WO2024181118A1

WO2024181118A1 - Resin composition, film, optical filter, solid-state imaging element, and image display device

Info

Publication number: WO2024181118A1
Application number: PCT/JP2024/004908
Authority: WO
Inventors: 俊佑柳; 憲晃佐藤
Original assignee: 富士フイルム株式会社
Priority date: 2023-02-27
Filing date: 2024-02-14
Publication date: 2024-09-06

Abstract

Provided are: a resin composition comprising a colorant A including a pigment and a resin B, wherein the content of the colorant A is 50 mass% or higher relative to a total solid content in the resin composition and the resin B includes a resin b having a repeating unit b1 represented by formula (b1-1) and a repeating unit b2 having an acid group; and a film, an optical filter, a solid-state imaging element, and an image display device each obtained using the resin composition.

Description

Resin composition, film, optical filter, solid-state imaging device and image display device

The present invention relates to a resin composition containing a colorant. The present invention also relates to a film, an optical filter, a solid-state imaging device, and an image display device that use the resin composition.

As described in Patent Document 1, optical filters such as color filters are manufactured using a resin composition containing a color material and a resin.

JP 2020-098347 A

In recent years, there has been a strong demand for smaller and thinner solid-state imaging devices. For this reason, there has also been a demand in recent years for films containing color materials, such as color filters, used in solid-state imaging devices to be thinner. In order to achieve thinner films while maintaining the desired spectral performance, it is necessary to increase the concentration of color materials in the resin composition used to form the film.

However, when a pigment-containing coloring material is used, increasing the coloring material concentration in the resin composition reduces the relative proportion of materials that can be adsorbed by the pigment, such as the resin, so the pigment tends to aggregate during storage of the resin composition, and the viscosity of the resin composition tends to increase over time.

Therefore, an object of the present invention is to provide a resin composition having excellent storage stability. Another object of the present invention is to provide a film, an optical filter, a solid-state imaging device, and an image display device.

The inventors have found through their research that the above object can be achieved by using the resin composition described below, and have completed the present invention. Therefore, the present invention provides the following.

<1> A resin composition comprising a color material A containing a pigment and a resin B,
The content of the color material A in the total solid content of the resin composition is 50% by mass or more,
The resin B is a resin composition containing a resin b having a repeating unit b1 represented by formula (b1-1) and a repeating unit b2 having an acid group;
In formula (b1-1), R ^b11 represents a hydrogen atom or an alkyl group.
R ^b12 represents a polycyclic aromatic ring group, an unsubstituted alkyl group having 3 to 8 carbon atoms, a monocyclic aromatic hydrocarbon group having an electron-withdrawing group or an electron-donating group as a substituent, or a monocyclic aromatic heterocyclic group which may have an electron-withdrawing group or an electron-donating group as a substituent.
<2> The resin composition according to <1>, wherein R ^b12 in the formula (b1-1) is a monocyclic aromatic hydrocarbon group having an electron-withdrawing group or an electron-donating group as a substituent, or a monocyclic aromatic heterocyclic group which may have an electron-withdrawing group or an electron-donating group as a substituent.
<3> The resin composition according to <1> or <2>, wherein the content of the repeating unit b1 in the resin b is 5 to 55 mol %.
<4> The resin b has a content of the repeating unit b1 in a total molar amount of the repeating unit b1 and the repeating unit b2 of 20 to 70 mol %. The resin composition according to any one of <1> to <3>.
<5> The resin composition according to any one of <1> to <4>, wherein the resin b further includes a repeating unit b3 having a graft chain.
<6> The resin composition according to <5>, wherein the graft chain is a polymer chain containing a polyalkyleneoxy structure.
<7> The resin composition according to any one of <1> to <6>, wherein the pigment includes at least one selected from the group consisting of a diketopyrrolopyrrole pigment, an isoindoline pigment, a quinophthalone pigment, and an azo pigment.
<8> The resin composition according to any one of <1> to <7>, further comprising a polymerizable compound and a photopolymerization initiator.
<9> A film obtained by using the resin composition according to any one of <1> to <8>.
<10> An optical filter comprising the film according to <9>.
<11> A solid-state imaging device comprising the film according to <9>.
<12> An image display device comprising the film according to <9>.

