mJ / cm 2 .

[0803] B: The above minimum exposure is 100 or more and less than 200 mJ / cm 2 .

[0804] C: The above minimum exposure is 200 or more and less than 500 mJ / cm 2 .

[0805] D: The above minimum exposure is 500 or more and less than 1,000 mJ / cm 2 .

[0806] E: The above minimum exposure is 1,000mJ / cm 2 above.

[0807] 〔Evaluation of dispersion storage stability〕

[0808] In each embodiment and comparative example, the viscosity (mPa·s) of the colored resin composition or the comparative composition was measured using "RE-85L" manufactured by TOKI SANGYO CO., LTD. After the above measurement, the colored resin composition was left to stand at 45°C, protected from light, for 3 days, and the viscosity (mPa·s) was measured again. The storage stability was evaluated by the viscosity difference (ΔVis) before and after the above-mentioned standing according to the following evaluation criteria. The evaluation results are recorded in the "Dispersion Storage Stability" column of Table 16. It can be said that the smaller the value of the viscosity difference (ΔVis), the better the storage stability of the composition. Regarding the above viscosity measurements, the measurements were performed in a laboratory where the temperature and humidity were managed at 22±5°C and 60±20%, and the temperature of the composition was adjusted to 25°C.

[0809] -Evaluation Criteria-

[0810] A: ΔVis is 0.5 mPa·s or less.

[0811] B: ΔVis exceeds 0.5 mPa·s and is 1.0 mPa·s or less.

[0812] C: ΔVis exceeds 1.0 mPa·s and is 2.0 mPa·s or less.

[0813] D: ΔVis exceeds 2.0 mPa·s and is 2.5 mPa·s or less.

[0814] E: ΔVis exceeds 2.5 mPa·s.

[0815] [Evaluation of spectral changes]

[0816] In each embodiment and comparative example, a colored resin composition or a comparative composition was applied to a glass substrate using a spin coater, and dried (prebaked) at 100°C for 120 seconds using a hot plate, and then heated (postbaked) at 200°C for 30 minutes using an oven to produce a film with a thickness of 0.60 μm. The transmittance Tr1 of the obtained film at a wavelength of 450 nm was measured using a Cary 5000 UV-Vis-NIR spectrophotometer (manufactured by Agilent Technologies Japan, Ltd.). Then, the obtained film was heat treated at 300°C for 5 hours in a nitrogen environment. The transmittance Tr2 of the film after heat treatment at a wavelength of 450 nm was measured.

[0817] The absolute value ΔT of the difference between Tr1 and Tr2 was calculated, and the spectral change was evaluated according to the following evaluation criteria. The evaluation results are recorded in the "Spectral Change" column of Table 16. It can be said that the smaller the ΔT, the less likely it is to cause spectral change, so it is preferred. The above Tr1 and Tr2 were measured in a laboratory where the temperature and humidity were managed at 22±5℃ and 60±20%, and the temperature adjustment was implemented to set the substrate temperature to 25℃.

[0818] -Evaluation Criteria-

[0819] A: ΔT is 0.1% or less.

[0820] B: ΔT exceeds 0.1% and is 0.5% or less.

[0821] C: ΔT exceeds 0.5% and is 1% or less.

[0822] D: ΔT exceeds 1% and is 5% or less.

[0823] E: ΔT exceeds 5%.

[0824] [Evaluation of film shrinkage]

[0825] In each embodiment and comparative example, a colored resin composition or a comparative composition was applied to a glass substrate using a spin coater, and dried (pre-baked) at 100°C for 120 seconds using a hot plate, and then heated (post-baked) at 200°C for 30 minutes using an oven to produce a film with a thickness of 0.60 μm. Regarding the film thickness, a portion of the film was removed to expose the surface of the glass substrate, and a probe profiler (DektakXT, manufactured by Bruker Corporation) was used to measure the step difference between the surface of the glass substrate and the coating film (the thickness of the coating film). Then, the obtained film was heat-treated at 300°C for 5 hours in a nitrogen environment. The film thickness of the film after the heat treatment was measured in the same manner, and the film shrinkage was calculated by the following formula, and the film shrinkage was evaluated according to the following evaluation criteria. The evaluation results are recorded in the "Film Shrinkage" column of Table 16. T0 and T1 described below were measured in a laboratory where the temperature and humidity were controlled at 22±5°C and 60±20%, and the substrate temperature was adjusted to 25°C. It can be said that the smaller the film shrinkage rate, the more suppressed the film shrinkage is, which is a preferred result.

