Compound

Abstract

To provide a novel compound.SOLUTION: The present invention provides a compound represented by the formula (EDM1). In the formula (EDM1), RED1 represents an acid anhydride group, LpED1 represents a n+1 valent group, the n+1 valent group is a hydrocarbon group, or a group consisting of a hydrocarbon group combined with at least one group selected from -NRpED1-, -N<, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NRpED1CO- and -CONRpED1-, RpED1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, LpED2 represents -O- or -S-, PED1 represents a polymer chain including a repeating unit represented by one of formula (P1-1)-formula (P1-4), and n represents an integer of 1-4.

Description

Technical Field

[0001] The present invention relates to a resin composition, a film, an optical filter, a solid-state imaging device, an image display device, a resin, and a compound.

Background Art

[0002] In recent years, due to the widespread use of digital cameras, mobile phones with cameras, etc., the demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors has been growing significantly. A film containing a pigment such as a color filter is used for the solid-state imaging device. The film containing a coloring material such as a color filter is manufactured using a resin composition containing a pigment, a resin, and a solvent.

[0003] For example, Patent Document 1 describes a resin composition containing a pigment, a dispersant, a binder resin, an epoxy compound, and a solvent, wherein the dispersant is obtained by reacting an acid anhydride group in at least one acid anhydride (b) selected from tetracarboxylic acid anhydride (b1) and tricarboxylic acid anhydride (b2) with a hydroxyl group in a hydroxyl group-containing compound (a) to form a polyester moiety X1' having a carboxy group, and a vinyl polymer moiety X2' formed by radical polymerization of an ethylenically unsaturated monomer (c) and having a thermally crosslinkable functional group, and the thermally crosslinkable functional group is at least one selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group, a blocked isocyanate group, and a (meth)acryloyl group. An invention related to a resin composition containing a dispersant (X) is described.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] In a resin composition containing a pigment, a resin, and a solvent, it is preferable that the dispersibility of the pigment is good. If the dispersibility of the pigment is insufficient, the pigment may aggregate and coarsen in the resin composition, or the viscosity of the resin composition may easily increase. Also, even if the viscosity of the resin composition immediately after production is low, the viscosity may increase with time.

[0006] According to the study by the present inventors, it has been found that even in the resin composition described in Patent Document 1, the dispersibility of the pigment is not sufficient and there is room for further improvement.

[0007] Therefore, an object of the present invention is to provide a resin composition excellent in the dispersibility of a pigment. Another object of the present invention is to provide a film, an optical filter, a solid-state imaging device, and an image display device using the resin composition. Further, an object of the present invention is to provide a resin and a compound.

Means for Solving the Problems

[0008] Examples of typical embodiments of the present invention are shown below. <1> A coloring material A containing a pigment, a resin B, and a solvent C, and the above resin B contains a resin b-1 having a structure represented by formula (1), a resin composition;

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Advantages of the Invention

[0009] According to the present invention, a resin composition excellent in pigment dispersibility can be provided. Further, a film, an optical filter, a solid-state imaging device and an image display device using the resin composition can be provided. Further, a resin and a compound can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

[0010] Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the disclosed embodiments. In this specification, "~" is used to mean including the numerical values described before and after it as the lower limit value and the upper limit value. In the notation of a group (atomic group) in this specification, a notation that does not indicate substitution or non-substitution includes both a group (atomic group) having no substituent and a group (atomic group) having a substituent together with the group having no substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In this specification, "exposure" means, unless otherwise specified, not only exposure using light but also drawing using particle beams such as electron beams and ion beams is included in exposure. Further, examples of the light used for exposure include actinic rays or radiation such as the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams. In this specification, the (meth)allyl group represents both allyl and methallyl, or either one, "(meth)acrylate" represents both acrylate and methacrylate, or either one, "(meth)acrylic" represents both acrylic and methacrylic, or either one, and "(meth)acryloyl" represents both acryloyl and methacryloyl, or either one. In this specification, the weight average molecular weight and the number average molecular weight are values in terms of polystyrene measured by the GPC (gel permeation chromatography) method. In this specification, near-infrared rays refer to light having a wavelength of 700 to 2500 nm. In this specification, the total solid content means the total mass of the components obtained by removing the solvent from all the components of the composition. In this specification, the term "step" does not refer only to an independent step, but is included in this term if the intended action of the step is achieved even when it cannot be clearly distinguished from other steps. In this specification, a pigment means a compound that is hardly soluble in a solvent. In this specification, symbols (such as A etc.) appended before or after a name are terms used to distinguish components, and do not limit the type of components, the number of components, and the superiority or inferiority of components.

[0011] <Resin composition> The resin composition of the present invention contains a coloring material A containing a pigment, a resin B, and a solvent C, and the resin B is characterized by containing a resin b-1 (hereinafter also referred to as a specific resin) having a structure represented by formula (1).

[0012] The resin composition of the present invention is excellent in the dispersibility of the pigment. Although the detailed reason for obtaining such an effect is unknown, in the specific resin, an amide group (-C(=O)-NR 1 -, -C(=O)-NR 21 -) is bonded to X which is a tetravalent linking group, so the adsorption of the specific resin onto the pigment surface is promoted. Also, since this specific resin has a polymer chain P 22 1 1 1 1 It is presumed that as a result, the polymer chain P can serve as a steric repulsion group to suppress the aggregation of pigments and the like, and thus a resin composition excellent in the dispersibility of the pigment can be obtained.

[0013] Further, by using the resin composition of the present invention, a film excellent in heat resistance that is hardly decomposed even at high temperatures and hardly undergoes film shrinkage even after heat treatment at high temperatures can be formed. Therefore, even when a heat treatment at a high temperature (for example, 300 °C or higher) is performed on the obtained film after forming a film using the resin composition of the present invention, film shrinkage can be suppressed, and even when another film such as an inorganic film is formed on the film, the occurrence of cracks in the other film can be suppressed. Therefore, according to the resin composition of the present invention, the process window of the process after manufacturing the film can be widened.

[0014] When a film with a thickness of 0.60 μm is formed by heating the 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, more preferably 80% or more, and still more preferably 90% or more of the thickness of the film before heat treatment. Also, the thickness of the film after heat treatment at 350°C for 5 hours in a nitrogen atmosphere is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more of the thickness of the film before heat treatment. Also, the thickness of the film after heat treatment at 400°C for 5 hours in a nitrogen atmosphere is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more of the thickness of the film before heat treatment. The above physical properties can be achieved by methods such as adjusting the type and content of the specific resin used.

[0015] When a film with a thickness of 0.60 μm is formed by heating the resin composition of the present invention at 200°C for 30 minutes, when the film is heat treated at 300°C for 5 hours in a nitrogen atmosphere, the change rate ΔA of the absorbance represented by the following formula (A1) of the film after heat treatment is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less, and particularly preferably 35% or less. ΔA(%) = |100 - (A2 / A1)×100| ···(A1) ΔA is the change rate of the absorbance of the film after heat treatment, A1 is the maximum value of the absorbance in the wavelength range of 400 to 1100 nm of the film before heat treatment, A2 is the absorbance of the film after heat treatment, and is the absorbance at the wavelength showing the maximum value of the absorbance in the wavelength range of 400 to 1100 nm of the film before heat treatment. The above physical properties can be achieved by methods such as adjusting the type and content of the specific resin used.

[0016] Further, when a film with a thickness of 0.60 μm is formed by heating the resin composition of the present invention at 200°C for 30 minutes, the absolute value of the difference between the wavelength λ1 showing the maximum absorbance in the wavelength range of 400 to 1100 nm of the film and the wavelength λ2 showing the maximum absorbance of the film after heat treatment at 300°C for 5 hours in a nitrogen atmosphere is preferably 50 nm or less, more preferably 45 nm or less, and still more preferably 40 nm or less. The above physical properties can be achieved by methods such as adjusting the type and content of the specific resin used.

[0017] Further, when a film with a thickness of 0.60 μm is formed by heating the resin composition of the present invention at 200°C for 30 minutes, when the film is heat-treated at 300°C for 5 hours in a nitrogen atmosphere, the change rate ΔA of the absorbance in the wavelength range of 400 to 1100 nm of the film after heat treatment λ The maximum value of is preferably 30% or less, more preferably 27% or less, and still more preferably 25% or less. The change rate of absorbance is a value calculated from the following formula (2). ΔA λ =|100 - (A2 λ / A1 λ ) × 100| ···(2) ΔA λ is the change rate of the absorbance at the wavelength λ of the film after heat treatment, A1 λ is the absorbance at the wavelength λ of the film before heat treatment, A2 λ is the absorbance at the wavelength λ of the film after heat treatment. The above physical properties can be achieved by methods such as adjusting the type and content of the specific resin used.

[0018] The resin composition of the present invention is preferably used as a resin composition for an optical filter. Examples of the optical filter include a color filter, a near-infrared transmission filter, a near-infrared cut filter, etc., and a color filter is preferred. Further, the resin composition of the present invention can be preferably used as a resin composition for a solid-state imaging device, and more preferably used as a resin composition for forming pixels of an optical filter used in a solid-state imaging device.

[0019] Examples of the color filter include a filter having a colored pixel that transmits light of a specific wavelength, and it is preferably a filter having at least one colored pixel selected from a red pixel, a blue pixel, a green pixel, a yellow pixel, a cyan pixel, and a magenta pixel. The color filter can be formed using a resin composition containing a colored pigment.

[0020] Examples of the near-infrared cut filter include a filter having a maximum absorption wavelength in the range of 700 to 1800 nm. The maximum absorption wavelength of the near-infrared cut filter preferably exists in the range of 700 to 1300 nm, and more preferably exists in the range of 700 to 1100 nm. Further, the transmittance in the entire range of 400 to 650 nm of the near-infrared cut filter is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. Also, the transmittance at at least one point in the range of 700 to 1800 nm is preferably 20% or less. Further, the absorbance ratio Amax / A550, which is 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, is preferably 20 to 500, more preferably 50 to 500, still more preferably 70 to 450, and particularly preferably 100 to 400. The near-infrared cut filter can be formed using a resin composition containing a near-infrared absorbing pigment.

[0021] The near-infrared transmission filter is a filter that transmits at least a part of near-infrared rays. Preferably, the near-infrared transmission filter is a filter that blocks at least a part of visible light and transmits at least a part of near-infrared rays. As the near-infrared transmission filter, a filter satisfying the spectral characteristics that the maximum value of the transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1100 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more) is preferably cited. Preferably, the near-infrared transmission filter is a filter satisfying any one of the following spectral characteristics (1) to (5). (1): A filter in which the maximum value of the transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 800 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more). (2): A filter in which the maximum value of the transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 900 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more). (3): A filter in which the maximum value of the transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1000 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more). (4): A filter in which the maximum value of the transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1100 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more). (5) A filter having a maximum transmittance in the wavelength range of 400 to 1050 nm of 20% or less (preferably 15% or less, more preferably 10% or less) and a minimum transmittance in the wavelength range of 1200 to 1500 nm of 70% or more (preferably 75% or more, more preferably 80% or more).

[0022] As a preferred embodiment of the spectral characteristics provided by the resin composition of the present invention, there is an embodiment in which when a film having a thickness of 5 μm is formed using the resin composition, the maximum value of the light transmittance in the wavelength range of 360 to 700 nm in the thickness direction of the film is 50% or more. The resin composition satisfying such spectral characteristics can be preferably used as a resin composition for forming pixels of a color filter. Specifically, it can be preferably used as a resin composition for forming colored pixels selected from red pixels, blue pixels, green pixels, yellow pixels, cyan pixels, and magenta pixels.

[0023] The resin composition having the above spectral characteristics preferably contains a colored pigment. For example, a resin composition containing a red pigment and a yellow pigment can be preferably used as a resin composition for forming red pixels. Also, a resin composition containing a blue pigment and a purple pigment can be preferably used as a resin composition for forming blue pixels. Further, a resin composition containing a green pigment can be preferably used as a resin composition for forming green or cyan pixels. When the resin composition is used as a resin composition for forming green pixels, it is also preferable to further contain a yellow pigment in addition to the green pigment.

[0024] As another preferred embodiment of the spectral characteristics provided by the resin composition of the present invention, there is an embodiment in which Amin / B, which is the ratio of the minimum absorbance Amin in the wavelength range of 400 to 640 nm to the absorbance B at a wavelength of 1500 nm, satisfies the spectral characteristics of being 5 or more. The resin composition satisfying such spectral characteristics can be preferably used as a resin composition for forming a near-infrared transmission filter. The value of Amin / B, which is the ratio of the absorbances described above, is preferably 7.5 or more, more preferably 15 or more, and still more preferably 30 or more.

[0025] Here, the absorbance Aλ at wavelength λ is defined by the following formula (λ1). Aλ = -log(Tλ / 100) ···(λ1) Aλ is the absorbance at wavelength λ, and Tλ is the transmittance (%) at wavelength λ. In the present invention, the absorbance value may be a value measured in a solution state or a value of a film formed using the composition. When measuring the absorbance in the film state, it is preferable to measure using a film obtained by applying the composition on a glass substrate by a method such as spin coating and drying at 100°C for 120 seconds using a hot plate or the like.

[0026] The resin composition of the present invention preferably satisfies any one of the following spectral characteristics (Ir1) to (Ir5). (Ir1): The value of A1 / B1, which is the ratio of the minimum absorbance value A1 in the wavelength range of 400 to 640 nm and the maximum absorbance value B1 in the wavelength range of 800 to 1500 nm, is 4.5 or more, preferably 7.5 or more, more preferably 15 or more, and still more preferably 30 or more. According to this aspect, a film that can block light in the wavelength range of 400 to 640 nm and transmit light with a wavelength exceeding 750 nm can be formed. (Ir2): The value of A2 / B2, which is the ratio of the minimum absorbance value A2 in the wavelength range of 400 to 750 nm and the maximum absorbance value B2 in the wavelength range of 900 to 1500 nm, is 4.5 or more, preferably 7.5 or more, more preferably 15 or more, and still more preferably 30 or more. According to this aspect, a film that can block light in the wavelength range of 400 to 750 nm and transmit light with a wavelength exceeding 850 nm can be formed. (Ir3): The value of A3 / B3, which is the ratio of the minimum absorbance A3 in the wavelength range of 400 to 830 nm to the maximum absorbance B3 in the wavelength range of 1000 to 1500 nm, is 4.5 or more, preferably 7.5 or more, more preferably 15 or more, and still more preferably 30 or more. According to this aspect, a film that can block light in the wavelength range of 400 to 830 nm and transmit light with a wavelength exceeding 950 nm can be formed. (Ir4): The value of A4 / B4, which is the ratio of the minimum absorbance A4 in the wavelength range of 400 to 950 nm to the maximum absorbance B4 in the wavelength range of 1100 to 1500 nm, is 4.5 or more, preferably 7.5 or more, more preferably 15 or more, and still more preferably 30 or more. According to this aspect, a film that can block light in the wavelength range of 400 to 950 nm and transmit light with a wavelength exceeding 1050 nm can be formed. (Ir5): The value of A5 / B5, which is the ratio of the minimum absorbance A5 in the wavelength range of 400 to 1050 nm to the maximum absorbance B5 in the wavelength range of 1200 to 1500 nm, is 4.5 or more, preferably 7.5 or more, more preferably 15 or more, and still more preferably 30 or more. According to this aspect, a film that can block light in the wavelength range of 400 to 1050 nm and transmit light with a wavelength exceeding 1150 nm can be formed.

[0027] The resin composition of the present invention is also preferably a resin composition for pattern formation by photolithography. According to this aspect, fine-sized pixels can be easily formed. Therefore, it can be particularly preferably used as a resin composition for forming pixels of an optical filter used in a solid-state imaging device. For example, a resin composition containing a component having an ethylenically unsaturated bond-containing group (for example, a resin having an ethylenically unsaturated bond-containing group or a monomer having an ethylenically unsaturated bond-containing group) and a photopolymerization initiator can be preferably used as a resin composition for pattern formation by photolithography. It is also preferable that the resin composition for pattern formation by photolithography further contains an alkali-soluble resin.

[0028] The resin composition of the present invention can also be used as a resin composition for forming a black matrix or a light-shielding film.

[0029] Hereinafter, each component used in the resin composition of the present invention will be described.

[0030] <Colorant A> The resin composition of the present invention contains a colorant A (hereinafter referred to as a colorant). Examples of the colorant include a white colorant, a black colorant, a colored colorant, and a near-infrared absorbing colorant. In the present invention, the white colorant includes not only pure white but also colorants of light gray close to white (for example, off-white, light gray, etc.).

[0031] The colorant preferably contains at least one selected from the group consisting of a colored colorant, a black colorant, and a near-infrared absorbing colorant, more preferably contains at least one selected from the group consisting of a colored colorant and a near-infrared absorbing colorant, still more preferably contains a colored colorant, and still more preferably contains at least one colored colorant selected from the group consisting of a red colorant, a yellow colorant, a blue colorant, and a purple colorant.

[0032] Also, the colorant preferably contains a colored colorant and a near-infrared absorbing colorant, and preferably contains two or more colored colorants and a near-infrared absorbing colorant. Also, black may be formed by a combination of two or more colored colorants. Also, the colorant preferably contains a black colorant and a near-infrared absorbing colorant. According to these embodiments, the resin composition of the present invention can be preferably used as a resin composition for forming a near-infrared transmission filter. For the combination of colorants that form black by a combination of two or more colored colorants, reference can be made to JP-A-2013-077009, JP-A-2014-130338, WO 2015 / 166779, etc.

[0033] As the coloring material contained in the coloring composition of the present invention, those containing a pigment are used. The pigment may be either an inorganic pigment or an organic pigment, but is preferably an organic pigment from the viewpoints of a large number of color variations, ease of dispersion, safety, etc. Further, the pigment preferably contains at least one selected from chromatic pigments and near-infrared absorbing pigments, and more preferably contains a chromatic pigment.

[0034] Further, 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, and more preferably contains at least one selected from phthalocyanine pigments, diketopyrrolopyrrole pigments, and pyrrolopyrrole pigments, and still more preferably contains a phthalocyanine pigment or a diketopyrrolopyrrole pigment. Further, phthalocyanine pigments are preferred because it is easy to form a film whose spectral characteristics hardly change even after heating at a high temperature (for example, 300 ° C or higher), and phthalocyanine pigments having no central metal or phthalocyanine pigments having copper or zinc as the central metal are preferred.

[0035] The average primary particle diameter 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 still more preferably 100 nm or less. When the average primary particle diameter of the pigment is within the above range, the dispersion stability of the pigment in the resin composition is good. In the present invention, the primary particle diameter of the pigment can be determined from a photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is determined, and the equivalent circle diameter corresponding thereto is calculated as the primary particle diameter of the pigment. Further, the average primary particle diameter in the present invention is the arithmetic average value of the primary particle diameters of 400 primary particles of the pigment. Further, the primary particles of the pigment refer to independent particles without aggregation.

[0036] (Chromatic coloring material) Examples of the colored pigments include those having a maximum absorption wavelength in the range of 400 to 700 nm. For example, yellow pigments, orange pigments, red pigments, green pigments, purple pigments, blue pigments and the like can be mentioned. From the viewpoint of heat resistance, the colored pigments are preferably pigments (colored pigments), more preferably red pigments, yellow pigments, and blue pigments, and still more preferably red pigments and blue pigments. Specific examples of the colored pigments include, for example, those shown below.