The present invention can provide a resin composition with excellent storage stability. It can also provide a film, an optical filter, a solid-state imaging device, and an image display device.

The present invention will be described in detail below.
In this specification, the use of "to" means that the numerical values before and after it are included as the lower limit and upper limit.
In the description of groups (atomic groups) in this specification, when there is no indication of whether they are substituted or unsubstituted, the term encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, the term "alkyl group" encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups).
In this specification, unless otherwise specified, the term "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, active rays or radiation such as electron beams.
In this specification, "(meth)acrylate" refers to both or either of acrylate and methacrylate, "(meth)acrylic" refers to both or either of acrylic and methacrylic, and "(meth)acryloyl" refers to both or either of acryloyl and methacryloyl.
In this specification, in the structural formulae, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, the weight average molecular weight and number average molecular weight are values calculated as polystyrene standards measured by GPC (gel permeation chromatography).
In this specification, the total solids content refers to the total mass of all components of the composition excluding the solvent.
In this specification, a pigment means a coloring material that is difficult to dissolve in a solvent.
In this specification, the term "process" refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the process achieves its intended effect.

<Resin Composition>
The resin composition of the present invention is a resin composition containing a color material A containing a pigment and a resin B,
The content of the color material A in the total solid content of the resin composition is 50 mass% or more,
Resin B is characterized by containing a resin b having a repeating unit b1 represented by formula (b1-1) and a repeating unit b2 having an acid group.

According to the resin composition of the present invention, by including the above-mentioned resin b, even if the content of the color material A in the total solid content of the resin composition is 50 mass% or more, the increase in viscosity of the resin composition over time can be suppressed. Therefore, the resin composition of the present invention has excellent storage stability. It is presumed that the reason for obtaining such an effect is as follows. The repeating unit b1 represented by formula (b1-1) of the resin b has a structure in which a specific group defined by R ^b12 is bonded to an amide group (-NHCO-), and therefore it is presumed that the repeating unit b1 is easily interacted with the pigment by hydrogen bonding or the like at the site of the amide group. In addition, since the resin b further includes a repeating unit b2 having an acid group, it is presumed that the acid group in the repeating unit b2 also interacts with the pigment, and it is presumed that the acid group can also be adsorbed with the pigment at the site of the acid group. For this reason, it is presumed that the resin b is firmly adsorbed to the surface of the pigment, and the resin b is present in the vicinity of the pigment in the resin composition. For this reason, it is presumed that the aggregation of the pigment can be suppressed by the resin b, and as a result, the storage stability of the resin composition can be improved.

In addition, the resin composition of the present invention has excellent pigment dispersibility because the resin b can suppress pigment aggregation, and can also suppress the generation of coarse particles.

Furthermore, when the resin composition of the present invention is used to form a pattern by photolithography, the occurrence of development residues can also be suppressed. The reason for this effect is presumably that the resin b is firmly adsorbed to the surface of the pigment, which enhances the emulsifying action of the pigment during development, allowing the resin composition in the unexposed areas to be efficiently developed and removed. For this reason, the resin composition of the present invention can also suppress the occurrence of development residues. When the resin composition of the present invention is used for pattern formation by photolithography, it is preferable that the resin composition of the present invention contains a polymerizable compound and a photopolymerization initiator.

The resin composition of the present invention is preferably used as a resin composition for optical filters. Examples of optical filters include color filters, near-infrared transmission filters, and near-infrared cut filters, and color filters are preferred. The resin composition of the present invention is also preferably used for solid-state imaging devices. More specifically, it is preferably used as a resin composition for optical filters used in solid-state imaging devices, and is even more preferably used as a resin composition for forming colored pixels of color filters used in solid-state imaging devices.

An example of a color filter is a filter having colored pixels that transmit light of a specific wavelength. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels, with red pixels being more preferable. The colored pixels of the color filter can be formed using a resin composition that contains a chromatic colorant.