[0826] Film shrinkage (%) = (1-(T1 / T0)) × 100

[0827] T0: Film thickness of the film just produced (= 0.60 μm)

[0828] T1: Film thickness after heating at 300°C for 5 hours in a nitrogen environment

[0829] -Evaluation Criteria-

[0830] A: The film shrinkage rate is 1% or less.

[0831] B: The film shrinkage ratio exceeds 1% and is 5% or less.

[0832] C: The film shrinkage ratio is more than 5% and 10% or less.

[0833] D: The film shrinkage ratio exceeds 10% and is 30% or less.

[0834] E: The film shrinkage rate exceeds 30%.

[0835] 〔Cracked Evaluation〕

[0836] In each of the examples and comparative examples, the colored resin composition or the comparative composition was applied onto a glass substrate using a spin coater, dried (prebaked) at 100° C. for 120 seconds using a hot plate, and then heated (postbaked) at 200° C. for 30 minutes using an oven to produce a film having a thickness of 0.60 μm.

[0837] Next, an inorganic film was formed by sputtering a 200 nm layer of SiO2 on the surface of the obtained film. The film with the inorganic film formed on the surface was heated at 300°C for 5 hours in a nitrogen environment. The surface of the inorganic film after the heat treatment was observed using an optical microscope, and the number of micrometers per 1 cm was counted. 2 The number of cracks was counted and the presence or absence of cracks was evaluated according to the following evaluation criteria. The evaluation results are recorded in the "Cracks" column of Table 16.

[0838] -Evaluation Criteria-

[0839] A: Every 1cm 2 The number of cracks is 0.

[0840] B: Every 1cm 2 The number of cracks is 1 to 10.

[0841] C: Every 1cm 2 The number of cracks is 11 to 50.

[0842] D: Every 1cm 2 The number of cracks ranges from 51 to 100.

[0843] E: Every 1cm 2 The number of cracks is more than 101.

[0844] [Table 16]

[0845]

[0846] When the colored resin composition of the example was used, the occurrence of cracks was suppressed compared to when the comparative composition of Comparative Example 1 or Comparative Example 2 was used. Therefore, it can be said that the process window in the steps after film production can be expanded compared to the comparative composition of Comparative Example 1 or Comparative Example 2.

[0847] (Example 100: Pattern formation by photolithography)

[0848] On a silicon wafer, the colored resin composition of Example 9 was applied using a spin coater, dried (pre-baked) at 100° C. for 120 seconds using a hot plate, and then heated (post-baked) at 200° C. for 30 minutes using an oven to form a resin composition layer with a thickness of 0.60 μm.

[0849] Next, a mask pattern having a square non-mask portion with a side of 1.1 μm was arranged in an area of ​​4 mm×3 mm, and an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was used at 500 mJ / cm 2 The resin composition layer was exposed by irradiating light with a wavelength of 365 nm at an exposure amount of .

[0850] Next, the silicon wafer having the exposed resin composition layer formed thereon was placed on a horizontal rotating table of a spin / spray developer (DW-30 model, manufactured by CHEMITRONICS CO., LTD.), and a developer (CD-2000, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was used to perform spin immersion development at 23°C for 60 seconds. Next, while the silicon wafer was rotated at a rotation speed of 50 rpm, pure water was supplied from a nozzle in a spray state from above the rotation center for rinsing treatment, and then spray drying was performed to form a pattern (pixel).

[0851] The produced patterned silicon wafer was divided into two parts, one of which was heat-treated at 300°C for 5 hours in a nitrogen environment (hereinafter, one of which is referred to as the substrate before the 300°C heat treatment and the other is referred to as the substrate after the 300°C heat treatment). When the cross-section of the resist pattern formed on the substrate before the 300°C heat treatment and the substrate after the 300°C heat treatment was evaluated using a scanning electron microscope (SEM), the height of the resist pattern formed on the substrate after the 300°C heat treatment was 71% of the height of the resist pattern formed on the substrate before the 300°C heat treatment.