[0037] C.I. 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, 215, 228, 231, 232 (methine series), 233 (quinoline series), 234 (aminoketone series), 235 (aminoketone series), 236 (aminoketone series), etc. (the above are yellow pigments), C.I. 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), C.I. 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, 144, 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, 269, 270, 272, 279, 291, 294 (xanthene series, Organo Ultramarine, Bluish Red), 295 (monoazo series), 296 (diazo series), 297 (aminoketone series), etc. (the above are red pigments), C.I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64 (phthalocyanine series), 65 (phthalocyanine series), 66 (phthalocyanine series), etc. (the above are green pigments), C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane series), 61 (xanthene series), etc. (the above are purple pigments), C.I. 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).

[0038] Among these chromatic pigments, as red pigments, C.I. Pigment Red 254, C.I. Pigment Red 264, C.I. Pigment Red 272, C.I. Pigment Red 122, and C.I. Pigment Red 177 are preferred because they are likely to form a film with less spectral property variation even after heating at a high temperature (for example, 300 °C or higher). Also, as blue pigments, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, and C.I. Pigment Blue 16 are preferred.

[0039] Also, as the green pigment, 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 per molecule can also be used. Specific examples include the compounds described in International Publication No. WO2015 / 118720. Also, as the green pigment, compounds described in the specification of Chinese Patent Application No. 106909027, phthalocyanine compounds having a phosphate ester as a ligand described in International Publication No. WO2012 / 102395, phthalocyanine compounds described in JP-A-2019-008014, phthalocyanine compounds described in JP-A-2018-180023, compounds described in JP-A-2019-038958, etc. can also be used.

[0040] Also, as the blue pigment, an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples include the compounds described in paragraph numbers 0022 to 0030 of JP-A-2012-247591 and paragraph number 0047 of JP-A-2011-157478.

[0041] Also, as the yellow pigment, the compounds described in JP-A No. 2017-201003, the compounds described in JP-A No. 2017-197719, the compounds described in paragraphs 0011 to 0062 and 0137 to 0276 of JP-A No. 2017-171912, the compounds described in paragraphs 0010 to 0062 and 0138 to 0295 of JP-A No. 2017-171913, the compounds described in paragraphs 0011 to 0062 and 0139 to 0190 of JP-A No. 2017-171914, the compounds described in paragraphs 0010 to 0065 and 0142 to 0222 of JP-A No. 2017-171915, the quinophthalone compounds described in paragraphs 0011 to 0034 of JP-A No. 2013-054339, the quinophthalone compounds described in paragraphs 0013 to 0058 of JP-A No. 2014-026228, the isoindoline compounds described in JP-A No. 2018-062644, the quinophthalone compounds described in JP-A No. 2018-203798, the quinophthalone compounds described in JP-A No. 2018-062578, the quinophthalone compounds described in Patent No. 6432076, the quinophthalone compounds described in JP-A No. 2018-155881, the quinophthalone compounds described in JP-A No. 2018-111757, the quinophthalone compounds described in JP-A No. 2018-040835, the quinophthalone compounds described in JP-A No. 2017-197640, the quinophthalone compounds described in JP-A No. 2016-145282, the quinophthalone compounds described in JP-A No. 2014-085565, the quinophthalone compounds described in JP-A No. 2014-021139, the quinophthalone compounds described in JP-A No. 2013-209614, the quinophthalone compounds described in JP-A No. 2013-209435, the quinophthalone compounds described in JP-A No. 2013-181015, the quinophthalone compounds described in JP-A No. 2013-061622, the quinophthalone compounds described in JP-A No. 2013-032486, the quinophthalone compounds described in JP-A No. 2012-226110, the quinophthalone compounds described in JP-A No. 2008-074987, the quinophthalone compounds described in JP-A No. 2008-081565, the quinophthalone compounds described in JP-A No. 2008-074986, the quinophthalone compounds described in JP-A No. 2008-074985, the quinophthalone compounds described in JP-A No. 2008-050420The quinophthalone compounds described in JP-A No. 2008-031281, the quinophthalone compounds described in JP-B No. 48-032765, the quinophthalone compounds described in JP-A No. 2019-008014, the quinophthalone compounds described in Patent No. 6607427, the compounds described in Korean Patent Publication No. 10-2014-0034963, the compounds described in JP-A No. 2017-095706, the compounds described in Taiwan Patent Application Publication No. 201920495, the compounds described in Patent No. 6607427, the quinophthalone dimer described in JP-A No. 2020-033521, the compounds represented by the following formula (QP1), and the compounds represented by the following formula (QP2) can also be used. Also, those obtained by multimerizing these compounds are preferably used from the viewpoint of improving the color value.

Chemical formula

[0042] 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 formula (QP1) include the compounds described in paragraph number 0016 of Patent No. 6443711.

Chemical formula

[0043] In formula (QP2), Y 1 ~Y 3 each independently represents a halogen atom. n and m represent integers from 0 to 6, and p represents an integer from 0 to 5. (n + m) is 1 or more. Specific examples of the compound represented by formula (QP2) include the compounds described in paragraph numbers 0047 to 0048 of Patent No. 6432077.

[0044] As the red pigment, a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, a diketopyrrolopyrrole compound described in paragraphs 0016 to 0022 of Patent No. 6248838, a diketopyrrolopyrrole compound described in International Publication No. 2012 / 102399, a diketopyrrolopyrrole compound described in International Publication No. 2012 / 117965, a naphthol azo compound described in JP-A-2012-229344, a compound described in Patent No. 6516119, a compound described in Patent No. 6525101, etc. can also be used. Further, as the red pigment, a compound having a structure in which an aromatic hydrocarbon group having a group to which an oxygen atom, a sulfur atom or a nitrogen atom is bonded introduced thereto is bonded to a diketopyrrolopyrrole skeleton can also be used. Such a compound is preferably a compound represented by formula (DPP1), and more preferably a compound represented by formula (DPP2).

Chemical formula

[0045] In the above formula, R 11 and R 13 each independently represent a substituent, R 12 and R 14 each independently represent 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, X 12 and X 14 each independently represent an oxygen atom, a sulfur atom or a nitrogen atom, when X 12 is an oxygen atom or a sulfur atom, m12 represents 1, when X 12 is a nitrogen atom, m12 represents 2, when X 14 is an oxygen atom or a sulfur atom, m14 represents 1, when X 14 is a nitrogen atom, m14 represents 2. R 11 and R 13Examples of the substituent represented by [are preferably 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, a sulfo group, etc.

[0046] Regarding the diffraction angles that various pigments preferably have, reference can be made to the descriptions in Japanese Patent No. 6561862, Japanese Patent No. 6413872, and Japanese Patent No. 6281345, and the contents thereof are incorporated herein.

[0047] Examples of the colored dyes include pyrazole azo compounds, anilino azo compounds, triarylmethane compounds, anthraquinone compounds, anthrapyridone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, xanthene compounds, phthalocyanine compounds, benzopyran compounds, indigo compounds, and pyromethene compounds. Further, the methine dyes described in JP-A-2019-073695, the methine dyes described in JP-A-2019-073696, the methine dyes described in JP-A-2019-073697, and the methine dyes described in JP-A-2019-073698 can also be used.

[0048] Two or more colored colorants may be used in combination. Further, when two or more colored colorants are used in combination, black may be formed by a combination of two or more colored colorants. Examples of such combinations include the following modes (1) to (7). When two or more colored colorants are contained in the resin composition and black is exhibited by a combination of two or more colored colorants, the resin composition of the present invention can be preferably used as a resin composition for forming a near-infrared transmission filter. (1) A mode containing a red colorant and a blue colorant. (2) A mode containing a red colorant, a blue colorant, and a yellow colorant. (3) A mode containing a red colorant, a blue colorant, a yellow colorant, and a purple colorant. (4) A mode containing a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant. (5) A mode containing a red colorant, a blue colorant, a yellow colorant, and a green colorant. (6) A mode containing a red colorant, a blue colorant, and a green colorant. (7) A mode containing a yellow colorant and a purple colorant.

[0049] (White colorant) Examples of the white colorant include inorganic pigments (white pigments) such as titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, and zinc sulfide. The white pigment preferably has particles having titanium atoms, and more preferably titanium oxide. Further, the white pigment preferably has particles with a refractive index of 2.10 or more with respect to light having a wavelength of 589 nm. The aforementioned refractive index is preferably 2.10 to 3.00, and more preferably 2.50 to 2.75.

[0050] Also, as the white pigment, titanium oxide described in "Physical Properties and Application Technology of Titanium Oxide, written by Manabu Kiyono, pages 13 - 45, published on June 25, 1991, published by Gihodo Publishing Co., Ltd." can also be used.

[0051] The white pigment may be not only composed of a single inorganic substance, but also particles combined with other materials may be used. For example, it is preferable to use particles having pores or other materials inside, particles with a large number of inorganic particles attached to the core particles, or core and shell composite particles composed of core particles made of polymer particles and shell layers made of inorganic nanoparticles. As the core and shell composite particles composed of core particles made of the above polymer particles and shell layers made of inorganic nanoparticles, for example, the descriptions in paragraphs 0012 - 0042 of JP-A 2015 - 047520 can be referred to, and this content is incorporated herein.

[0052] As the white pigment, hollow inorganic particles can also be used. The hollow inorganic particles refer to inorganic particles having a structure with a cavity inside, that is, inorganic particles having a cavity surrounded by an outer shell. Examples of the hollow inorganic particles include those described in JP-A-2011-075786, WO 2013 / 061621, JP-A-2015-164881, etc., and the contents thereof are incorporated herein.

[0053] (Black colorant) The black colorant is not particularly limited, and known ones can be used. For example, as the inorganic black colorant, inorganic pigments (black pigments) such as carbon black, titanium black, and graphite can be mentioned. Carbon black and titanium black are preferred, and titanium black is more preferred. Titanium black is black particles containing titanium atoms, and lower-order titanium oxides and titanium oxynitrides are preferred. Titanium black can be surface-modified as necessary for purposes such as improving dispersibility and suppressing aggregation. For example, it is possible to coat the surface of titanium black with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Also, treatment with a water-repellent substance as disclosed in JP-A-2007-302836 is possible. Examples of the black pigment include Color Index (C.I.) Pigment Black 1, 7, etc. Titanium black preferably has a small primary particle diameter and an average primary particle diameter for each individual particle. Specifically, the average primary particle diameter is preferably 10 to 45 nm. Titanium black can also be used as a dispersion. For example, a dispersion containing titanium black particles and silica particles and having the content ratio of Si atoms to Ti atoms in the dispersion adjusted to the range of 0.20 to 0.50 can be mentioned. Regarding the above dispersion, reference can be made to the description in paragraphs 0020 to 0105 of JP-A-2012-169556, and the contents thereof are incorporated herein. Examples of commercially available products of titanium black include Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilack D (trade name: manufactured by Akaho Kasei Co., Ltd.), etc.

[0054] Examples of the organic black colorant include bisbenzofuranone compounds, azomethine compounds, perylene compounds, azo compounds, etc. Examples of the bisbenzofuranone compounds include the compounds described in JP-T-2010-534726, JP-T-2012-515233, JP-T-2012-515234, etc., and are available, for example, as "Irgaphor Black" manufactured by BASF. Examples of the perylene compounds include the compounds described in paragraphs Nos. 0016 to 0020 of JP-A-2017-226821, C.I. Pigment Black 31, 32, etc. Examples of the azomethine compounds include the compounds described in JP-A-01-170601, JP-A-02-034664, etc., and are available, for example, as "Chromophine Black A1103" manufactured by Dainichi Seika Chemicals Co., Ltd.

[0055] The colorant used in the resin composition of the present invention may be only the above-described black colorant, or may further contain a colored colorant. According to this aspect, a resin composition capable of forming a film excellent in light-shielding property in the visible region can be easily obtained. When a black colorant and a colored colorant are used in combination as the colorant, the mass ratio of the two is preferably black colorant:colored colorant = 100:10 to 300, more preferably 100:20 to 200. Further, it is preferable to use a black pigment as the black colorant, and it is preferable to use a colored pigment as the colored colorant.

[0056] Preferable combinations of the black colorant and the colored colorant include, for example, the following. (A-1) An embodiment containing an organic black colorant and a blue colorant. (A-2) An embodiment containing an organic black colorant, a blue colorant, and a yellow colorant. (A-3) An embodiment containing an organic black colorant, a blue colorant, a yellow colorant, and a red colorant. (A-4) An embodiment containing an organic black colorant, a blue colorant, a yellow colorant, and a purple colorant.

[0057] In the aspect of (A-1) above, the mass ratio of the organic black colorant to the blue colorant is preferably from 100:1 to 70, more preferably from 100:5 to 60, and even more preferably from 100:10 to 50, in terms of organic black colorant:blue colorant. In the aspect of (A-2) above, the mass ratio of the organic black colorant, the blue colorant, and the yellow colorant is preferably from 100:10 to 90:10 to 90, more preferably from 100:15 to 85:15 to 80, and even more preferably from 100:20 to 80:20 to 70, in terms of organic black colorant:blue colorant:yellow colorant. In the aspect of (A-3) above, the mass ratio of the organic black colorant, the blue colorant, the yellow colorant, and the red colorant is preferably from 100:20 to 150:1 to 60:10 to 100, more preferably from 100:30 to 130:5 to 50:20 to 90, and even more preferably from 100:40 to 120:10 to 40:30 to 80, in terms of organic black colorant:blue colorant:yellow colorant:red colorant. In the aspect of (A-4) above, the mass ratio of the organic black colorant, the blue colorant, the yellow colorant, and the purple colorant is preferably from 100:20 to 150:1 to 60:10 to 100, more preferably from 100:30 to 130:5 to 50:20 to 90, and even more preferably from 100:40 to 120:10 to 40:30 to 80, in terms of organic black colorant:blue colorant:yellow colorant:purple colorant.

[0058] (Near-infrared absorbing colorant) The near-infrared absorbing colorant is preferably a pigment, and more preferably an organic pigment. Further, the near-infrared absorbing colorant preferably has a maximum absorption wavelength in the range exceeding 700 nm and not exceeding 1400 nm. Also, the maximum absorption wavelength of the near-infrared absorbing colorant is preferably not exceeding 1200 nm, more preferably not exceeding 1000 nm, and even more preferably not exceeding 950 nm. Also, the near-infrared absorbing colorant has an absorbance A at a wavelength of 550 nm 550 and an absorbance A at the maximum absorption wavelength max and the ratio of A 550 / A maxIt is preferably 0.1 or less, more preferably 0.05 or less, still more preferably 0.03 or less, and particularly preferably 0.02 or less. The lower limit is not particularly limited, and for example, it can be 0.0001 or more, or can be 0.0005 or more. If the ratio of the absorbance is within the above range, a near-infrared absorbing colorant excellent in visible light transparency and near-infrared ray shielding property can be obtained. In the present invention, the maximum absorption wavelength and the absorbance value at each wavelength of the near-infrared absorbing colorant are values obtained from the absorption spectrum of a film formed using a resin composition containing the near-infrared absorbing colorant.

[0059] The near-infrared absorbing colorant is not particularly limited, and examples thereof include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, and the like. Examples of the pyrrolopyrrole compound include the compounds described in paragraph numbers 0016 to 0058 of JP-A No. 2009-263614, the compounds described in paragraph numbers 0037 to 0052 of JP-A No. 2011-068731, and the compounds described in paragraph numbers 0010 to 0033 of International Publication No. 2015 / 166873. Examples of the squarylium compound include the compounds described in paragraph numbers 0044 to 0049 of JP-A No. 2011-208101, the compounds described in paragraph numbers 0060 to 0061 of Patent No. 6065169, the compound described in paragraph number 0040 of International Publication No. 2016 / 181987, the compounds described in JP-A No. 2015-176046, the compound described in paragraph number 0072 of International Publication No. 2016 / 190162, the compounds described in paragraph numbers 0196 to 0228 of JP-A No. 2016-074649, the compound described in paragraph number 0124 of JP-A No. 2017-067963, the compounds described in International Publication No. 2017 / 135359, the compounds described in JP-A No. 2017-114956, the compounds described in Patent No. 6197940, and the compounds described in International Publication No. 2016 / 120166. Examples of the cyanine compound include the compounds described in paragraph numbers 0044 to 0045 of JP-A No. 2009-108267, the compounds described in paragraph numbers 0026 to 0030 of JP-A No. 2002-194040, the compounds described in JP-A No. 2015-172004, the compounds described in JP-A No. 2015-172102, the compounds described in JP-A No. 2008-088426, the compound described in paragraph number 0090 of International Publication No. 2016 / 190162, and the compounds described in JP-A No. 2017-031394. Examples of the croconium compound include the compounds described in JP-A No. 2017-082029.Examples of the iminium compound include the compounds described in JP-T-2008-528706, the compounds described in JP-A-2012-012399, the compounds described in JP-A-2007-092060, and the compounds described in paragraphs 0048 to 0063 of WO 2018 / 043564. Examples of the phthalocyanine compound include the compound described in paragraph 0093 of JP-A-2012-077153, oxytitanium phthalocyanine described in JP-A-2006-343631, the compounds described in paragraphs 0013 to 0029 of JP-A-2013-195480, vanadium phthalocyanine compounds described in JP-B-6081771, and the compounds described in WO 2020 / 071470. Examples of the naphthalocyanine compound include the compound described in paragraph 0093 of JP-A-2012-077153. Examples of the dithiolene metal complex include the compounds described in JP-B-5733804.

[0060] As the near-infrared absorbing colorant, a squarylium compound described in JP-A No. 2017-197437, a squarylium compound described in JP-A No. 2017-025311, a squarylium compound described in International Publication No. 2016 / 154782, a squarylium compound described in Patent No. 5884953, a squarylium compound described in Patent No. 6036689, a squarylium compound described in Patent No. 5810604, a squarylium compound described in paragraphs 0090 to 0107 of International Publication No. 2017 / 213047, a pyrrole ring-containing compound described in paragraphs 0019 to 0075 of JP-A No. 2018-054760, a pyrrole ring-containing compound described in paragraphs 0078 to 0082 of JP-A No. 2018-040955, a pyrrole ring-containing compound described in paragraphs 0043 to 0069 of JP-A No. 2018-002773, a squarylium compound having an aromatic ring at the α-position of an amide described in paragraphs 0024 to 0086 of JP-A No. 2018-041047, an amide-linked squarylium compound described in JP-A No. 2017-179131, a compound having a pyrrole bis-type squarylium skeleton or a croconium skeleton described in JP-A No. 2017-141215, a dihydrocarbazole bis-type squarylium compound described in JP-A No. 2017-082029, an asymmetric compound described in paragraphs 0027 to 0114 of JP-A No. 2017-068120, a pyrrole ring-containing compound (carbazole type) described in JP-A No. 2017-067963, a phthalocyanine compound described in Patent No. 6251530, JP-A No. 2013-077009, JP-A No. 2014-130338, a colorant described in International Publication No. 2015 / 166779, or a combination of colorants described in these documents can also be used.