The maximum absorption wavelength of the near-infrared cut filter is preferably in the wavelength range of 700 to 1800 nm, more preferably in the wavelength range of 700 to 1300 nm, and even more preferably in the wavelength range of 700 to 1000 nm. The transmittance of the near-infrared cut filter over the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. The transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less. The ratio of absorbance Amax at the maximum absorption wavelength of the near-infrared cut filter to absorbance A550 at a wavelength of 550 nm (absorbance Amax/absorbance A550) is preferably 20 to 500, more preferably 50 to 500, even 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 color material.

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

The resin composition of the present invention can also be used as a light-shielding film.

The solids concentration of the resin composition of the present invention is preferably 5 to 30% by mass. The lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

The components used in the resin composition of the present invention are described below.

<<Colorant A>>
The resin composition of the present invention contains a color material A (hereinafter, referred to as a color material). Examples of the color material include a white color material, a black color material, a chromatic color material, and a near-infrared absorbing color material. In addition, a pigment derivative can also be used as the color material. In the present invention, the white color material includes not only pure white color materials, but also light gray color materials close to white (e.g., grayish white, light gray, etc.).

The coloring material contained in the resin composition of the present invention is one that contains a pigment. The pigment may be either an inorganic pigment or an organic pigment, but from the standpoint of the wide range of color variations, ease of dispersion, safety, etc., it is preferable that the pigment is an organic pigment. In addition, it is preferable that the pigment contains at least one type selected from a chromatic pigment and a near-infrared absorbing pigment, and it is more preferable that the pigment contains a chromatic pigment.

Furthermore, the coloring material preferably contains at least one selected from the group consisting of phthalocyanine pigments, dioxazine pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, azo pigments, azomethine pigments, diketopyrrolopyrrole pigments, pyrrolopyrrole pigments, isoindoline pigments, and quinophthalone pigments, more preferably contains at least one selected from the group consisting of diketopyrrolopyrrole pigments, isoindoline pigments, quinophthalone pigments, and azo pigments, and even more preferably contains a diketopyrrolopyrrole pigment because this makes the effects of the present invention more pronounced.

The average primary particle diameter of the pigment and pigment derivative 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 even more preferably 100 nm or less. In this specification, the primary particle diameter of the pigment and pigment derivative can be determined from a photograph obtained by observing the primary particles of the pigment and pigment derivative with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is determined, and the corresponding circle equivalent diameter is calculated as the primary particle diameter of the pigment. The average primary particle diameter in the present invention is the arithmetic mean value of the primary particle diameters of 400 primary particles of the pigment. The primary particles of the pigment refer to independent particles without aggregation. The same applies to the average primary particle diameter of the pigment derivative.

The crystallite size of the pigment and pigment derivative is preferably 0.1 to 50 nm, more preferably 0.5 to 30 nm, and even more preferably 1 to 15 nm. The crystallite size can be determined from the half-width of the diffraction angle peak using an X-ray diffraction device, and is calculated using Scherrer's formula. The crystallite size of the organic pigment and pigment derivative can be adjusted by known methods such as adjusting the production conditions or grinding after production.

The specific surface area of the pigment and pigment derivative is preferably 1 to 300 m ² /g. The lower limit is preferably 10 m ² /g or more, more preferably 30 m ² /g or more. The upper limit is preferably 250 m ² /g or less, more preferably 200 m ² /g or less. The value of the specific surface area can be measured according to DIN 66131: determination of the specific surface area of solids by gas adsorption in accordance with the BET (Brunauer, Emmett and Teller) method.

The colorant contained in the resin composition of the present invention preferably contains a pigment and a pigment derivative. Examples of the pigment derivative include compounds having a structure in which an acid group or a basic group is bonded to a colorant skeleton. Details of the pigment derivative will be described later. The content of the pigment derivative is preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass, per 100 parts by mass of the pigment. Only one type of pigment derivative may be used, or two or more types may be used in combination.