Claims

1. A colored resin composition comprising: Resin; Colours; and Organic solvents, The resin includes at least one repeating unit selected from the repeating units represented by any one of the following formulas (1-1) to (1-3), The total amount of the repeating units represented by any one of the following formulae (1-1) to (1-3) is greater than 60 mol% relative to the total molar amount of all repeating units contained in the resin. The resin has an ethylenically unsaturated bond, and the group having the ethylenically unsaturated bond is a group represented by the following formula (F-2) or formula (F-3), The content of the colorant is 30% by mass or more relative to the total solid content of the composition. In formula (1-1), R 11 , R 12 and R 13 Each independently represents a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, Ar represents an aromatic group having 5 to 30 ring members, In formula (1-2), R 21 , R 22 and R 23 Each independently represents a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and R 24 and R 25 Each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, and R 24 and R 25 are optionally bonded to form a ring structure, In formula (1-3), R 31 , R 32 and R 33 Each independently represents a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and R 34 and R 35 Each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, and R 34 and R 35 are optionally bonded to form a ring structure, In formula (F-2), R F2 represents an alkylene group, a divalent aromatic hydrocarbon group, -C(=O)NR N -、-OC(=O)NR N -、-NR N C(=O)NR N - or a group formed by bonding two or more of these, R N represents a hydrogen atom or a hydrocarbon group, n represents an integer greater than 0, and R F3 represents a hydrogen atom or a methyl group, represents the bonding position with other structures, In formula (F-3), R F4 represents an alkylene group, a divalent aromatic hydrocarbon group, -C(=O)NR N -、-OC(=O)NR N -、-NR N C(=O)NR N - or a group formed by bonding two or more of these, R N represents a hydrogen atom or a hydrocarbon group, R F5 represents a hydrogen atom or a methyl group, Indicates bonding positions to other structures.

2. The colored resin composition according to claim 1, wherein In the resin, the content of the repeating unit derived from (meth)acrylic acid or a (meth)acrylate compound is 0 mol % to 20 mol % based on the total molar amount of all the repeating units contained in the resin.

3. The colored resin composition according to claim 1 or 2, wherein The resin has at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic group, a phosphoric acid group, and an amino group.

4. The colored resin composition according to claim 1 or 2, wherein The acid value of the resin is 20 mgKOH / g to 150 mgKOH / g.

5. The colored resin composition according to claim 1 or 2, wherein The C=C value of the resin is 0.1 mmol / g to 3 mmol / g.

6. The colored resin composition according to claim 1 or 2, wherein The resin is a grafted polymer or a star-shaped polymer.

7. The colored resin composition according to claim 1 or 2, wherein The resin has a molecular weight of 1,000 to 10,000 and does not contain a molecular chain of an acid group or a basic group.

8. The colored resin composition according to claim 7, wherein The molecular chain includes at least one selected from a repeating unit derived from a (meth)acrylate compound, a repeating unit derived from a (meth)acrylamide compound, a repeating unit derived from an aromatic vinyl compound, and a polyester structure.

9. The colored resin composition according to claim 1 or 2, wherein The resin includes the following resin 1 and the following resin 2, Resin 1: is the above resin, and contains an acid group and a group having an ethylenically unsaturated bond, Resin 2: is the above resin, and has at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic group, a phosphoric acid group, and an amino group, and a molecular chain having a molecular weight of 1,000 to 10,000 and no acid group.

10. The colored resin composition according to claim 1 or 2, wherein The colorant includes at least one colorant selected from a color colorant and a near infrared absorbing colorant.

11. The colored resin composition according to claim 1 or 2, wherein The pigments include color pigments and near infrared absorbing pigments.

12. The colored resin composition according to claim 1 or 2, wherein The colorant includes a black colorant.

13. The colored resin composition according to claim 1 or 2, wherein The colorant includes at least one colorant selected from red colorant, yellow colorant, blue colorant and purple colorant. 14 . The colored resin composition according to claim 1 , further comprising a photopolymerization initiator.

15. The colored resin composition according to claim 14, wherein The photopolymerization initiator is an oxime compound. 16 . The colored resin composition according to claim 1 , which is used for pattern formation by photolithography. 17 . The colored resin composition according to claim 1 , which is used for a solid-state imaging element. 18 . A film obtained from the colored resin composition according to claim 1 .

19. A color filter comprising the film according to claim 18. 20 . A solid-state imaging element comprising the film according to claim 18 .

21. An image display device comprising the film according to claim 18.

Images