[0061] The content of the colorant in the total solid content of the resin composition is preferably from 20 to 90% by mass. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less. In addition, the content of the pigment in the total solid of the resin composition is preferably 20 to 90% by mass. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less. In addition, the content of the dye in the coloring material is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less. In addition, it is also preferable that the resin composition of the present invention substantially does not contain a dye because it is easier to more effectively suppress the film thickness change when the obtained film is heated to a high temperature. When the resin composition of the present invention substantially does not contain a dye, the content of the dye in the total solid of the 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 not contained.

[0062] <Resin B> (Specific resin (resin b-1)) The resin composition of the present invention contains resin B (hereinafter also referred to as resin). The resin contained in the resin composition contains resin b-1 (hereinafter also referred to as specific resin) having a structure represented by formula (1). The specific resin is also a resin of the present invention. [Chemical formula] In formula (1), X 1 represents a tetravalent linking group, X 2 represents a divalent linking group, R 11 R 12 R 21 R 22 and R 23 each independently represents a hydrogen atom or a substituent, Lp 1 represents an n + 1-valent linking group, Lp 2 represents a divalent linking group, P 1 represents a polymer chain, n represents an integer of 1 or more.

[0063] [n] In formula (1), n represents an integer of 1 or more, preferably an integer of 1 to 4, more preferably 1 or 2, and still more preferably 1.

[0064] [X 1 In formula (1), X 1 The tetravalent linking group represented by is preferably a group containing a hydrocarbon group. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched, or cyclic. Further, the cyclic aliphatic hydrocarbon group may be a monocyclic or a condensed ring. Further, the cyclic aliphatic hydrocarbon group may have a crosslinked structure. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include the substituent T described later.

[0065] Examples of the group containing the above hydrocarbon group include a hydrocarbon group and a group in which two or more hydrocarbon groups are bonded by a single bond or a linking group.

[0066] Examples of the linking group for linking two or more of the above hydrocarbon groups include -NR X1 -, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NR X1 CO-, -CONR X1 - and -C(CF3)2-. R X1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom.

[0067] X 1 The tetravalent linking group represented by is preferably a group containing an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring, and more preferably a group containing an aromatic hydrocarbon ring. Further, X 1 ​The tetravalent linking group represented by is preferably a group containing a fluorine atom or a sulfonyl group (-SO2-) because it can improve the solubility of the specific resin in a solvent. Among them, X 1 The tetravalent linking group represented by is preferably a group containing a fluorine atom and an aromatic hydrocarbon ring because it has excellent solubility in a solvent of the specific resin and can form a film with excellent heat resistance. The group containing a fluorine atom and an aromatic hydrocarbon ring is preferably a group in which two or more aromatic hydrocarbon groups are bonded by a linking group, and the linking group is a linking group containing a fluorine atom, or a group in which two or more aromatic hydrocarbon groups are bonded by a single bond or a linking group, and the aromatic hydrocarbon group is a group substituted with a group containing a fluorine atom. Examples of the linking group containing a fluorine atom include -C(CF3)2-. The group containing a fluorine atom is preferably an alkyl fluoride group, and more preferably a trifluoromethyl group.

[0068] Also, X 1 The tetravalent linking group represented by is also preferably a group represented by any one of (D-1) to formula (D-3).

[0069]

Chemical formula

[0070] The aliphatic hydrocarbon ring represented by Cy in formula (D-1) to formula (D-3) may be a monocyclic ring or a condensed ring. Further, the aliphatic hydrocarbon ring may have a crosslinked structure. The aliphatic hydrocarbon ring represented by Cy is preferably a monocyclic aliphatic hydrocarbon ring or an aliphatic hydrocarbon ring having a crosslinked structure.

[0071] In formula (D-1), * 1 and * 2 , *3 and * 4 preferably exists at adjacent positions in the aliphatic hydrocarbon ring Cy.

[0072] R of formula (D-2) d1 represents a linear or branched aliphatic hydrocarbon group, preferably a linear or branched aliphatic saturated hydrocarbon group. The number of carbon atoms of the above aliphatic hydrocarbon group is preferably 2 to 10, more preferably 2 to 4, and still more preferably 2. In formula (D-2), * 3 and * 4 preferably exist one by one at adjacent carbon atoms in the aliphatic hydrocarbon group R d1 . In formula (D-2), * 3 and * 4 preferably exist at adjacent positions in the aliphatic hydrocarbon ring Cy.

[0073] In formula (D-3), X d1 represents a single bond or a divalent linking group, preferably a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(=O)2-, -NHC(=O)-, or a group formed by combining two or more of these. More preferably, it is a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -S(=O)2-. Still more preferably, it is -CH2-, -O-, -S-, -S(=O)2-, -C(CF3)2-, or -C(CH3)2-.

[0074] Also, the tetravalent linking group represented by X 1 is preferably a group represented by formula (E-1).

[0075]

Chemical formula

[0076] X 1 Specific examples of the tetravalent linking group represented by include groups having a structure represented by any of formulas (I-1) to (I-28).

Chemical formula

[0077] X 1 to X 3 Examples of the divalent linking group represented by include -C(Rx)2- (Rx represents a hydrogen atom or a substituent. When Rx is a substituent, they may combine with each other to form a ring), -O-, -SO2-, -CO-, -S-, -NR N -, a phenylene group, or a combination thereof. When Rx represents a substituent, specific examples thereof include an alkyl group which may be substituted with a fluorine atom. R Nrepresents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. X 1 ~X 3 each independently preferably represents a single bond, -SO2- or -C(Rx)2-, more preferably -SO2- or -C(Rx)2-, still more preferably -C(Rx)2-. Further, -C(Rx)2- preferably represents -C(CH3)2- or -C(CF3)2-, more preferably -C(CF3)2-.

[0078] L is preferably -CH=CH-.

[0079] R 1 and R 2 each independently is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom, a methyl group or an ethyl group, still more preferably a hydrogen atom.

[0080] [X 2 In formula (1), X 2 represents a divalent linking group. Examples of the divalent linking group represented by X 2 include a hydrocarbon group and a group formed by bonding two or more hydrocarbon groups with a single bond or a linking group. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched or cyclic. Further, the cyclic aliphatic hydrocarbon group may be a monocyclic group or a condensed ring group. Additionally, the cyclic aliphatic hydrocarbon group may have a crosslinked structure. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, still more preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include the substituent T described below. ​Examples of the linking group that links two or more of the above hydrocarbon groups include -O-, -S-, -C(CH3)2-, -C(CF3)2-, -CO-, -SO2-, -SiR2- (each R independently represents a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group), a polysiloxane group (-Si(R)-(O-Si) n -, R represents a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group. n represents an integer of 1 or more, preferably 1 to 10), and the like.

[0081] X 2 The divalent linking group represented by is preferably a group containing an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring, and more preferably a group containing an aromatic hydrocarbon ring. Also, X 2 The divalent linking group represented by is preferably a group containing a fluorine atom or a sulfonyl group (-SO2-) because it can improve the solubility of the specific resin in a solvent. Among them, X 2 The divalent linking group represented by is preferably a group containing a fluorine atom and an aromatic hydrocarbon ring because it has excellent solubility in a solvent of the specific resin and can form a film with excellent heat resistance. Examples of the group containing a fluorine atom and an aromatic hydrocarbon ring include a group in which two or more aromatic hydrocarbon groups are bonded by a linking group, a group in which the linking group contains a fluorine atom, or a group in which two or more aromatic hydrocarbon groups are bonded by a single bond or a linking group and the aromatic hydrocarbon group is substituted with a group containing a fluorine atom. Examples of the linking group containing a fluorine atom include -C(CF3)2-. Examples of the group containing a fluorine atom include a fluorinated alkyl group, and a trifluoromethyl group is more preferable. X 2 When the divalent linking group represented by contains a fluorine atom and an aromatic hydrocarbon ring, for example, a group having the following structure is preferable.

Chemical formula

[0082] X 2The divalent linking group represented by is preferably a group having a structure derived from a diamine compound. Examples of the diamine compound include the following compounds.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0083] [R 11 、R 12 、R 21 、R 22 and R 23 In formula (1), R 11 、R 12 、R 21 、R 22 and R 23 each independently represent a hydrogen atom or a substituent.

[0084] ​Examples of the substituent include an alkyl group, an aryl group, and a heterocyclic group. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 15, still more preferably 1 to 8, even more preferably 1 to 5, and particularly preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, with linear or branched being preferred and linear being more preferred. The number of carbon atoms of the aryl group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12. The heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. Examples of the type of heteroatom constituting the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom. The number of heteroatoms constituting the heterocyclic group is preferably 1 to 3. The heterocyclic group may be a monocyclic ring or a condensed ring. The above-described alkyl group, aryl group, and heterocyclic group may or may not have a substituent, and may be unsubstituted. Examples of the substituent include a substituent T described later, an ethylenically unsaturated bond-containing group, an epoxy group, an oxetanyl group, and a blocked isocyanate group.

[0085] In formula (1), R 11 and R 12 are preferably hydrogen atoms. Also, R 21 , R 22 and R 23 are preferably hydrogen atoms. Also, a part of them may form a carboxylate or an amine salt.

[0086] [Lp 1 In formula (1), Lp 1 represents an (n + 1)-valent linking group. Examples of the (n + 1)-valent linking group include a hydrocarbon group, -NRp-, -N<, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NRpCO-, -CONRp-, and a group formed by combining two or more of these. Rp represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and is preferably a hydrogen atom.

[0087] Examples of the (n + 1)-valent linking group include a group represented by formula (Lp-1) and a group represented by formula (Lp-2).​ [Chemical formula] In formula (Lp-1), Rp 1 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and Lp 1a represents a hydrocarbon group or a group in which two or more hydrocarbon groups are bonded by a single bond or a linking group. In formula (Lp-2), Lp 1b represents a hydrocarbon group or a group in which two or more hydrocarbon groups are bonded by a single bond or a linking group. In formulas (Lp-1) and (Lp-2), n represents an integer of 1 or more, *1 represents a bonding site with the carbonyl carbon in -NR 23 CO- in formula (1), and *2 represents a bonding site with Lp 2 in formula (1).

[0088] Rp 1 For the details of the alkyl group, aryl group, and heterocyclic group represented by, see R 11 , R 12 , R 21 , R 22 , and R 23 The groups described in the terms of and are exemplified.

[0089] Lp 1a and Lp 1b Examples of the hydrocarbon group represented by include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched, or cyclic. Further, the cyclic aliphatic hydrocarbon group may be a monocyclic ring or a condensed ring. Further, the cyclic aliphatic hydrocarbon group may have a crosslinked structure. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include the substituent T described later.

[0090] Examples of the linking group for linking two or more hydrocarbon groups include -NRp 1b-, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NRp 1b CO-, -CONRp 1b - can be mentioned. Rp 1b represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom.

[0091] Lp 1 The n + 1-valent linking group represented by Lp is preferably a group represented by formula (Lp-10), and more preferably a group represented by formula (Lp-11).

Chemical formula

[0092] As the n + 1-valent linking group represented by Lp in formula (Lp-10), there can be mentioned a hydrocarbon group, -NRp 11 -, -N<, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NRp 12 CO-, -CONRp 12 - and groups formed by combining two or more of these. Examples of the hydrocarbon group include those described above. Rp 12 - and groups formed by combining two or more of these. Examples of the hydrocarbon group include those described above. Rp12 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom.

[0093] Lp in formula (Lp-11) 12 The n+valent linking group represented by is preferably a hydrocarbon group, or a group in which two or more hydrocarbon groups are bonded by a single bond or a linking group. As the linking group for linking two or more hydrocarbon groups, -NRp 13 -, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NRp 13 CO- and -CONRp 13 - etc. are mentioned. Rp 13 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom.

[0094] Rp in formula (Lp-10) and formula (Lp-11) 11 Examples of the substituent represented by include the substituent T described later, and it is preferably a carboxy group, a halogen atom or a hydroxy group, and more preferably a carboxy group. n in formula (Lp-10) and formula (Lp-11) represents an integer of 1 or more, preferably an integer of 1 to 4, more preferably 1 or 2, and still more preferably 1. m in formula (Lp-10) and formula (Lp-11) represents an integer of 0 to 4, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and still more preferably 1 or 2. Also, among m Rp 11 at least one or more are preferably carboxy groups.

[0095] [Lp 2 In formula (1), Lp 2 represents a divalent linking group. Examples of the divalent linking group include a hydrocarbon group, -NRp 21 -, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NRp 21 CO-, -CONRp 21 ​- and groups formed by combining two or more of these. Rp 21 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom. The hydrocarbon group includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched or cyclic. The cyclic aliphatic hydrocarbon group may be monocyclic or condensed. The cyclic aliphatic hydrocarbon group may have a cross-linked structure. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group. The divalent linking group is preferably a group containing an oxygen atom or a sulfur atom, more preferably a group containing a sulfur atom, and still more preferably a group containing -S-.

[0096] Lp 2 The divalent linking group represented by is preferably -S- or -O-, more preferably -S-.

[0097] [P 1 In formula (1), P 1 represents a polymer chain. P 1 The weight average molecular weight of is preferably 500 to 50,000. The lower limit is preferably 800 or more, more preferably 1000 or more. The upper limit is preferably 20,000 or less, more preferably 10,000 or less. When the weight average molecular weight of the polymer chain is within the above range, better pigment dispersibility can be easily obtained. The weight average molecular weight of the polymer chain can be measured by GPC (gel permeation chromatography). More specifically, it can be calculated from the weight average molecular weight of the raw material monomer used for the introduction of the polymer chain.

[0098] P 1 ​The polymer chain represented by preferably contains a repeating unit of at least one structure selected from a poly(meth)acrylic structure, a polystyrene structure, a polyether structure, and a polyester structure, more preferably contains a repeating unit of at least one structure selected from a poly(meth)acrylic structure and a polystyrene structure, and even more preferably contains a repeating unit of a poly(meth)acrylic structure from the viewpoints of pigment dispersibility and heat resistance. P 1 It is also preferable that the polymer chain represented by contains a repeating unit of a polyether structure or a repeating unit of a polyester structure. P 1 When the polymer chain represented by contains a repeating unit of a polyether structure, the number of repeating units of the polyether structure is preferably 9 or more. P 1 When the polymer chain represented by contains a repeating unit of a polyester structure, the number of repeating units of the polyester structure is preferably 5 or more.

[0099] P 1 The polymer chain represented by may have a crosslinkable group. Examples of the crosslinkable group include ethylenically unsaturated bond-containing groups such as vinyl group, (meth)allyl group, and (meth)acryloyl group, cyclic ether groups such as epoxy group and oxetane group, and blocked isocyanate group. In the present specification, the blocked isocyanate group is a group capable of generating an isocyanate group by heat, and for example, a group obtained by reacting a blocking agent with an isocyanate group to protect the isocyanate group can be preferably exemplified. Examples of the blocking agent include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole-based compounds, imide-based compounds, etc. Regarding the blocking agent, the compounds described in paragraph numbers 0115 to 0117 of JP-A-2017-067930 can be mentioned, and this content is incorporated herein. Further, the blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 to 260°C.

[0100] P 1The polymer chain represented by also preferably has a tertiary alkyl group. Examples of the tertiary alkyl group include a t-butyl group.

[0101] P 1 The polymer chain represented by preferably contains a repeating unit represented by any one of Formula (P1-1) to Formula (P1-6), more preferably contains a repeating unit represented by Formula (P1-5) or Formula (P1-6), and even more preferably contains a repeating unit represented by Formula (P1-5). Also, P 1 The polymer chain represented by preferably contains a repeating unit represented by any one of Formula (P1-1) to Formula (P1-4). P 1 When the polymer chain represented by contains the repeating unit of Formula (P1-4), the number of repeating units of Formula (P1-4) is preferably 9 or more. P 1 When the polymer chain represented by contains the repeating units of Formula (P1-1) to Formula (P1-3), the number of repeating units of these structures is preferably 5 or more.

Chemical Formula

[0102] In the above formula, R G1 and R G2 each represent an alkylene group. R G1 and R G2 The alkylene group represented by is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a linear or branched alkylene group having 2 to 16 carbon atoms, and even more preferably a linear or branched alkylene group having 3 to 12 carbon atoms.

[0103] In the above formula, R G3 represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, or a hydroxymethyl group, and is preferably a hydrogen atom or a methyl group.

[0104] In the above formula, Q G1 represents -O- or -NR q -, and R qrepresents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Q G1 is preferably -O-. R q The number of carbon atoms of the alkyl group represented by is preferably 1 to 30, more preferably 1 to 15, still more preferably 1 to 8, even more preferably 1 to 5, and particularly preferably 1 to 3. The alkyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. R q The number of carbon atoms of the aryl group represented by is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12. R q The heterocyclic group represented by may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. Examples of the type of heteroatom constituting the heterocyclic group include a nitrogen atom, an oxygen atom, a sulfur atom, etc. The number of heteroatoms constituting the heterocyclic group is preferably 1 to 3. The heterocyclic group may be a monocyclic ring or a condensed ring. The above-mentioned alkyl group, aryl group and heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include the substituent T described later.

[0105] In the above formula, L G1 represents a single bond or an arylene group, and is preferably a single bond.

[0106] In the above formula, L G2 represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NR LG1 -, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NR LG1 CO-, -CONR LG1 -, and groups formed by combining two or more of these, and a group containing an alkylene group or an arylene group is preferred. R LG1represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and is preferably a hydrogen atom. The above-mentioned alkylene group and arylene group may or may not have a substituent. Examples of the substituent include the substituent T described later.

[0107] In the above formula, R G4 represents a hydrogen atom or a substituent. Examples of the substituent include a hydroxy group, a carboxy group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkyl thioether group, an aryl thioether group, a heterocyclic thioether group, an ethylenically unsaturated bond-containing group, an epoxy group, an oxetanyl group, and a blocked isocyanate group. R G4 is preferably at least one selected from an alkyl group, an aryl group, an ethylenically unsaturated bond-containing group, an epoxy group, and an oxetanyl group, and more preferably at least one selected from an ethylenically unsaturated bond-containing group, an epoxy group, an oxetanyl group, and a t-butyl group.

[0108] In the above formula, R G5 represents a hydrogen atom or a methyl group, and R G6 represents an aryl group. The number of carbon atoms of the aryl group represented by R G6 is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12. The aryl group represented by R G6 may have a substituent. Examples of the substituent include a hydroxy group, a carboxy group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkyl thioether group, an aryl thioether group, a heterocyclic thioether group, an ethylenically unsaturated bond-containing group, an epoxy group, an oxetanyl group, and a blocked isocyanate group.

[0109] P 1 The polymer chain represented by may contain two or more repeating units.