The coloring material contained in the resin composition of the present invention may further contain a dye. When a dye is contained, the content of the dye is preferably 10 to 100 parts by mass relative to 100 parts by mass of the pigment. The upper limit is preferably 80 parts by mass or less, and more preferably 70 parts by mass or less. The lower limit is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 40 parts by mass or more. Only one type of dye may be used, or two or more types may be used in combination.
It is also preferable that the coloring material contained in the resin composition of the present invention is substantially free of dye. According to this embodiment, a film having excellent light resistance and heat resistance can be formed. "Substantially free of dye" means that the content of the dye in the coloring material is 0.1% by mass or less, preferably 0.01% by mass or less, and more preferably no dye is contained.

(chromatic colorants)
Examples of chromatic colorants include colorants having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. Examples include yellow colorants, orange colorants, red colorants, green colorants, purple colorants, and blue colorants. From the viewpoint of heat resistance, the chromatic colorant is preferably a pigment (chromatic pigment), more preferably a red pigment, a yellow pigment, or a blue pigment, and even more preferably a red pigment or a blue pigment. Specific examples of chromatic pigments include those shown below.

The red colorant may be a diketopyrrolopyrrole compound, anthraquinone compound, an azo compound, a naphthol compound, an azomethine compound, a xanthene compound, a quinacridone compound, a perylene compound, or a thioindigo compound. A diketopyrrolopyrrole compound, an anthraquinone compound, or an azo compound is preferable, and a diketopyrrolopyrrole compound is more preferable. The red colorant is preferably a red pigment. The red pigment is preferably a diketopyrrolopyrrole pigment.

Specific examples of red colorants include C.I. (Color Index) 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, Examples of red pigments include 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, 295, 296, and 297. In addition, as a red colorant, a compound described in paragraph 0034 of International Publication No. 2022/085485 and a brominated diketopyrrolopyrrole compound described in JP-A-2020-085947 can also be used.

As red colorants, C.I. Pigment Red 122, 177, 224, 254, 255, 264, 269, and 272 are preferred, C.I. Pigment Red 254, 264, and 272 are more preferred, and C.I. Pigment Red 254 and 272 are even more preferred.

Green colorants include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred. The green colorant is preferably a green pigment. The green pigment is preferably a phthalocyanine pigment.

Specific examples of green colorants include green pigments such as C.I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66. In addition, halogenated zinc phthalocyanine pigments having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule can also be used as green colorants. Specific examples include the compounds described in WO 2015/118720. In addition, compounds described in paragraph 0029 of WO 2022/085485, aluminum phthalocyanine compounds described in JP 2020-070426 A, and diarylmethane compounds described in JP 2020-504758 A can also be used as green colorants.

As green colorants, C.I. Pigment Green 7, 36, 58, 62, and 63 are preferred, and C.I. Pigment Green 36 and 58 are more preferred.

Orange colorants include diketopyrrolopyrrole compounds and azo compounds, and are preferably diketopyrrolopyrrole compounds. The orange colorant is preferably an orange pigment. The orange pigment is preferably a diketopyrrolopyrrole pigment. Specific examples of orange colorants include orange pigments such as 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, and 73.

Examples of yellow colorants include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds, and perylene compounds. The yellow colorant is preferably a yellow pigment. The yellow pigment is preferably at least one selected from isoindoline pigments, quinophthalone pigments, and azo pigments. Specific examples of yellow colorants include 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, 233, 234, 235, 236, and other yellow pigments.

Furthermore, as the yellow coloring material, an azobarbituric acid nickel complex having the following structure can also be used.

Also, as yellow colorants, the compounds described in paragraphs 0031 to 0033 of WO 2022/085485, the methine dyes described in JP 2019-073695 A, and the methine dyes described in JP 2019-073696 A can be used.

Examples of purple colorants include oxazine compounds, quinacridone compounds, perylene compounds, and indigo compounds, with oxazine compounds being preferred. The purple colorant is preferably a purple pigment. Specific examples of purple colorants include purple pigments such as C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.