[0110] (Substituent T) An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), an alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), an aryl group (preferably an aryl group having 6 to 30 carbon atoms), an amino group (preferably an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably an aryloxy group having 6 to 30 carbon atoms), a heteroaryloxy group (preferably a heteroaryloxy group having 1 to 30 carbon atoms), an acyl group (preferably an acyl group having 2 to 30 carbon atoms), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms), an acyloxy group (preferably an acyloxy group having 2 to 30 carbon atoms), an acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms), a sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms), a carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms), an alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms), an arylthio group (preferably an arylthio group having 6 to 30 carbon atoms), a heteroarylthio group (preferably a heteroarylthio group having 1 to 30 carbon atoms), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 30 carbon atoms), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 30 carbon atoms), a heteroarylsulfonyl group (preferably a heteroarylsulfonyl group having 1 to 30 carbon atoms), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 30 carbon atoms), an arylsulfinyl group (preferably an arylsulfinyl group having 6 to 30 carbon atoms), a heteroarylsulfinyl group (preferably a heteroarylsulfinyl group having 1 to 30 carbon atoms), a ureido group (preferably a ureido group having 1 to 30 carbon atoms), a phosphoric acid amide group (preferably a phosphoric acid amide group having 1 to 30 carbon atoms), a hydroxy group, a mercapto group, a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a cyano group, a sulfo group, a carboxy group,Nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group. When these groups are further substitutable groups, they may further have substituents. Examples of the further substituents include the groups described for the substituent T above.

[0111] In a specific resin, the structure represented by the above formula (1) is preferably the structure represented by formula (1-1).

Chemical formula

[0112] X in formula (1-1) 1 , X 2 , R 11 , R 12 , R 21 , R 22 , R 23 , Lp 2 , P 1 and n are X in formula (1) 1 , X 2 , R 11 , R 12 , R 21 , R 22 , R 23 , Lp 2, P 1 is synonymous with n.

[0113] Lp in formula (1-1) 11 , Rp 11 and m are the Lp in formula (Lp-10) 11 , Rp 11 and m are synonymous.

[0114] The specific resin may contain an imide ring structure of the structure represented by the above formula (1).

[0115] The special resin may further contain a structure represented by formula (100). According to this aspect, better dispersibility can be obtained.

Chemical formula

[0116] R in formula (100) 111 , R 112 , R 121 , R 122 and P 101 are synonymous with R in formula (1) 11 , R 12 , R 21 , R 22 and P 1 and are synonymous.

[0117] In formula (100), q represents an integer of 1 or more, preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0118] X in equation (100) 102 The divalent linking group represented by is X in formula (1). 2 The preferred ranges are the same as those described above.

[0119] In formula (100), X 101 The 4+q-valent linking group represented by is preferably a group containing a hydrocarbon group. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The aliphatic hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The cyclic aliphatic hydrocarbon group may be a monocyclic or condensed ring. The cyclic aliphatic hydrocarbon group may have a crosslinked structure. The aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 20, and even more preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include the substituent T described above.

[0120] Examples of the group containing a hydrocarbon group include a hydrocarbon group and a group in which two or more hydrocarbon groups are linked together via a single bond or a linking group.

[0121] The linking group that links two or more hydrocarbon groups is -NRx 101 -, -N<, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NRx 101 CO-, -CONRx 101 - and -C(CF3)2-. Rx 101 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and is preferably a hydrogen atom. 101 The carbon atom of Lp 101 It is preferable that X 101 The nitrogen atom of Lp 101 It is also preferred that the compound is bonded to

[0122] X 101As the 4+q-valent linking group represented by [it], a group containing an aromatic hydrocarbon ring is preferred because it has a strong affinity for the pigment and is less likely to cause foreign substances. Examples of the group containing an aromatic hydrocarbon ring include the group represented by formula (X-1). [Chemical formula] In formula (X-1), *1 represents the bonding hand with P of formula (100) 101 and *2 represents the bonding hand with -CO- bonded to X of formula (100) 101 Rx 1 and Rx 2 each independently represent a substituent, m1 represents an integer from 0 to 3, m2 represents an integer from 0 to 3, n represents an integer of 1 or more, and X 100 represents a 2+n-valent linking group.

[0123] X 100 Examples of the 2+n-valent linking group represented by [it] include a hydrocarbon group, -NRx 101 -, -N<, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NRx 101 CO-, -CONRx 101 -, -C(CF3)2- and groups formed by combining two or more of these. Examples of the hydrocarbon group include those described above. Rx 101 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom.

[0124] Rx 1 and Rx 2 Examples of the substituent represented by [it] include the above-described substituent T. Specific examples include a halogen atom, an alkyl group, a carboxy group, etc.

[0125] m1 and m2 are each independently preferably an integer from 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0126] In formula (100), Lp 101 represents a divalent linking group. Examples of the divalent linking group include a hydrocarbon group, -NRL1 -, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NR L1 CO-, -CONR L1 -, and groups formed by combining two or more of these. R L1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom. The hydrocarbon group includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched or cyclic. Also, the cyclic aliphatic hydrocarbon group may be a monocyclic or a condensed ring. Further, the cyclic aliphatic hydrocarbon group may have a cross-linked structure. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10. The hydrocarbon group may have a substituent. The divalent linking group is preferably a group containing an oxygen atom or a sulfur atom, more preferably a group containing a sulfur atom, and still more preferably a group containing -S-.

[0127] Lp 101 The divalent linking group represented by Lp is preferably a group represented by formula (Lp-101) or formula (Lp-201), and more preferably a group represented by formula (Lp-101).

Chemical formula

[0128] Lp 111 Examples of the divalent linking group represented by Lp include a hydrocarbon group and a group having a structure in which two or more hydrocarbon groups are bonded by a single bond or a linking group. Examples of the linking group include -NR L1 -, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NR L1CO- and -CONR L1 - etc. R L1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably a hydrogen atom.

[0129] The specific resin may contain an imide ring structure represented by the above formula (100).

[0130] The acid value of the specific resin is preferably 10 to 150 mgKOH / g. The upper limit is preferably 100 mgKOH / g or less, more preferably 80 mgKOH / g or less. The lower limit is preferably 20 mgKOH / g or more, more preferably 30 mgKOH / g or more.

[0131] The weight average molecular weight (Mw) of the specific resin is preferably 2,000 to 200,000, more preferably 2,500 to 100,000, and still more preferably 3,000 to 50,000.

[0132] The 5% mass loss temperature of the specific resin by TG / DTA (thermogravimetry / differential thermal analysis) under a nitrogen atmosphere is preferably 280°C or higher, more preferably 300°C or higher, and still more preferably 320°C or higher. The upper limit of the above 5% mass loss temperature is not particularly limited, and may be, for example, 1,000°C or lower. The above 5% mass loss temperature is determined by a known TG / DTA measurement method as the temperature at which the mass loss rate becomes 5% when left standing at a specific temperature for 5 hours under a nitrogen atmosphere. Also, the mass loss rate of the specific resin when left standing at 300°C for 5 hours under a nitrogen atmosphere is preferably 10% or less, more preferably 5% or less, and still more preferably 2% or less. The lower limit of the above mass loss rate is not particularly limited, and may be 0% or more. The above mass loss rate is a value calculated as the ratio of the mass reduction of the specific resin before and after leaving it standing at 300°C for 5 hours under a nitrogen atmosphere.

[0133] A specific resin can be synthesized, for example, by reacting an acid dianhydride with a diamine compound to synthesize a polyamic acid, and then reacting a terminal blocking agent (terminal blocking agent macromonomer) having a group that reacts with the terminal amine site of the polyamic acid and a polymer chain, respectively. If necessary, a terminal blocking agent other than the terminal blocking agent macromonomer (other terminal blocking agent) may be further used. Examples of the other terminal blocking agent include monoamine, acid anhydride, monocarboxylic acid, monocarboxylic acid chloride, monocarboxylic acid halide compound, or monocarboxylic acid active ester.

[0134] The molar ratio of the acid dianhydride to the diamine compound is preferably 0.5 to 1.5 moles of the acid dianhydride per 1 mole of the diamine compound, more preferably 0.7 to 1.3 moles, and still more preferably 0.9 to 1.1 moles. Also, the molar ratio of the diamine compound to the terminal blocking agent macromonomer is preferably 0.1 to 2 moles of the terminal blocking agent macromonomer per 1 mole of the diamine compound, more preferably 0.2 to 1.5 moles, and still more preferably 0.5 to 1.2 moles.

[0135] Examples of the terminal blocking agent macromonomer include a compound represented by the formula (EDM). [Chemical formula] In the formula (EDM), R ED represents an acid anhydride group, an acid halide group, or an isocyanate group, Lp ED1 represents an (n + 1)-valent group, The above (n + 1)-valent group is a hydrocarbon group or a group having a structure combined with at least one group selected from -NRp ED1 -, -N<, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NRp ED1 CO- and -CONRp ED1 -, Rp ED1 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, LpED2 represents -O- or -S-, P ED1 represents a polymer chain, n represents an integer from 1 to 4.

[0136] R in formula (EDM) ED The acid anhydride group represented is preferably a cyclic acid anhydride group. R ED The acid anhydride group represented by R is preferably a group represented by formula (R ED1 -11) to formula (R ED1 -13), and more preferably a group represented by formula (R ED1 -13). Also, the acid halide group is preferably a group represented by formula (R ED1 -21).

Chemical formula

[0137] In the above formula, R ED11 represents a hydrogen atom or a substituent, R ED12 represents a substituent, R ED21 represents a halogen atom, r represents an integer from 0 to 3, and * represents a bonding hand with Lp ED1

[0138] R ED11 and R ED12 Examples of the substituent represented by include the above-described substituent T, and it is preferably a halogen atom, a carboxy group, an alkyl group, or a hydroxy group, and more preferably a carboxy group.

[0139] R ED21 The halogen atom represented by is preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

[0140] r is preferably an integer from 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0141] Lp in formula (EDM) ED1 ​Examples of the hydrocarbon group in [the compound] include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon group is preferably from 1 to 30, more preferably from 1 to 20, and still more preferably from 1 to 15. The aliphatic hydrocarbon group may be linear, branched, or cyclic. Further, the cyclic aliphatic hydrocarbon group may be a monocyclic group or a condensed ring group. Additionally, the cyclic aliphatic hydrocarbon group may have a crosslinked structure. The number of carbon atoms in the aromatic hydrocarbon group is preferably from 6 to 30, more preferably from 6 to 20, and still more preferably from 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include the above-described substituent T.

[0142] Lp in formula (EDM) ED2 represents -O- or -S-, and is preferably -S-. P in formula (EDM) ED1 The polymer chain represented by 1 is synonymous with the polymer chain represented by P in formula (1). n in formula (EDM) is preferably 1 or 2.

[0143] The end-capping agent macromonomer is preferably a compound having an acid anhydride group, more preferably a compound represented by formula (EDM1), and still more preferably a compound represented by formula (EDM2). The compound represented by formula (EDM1) and the compound represented by formula (EDM2) are compounds of the present invention. [Chemical formula] In formula (EDM1), R ED1 represents an acid anhydride group, Lp ED1 represents an (n + 1)-valent group, The above (n + 1)-valent group is a group having a structure in which a hydrocarbon group is combined with at least one group selected from -NRp ED1 -, -N<, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NRp ED1 CO- and -CONRp ED1 -, Rp ED1represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, Lp ED2 represents -O- or -S-, P ED1 represents a polymer chain containing a repeating unit represented by any one of Formula (P1-1) to Formula (P1-4), n represents an integer of 1 to 4.

Chemical formula

Chemical formula

[0144] The acid anhydride group represented by R in Formula (EDM1) ED1 is synonymous with the acid anhydride group described by R in Formula (EDM). ED P in Formula (EDM1)ED1 Regarding the details of the polymer chain represented by, P in formula (1) 1 is the same as that described for the polymer chain represented by. Lp of formula (EDM1) ED1 , Lp ED2 and n are Lp of formula (EDM) ED1 , Lp ED2 and n are synonymous.

[0145] In formula (EDM2), r represents an integer from 0 to 3, preferably r is an integer from 0 to 2, more preferably 0 or 1, and still more preferably 0. Lp of formula (EDM2) ED1a The hydrocarbon group in is synonymous with the hydrocarbon group described in formula (EDM). The n+valent group represented by Lp of formula (EDM2) ED1a is preferably a hydrocarbon group. P of formula (EDM2) ED1 Regarding the details of the polymer chain represented by, P in formula (1) 1 is the same as that described for the polymer chain represented by. Lp of formula (EDM2) ED2 and n are Lp of formula (EDM) ED2 and n are synonymous.

[0146] Specific examples of the end-capping agent macromonomer include end-capping agent macromonomers EDM-1 to EDM-40 described in the examples below.

[0147] The end-capping agent macromonomer can be synthesized, for example, by the following method. (1) A method of synthesizing by subjecting a macromonomer obtained by radical polymerization of a radically polymerizable compound using a chain transfer agent having one hydroxy group, one or two mercapto groups to an esterification reaction with an acid anhydride or acid anhydride chloride. (2) A method of synthesizing by subjecting a compound having two mercapto groups to an en-thiol reaction with an acid anhydride having an ethylenically unsaturated bond-containing group and then subjecting the lactone to ring-opening polymerization. (3) A method of synthesizing a macromonomer obtained by radical polymerization of a radically polymerizable compound using a chain transfer agent having one hydroxy group and one or two mercapto groups by coupling reaction with an acid anhydride having a halogen atom. (4) A method of synthesizing by reacting a compound having one acid anhydride group and a carboxy group or an acid halide group with a polymer having a hydroxy group or an amino group at the terminal. As the compound having one acid anhydride group and a carboxy group or an acid halide group used in this synthesis, trimellitic anhydride and trimellitic anhydride chloride are preferable because a macromonomer can be synthesized with high purity and high yield. (5) A method of synthesizing by acid chlorination of a macromonomer obtained by radical polymerization of a radically polymerizable compound using a chain transfer agent having one carboxy group and one mercapto group (for example, mercaptopropionic acid, etc.). (6) A method of synthesizing by subjecting a macromonomer obtained by ring-opening polymerization of a lactone using a compound having one or two hydroxy groups and one mercapto group (for example, mercaptoethanol, mercaptopropanol, mercaptohexanol, mercapto glycerol, etc.) to an en-thiol reaction with a compound having an isocyanate group and an unsaturated bond-containing group. Since the terminal-blocking agent macromonomer may cause denaturation and corrosion if hydrochloric acid remains, it is preferably removed. When using acid anhydride chloride as a raw material, it is preferable to mix the raw materials in the presence of a base and then separate the resulting hydrochloride for synthesis. The base may be an organic base or an inorganic base. In the case of an organic base, a tertiary alkylamine, a tertiary aromatic amine, a heterocyclic aromatic amine, etc. are used. For example, triethylamine, diisopropylethylamine, tributylamine, diethylaniline, pyridine, 4,4-dimethylaminopyridine, 2-picoline, 2,6-lutidine, imidazole, 1-methylimidazole, 1-ethylimidazole, triazole, tetrazole, etc. can be mentioned. Examples of the separation method include filtration using a filter (natural filtration, pressure filtration, vacuum filtration, centrifugal filtration), liquid separation between an organic layer and an aqueous layer, centrifugation, adsorption (silica gel column, activated carbon, etc.).

[0148] (Other resins) The resin composition of the present invention may contain other resins other than the specific resin described above as the resin. Examples of other resins include resins having alkali developability or resins as dispersants. Further, it may contain by-products during the synthesis of the specific resin, such as decomposition products of the terminal-blocking agent macromonomer and reaction products of diamine and the terminal-blocking agent macromonomer.

[0149] [Resin having alkali developability] The weight average molecular weight (Mw) of the resin having alkali developability is preferably 3000 to 2000000. The upper limit is more preferably 1000000 or less, and even more preferably 500000 or less. The lower limit is more preferably 4000 or more, and even more preferably 5000 or more.

[0150] Examples of the resin having alkali developability include (meth)acrylic resins, polyimine resins, polyether resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, polyimide resins, etc. Among them, (meth)acrylic resins and polyimine resins are preferred, and (meth)acrylic resins are more preferred. As other resins, resins described in paragraph numbers 0041 to 0060 of JP-A-2017-206689, resins described in paragraph numbers 0022 to 0071 of JP-A-2018-010856, resins described in JP-A-2017-057265, resins described in JP-A-2017-032685, resins described in JP-A-2017-075248, and resins described in JP-A-2017-066240 can also be used.

[0151] In addition, as the resin having alkali developability, it is preferable to use a resin having an acid group. According to this embodiment, the developability of the resin composition can be further improved. Examples of the acid group include phenolic hydroxy group, carboxy group, sulfo group, phosphoric acid group, phosphonic acid group, active imide group, sulfonamide group, etc., and a carboxy group is preferred. As the resin having an acid group, a resin obtained by reacting an acid anhydride with a hydroxy group generated by epoxy ring opening to introduce an acid group may also be used. Examples of such a resin include the resin described in Japanese Patent No. 6349629. The resin having an acid group can be used, for example, as an alkali-soluble resin.

[0152] The resin having alkali developability preferably contains a repeating unit having an acid group in the side chain, and more preferably contains 1 to 70 mol% of the repeating unit having an acid group in the side chain in all the 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.

[0153] The acid value of the resin having alkali developability is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, still more preferably 120 mgKOH / g or less, and particularly preferably 100 mgKOH / g or less. Further, 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 still more preferably 20 mgKOH / g or more.

[0154] The resin having alkali developability preferably further has an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, an allyl group, and a (meth)acryloyl group. An allyl group and a (meth)acryloyl group are preferable, and a (meth)acryloyl group is more preferable.

[0155] The resin having an ethylenically unsaturated bond-containing group preferably contains a repeating unit having an ethylenically unsaturated bond-containing group in the side chain, and more preferably contains 5 to 80 mol% of the repeating unit having an ethylenically unsaturated bond-containing group in the side chain in all the repeating units of the resin. The upper limit of the content of the repeating unit having an ethylenically unsaturated bond-containing group in the side chain is preferably 60 mol% or less, and more preferably 40 mol% or less. The lower limit of the content of the repeating unit having an ethylenically unsaturated bond-containing group in the side chain is preferably 10 mol% or more, and more preferably 15 mol% or more.

[0156] The resin having alkali developability preferably contains a repeating unit derived from a monomer component containing a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may also be referred to as "ether dimer").

[0157]

Chemical formula

[0158] In formula (ED1), R 1 and R 2Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

Chemical formula

[0159] As a specific example of the ether dimer, for example, reference can be made to paragraph number 0317 of JP-A-2013-029760, and this content is incorporated herein.

[0160] The resin having alkali developability preferably contains a repeating unit derived from a compound represented by the following formula (X).

Chemical formula

[0161] Examples of the resin having alkali developability include resins having the following structures. In the following structural formulas, Me represents a methyl group.

Chemical formula

[0162] 〔Dispersant〕 The 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 a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is larger than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups occupies 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%, and more preferably a resin consisting essentially of only acid groups. The acid group of the acidic dispersant (acidic resin) is preferably a carboxy 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 even more preferably 60 to 105 mgKOH / g. Further, the basic dispersant (basic resin) refers to a resin in which the amount of basic groups is larger than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%. The basic group of the basic dispersant is preferably an amino group.

[0163] The resin used as the dispersant preferably contains a repeating unit having an acid group.

[0164] The resin used as the dispersant is also preferably a graft polymer. Examples of the graft polymer include the resins described in paragraphs 0025 to 0094 of JP-A-2012-255128, the content of which is incorporated herein.

[0165] The resin used as the dispersant is also preferably a polyimine-based dispersant (polyimine resin) containing a nitrogen atom in at least one of the main chain and the side chain. As the polyimine-based dispersant, a resin having a main chain having a partial structure having a functional group with a pKa of 14 or less and a side chain having 40 to 10,000 atoms, and having a basic nitrogen atom in at least one of the main chain and the side chain is preferred. The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity. Examples of the polyimine-based dispersant include the resins described in paragraphs 0102 to 0166 of JP-A-2012-255128, the content of which is incorporated herein.

[0166] The resin used as the dispersant is preferably a resin having a structure in which a plurality of polymer chains are bonded to the core part. Examples of such resins include dendrimers (including star polymers). Specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraph numbers 0196 to 0209 of JP-A-2013-043962.

[0167] The dispersant is also available as a commercial product. Specific examples thereof include the DISPERBYK series manufactured by BYK Chemie (for example, DISPERBYK-111, 161, etc.), the Solsperse series manufactured by Lubrizol (for example, Solsperse 36000, etc.). In addition, the pigment dispersants described in paragraph numbers 0041 to 0130 of JP-A-2014-130338 can also be used, and this content is incorporated herein. Further, the dispersant may be a compound 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.

[0168] Note that the resin described as the above dispersant can also be used for applications other than the dispersant. For example, it can also be used as a binder.

[0169] The content of the resin in the total solid content of the resin composition is preferably 5 to 60% by mass. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less.

[0170] The content of the above-mentioned specific resin in the total solid content of the resin composition is preferably 5 to 60% by mass. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less.

[0171] The content of the above-specified resin is preferably 10 to 80 parts by mass with respect to 100 parts by mass of the pigment. The lower limit is preferably 20 parts by mass or more, more preferably 30 parts by mass or more. The upper limit is preferably 70 parts by mass or less, more preferably 50 parts by mass or less.

[0172] In addition, in the resin composition, in the components excluding the coloring material from the total solid content of the resin composition, it is preferable to contain 20% by mass or more of the specified resin, more preferably 30% by mass or more, and still more preferably 40% by mass or more. The upper limit can be 100% by mass, can be 90% by mass or less, and can also be 85% by mass or less. If the content of the specified resin is within the above range, it is easy to form a film excellent in heat resistance, and it is easier to suppress film shrinkage after heating, etc. Furthermore, when an inorganic film or the like is formed on the surface of the film obtained by using the resin composition of the present invention, even when this laminate is exposed to a high temperature, it is possible to suppress the occurrence of cracks or the like in the inorganic film. In addition, the total content of the coloring material and the above-specified resin in the total solid content of the resin composition is preferably 25 to 100% by mass. The lower limit is more preferably 30% by mass or more, and still more preferably 40% by mass or more. The upper limit is more preferably 90% by mass or less, and still more preferably 80% by mass or less.

[0173] In the resin composition, the content of the other resins described above is preferably 230 parts by mass or less, more preferably 200 parts by mass or less, and still more preferably 150 parts by mass or less with respect to 100 parts by mass of the above-specified resin. The lower limit may be 0 parts by mass, can be 5 parts by mass or more, and can also be 10 parts by mass or more. Also, it is preferable that the resin composition does not substantially contain the other resins described above. According to this aspect, it is easy to form a film having more excellent heat resistance. The case of not substantially containing other resins means 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 containing.

[0174] <Solvent C> The resin composition of the present invention contains Solvent C (hereinafter referred to as "solvent"). The solvent is not particularly limited as long as the solubility of each component and the coatability of the resin composition are satisfied. The solvent is preferably an organic solvent. Examples of the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents, etc., and it is preferably at least one selected from ester solvents, ether solvents, alcohol solvents, and ketone solvents. For details of these, paragraph number 0223 of International Publication No. 2015 / 166779 can be referred to, and this content is incorporated herein. Also, an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma-butyrolactone, sulfolane, anisole, etc. However, aromatic hydrocarbons (such as benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may be preferably reduced for reasons such as environmental aspects (for example, it can be 50 ppm by mass (parts per million) or less, 10 ppm by mass or less, or 1 ppm by mass or less based on the total amount of the organic solvent).

[0175] In the present invention, it is preferable to use an organic solvent with a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, an organic solvent at the mass ppt (parts per trillion) level may be used, and such an organic solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015). Examples of methods for removing impurities such as metals from the organic solvent include distillation (such as molecular distillation and thin-film distillation) and filtration using a filter. The filter pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon.

[0176] The organic solvent may contain isomers (compounds having the same number of atoms but different structures). Also, only one type of isomer may be contained, or a plurality of types may be contained.

[0177] The content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially free of peroxide.

[0178] The content of the solvent in the resin composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 90% by mass.

[0179] <Pigment Derivative> The resin composition of the present invention preferably contains a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of the chromophore is substituted with an acid group, a basic group, or a phthalimidomethyl group. Examples of the chromophore constituting the pigment derivative include 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 perinone skeleton, a perylene skeleton, a thioindigo skeleton, an isoindoline skeleton, an isoindolinone skeleton, a quinophthalone skeleton, a fluorene skeleton, a metal complex skeleton, etc. Among them, a quinoline skeleton, a benzimidazolone skeleton, a diketopyrrolopyrrole skeleton, an azo skeleton, a quinophthalone skeleton, an isoindoline skeleton, and a phthalocyanine skeleton are preferred, and an azo skeleton and a benzimidazolone skeleton are more preferred. As the acid group of the pigment derivative, a sulfo group and a carboxy group are preferred, and a sulfo group is more preferred. As the basic group of the pigment derivative, an amino group is preferred, and a tertiary amino group is more preferred.

[0180] As the pigment derivative, a pigment derivative excellent in visible light transparency (hereinafter also referred to as a transparent pigment derivative) can also be used. The maximum value (εmax) of the molar extinction coefficient in the wavelength range of 400 to 700 nm of the transparent pigment derivative is preferably 3000 L·mol -1 ·cm -1 or less, more preferably 1000 L·mol -1 ·cm -1 or less, and even more preferably 100 L·mol -1 ·cm -1 or less. The lower limit of εmax is, for example, 1 L·mol -1 ·cm -1 or more, and may also be 10 L·mol -1 ·cm -1 or more.

[0181] Specific examples of the pigment derivative include compounds described in JP-A-56-118462, JP-A-63-264674, JP-A-01-217077, JP-A-03-009961, JP-A-03-026767, JP-A-03-153780, JP-A-03-045662, JP-A-04-285669, JP-A-06-145546, JP-A-06-212088, JP-A-06-240158, JP-A-10-030063, JP-A-10-195326, paragraph numbers 0086 to 0098 of International Publication No. 2011 / 024896, paragraph numbers 0063 to 0094 of International Publication No. 2012 / 102399, paragraph number 0082 of International Publication No. 2017 / 038252, paragraph number 0171 of JP-A-2015-151530, paragraph numbers 0162 to 0183 of JP-A-2011-252065, JP-A-03-081972, Patent No. 5299151, JP-A-2015-172732, JP-A-2014-199308, JP-A-2014-085562, JP-A-2014-035351, JP-A-2008-081565, and JP-A-2019-109512.

[0182] The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, per 100 parts by mass of the pigment. Only one kind of the pigment derivative may be used, or two or more kinds may be used in combination.

[0183] <Polymerizable monomer> The resin composition of the present invention preferably contains a polymerizable monomer. As the polymerizable monomer, for example, known compounds that can be crosslinked by radicals, acids, or heat can be used. Examples of the polymerizable monomer include compounds having an ethylenically unsaturated bond-containing group, compounds having a cyclic ether group, etc., and it is preferably a compound having an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, etc. Examples of the cyclic ether group include an epoxy group, an oxetane group, etc. The compound having an ethylenically unsaturated bond-containing group can be preferably used as a radical polymerizable monomer. Also, the compound having a cyclic ether group can be preferably used as a cationic polymerizable monomer. The polymerizable monomer is preferably a polyfunctional polymerizable monomer. That is, the polymerizable monomer is preferably a monomer having two or more polymerizable groups such as an ethylenically unsaturated bond-containing group or a cyclic ether group.

[0184] <o001409>The molecular weight of the polymerizable monomer is preferably from 100 to 3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is more preferably 150 or more, and even more preferably 250 or more.

[0185] (Compound having an ethylenically unsaturated bond-containing group) It should be noted that there is a misspelling in the original text where "o001409" should probably be " ". This has been maintained in the translation as it is not clear if it is an actual error or a specific notation. If it is an error, it should be corrected in the original text for better understanding.As the compound having an ethylenically unsaturated bond-containing group used as the coincidence monomer, it is preferably a polyfunctional compound. That is, it is preferably a compound containing two or more ethylenically unsaturated bond-containing groups, more preferably a compound containing three or more ethylenically unsaturated bond-containing groups, still more preferably a compound containing 3 to 15 ethylenically unsaturated bond-containing groups, and even more preferably a compound containing 3 to 6 ethylenically unsaturated bond-containing groups. Further, the compound having an ethylenically unsaturated bond-containing group is preferably a (meth)acrylate compound having 3 to 15 functional groups, and more preferably a (meth)acrylate compound having 3 to 6 functional groups. Specific examples of the compound having an ethylenically unsaturated bond-containing group include the compounds described in paragraph numbers 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-029760, paragraph numbers 0254 to 0257 of JP-A-2008-292970, paragraph numbers 0034 to 0038 of JP-A-2013-253224, paragraph number 0477 of JP-A-2012-208494, JP-A-2017-048367, Patent No. 6057891, Patent No. 6031807, and JP-A-2017-194662, and the contents thereof are incorporated herein.

[0186] Examples of the compound having an ethylenically unsaturated bond-containing group include dipentaerythritol tri(meth)acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (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 a compound having a structure in which these (meth)acryloyl groups are bonded via an ethylene glycol and / or propylene glycol residue (for example, SR454 and SR499 commercially available from Sartomer). Further, examples of the compound having an ethylenically unsaturated bond-containing group include diglycerin 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.), Light Acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like can also be used.

[0187] In addition, as the compound having an ethylenically unsaturated bond-containing group, trifunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide-modified tri(meth)acrylate, trimethylolpropane ethylene oxide-modified tri(meth)acrylate, ethylene oxide-modified tri(meth)acrylate isocyanurate, and pentaerythritol tri(meth)acrylate are preferably used. Commercially available trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M-452, 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, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.), and the like.

[0188] As the compound having an ethylenically unsaturated bond-containing group, a compound having an acid group can also be used. By using a compound having an acid group, the generation of development residues can be suppressed. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, etc., and a carboxy group is preferred. Commercially available polymerizable monomers 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 monomer having an acid group is 0.1 to 40 mgKOH / g, 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 in terms of production and handling.

[0189] It is also a preferred embodiment that the compound having an ethylenically unsaturated bond-containing group is a compound having a caprolactone structure. Compounds having a caprolactone structure are commercially available, for example, from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and examples include DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc.

[0190] As the compound having an ethylenically unsaturated bond-containing group, a compound having an alkyleneoxy group can also be used. The compound having an alkyleneoxy group is preferably a compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a compound having an ethyleneoxy group, and even more preferably a 3- to 6-functional (meth)acrylate compound having 4 to 20 ethyleneoxy groups. Commercially available products of the compound having an alkyleneoxy group include, for example, SR-494, a 4-functional (meth)acrylate having 4 ethyleneoxy groups manufactured by Sartomer, and KAYARAD TPA-330, a 3-functional (meth)acrylate having 3 isobutyleneoxy groups.

[0191] As the compound having an ethylenically unsaturated bond-containing group, a compound having a fluorene skeleton can also be used. Commercially available products of the compound having a fluorene skeleton include Ogsole EA-0200, EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., (meth)acrylate monomer having a fluorene skeleton), etc.

[0192] As the compound having an ethylenically unsaturated bond-containing group, it is also preferable to use a compound that substantially does not contain environmentally regulated substances such as toluene. Commercially available products of such compounds include KAYARAD DPHA LT, KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.), etc.

[0193] Examples of the compound having an ethylenically unsaturated bond-containing group include urethane acrylates as described in Japanese Patent Publication No. Sho 48-041708, Japanese Unexamined Patent Application Publication No. Sho 51-037193, Japanese Examined Patent Publication No. Hei 02-032293, and Japanese Examined Patent Publication No. Hei 02-016765, and urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. Sho 58-049860, Japanese Patent Publication No. Sho 56-017654, Japanese Examined Patent Publication No. Hei 62-039417, and Japanese Examined Patent Publication No. Hei 62-039418. It is also preferable to use a polymerizable compound having an amino structure or a sulfide structure in the molecule as described in Japanese Unexamined Patent Application Publication No. Sho 63-277653, Japanese Unexamined Patent Application Publication No. Sho 63-260909, and Japanese Unexamined Patent Application Publication No. Hei 01-105238. As the polymerizable compound, 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 also be used.

[0194] (Compound having a cyclic ether group) Examples of the compound having a cyclic ether group that can also be used as a polymerizable monomer include a compound having an epoxy group (hereinafter also referred to as an epoxy compound) and a compound having an oxetane group (hereinafter also referred to as an oxetane compound). The epoxy compound is preferably a polyfunctional epoxy compound. That is, the epoxy compound preferably has two or more epoxy groups. The upper limit of the number of epoxy groups is preferably 20 or less, more preferably 10 or less. The oxetane compound is preferably a polyfunctional oxetane compound. That is, the oxetane compound preferably has two or more oxetane groups. The upper limit of the number of oxetane groups is preferably 20 or less, more preferably 10 or less.

[0195] Examples of commercially available epoxy compounds include JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Corporation), JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation), and other commercially available products described in paragraph 0189 of JP-A-2011-221494. Other commercially available products include ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (all manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (all manufactured by ADEKA Corporation), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402, EX-111, EX-121, EX-141, EX-145, EX-146, EX-147, EX-171, EX-192 (all manufactured by Nagase ChemteX Corporation), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Celoxide 2021P, 2081, 2000, 3000, EHPE3150, Epolead GT400, Cellbinase B0134, B0177 (all manufactured by Daicel Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Company, Inc.), and the like.

[0196] Examples of commercially available oxetane compounds include OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ TX-100 (all manufactured by Toagosei Co., Ltd.), and the like can be used.

[0197] The content of the polymerizable monomer in the total solid of the resin composition is preferably 0.1 to 40% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less.

[0198] When using a compound having an ethylenically unsaturated bond-containing group as the polymerizable monomer, the content of the compound having an ethylenically unsaturated bond-containing group as the polymerizable monomer is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the specific resin described above. The lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less.

[0199] When using a compound having a cyclic ether group as the polymerizable monomer, the content of the compound having a cyclic ether group as the polymerizable monomer is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the specific resin described above. The lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less.

[0200] When using a compound having an ethylenically unsaturated bond-containing group and a compound having a cyclic ether group as the polymerizable monomer, the resin composition preferably contains 10 to 500 parts by mass of the compound having a cyclic ether group with respect to 100 parts by mass of the compound having an ethylenically unsaturated bond-containing group. The lower limit is preferably 20 parts by mass or more, more preferably 30 parts by mass or more. The upper limit is preferably 400 parts by mass or less, more preferably 300 parts by mass or less. If the ratio of both is within the above range, a film having better heat resistance (crack suppression and film shrinkage suppression) can be formed.

[0201] <Photoinitiator> The resin composition of the present invention preferably contains a photoinitiator. The photoinitiator is not particularly limited and can be appropriately selected from known photoinitiators. For example, a compound having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. The photoinitiator is preferably a photo radical polymerization initiator.

[0202] Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having an imidazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, etc. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably a trihalomethyltriazine compound, a biimidazole compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, and a 3-arylsubstituted coumarin compound, more preferably a compound selected from a biimidazole compound, an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound, and still more preferably an oxime compound. Further, examples of the photopolymerization initiator include compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in JP-A-2019-043864, photopolymerization initiators described in JP-A-2019-044030, and peroxide-based initiators described in JP-A-2019-167313, and the contents thereof are incorporated herein.

[0203] Examples of the biimidazole compounds 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, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (manufactured by BASF), and the like. Examples of commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (manufactured by BASF), and the like. Examples of commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (manufactured by BASF), and the like.

[0204] 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 J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), compounds described in JP-A-2000-066385, compounds described in JP-T-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, compounds described in Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in JP-A-2017-198865, compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, compounds described in International Publication No. 2013 / 167515, and the like. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (all manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photoinitiator 2 described in JP-A-2012-014052). Further, as the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and being difficult to discolor.Examples of commercially available products include Adeka Arcles NCI-730, NCI-831, NCI-930 (above, manufactured by ADEKA CORPORATION), etc.

[0205] 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 the compounds described in JP-A-2014-137466.

[0206] Also, as the photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can be used. Specific examples of such an oxime compound include the compounds described in International Publication No. 2013 / 083505.

[0207] 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 the compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-T-2014-500852, and compound (C-3) described in JP-A-2013-164471.

[0208] As the photopolymerization initiator, an oxime compound in which a substituent having a hydroxy group is bonded to a carbazole skeleton can also be used. Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019 / 088055.

[0209] As the photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP-A-2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of JP-A-2014-137466, the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, and Adeka Arcles NCI-831 (manufactured by ADEKA CORPORATION).

[0210] As a photoinitiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. 2015 / 036910.

[0211] As a photoinitiator, an oxime compound in which a substituent having a hydroxy group is bonded to a carbazole skeleton can also be used. Examples of such photoinitiators include the compounds described in International Publication No. 2019 / 088055.

[0212] Specific examples of the oxime compound are shown below, but the present invention is not limited thereto.

[0213]

Chemical formula

Chemical formula

[0214] 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. Further, from the viewpoint of sensitivity, the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably 1000 to 300000, still more preferably 2000 to 300000, and particularly preferably 5000 to 200000. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferably measured at a concentration of 0.01 g / L using ethyl acetate with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

[0215] As the photoinitiator, a bifunctional or trifunctional or higher-functional photo radical polymerization initiator may be used. By using such a photo radical polymerization initiator, two or more radicals are generated from one molecule of the photo radical polymerization initiator, so that good sensitivity can be obtained. Further, when a compound having an asymmetric structure is used, the crystallinity is reduced, the solubility in a solvent or the like is improved, and it is difficult to precipitate over time, and the stability over time of the resin composition can be improved. Specific examples of the bifunctional or trifunctional or higher-functional photo radical polymerization initiator include those described in JP-T-2010-527339, JP-T-2011-524436, WO 2015 / 004565, paragraph numbers 0407 to 0412 of JP-T-2016-532675, dimer of oxime compounds described in paragraph numbers 0039 to 0055 of WO 2017 / 033680, compound (E) and compound (G) described in JP-T-2013-522445, Cmpd1 to 7 described in WO 2016 / 034963, oxime ester photoinitiators described in paragraph number 0007 of JP-T-2017-523465, photoinitiators described in paragraph numbers 0020 to 0033 of JP 2017-167399 A, photo radical polymerization initiator (A) described in paragraph numbers 0017 to 0026 of JP 2017-151342 A, oxime compounds described in Patent No. 6469669, and the like.

[0216] The content of the photoinitiator in the total solid content of the resin composition is preferably 0.1 to 30% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less. Only one kind of photoinitiator may be used, or two or more kinds may be used.