Examples of blue colorants include phthalocyanine compounds and squarylium compounds, and are preferably phthalocyanine compounds. The blue colorant is preferably a blue pigment. The blue pigment is preferably a phthalocyanine pigment. Specific examples of blue colorants include blue pigments such as 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, and 88. Aluminum phthalocyanine compounds having phosphorus atoms can also be used as blue colorants. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP-A No. 2012-247591 and paragraph 0047 of JP-A No. 2011-157478.

Dyes can also be used as chromatic colorants. There are no particular limitations on the dyes, and any known dyes can be used. Examples include pyrazole azo dyes, anilino azo dyes, triarylmethane dyes, anthraquinone dyes, anthrapyridone dyes, benzylidene dyes, oxonol dyes, pyrazolotriazole azo dyes, pyridone azo dyes, cyanine dyes, phenothiazine dyes, pyrrolopyrazole azomethine dyes, xanthene dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, and pyrromethene dyes.

A dye polymer can also be used as a chromatic colorant. The dye polymer is preferably a dye dissolved in a solvent. The dye polymer may form particles. When the dye polymer is a particle, it is usually used in a state dispersed in a solvent. A particulate dye polymer can be obtained by, for example, emulsion polymerization, and examples of the compound and manufacturing method described in JP-A-2015-214682 include the compound and manufacturing method described in JP-A-2015-214682. The dye polymer has two or more dye structures in one molecule, and preferably has three or more dye structures. There is no particular limit to the upper limit, but it can be 100 or less. The multiple dye structures in one molecule may be the same dye structure or different dye structures. The weight average molecular weight (Mw) of the dye polymer is preferably 2,000 to 50,000. The lower limit is more preferably 3,000 or more, and even more preferably 6,000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less. The dye multimer may be a compound described in JP2011-213925A, JP2013-041097A, JP2015-028144A, JP2015-030742A, WO2016/031442, etc.

As chromatic colorants, there may be mentioned a triarylmethane dye polymer described in Korean Patent Publication No. 10-2020-0028160, a xanthene compound described in JP 2020-117638 A, a phthalocyanine compound described in WO 2020/174991 A, an isoindoline compound or a salt thereof described in JP 2020-160279 A, a compound represented by formula 1 described in Korean Patent Publication No. 10-2020-0069442 A, a compound represented by formula 1 described in Korean Patent Publication No. 10-2020-0069730 A, a compound represented by formula 1 described in Korean Patent Publication No. 10-2020-0069070 A, Compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069067, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069062, halogenated zinc phthalocyanine pigments described in Japanese Patent No. 6809649, isoindoline compounds described in JP-A-2020-180176, phenothiazine compounds described in JP-A-2021-187913, halogenated zinc phthalocyanines described in WO 2022/004261, and halogenated zinc phthalocyanines described in WO 2021/250883 can be used. The other colorant may be a rotaxane, and the dye skeleton may be used in the cyclic structure of the rotaxane, may be used in the rod-shaped structure, or may be used in both structures. Other colorants include quinophthalone compounds represented by formula 1 in Korean Patent Publication No. 10-2020-0030759, polymer dyes described in Korean Patent Publication No. 10-2020-0061793, colorants described in JP-A-2022-029701, isoindoline compounds described in WO 2022/014635, aluminum phthalocyanine compounds described in WO 2022/024926, compounds described in JP-A-2022-045895, compounds described in WO 2022/050051, compounds described in JP-A-2020-090676, compounds described in JP-A-2020-055956, compounds described in JP-A-2021-031681, compounds described in JP-A-2022-056354, and compounds described in U.S. Patent Application Publication No. Compounds described in JP 2021/0355327, compounds described in WO 2022/065357, compounds described in JP 2020-045436, compounds described in Korean Patent Publication No. 10-2021-0146726, compounds described in JP 2018-178039, compounds described in Chinese Patent Application Publication No. 113881244, compounds described in Chinese Patent Application Publication No. 113881245, compounds described in Chinese Patent Application Publication No. 113881246, compounds described in JP 2022-104822, compounds described in JP 2022-096701, compounds described in JP 2020-023652, green pigments described on pages 80 to 84 of the Journal of the Color Materials Association (published in 2022), and the like can also be used.