[0217] <Silane coupling agent> The resin composition of the present invention can contain a silane coupling agent. In this specification, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Further, the hydrolyzable group refers to a substituent directly bonded to a silicon atom and capable of forming a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, etc., and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Further, examples of the functional group other than the hydrolyzable group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a mercapto group, an epoxy group, an amino group, a ureido group, a sulfide group, an isocyanate group, a phenyl group, etc., and an amino group, a (meth)acryloyl group, and an epoxy group are preferable. Specific examples of the silane coupling agent include the compounds described in paragraph numbers 0018 to 0036 of JP-A-2009-288703 and the compounds described in paragraph numbers 0056 to 0066 of JP-A-2009-242604, and the contents of these are incorporated into this specification.

[0218] The content of the silane coupling agent in the total solid content of the resin composition is preferably 0.1 to 5% by mass. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The silane coupling agent may be only one kind or two or more kinds.

[0219] <Curing accelerator> The resin composition of the present invention can further contain a curing accelerator for the purpose of promoting the reaction of resins or polymerizable compounds or lowering the curing temperature. Examples of the curing accelerator include methylol compounds (compounds exemplified as crosslinking agents in paragraph number 0246 of JP-A-2015-034963), amines, phosphonium salts, amidine salts, amide compounds (the above are curing agents described in paragraph number 0186 of JP-A-2013-041165, for example), base generators (ionic compounds described in JP-A-2014-055114, for example), cyanate compounds (compounds described in paragraph number 0071 of JP-A-2012-150180, for example), alkoxysilane compounds (alkoxysilane compounds having an epoxy group described in JP-A-2011-253054, for example), onium salt compounds (compounds exemplified as acid generators in paragraph number 0216 of JP-A-2015-034963, compounds described in JP-A-2009-180949, for example), and the like can also be used.

[0220] When the 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 resin composition.

[0221] <Polymerization inhibitor> The resin composition of the present invention can 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-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerium(I) salts, etc.). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the resin composition is preferably 0.0001 to 5% by mass.

[0222] <Surfactant> The resin composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. Examples of the surfactant include those described in paragraph numbers 0238 to 0245 of International Publication No. 2015 / 166779, and the content is incorporated herein.

[0223] The surfactant is preferably a fluorosurfactant. By incorporating a fluorosurfactant into the resin composition, the liquid properties (especially fluidity) can be further improved, and the liquid-saving property can be further enhanced. In addition, a film with less thickness unevenness can also be formed.

[0224] The fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorosurfactant having a fluorine content within this range is effective in terms of the uniformity of the thickness of the coating film and the liquid-saving property, and also has good solubility in the resin composition.

[0225] Examples of the fluorosurfactant include surfactants described in paragraph numbers 0060 to 0064 of JP-A-2014-041318 (paragraph numbers 0060 to 0064 of corresponding International Publication No. 2014 / 017669), surfactants described in paragraph numbers 0117 to 0132 of JP-A-2011-132503, and surfactants described in JP-A-2020-008634, the contents of which are incorporated herein. Examples of commercially available products of the fluorosurfactant include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (manufactured by DIC Corporation), Fluorad FC430, FC431, FC171 (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 (manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), Ftergent 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F (manufactured by NEOS Co., Ltd.), etc.

[0226] Further, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorosurfactant. Such a fluorosurfactant can refer to the description of JP-A-2016-216602, the content of which is incorporated herein.

[0227] Fluorine-based surfactants can also use block polymers. For example, the compounds described in JP-A-2011-089090 can be mentioned. Fluorine-based surfactants can also preferably use a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy group, propyleneoxy group). The following compounds are also exemplified as the fluorine-based surfactants used in the present invention.

Chemical formula

[0228] In addition, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, such as Megafac RS-101, RS-102, RS-718K, RS-72-K, etc. manufactured by DIC Corporation. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.

[0229] The content of the surfactant in the total solid content of the resin composition is preferably 0.001% by mass to 5.0% by mass, and more preferably 0.005% to 3.0% by mass. The surfactant may be only one kind or two or more kinds. In the case of two or more kinds, the total amount is preferably within the above range.

[0230] <UV absorber> The resin composition of the present invention can contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, etc. can be used. Regarding the details of these, the descriptions in paragraph numbers 0052 to 0072 of JP-A-2012-208374, paragraph numbers 0317 to 0334 of JP-A-2013-068814, and paragraph numbers 0061 to 0080 of JP-A-2016-162946 can be referred to, and the contents of these are incorporated herein. Examples of commercially available products of the ultraviolet absorber include UV-503 (manufactured by Daito Chemical Co., Ltd.). Further, as the benzotriazole compound, the MYUA series manufactured by Miyoshi Oil & Fat Co., Ltd. (Chemical Industry Daily, February 1, 2016) can be mentioned. Also, as the ultraviolet absorber, the compounds described in paragraph numbers 0049 to 0059 of Japanese Patent No. 6268967 can be used. The content of the ultraviolet absorber in the total solid content of the resin composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. Only one kind of ultraviolet absorber may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount is within the above range.

[0231] <Antioxidant> The resin composition of the present invention can contain an antioxidant. Examples of the antioxidant include phenolic compounds, phosphite ester compounds, thioether compounds, etc. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. Preferred phenolic compounds include hindered phenolic compounds. Compounds having a substituent at the site (ortho position) adjacent to the phenolic hydroxy group are preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. Further, as the antioxidant, a compound having a phenol group and a phosphite ester group in the same molecule is also preferred. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. Further, as the antioxidant, the compound described in Korean Patent Publication No. 10-2019-0059371 can also be used. The content of the antioxidant in the total solid content of the resin composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass. Only one kind of antioxidant may be used, or two or more kinds may be used. When two or more kinds are used, the total amount is preferably within the above range.

[0232] <Other Components> The resin composition of the present invention may contain, if necessary, a sensitizer, a filler, a heat curing accelerator, a plasticizer, and other auxiliaries (for example, conductive particles, fillers, defoaming agents, flame retardants, leveling agents, peeling accelerators, fragrances, surface tension adjusters, chain transfer agents, etc.). By appropriately containing these components, properties such as film physical properties can be adjusted. These components can refer to, for example, the descriptions from paragraph number 0183 and subsequent in JP-A-2012-003225 (corresponding to paragraph number 0237 in the specification of US Patent Application Publication No. 2013 / 0034812), the descriptions in paragraph numbers 0101 to 0104, 0107 to 0109, etc. in JP-A-2008-250074, and these contents are incorporated into this specification. Further, the resin composition may contain a latent antioxidant if necessary. As the latent antioxidant, a compound in which a site functioning as an antioxidant is protected by a protecting group, and the protecting group is eliminated by heating at 100 to 250 °C or heating at 80 to 200 °C in the presence of an acid / base catalyst to function as an antioxidant can be mentioned. Examples of the latent antioxidant include the compounds described in WO 2014 / 021023, WO 2017 / 030005, and JP-A-2017-008219. Commercially available products include Adeka Arcles GPA-5001 (manufactured by ADEKA CORPORATION), etc.

[0233] The resin composition of the present invention may contain a metal oxide to adjust the refractive index of the resulting film. Examples of the metal oxide include TiO2, ZrO2, Al2O3, SiO2, etc. The primary particle diameter of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, and still more preferably 5 to 50 nm. The metal oxide may have a core-shell structure. Also, in this case, the core part may be hollow.

[0234] The resin composition of the present invention may contain a light resistance improver. Examples of the light resistance improver include the compounds described in paragraph numbers 0036 to 0037 of JP-A-2017-198787, the compounds described in paragraph numbers 0029 to 0034 of JP-A-2017-146350, the compounds described in paragraph numbers 0036 to 0037 and 0049 to 0052 of JP-A-2017-129774, the compounds described in paragraph numbers 0031 to 0034 and 0058 to 0059 of JP-A-2017-129674, the compounds described in paragraph numbers 0036 to 0037 and 0051 to 0054 of JP-A-2017-122803, the compounds described in paragraph numbers 0025 to 0039 of International Publication No. 2017 / 164127, the compounds described in paragraph numbers 0034 to 0047 of JP-A-2017-186546, the compounds described in paragraph numbers 0019 to 0041 of JP-A-2015-025116, the compounds described in paragraph numbers 0101 to 0125 of JP-A-2012-145604, the compounds described in paragraph numbers 0018 to 0021 of JP-A-2012-103475, the compounds described in paragraph numbers 0015 to 0018 of JP-A-2011-257591, the compounds described in paragraph numbers 0017 to 0021 of JP-A-2011-191483, the compounds described in paragraph numbers 0108 to 0116 of JP-A-2011-145668, the compounds described in paragraph numbers 0103 to 0153 of JP-A-2011-253174, and the like.

[0235] The resin composition of the present invention preferably has a content of free metal not bound or coordinated with a pigment or the like of 100 ppm or less, more preferably 50 ppm or less, still more preferably 10 ppm or less, and particularly preferably substantially not contained. According to this aspect, effects such as stabilization of pigment dispersibility (aggregation inhibition), improvement of spectral characteristics accompanying improvement of dispersibility, stabilization of curable components, suppression of conductivity fluctuations accompanying elution of metal atoms and metal ions, and improvement of display characteristics can be expected. In addition, the effects described in JP-A-2012-153796, JP-A-2000-345085, JP-A-2005-200560, JP-A-08-043620, JP-A-2004-145078, JP-A-2014-119487, JP-A-2010-083997, JP-A-2017-090930, JP-A-2018-025612, JP-A-2018-025797, JP-A-2017-155228, JP-A-2018-036521, etc. can also be obtained. Examples of the types of the above free metals include 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. Further, the resin composition of the present invention preferably has a content of free halogen not bound or coordinated with a pigment or the like of 100 ppm or less, more preferably 50 ppm or less, still more preferably 10 ppm or less, and particularly preferably substantially not contained. Examples of the halogen include F, Cl, Br, I and their anions. Examples of methods for reducing free metals and halogens in the resin composition include washing with ion-exchanged water, filtration, ultrafiltration, purification with an ion-exchange resin, etc.

[0236] From the perspective of environmental regulations, the use of perfluoroalkyl sulfonic acids and their salts, as well as perfluoroalkyl carboxylic acids and their salts, may be restricted. In the resin composition of the present invention, when reducing the content of the above-mentioned compounds, the content of perfluoroalkyl sulfonic acid (especially perfluoroalkyl sulfonic acid with 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts, as well as perfluoroalkyl carboxylic acid (especially perfluoroalkyl carboxylic acid with 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts, is preferably in the range of 0.01 ppb to 1,000 ppb, more preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb, based on the total solid content of the resin composition. The resin composition of the present invention may not substantially contain perfluoroalkyl sulfonic acids and their salts, as well as perfluoroalkyl carboxylic acids and their salts. For example, by using compounds that can substitute for perfluoroalkyl sulfonic acids and their salts, as well as compounds that can substitute for perfluoroalkyl carboxylic acids and their salts, a resin composition that does not substantially contain perfluoroalkyl sulfonic acids and their salts, as well as perfluoroalkyl carboxylic acids and their salts, may be selected. Examples of compounds that can substitute for regulated compounds include compounds excluded from the regulated targets due to differences in the number of carbon atoms in the perfluoroalkyl group. However, the above content does not prevent the use of perfluoroalkyl sulfonic acids and their salts, as well as perfluoroalkyl carboxylic acids and their salts. The resin composition of the present invention may contain perfluoroalkyl sulfonic acids and their salts, as well as perfluoroalkyl carboxylic acids and their salts, within the maximum allowable range.

[0237] It is also preferable that the resin composition of the present invention does not substantially contain terephthalic acid ester. Here, "not substantially contain" means that the content of terephthalic acid ester is 1000 mass ppb or less in the total amount of the resin composition, more preferably 100 mass ppb or less, and particularly preferably zero.

[0238] <Container> As the container for housing the resin composition, there are no particular limitations, and known containers can be used. Also, as the container, for the purpose of suppressing the mixing of impurities into the raw materials and the resin composition, it is also preferable to use a multilayer bottle having an inner wall of the container composed of six types of resins in six layers or a bottle having a seven-layer structure of six types of resins. Examples of such containers include the containers described in JP-A-2015-123351. Further, it is also preferable that the inner wall of the container is made of glass, stainless steel, etc. for the purpose of preventing elution of metal from the inner wall of the container, enhancing the storage stability of the resin composition, suppressing component deterioration, etc.

[0239] <Method for preparing resin composition> The resin composition of the present invention can be prepared by mixing the aforementioned components. When preparing the resin composition, all the components may be simultaneously dissolved and / or dispersed in an organic solvent to prepare the resin composition, or, if necessary, each component may be appropriately prepared as two or more solutions or dispersions, and these may be mixed at the time of use (coating) to prepare the resin composition.

[0240] In addition, when preparing the resin composition, it is preferable to include a process of dispersing the pigment. In the process of dispersing the pigment, examples of the mechanical force used for dispersing the pigment include compression, squeezing, impact, shearing, cavitation, etc. Specific examples of these processes include bead mill, sand mill, roll mill, ball mill, paint shaker, microfluidizer, high-speed impeller, sand grinder, flow jet mixer, high-pressure wet atomization, ultrasonic dispersion, etc. In addition, in the grinding of the pigment in a sand mill (bead mill), it is preferable to perform the treatment under conditions that improve the grinding efficiency, such as using beads with a small diameter and increasing the filling rate of the beads. Further, it is preferable to remove coarse particles by filtration, centrifugation, etc. after the grinding treatment. In addition, the process and disperser for dispersing the pigment can preferably use the processes and dispersers described in "Complete Collection of Dispersion Technologies, published by Information Organization, Ltd., July 15, 2005" and "Practical Comprehensive Data Collection on Dispersion Technologies and Industrial Applications Centered on Suspensions (Solid / Liquid Dispersion Systems), published by the Publishing Department of the Management Development Center, October 10, 1978", and paragraph number 0022 of Japanese Patent Application Laid-Open No. 2015-157893. In addition, in the process of dispersing the pigment, the particle size reduction treatment may be performed in the salt milling step. The materials, equipment, treatment conditions, etc. used in the salt milling step can refer to, for example, the descriptions in Japanese Patent Application Laid-Open No. 2015-194521 and Japanese Patent Application Laid-Open No. 2012-046629.

[0241] In the preparation of the resin composition, for the purpose of removing foreign matters and reducing defects, etc., it is preferable to filter the resin composition with a filter. As the filter, any filter that has been conventionally used for filtration purposes, etc. can be used without particular limitation. For example, filters made of materials such as fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins such as nylon (e.g., nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (including high-density and ultra-high molecular weight polyolefin resins) can be mentioned. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.

[0242] The pore diameter of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and still more preferably 0.05 to 0.5 μm. If the pore diameter of the filter is within the above range, fine foreign matters can be removed more reliably. Regarding the pore diameter value of the filter, the nominal value of the filter manufacturer can be referred to. As the filter, various filters provided by Nippon Paul Co., Ltd. (such as DFA4201NXEY, DFA4201NAEY, DFA4201J006P), Advantec Toyo Co., Ltd., Nippon Integris Co., Ltd. (former Nippon Microlith Co., Ltd.), and Kits Microfilter Co., Ltd. can be used.

[0243] Also, it is preferable to use a fibrous filter medium as the filter. Examples of the fibrous filter medium include polypropylene fiber, nylon fiber, and glass fiber. Commercially available products include the SBP type series (such as SBP008), TPR type series (such as TPR002, TPR005), and SHPX type series (such as SHPX003) manufactured by Rock Techno Co., Ltd.

[0244] When using the filter, different filters (for example, the first filter and the second filter, etc.) may be combined. In that case, the filtration by each filter may be performed only once or may be performed two or more times. Also, filters with different pore diameters may be combined within the above-mentioned range. Also, the filtration by the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration may be performed by the second filter. Also, the filter can be appropriately selected according to the hydrophilicity and hydrophobicity of the resin composition.

[0245] (film) The film of the present invention is a film obtained from the resin composition of the present invention described above. The film of the present invention can be used for optical filters such as color filters, near-infrared transmission filters, and near-infrared cut filters. Also, the film of the present invention can also be used for black matrices and light-shielding films.

[0246] 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 even more 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 even more preferably 0.3 μm or more.

[0247] When the film of the present invention is used as a color filter, the film of the present invention preferably has a hue of green, red, blue, cyan, magenta or yellow. Further, the film of the present invention can be preferably used as a colored pixel of a color filter. Examples of the colored pixel include a red pixel, a green pixel, a blue pixel, a magenta pixel, a cyan pixel, and a yellow pixel.

[0248] When the film of the present invention is used as a near-infrared cut filter, the maximum absorption wavelength of the film of the present invention preferably exists in the range of wavelengths 700 to 1800 nm, more preferably in the range of wavelengths 700 to 1300 nm, and even more preferably in the range of wavelengths 700 to 1100 nm. Further, the transmittance of the film in the entire range of wavelengths 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. Further, the transmittance of the film at at least one point in the range of wavelengths 700 to 1800 nm is preferably 20% or less. Further, the absorbance ratio Amax / A550, which is the ratio of the absorbance Amax at the maximum absorption wavelength to the absorbance A550 at a wavelength of 550 nm, is preferably 20 to 500, more preferably 50 to 500, even more preferably 70 to 450, and particularly preferably 100 to 400.

[0249] When the film of the present invention is used as a near-infrared transmission filter, the film of the present invention preferably has any one of the following spectral characteristics (i1) to (i5). (i1): A filter in which the maximum transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 800 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectral characteristics can block light in the wavelength range of 400 to 640 nm and transmit light with a wavelength exceeding 750 nm. (i2): A filter in which the maximum transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 900 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectral characteristics can block light in the wavelength range of 400 to 750 nm and transmit light with a wavelength exceeding 850 nm. (i3): A filter in which the maximum transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 1000 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectral characteristics can block light in the wavelength range of 400 to 830 nm and transmit light with a wavelength exceeding 950 nm. (i4): A filter in which the maximum transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 1100 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectral characteristics can block light in the wavelength range of 400 to 950 nm and transmit light with a wavelength exceeding 1050 nm. (i5): A filter having a maximum transmittance in the range of 400 to 1050 nm of 20% or less (preferably 15% or less, more preferably 10% or less), and a minimum transmittance in the range of 1200 to 1500 nm of 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectral characteristics can block light in the range of 400 to 1050 nm and transmit light with a wavelength exceeding 1150 nm.

[0250] Preferably, the thickness of the film of the present invention after heat treatment at 300 °C for 5 hours in a nitrogen atmosphere is 70% or more of the thickness of the film before heat treatment, more preferably 80% or more, still more preferably 90% or more, even more preferably 95% or more, and particularly preferably 99% or more. Also, preferably, the thickness of the film after heat treatment at 350 °C for 5 hours in a nitrogen atmosphere is 70% or more of the thickness of the film before heat treatment, more preferably 80% or more, still more preferably 90% or more, even more preferably 95% or more, and particularly preferably 99% or more. Also, preferably, the thickness of the film after heat treatment at 400 °C for 5 hours in a nitrogen atmosphere is 70% or more of the thickness of the film before heat treatment, more preferably 80% or more, still more preferably 90% or more, even more preferably 95% or more, and particularly preferably 99% or more.

[0251] <Method for manufacturing the film> The film of the present invention can be manufactured through a step of applying the resin composition of the present invention described above onto a support. In the method for manufacturing the film of the present invention, it is preferably further included a step of forming a pattern (pixel). Examples of the method for forming the pattern (pixel) include a photolithography method and a dry etching method, and the photolithography method is preferred.

[0252] (Photolithography method) First, the case of manufacturing a film by forming a pattern by photolithography will be described. Pattern formation by photolithography preferably includes a step of forming a resin composition layer on a support using the resin composition of the present invention, a step of exposing the resin composition layer in a pattern, and a step of developing and removing the unexposed portion of the resin composition layer to form a pattern (pixel). If necessary, a step of baking the resin composition layer (pre-bake step) and a step of baking the developed pattern (pixel) (post-bake step) may be provided.

[0253] In the step of forming the resin composition layer, a resin composition layer is formed on a support using the resin composition of the present invention. The support is not particularly limited and can be appropriately selected according to the application. For example, a glass substrate, a silicon substrate, etc. may be mentioned, and a silicon substrate is preferred. Further, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. may be formed on the silicon substrate. Further, a black matrix for isolating each pixel may be formed on the silicon substrate. Further, a base layer may be provided on the silicon substrate for improving adhesion to the upper layer, preventing diffusion of substances, or flattening the substrate surface. The surface contact angle of the base layer is preferably 20 to 70° when measured with diiodomethane. Further, it is preferably 30 to 80° when measured with water. If the surface contact angle of the base layer is within the above range, the coatability of the resin composition is good. The adjustment of the surface contact angle of the base layer can be performed by, for example, a method such as adding a surfactant.

[0254] As a method for applying the resin composition, a known method can be used. For example, the dropping method (drop casting); the slit coating method; the spray method; the roll coating method; the spin coating method; the casting coating method; the slit and spin method; the prewet method (for example, the method described in JP-A-2009-145395); ejection system printing such as inkjet (for example, on-demand system, piezo system, thermal system), nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, and other various printing methods; the transfer method using a mold or the like; the nanoimprint method, etc. The application method in inkjet is not particularly limited, and for example, the method shown in "Spreadable and Usable Inkjet - Infinite Possibilities in Patents -", published in February 2005, Sumitomo Chemical Research (especially pages 115 to 133), and the methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, etc. can be mentioned. Further, as the method for applying the resin composition, the methods described in WO 2017 / 030174 and WO 2017 / 018419 can also be used, and the contents thereof are incorporated herein.

[0255] The resin composition layer formed on the support may be dried (prebaked). When manufacturing a film by a low-temperature process, prebaking may not be necessary. When prebaking is performed, the prebaking temperature is preferably 150°C or lower, more preferably 120°C or lower, and still more preferably 110°C or lower. The lower limit can be, for example, 50°C or higher, or 80°C or higher. The prebaking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and still more preferably 80 to 220 seconds. Prebaking can be performed on a hot plate, in an oven, or the like.

[0256] Next, the resin composition layer is exposed in a pattern (exposure step). For example, the resin composition layer can be exposed in a pattern by exposing it through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. Thereby, the exposed portion can be cured.

[0257] Examples of the radiation (light) that can be used for exposure include g-line, i-line, etc. Also, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can be used. Examples of light with a wavelength of 300 nm or less include KrF line (wavelength 248 nm), ArF line (wavelength 193 nm), etc., and KrF line (wavelength 248 nm) is preferred. Also, light sources with longer wavelengths of 300 nm or more can be used.

[0258] Also, during exposure, the light may be continuously irradiated for exposure, or pulsed irradiation for exposure (pulse exposure) may be performed. Note that pulse exposure is an exposure method in which light irradiation and pause are repeated in a short time cycle (for example, at the millisecond level or less). In the case of pulse exposure, the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and even more preferably 30 nanoseconds or less. The lower limit of the pulse width is not particularly limited, but can be 1 femtosecond (fs) or more, and can also be 10 femtoseconds or more. The frequency is preferably 1 kHz or more, more preferably 2 kHz or more, and even more preferably 4 kHz or more. The upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and even more preferably 10 kHz or less. The maximum instantaneous illuminance is preferably 50000000 W / m 2 or more, more preferably 100000000 W / m 2 or more, and even more preferably 200000000 W / m 2 or more. Also, the upper limit of the maximum instantaneous illuminance is preferably 1000000000 W / m 2 or less, more preferably 800000000 W / m 2 or less, and even more preferably 5**********W / m2 It is more preferable that the following conditions are met. The pulse width is the time during which light is irradiated in a pulse period. The frequency is the number of pulse periods per second. The maximum instantaneous illuminance is the average illuminance within the time during which light is irradiated in a pulse period. The pulse period is the period in which one cycle consists of light irradiation and rest in pulsed exposure.

[0259] The irradiation dose (exposure dose) is, for example, 0.03 to 2.5 J / cm 2 is preferable, and 0.05 to 1.0 J / cm 2 is more preferable. The oxygen concentration during exposure can be appropriately selected. In addition to performing the process under the atmosphere, for example, exposure may be carried out in a low-oxygen atmosphere with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially oxygen-free), or exposure may be carried out in a high-oxygen atmosphere with an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume). Also, the exposure illuminance can be appropriately set, and it is usually 1000 W / m 2 ~100000 W / m 2 (for example, 5000 W / m 2 , 15000 W / m 2 , or 35000 W / m 2 ) and can be selected from this range. The oxygen concentration and the exposure illuminance can be appropriately combined. For example, an oxygen concentration of 10% by volume and an illuminance of 10000 W / m 2 , an oxygen concentration of 35% by volume and an illuminance of 20000 W / m 2 etc. can be used.

[0260] Next, the unexposed portion of the resin composition layer is developed and removed to form a pattern (pixel). The development and removal of the unexposed portion of the resin composition layer can be performed using a developer. As a result, the resin composition layer in the unexposed portion in the exposure process elutes into the developer, and only the photocured portion remains. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. Also, in order to improve the residue removability, the process of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.

[0261] The developing solution includes organic solvents, alkaline developing solutions, etc., and an alkaline developing solution is preferably used. As the alkaline developing solution, an alkaline aqueous solution (alkaline developing solution) obtained by diluting an alkaline agent with pure water is preferred. Examples of the alkaline agent include organic alkaline compounds such as ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, 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, and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, and sodium metasilicate. Alkaline agents with larger molecular weights are preferred in terms of the 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. Further, the developing solution may further contain a surfactant. Examples of the surfactant include the surfactants described above, and nonionic surfactants are preferred. From the viewpoints of convenience in transfer and storage, etc., the developing solution may be once manufactured as a concentrated solution and diluted to the required concentration at the time of use. The dilution ratio is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times. Also, it is preferable to wash (rinse) with pure water after development. Also, the rinsing is preferably performed by supplying a rinse solution to the resin composition layer after development while rotating the support on which the resin composition layer after development is formed. Also, it is preferable to move the nozzle for discharging the rinse solution from the central part to the peripheral part of the support. At this time, when moving the nozzle from the central part to the peripheral part of the support, the moving speed of the nozzle may be gradually decreased while moving. By performing rinsing in this way, the in-plane variation of the rinsing can be suppressed. Also, the same effect can be obtained by gradually decreasing the rotation speed of the support while moving the nozzle from the central part to the peripheral part of the support.

[0262] After development, it is preferable to perform additional exposure treatment or heat treatment (post-bake) after drying. The additional exposure treatment and post-bake are post-development curing treatments for making the curing complete. The heating temperature in the post-bake is preferably, for example, 100 to 240°C, more preferably 200 to 240°C. The post-bake can be performed continuously or batchwise on the film after development using heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so as to meet the above conditions. When performing the additional exposure treatment, the light used for exposure is preferably light having a wavelength of 400 nm or less. Also, the additional exposure treatment may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.

[0263] (Dry etching method) Pattern formation by the dry etching method includes a step of forming a resin composition layer on a support using the resin composition of the present invention and curing the entire resin composition layer to form a cured product layer, a step of forming a photoresist layer on the cured product layer, a step of exposing the photoresist layer in a pattern and then developing to form a resist pattern, and a step of dry etching the cured product layer using an etching gas with the resist pattern as a mask. It is preferable to further perform a pre-bake treatment in the formation of the photoresist layer. In particular, as the photoresist layer formation process, a form in which a heat treatment after exposure and a heat treatment after development (post-bake treatment) are carried out is desirable. Regarding pattern formation by the dry etching method, the descriptions in paragraphs Nos. 0010 to 0067 of JP-A-2013-064993 can be referred to, and this content is incorporated herein.

[0264] <Optical filter> The optical filter of the present invention has the film of the present invention described above. Examples of the type of optical filter include a color filter, a near-infrared transmission filter, a near-infrared cut filter, etc., and a color filter is preferred. As the color filter, it is preferable to have the film of the present invention as a colored pixel of the color filter. The optical filter of the present invention can be used in solid-state imaging devices such as CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor), and image display devices.

[0265] In the optical filter, the film thickness of the film of the present invention can be appropriately adjusted according to the purpose. The film thickness is preferably 5 μm or less, more preferably 1 μm or less, and even more preferably 0.6 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 even more preferably 0.3 μm or more.

[0266] The width of the pixels included in the optical filter is preferably 0.4 to 10.0 μm. The lower limit is preferably 0.4 μm or more, more preferably 0.5 μm or more, and even more preferably 0.6 μm or more. The upper limit is preferably 5.0 μm or less, more preferably 2.0 μm or less, even more preferably 1.0 μm or less, and still more preferably 0.8 μm or less. Also, the Young's modulus of the pixels is preferably 0.5 to 20 GPa, and more preferably 2.5 to 15 GPa.

[0267] Each pixel included in the optical filter preferably has high flatness. Specifically, the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and even more preferably 15 nm or less. Although the lower limit is not defined, for example, it is preferably 0.1 nm or more. The surface roughness of the pixel can be measured using, for example, AFM (Atomic Force Microscope) Dimension 3100 manufactured by Veeco. Also, the contact angle of water on the pixel can be set to an appropriate preferred value, but typically it is 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.). Also, the volume resistivity of the pixel is preferably high. Specifically, the volume resistivity of the pixel is preferably 10 9 Ω·cm or more, and more preferably 10 11 Ω·cm or more. Although the upper limit is not defined, for example, it is preferably 10 14 Ω·cm or less. The volume resistivity of the pixel can be measured using a super high resistance meter 5410 (manufactured by Advantest).

[0268] In the optical filter, a protective layer may be provided on the surface of the film of the present invention. By providing the protective layer, various functions such as oxygen barrier, antireflection, hydrophilization / hydrophobization, 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, more preferably 0.1 to 5 μm. Examples of the method for forming the protective layer include a method of applying a resin composition for forming a protective layer dissolved in an organic solvent, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive. Examples of the components constituting the protective layer include (meth)acrylic resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane 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., and two or more of these components may be contained. For example, in the case of a protective layer for the purpose of oxygen barrier, the protective layer preferably contains a polyol resin, SiO2, and Si2N4. Also, in the case of a protective layer for the purpose of antireflection, the protective layer preferably contains a (meth)acrylic resin and a fluororesin.

[0269] When forming the protective layer by applying the resin composition for forming the protective layer, as the coating method of the resin composition for forming the protective layer, known methods such as spin coating method, casting method, screen printing method, inkjet method, etc. can be used. As the organic solvent contained in the resin composition for forming the protective layer, known organic solvents (for example, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used. When forming the protective layer by chemical vapor deposition method, as the chemical vapor deposition method, known chemical vapor deposition methods (thermal chemical vapor deposition method, plasma chemical vapor deposition method, photo chemical vapor deposition method) can be used.

[0270] The protective layer may contain additives such as organic and inorganic fine particles, light absorbers for specific wavelengths (e.g., ultraviolet rays, near-infrared rays, etc.), refractive index adjusters, antioxidants, adhesives, surfactants, etc. as needed. Examples of the organic and inorganic fine particles include, for example, polymer fine particles (e.g., silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, oxynitride titanium, magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, etc. Known light absorbers for specific wavelengths can be used. The content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by mass, more preferably 1 to 60% by mass, based on the total mass of the protective layer. Further, as the protective layer, the protective layer described in paragraphs 0073 to 0092 of JP-A-2017-151176 can also be used.

[0271] The optical filter may have a structure in which each pixel is embedded in a space partitioned, for example, in a lattice pattern by partition walls. Further, the resin composition of the present invention can also be suitably used for the pixel configuration described in International Publication No. 2019 / 102887.

[0272] <Solid-state imaging device> The solid-state imaging device of the present invention has the film of the present invention described above. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it includes the film of the present invention and functions as a solid-state imaging device. For example, the following configurations can be mentioned.

[0273] On a substrate, there are a plurality of photodiodes constituting a light-receiving area of a solid-state imaging device (such as a CCD (charge-coupled device) image sensor, a CMOS (complementary metal-oxide semiconductor) image sensor, etc.) and transfer electrodes made of polysilicon or the like. There is a light-shielding film with an opening only in the light-receiving part of the photodiode on the photodiode and the transfer electrode. There is a device protection film made of silicon nitride or the like formed so as to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode on the light-shielding film. It has a configuration with a color filter on the device protection film. Further, it may have a configuration with condensing means (for example, a microlens or the like. The same applies hereinafter) on the device protection film and under the color filter (the side closer to the substrate), or a configuration with condensing means on the color filter. Also, the color filter may have a structure in which each colored pixel is embedded in a space partitioned, for example, in a lattice shape by partition walls. In this case, it is preferable that the partition walls have a lower refractive index than each colored pixel. Examples of the imaging device having such a structure include the devices described in JP-A-2012-227478, JP-A-2014-179577, International Publication No. 2018 / 043654, and US Patent Application Publication No. 2018 / 0040656. Also, like JP-A-2019-211559, an ultraviolet absorption layer may be provided in the structure of the solid-state imaging device to improve light resistance. The imaging device provided with the solid-state imaging device of the present invention can be used not only for a digital camera and an electronic device having an imaging function (such as a mobile phone), but also for an in-vehicle camera and a surveillance camera. Furthermore, the solid-state imaging device incorporating the color filter of the present invention may incorporate, in addition to the color filter of the present invention, another color filter, a near-infrared cut filter, an organic photoelectric conversion film, or the like.

[0274] <Image display device> The image display device of the present invention has the film of the present invention described above. Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device. Regarding the definition of the image display device and the details of each image display device, they are described in, for example, "Electronic Display Device (written by Akio Sasaki, published by Kogyo Chosa Kai, Inc. in 1990)", "Display Device (written by Junsho Ibuki, published by Sangyo Tosho Co., Ltd. in 1990)". Also, regarding the liquid crystal display device, it is described in, for example, "Next-generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosa Kai, Inc. in 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied, and it can be applied to various types of liquid crystal display devices described in the above "Next-generation Liquid Crystal Display Technology", for example.

Example

[0275] The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0276] <Measurement of Weight-average Molecular Weight (Mw) of Sample> The weight-average molecular weight of the sample was measured by gel permeation chromatography (GPC) under the following conditions. Type of column: Column connected with TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 Developing solvent: Tetrahydrofuran Column temperature: 40 °C Flow rate (sample injection volume): 1.0 μL (sample concentration: 0.1 mass%) Device name: HLC-8220GPC manufactured by Tosoh Corporation Detector: RI (refractive index) detector Calibration curve base resin: Polystyrene resin

[0277] <Measurement of Acid Value of Sample> The acid value of the sample represents the mass of potassium hydroxide required to neutralize the acidic components per 1 g of the solid content in the sample. The acid value of the sample was measured as follows. That is, the measurement sample was dissolved in a mixed solvent of tetrahydrofuran / water = 9 / 1 (mass ratio), and the resulting solution was subjected to neutralization titration with a 0.1 mol / L aqueous potassium hydroxide solution at 25°C using a potentiometric titrator (trade name: AT-510, manufactured by Kyoto Electronics Industry Co., Ltd.). Using the inflection point of the titration pH curve as the titration end point, the acid value was calculated by the following formula. A = 56.11×Vs×0.5×f / w A: Acid value (mgKOH / g) Vs: Amount of 0.1 mol / L aqueous potassium hydroxide solution used for titration (mL) f: Normality of 0.1 mol / L aqueous potassium hydroxide solution w: Mass of the sample (g) (in terms of solid content conversion)

[0278] <Synthesis of terminal-blocking agent macromonomer> (Synthesis Example 1-1) Synthesis example of terminal-blocking agent macromonomer EDM-1 2.3 g of 2-mercaptoethanol, 35 g of ε-caprolactone, and 0.5 g of monobutyltin oxide were added to a three-necked flask purged with nitrogen, and the mixture was heated and stirred at 90°C for 2 hours and then at 120°C for 6 hours to obtain a polymer having SH groups and OH groups at both ends of the polyester. After cooling to 5°C, 0.5 g of acetyl chloride was added and the mixture was further stirred for 2 hours to block the OH group terminal and obtain a polymer having a SH group at one end. Next, 4.1 g of 2-acryloyloxyethyl isocyanate (Karenz AOI, manufactured by Showa Denko K.K.) and 0.3 g of a polymerization initiator (V-601, manufactured by Fuji Film Wako Pure Chemical Corporation) were added, and the mixture was heated and stirred at 80°C for 2 hours to carry out an enethiol reaction to obtain the terminal-blocking agent macromonomer EDM-1.

[0279] (Synthesis Examples 1-2, 1-3) Synthesis examples of terminal-blocking agent macromonomers EDM-2 and EDM-3 The terminal-blocking agent macromonomers EDM-2 and EDM-3 were synthesized in the same manner as in Synthesis Example 1-1.

[0280] (Synthesis Example 1-4) Synthesis Example of Terminal Capping Agent Macromonomer EDM-4 181.3 g of methyl methacrylate and 200.2 g of butyl acrylate were added to a three-necked flask purged with nitrogen and diluted with 590 g of propylene glycol monomethyl ether acetate. This was heated to 75°C under a nitrogen atmosphere. Next, 9.2 g of 3-mercaptopropionic acid and 2.2 g of a polymerization initiator (V-601, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were added, and the mixture was heated and stirred at 75°C for 8 hours under a nitrogen atmosphere. 7.3 g of thionyl chloride was added to the obtained polymer solution, and the mixture was further heated and stirred at 75°C for 2 hours. The weight average molecular weight of the obtained terminal capping agent macromonomer EDM-4 was 7400.

[0281] (Synthesis Example 1-5) Synthesis Example of Terminal Capping Agent Macromonomer EDM-5 The terminal capping agent macromonomer EDM-5 was synthesized in the same manner as in Synthesis Example 1-4.

[0282] (Synthesis Example 1-6) Synthesis Example of Terminal Capping Agent Macromonomer EDM-6 181.3 g of methyl methacrylate and 200.2 g of butyl acrylate were added to a three-necked flask purged with nitrogen and diluted with 590 g of propylene glycol monomethyl ether acetate. This was heated to 75°C under a nitrogen atmosphere. Next, 19.9 g of 6-mercaptohexanol and 2.2 g of a polymerization initiator (V-601, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were added, and the mixture was heated and stirred at 75°C for 8 hours under a nitrogen atmosphere. 37.3 g of pyromellitic dianhydride was added to the obtained polymer solution, and the mixture was further heated and stirred at 75°C for 2 hours. Unreacted pyromellitic dianhydride was removed by filtration as an insoluble matter. The weight average molecular weight of the obtained terminal capping agent macromonomer EDM-6 was 2400.