Two or more chromatic coloring materials may be used in combination. When two or more chromatic coloring materials are used in combination, the two or more chromatic coloring materials may form a black color. Examples of such combinations include the following embodiments (1) to (7). When the resin composition contains two or more chromatic coloring materials and exhibits a black color through a combination of two or more chromatic coloring materials, the resin composition of the present invention can be preferably used as a resin composition for forming a near-infrared transmission filter.
(1) An embodiment containing a red color material and a blue color material.
(2) An embodiment containing a red color material, a blue color material, and a yellow color material.
(3) An embodiment containing a red color material, a blue color material, a yellow color material, and a purple color material.
(4) An embodiment containing a red color material, a blue color material, a yellow color material, a purple color material, and a green color material.
(5) An embodiment containing a red color material, a blue color material, a yellow color material, and a green color material.
(6) An embodiment containing a red color material, a blue color material, and a green color material.
(7) An embodiment containing a yellow color material and a purple color material.

(White color material)
Examples of the white coloring material include inorganic 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, and zinc sulfide. The white coloring material can be the white pigment described in paragraphs 0040 to 0043 of WO 2022/085485.

(Black color material)
The black coloring material is not particularly limited, and any known material can be used. The black coloring material may be an inorganic black coloring material or an organic black coloring material. The black coloring material is preferably a pigment. In this specification, the black coloring material means a coloring material that exhibits absorption over the entire wavelength range of 400 to 700 nm.

Examples of inorganic black colorants include carbon black, titanium black, graphite, etc., with carbon black and titanium black being preferred, and titanium black being more preferred. Titanium black is black particles containing titanium atoms, and low-order titanium oxide and titanium oxynitride are preferred. As titanium black, the titanium black described in paragraph 0044 of WO 2022/085485 can be used.

Examples of organic black coloring materials include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred. As the organic black coloring material, the compounds described in paragraph number 0166 of WO 2022/065215 can be used. In addition, perylene black (Lumogen Black FK4280, etc.) described in paragraphs 0016 to 0020 of JP 2017-226821 A can also be used as the organic black coloring material.

(Near infrared absorbing colorant)
The near-infrared absorbing colorant is preferably a compound having a maximum absorption wavelength longer than 700 nm. The near-infrared absorbing colorant is preferably a compound having a maximum absorption wavelength in the range of more than 700 nm to 1800 nm, more preferably a compound having a maximum absorption wavelength in the range of more than 700 nm to 1400 nm, even more preferably a compound having a maximum absorption wavelength in the range of more than 700 nm to 1200 nm, and particularly preferably a compound having a maximum absorption wavelength in the range of more than 700 nm to 1000 nm. In addition, the ratio A ¹ /A ² between the absorbance A ¹ at a wavelength of 500 nm of the near-infrared absorbing colorant and the absorbance A ² at the maximum absorption wavelength is preferably 0.08 or less, more preferably 0.04 or less. In addition, the near-infrared absorbing colorant is preferably a pigment, more preferably an organic pigment.

Near-infrared absorbing colorants 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, pyrromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, metal borides, etc. Specific examples of these include the compounds described in paragraph 0114 of WO 2022/065215. In addition, as the infrared absorbing colorant, the compound described in paragraph 0121 of WO 2022/065215, the squarylium compound described in JP 2020-075959 A, the copper complex described in Korean Patent Publication No. 10-2019-0135217, the croconic acid compound described in JP 2021-195515 A, and the near infrared absorbing dye described in JP 2022-022070 A can also be used.

(Pigment derivatives)
In the present invention, a pigment derivative can also be used as the coloring material. In the present invention, it is preferable to use a pigment and a pigment derivative in combination. Examples of the pigment derivative include a compound having a structure in which an acid group or a basic group is bonded to a color skeleton.