[0283] (Synthesis Example 1-7) Synthesis Example of Terminal Capping Agent Macromonomer EDM-7 The terminal capping agent macromonomer EDM-7 was synthesized in the same manner as in Synthesis Example 1-6.

[0284] (Synthesis Example 1-8) Synthesis Example of Terminal Capping Agent Macromonomer EDM-8 A nitrogen-purged three-neck flask was charged with 6.1 g of 6-mercaptohexanol, 35 g of ε-caprolactone, and 0.5 g of monobutyltin oxide. The mixture was heated and stirred at 90°C for 2 hours and then at 120°C for 6 hours to obtain a polyester polymer with both SH and OH groups at both ends. After cooling to 5°C, 0.5 g of acetyl chloride was added and stirred for an additional 2 hours to cap the OH end, yielding a polymer with one SH end. Next, 5.5 g of itaconic anhydride and 0.3 g of a polymerization initiator (V-601, Fujifilm Wako Pure Chemical Industries, Ltd.) were added and heated and stirred at 80°C for 2 hours to carry out an ene-thiol reaction, yielding the end-capping macromonomer EDM-8.

[0285] (Synthesis Examples 1-9 to 1-15) Synthesis Examples of End-Capping Agent Macromonomers EDM-9 to EDM-15 End-capping agent macromonomers EDM-9 to EDM-15 were synthesized in the same manner as in Synthesis Example 1-8.

[0286] (Synthesis Example 1-16) Synthesis example of end-capping agent macromonomer EDM-16 281.3 g of methyl methacrylate and 100.2 g of butyl acrylate were added to a nitrogen-purged three-neck flask and diluted with 590 g of propylene glycol monomethyl ether acetate. This mixture was heated to 75°C under a nitrogen atmosphere. Next, 13.9 g of a chain transfer agent (AAA-1) and 2.5 g of a polymerization initiator (V-601, Fujifilm Wako Pure Chemical Industries, Ltd.) were added, and the mixture was heated and stirred at 75°C for 8 hours under a nitrogen atmosphere. The resulting end-capping agent macromonomer EDM-16 had a weight-average molecular weight of 7,400. [ka]

[0287] (Synthesis Examples 1-17 to 1-20) Synthesis Examples of End-Capping Agent Macromonomers EDM-17 to EDM-20 End-capping agent macromonomers EDM-17 to EDM-20 were synthesized in the same manner as in Synthesis Example 1-16.

[0288] (Synthesis Example 1-21) Synthesis example of end-capping agent macromonomer EDM-21 151.3 g of methyl methacrylate and 230.2 g of butyl acrylate were added to a nitrogen-substituted three-necked flask and diluted with 590 g of propylene glycol monomethyl ether acetate. This was heated to 75°C under a nitrogen atmosphere. Next, 20.9 g of 6-mercaptohexanol and 2.0 g of a polymerization initiator (V-601, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were added, and the mixture was heated and stirred at 75°C for 8 hours under a nitrogen atmosphere. The obtained polymer solution having terminal hydroxy groups was cooled to 5°C, 32.1 g of trimellitic anhydride chloride was added, and 15.3 g of pyridine was added dropwise over 6 hours. Further, the mixture was stirred at room temperature for 24 hours, and insoluble matters were removed by filtration. The weight-average molecular weight of the obtained end-capping agent macromonomer EDM-21 was 7800.

[0289] (Synthesis Examples 1-22 to 1-40) Synthesis Examples of End-Capping Agent Macromonomers EDM-22 to EDM-40 In the same manner as in Synthesis Example 1-21, end-capping agent macromonomers EDM-22 to EDM-40 were synthesized.

[0290] The structures and weight-average molecular weights (Mw) of the end-capping agent macromonomers EDM-1 to EDM-40 are shown below. In Poly, the numerical values attached to the repeating units of EDM-1 to EDM-3, EDM-8 to EDM-15, and EDM-27 to EDM-29 represent the number of repeating units, and the numerical values attached to the repeating units of EDM-4, EDM-6, EDM-16, EDM-19 to EDM-21, EDM-24 to EDM-26, EDM-30, EDM-33 to EDM-36, EDM-39, and EDM-40 represent the molar ratios of the repeating units. Also, the structure described in Poly is P of formula (1) 1 is as follows. [Table 1] [Table 2] [Table 3]

[0291] <Synthesis Example of Resin> (Synthesis Example 2-1) Synthesis of Resin B-1 3.3 g of 1,3-phenylenediamine (diamine DA-1, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to a three-necked flask purged with nitrogen, and 10 g of propylene glycol monomethyl ether acetate was added thereto, followed by heating to 40°C. 2.2 g of pyromellitic dianhydride (acid dianhydride AA-1, manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto, and the mixture was heated and stirred at 40°C for 6 hours to obtain an amic acid prepolymer having amino groups at both ends. 19 g (in terms of solid content) of a terminal blocking agent macromonomer EDM-1 was added to this prepolymer solution, and the mixture was heated and stirred at 40°C for 2 hours to obtain a 30% propylene glycol monomethyl ether acetate solution of Resin B-1. The weight average molecular weight of the obtained Resin B-1 was 20,600, and the acid value was 55 mgKOH / g.

[0292] (Synthesis Examples 2-2 to 2-93) Synthesis of Resins B-2 to B-93 Resins B-2 to B-93 were synthesized in the same manner as in Synthesis Example 2-1, except that the acid dianhydride, diamine, terminal blocking agent macromonomer, and terminal blocking agent were changed to the types and charged amounts described in the following table. The weight average molecular weight (Mw) and acid value of each resin are shown in accordance with the following table.

[0293]

Table 4

[0294]

Table 5

[0295]

Table 6

[0296] The terminal blocking agent macromonomers EDM-1 to EDM-40 are compounds having the structures described above. Also, the acid dianhydrides AA-1 to AA-8, the diamines DA-1 to DA-7, and the terminal blocking agents ED-1 to ED-3 are compounds having the structures shown below.

[0297]

Chemical formula

[0298]

Chemical formula

[0299]

Chemical formula

[0300] <Production of dispersion liquid> A mixed solution obtained by mixing the raw materials described in the following table was mixed and dispersed for 3 hours using a bead mill (using zirconia beads with a diameter of 0.3 mm), and then further dispersed under a pressure of 2000 MPa at a flow rate of 500 g / min using a high-pressure homogenizer NANO-3000-10 (manufactured by Nippon BEE International Co., Ltd.) equipped with a decompression mechanism. This dispersion treatment was repeated 10 times to obtain each dispersion liquid.

[0301]

Table 7

Table 8

Table 9

Table 10

Table 11

Table 12

Table 13

Table 14

[0302] The unit of the numerical values described in the above table is parts by mass. Among the raw materials shown in the above table, the details of the raw materials indicated by abbreviations are as follows. 〔Colorant〕 PR264: C.I. Pigment Red 264 (red pigment, diketopyrrolopyrrole pigment) PR254: C.I. Pigment Red 254 (red pigment, diketopyrrolopyrrole pigment) PR179: C.I. Pigment Red 179 PB15:6: C.I. Pigment Blue 15:6 (blue pigment, phthalocyanine pigment) PB16: C.I. Pigment Blue 16 (blue pigment, phthalocyanine pigment) PG7: C.I. Pigment Green 7 PG36: C.I. Pigment Green 36 PG58: C.I. Pigment Green 58 PY129: C.I. Pigment Yellow 129 PY185: C.I. Pigment Yellow 185 PY215: C.I. Pigment Yellow 215 PV23: C.I. Pigment Violet 23 IRGAPHORE: Irgaphor Black S 0100 CF (manufactured by BASF, compound with the following structure, lactam pigment)

Chemical formula

Chemical formula

[0303] [Pigment Derivative] Derivative 1: A compound with the following structure [Chemical formula] Derivative 2: A compound with the following structure [Chemical formula]

[0304] [Resin (Dispersant)] (Specific Resin) B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, B-9, B-10, B-11, B-12, B-13, B-14, B-15, B-16, B-17, B-18, B-19, B-20, B-21, B-22, B-23, B-24, B-25, B-26, B-27, B-28, B-29, B-30, B-31, B-32, B-33, B-46, B-47, B-48, B-49, B-50, B-51, B-52, B-53, B-54, B-55, B-56, B-58, B-59, B-60, B-61, B-62, B-63, B-65, B-67, B-69, B-71, B-73, B-74, B-75, B-77, B-78, B-79, B-80, B-81, B-82, B-83, B-84, B-85, B-86, B-90, B-91, B-92, B-93: The above-mentioned resin

[0305] (Comparative Resin) cB-1: A resin with the following structure (weight average molecular weight is 10885, acid value is 74 mg KOH / g. The description of "Polym" indicates that the polymer chain with the repeating unit of the structure shown by "Polym" bonded by the number of subscript numerical values is bonded to the sulfur atom (S).) [Chemical formula]

[0306] [Solvent] C-1: Propylene Glycol Monomethyl Ether Acetate C-2: Propylene Glycol Monomethyl Ether C-3: Cyclohexanone

[0307] <Manufacture of resin composition> The raw materials described in the following table were mixed to prepare the resin compositions of the examples and comparative examples.

[0308]

Table 15

Table 16

[0309]

Table 17

[0310] Among the raw materials described in the above table, the details of the raw materials indicated by abbreviations are as follows.

[0311] 〔Dispersion liquid〕 Dispersion liquids R1 to R26, B1 to B25, G1 to G27, Bk1 to Bk20, CR1, CB1, CG1, CBk1 to 3: The above-described dispersion liquids

[0312] 〔Resin〕 Ba-1: Resin with the following structure (the numerical values attached to the main chain are molar ratios. Weight average molecular weight 11000)

Chemical formula

Chemical formula

Chemical formula

[0313] [Polymerizable monomer] D-1: Acrylate compound (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) D-2: Epoxy compound (TETRAD-X, manufactured by Mitsubishi Gas Chemical Company, Inc., N,N,N‘,N’-tetraglycidyl-m-xylenediamine) D-3: Oxetane compound (OXT-221, manufactured by Toagosei Co., Ltd., 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane) D-4: Oxetane compound (OX-SQ TX-100, manufactured by Toagosei Co., Ltd.)

[0314] [Photoinitiator] E-1: Omnirad 379EG (manufactured by IGM Resins B.V., 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one) E-2: Irgacure OXE01 (manufactured by BASF, oxime compound) E-3: Compound with the following structure [Chemical formula]

[0315] [Solvent] C-1: Propylene glycol monomethyl ether acetate C-2: Propylene glycol monomethyl ether C-3: Cyclohexanone

[0316] [Evaluation] [Evaluation of dispersibility] (Storage stability) In each of the examples and comparative examples, the viscosity (mPa·s) of the resin composition was measured using "RE-85L" manufactured by Toki Sangyo Co., Ltd. After the above measurement, the resin composition was allowed to stand under the conditions of 45°C, light shielding, and for 3 days, and the viscosity (mPa·s) was measured again. The storage stability was evaluated according to the following evaluation criteria based on the viscosity difference (ΔVis) before and after the standing. The smaller the numerical value of the viscosity difference (ΔVis), the better the storage stability of the resin composition and the better the dispersibility of the pigment. All of the above viscosity measurements were performed in a laboratory where the temperature and humidity were controlled at 22 ± 5°C and 60 ± 20%, respectively, with the temperature of the resin composition adjusted to 25°C.

[0317] - Evaluation Criteria - A: ΔVis was 0.5 mPa·s or less. B: ΔVis exceeded 0.5 mPa·s and was 1.0 mPa·s or less. C: ΔVis exceeded 1.0 mPa·s and was 2.0 mPa·s or less. D: ΔVis exceeded 2.0 mPa·s and was 2.5 mPa·s or less. E: ΔVis exceeded 2.5 mPa·s.

[0318] (Particle Size) Using a dynamic light scattering particle size distribution measuring device (LB-500 manufactured by Horiba, Ltd.) conforming to JIS8826:2005, the resin composition obtained above was aliquoted into 20 ml sample bottles and diluted and adjusted with propylene glycol monomethyl ether acetate so that the solid content concentration became 0.2 mass%. Using a 2 ml quartz cell for measurement at a temperature of 25°C, data acquisition of the above dilution was performed 50 times, and the number average particle size of the pigment (number average particle diameter) of the arithmetic mean based on the number was determined. It can be said that the smaller the value of the number average particle size of the pigment, the better the dispersibility of the pigment. - Evaluation Criteria - A: The number average particle size of the pigment was 0.05 μm or less. B: The number average particle size of the pigment exceeded 0.05 μm and was 0.10 μm or less. C: The number average particle size of the pigment exceeded 0.10 μm and was 0.20 μm or less. D: The number average particle diameter of the pigment exceeded 0.20 μm and was 0.50 μm or less. E: The number average particle diameter of the pigment exceeded 0.50 μm.

[0319] 〔Evaluation of film shrinkage rate〕 In each of the examples and comparative examples, the resin composition was applied onto a glass substrate by spin coating, 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. The film thickness was measured by shaving a part of the film to expose the surface of the glass substrate and measuring the step (film thickness of the coating film) between the surface of the glass substrate and the coating film using a stylus profilometer (DektakXT, manufactured by BRUKER). Next, the obtained film was heat-treated at 300 °C for 5 hours in a nitrogen atmosphere. The film thickness of the film after the heat treatment was measured in the same manner, and the film shrinkage rate was determined from the following formula, and the film shrinkage rate was evaluated according to the following evaluation criteria. T0 and T1 below were both measured in a laboratory where the temperature and humidity were controlled at 22 ± 5 °C and 60 ± 20%, respectively, with the substrate temperature adjusted to 25 °C. The smaller the film shrinkage rate, the more the film shrinkage is suppressed, and it can be said that the result is preferable. Film shrinkage rate (%) = (1 - (T1 / T0)) × 100 T0: Film thickness immediately after production (= 0.60 μm) T1: Film thickness after heat treatment at 300 °C for 5 hours in a nitrogen atmosphere - Evaluation criteria - A: The film shrinkage rate was 1% or less. B: The film shrinkage rate exceeded 1% and was 5% or less. C: The film shrinkage rate exceeded 5% and was 10% or less. D: The film shrinkage rate exceeded 10% and was 30% or less. E: The film shrinkage rate exceeded 30%.

[0320] 〔Evaluation of cracks〕 In each of the examples and comparative examples, the resin composition was applied onto a glass substrate by spin coating, 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. Subsequently, 200 nm of SiO2 was laminated on the surface of the obtained film by sputtering to form an inorganic film. The film with the inorganic film formed on its surface was heat-treated at 300 °C for 5 hours in a nitrogen atmosphere. The surface of the inorganic film after the heat treatment was observed with an optical microscope, and the number of cracks per 1 cm 2 was counted, and the presence or absence of cracks was evaluated according to the following evaluation criteria. - Evaluation Criteria - A: The number of cracks per 1 cm 2 was 0. B: The number of cracks per 1 cm 2 was 1 to 10. C: The number of cracks per 1 cm 2 was 11 to 50. D: The number of cracks per 1 cm 2 was 51 to 100. E: The number of cracks per 1 cm 2 was 101 or more.

[0321]

Table 18

[0322]

Table 19

[0323]

Table 20

[0324] When using the resin composition of the example, compared with the case of using the resin composition of the comparative example, the evaluation of storage stability and particle size was excellent in both cases, and the dispersibility of the pigment was excellent. Furthermore, when using the resin composition of the example, compared with the case of using the resin composition of the comparative example, the film shrinkage rate was small in both cases, and the generation of cracks was suppressed. Therefore, it can be said that it is possible to expand the process window in the process after manufacturing the film as compared with the resin composition of the comparative example.

[0325] (Example 1000: Pattern formation by photolithography method) On a silicon wafer, the resin composition of Example 1 was spin-coated, dried at 100 °C for 120 seconds (pre-bake) using a hot plate, and then heated at 200 °C for 30 minutes (post-bake) using an oven to form a resin composition layer with a thickness of 0.60 μm. Next, for this resin composition layer, through a mask pattern in which non-mask portions in the shape of a square with a side length of 1.1 μm were arranged in a 4 mm × 3 mm region, light with a wavelength of 365 nm was irradiated with an exposure dose of 500 mJ / cm 2 and exposed using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.). Next, the silicon wafer on which the exposed resin composition layer was formed was placed on the horizontal rotation table of a spin shower developer (DW-30 type, manufactured by Chemtronics Co., Ltd.), and paddle development was performed at 23 °C for 60 seconds using a developer (CD-2000, manufactured by Fujifilm Electronic Materials Co., Ltd.). Next, while rotating the silicon wafer at a rotation speed of 50 rpm, pure water was supplied in a shower form from a spray nozzle above the center of rotation to perform a rinse process, and then spray drying was performed to form a pattern (pixel).

[0326] The fabricated silicon wafer with pixels was divided into two parts, and one part was heat-treated at 300 °C for 5 hours in a nitrogen atmosphere (hereinafter, one part is referred to as the substrate before the 300 °C heat treatment, and the other part is referred to as the substrate after the 300 °C heat treatment). When the cross-sections of the pixels formed on the substrate before the 300 °C heat treatment and the substrate after the 300 °C heat treatment were evaluated with a scanning electron microscope (SEM), the height (thickness) of the pixels formed on the substrate after the 300 °C heat treatment was 97% of the height (thickness) of the pixels formed on the substrate before the 300 °C heat treatment.

Claims

1. A compound represented by formula (EDM1); 【Chemical Formula 1】 In formula (EDM1), R ＥＤ１ represents an acid anhydride group, Lp ＥＤ１ represents an (n + 1)-valent group, and the (n + 1)-valent group is a group having a structure in which a hydrocarbon group is combined with at least one group selected from -NRpED1-, -O-, -COO-, -OCO-, -S-, -NRpED1CO- and -CONRpED1-, and the bonding end with LpED2 is a hydrocarbon group, Rp ＥＤ１ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, Lp ＥＤ２ represents -O- or -S-, P ＥＤ１ represents a polymer chain containing a repeating unit represented by any one of formula (P1-1) to formula (P1-3), wherein the number of the repeating units is 5 or more, and when LpED2 is -O-, the bonding end of PED1 with LpED2 is -CO- n represents 1 or 2; 【Chemical 2】 In formulas (P1-1) to (P1-3), RG1 represents an alkylene group.

2. The compound according to claim 1, wherein the compound represented by the formula (EDM1) is a compound represented by the formula (EDM2); 【Chemical Formula 3】 In formula (EDM2), R ＥＤ１２ represents a halogen atom, an alkyl group, a carboxy group or a hydroxy group, Lp ＥＤ１ａ represents an (n + 1)-valent group, and the (n + 1)-valent group represents a hydrocarbon group, Lp ＥＤ２ represents -O- or -S-, P ＥＤ１ represents a polymer chain containing a repeating unit represented by any one of the formulas (P1-1) to (P1-3), wherein the number of the repeating units is 5 or more. When LpED2 is -O-, the binding end of PED1 with LpED2 is -CO- r represents an integer from 0 to 3, n represents 1 or 2.

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