　Examples of the pigment skeletons that make up the pigment derivatives include a quinoline dye skeleton, a benzimidazolone dye skeleton, a benzisoindole dye skeleton, a benzothiazole dye skeleton, an iminium dye skeleton, a squarylium dye skeleton, a croconium dye skeleton, an oxonol dye skeleton, a pyrrolopyrrole dye skeleton, a diketopyrrolopyrrole dye skeleton, an azo dye skeleton, an azomethine dye skeleton, a phthalocyanine dye skeleton, a naphthalocyanine dye skeleton, an anthraquinone dye skeleton, a quinacridone dye skeleton, a dioxazine dye skeleton, a perinone dye skeleton, a perylene dye skeleton, a thioindigo dye skeleton, an isoindoline dye skeleton, an isoindolinone dye skeleton, a quinophthalone dye skeleton, a dithiol dye skeleton, a triarylmethane dye skeleton, and a pyrromethene dye skeleton.

Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonic acid amide group, an imide acid group, and salts thereof. Examples of atoms or atomic groups constituting the salt include an alkali metal ion (Li ⁺ , Na ⁺ , K ⁺ , etc.), an alkaline earth metal ion (Ca ²⁺ , Mg ²⁺ , etc.), an ammonium ion, an imidazolium ion, a pyridinium ion, and a phosphonium ion. Examples of the carboxylic acid amide group include a group represented by -NHCOR ^X1 . Examples of the sulfonic acid amide group include a group represented by -NHSO ₂ R ^X2 . Examples of the imide acid group include a group represented by -SO ₂ NHSO ₂ R ^X3 , -CONHSO ₂ R ^X4 , -CONHCOR ^X5 , or -SO ₂ NHCOR ^X6 , and more preferably -SO ₂ NHSO ₂ R ^X3 . R ^x1 to R ^x6 each independently represent an alkyl group or an aryl group. The alkyl group and aryl group represented by R ^x1 to R ^x6 may have a substituent. The substituent is preferably a halogen atom, and more preferably a fluorine atom.

Basic groups include amino groups, pyridinyl groups and their salts, ammonium salts, and phthalimidomethyl groups. Atoms or atomic groups that make up the salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.

Specific examples of pigment derivatives include the compounds described in the Examples below, the compounds described in paragraph 0124 of WO 2022/085485, the benzimidazolone compounds or salts thereof described in JP 2018-168244 A, and compounds having an isoindoline skeleton described in general formula (1) of Japanese Patent No. 6996282.

The content of the colorant in the total solid content of the resin composition is 50% by mass or more, preferably 55% by mass or more, and more preferably 60% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 77.5% by mass or less, and even more preferably 75% by mass or less.

The pigment content in the total solid content of the resin composition is preferably 30% by mass or more, more preferably 45% by mass or more, and even more preferably 55% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 77.5% by mass or less, and even more preferably 75% by mass or less. The resin composition of the present invention has excellent storage stability even when the pigment content is high, so that the effect of the present invention is more pronounced when the pigment content is high.

The content of the pigment in the coloring material is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 70 to 100% by mass. The total content of the pigment and pigment derivative in the coloring material is preferably 25 to 100% by mass, more preferably 55 to 100% by mass, and even more preferably 75 to 100% by mass.

<<Resin B>>
The resin composition of the present invention contains resin B (hereinafter referred to as resin). The resin is blended, for example, for dispersing pigments in the resin composition or for use as a binder. A resin used mainly for dispersing pigments in a resin composition is also called a dispersant. However, such uses of the resin are merely examples, and the resin can also be used for purposes other than such uses.

(Specific resin)
The resin contained in the resin composition of the present invention includes a resin b (hereinafter also referred to as a specific resin) having a repeating unit b1 represented by formula (b1-1) and a repeating unit b2 having an acid group. The specific resin will be described below.

[Repeating unit b1]
The specific resin contains a repeating unit b1 represented by formula (b1-1) (hereinafter also referred to as repeating unit b1).
In formula (b1-1), R ^b11 represents a hydrogen atom or an alkyl group.
R ^b12 represents a polycyclic aromatic ring group, an unsubstituted alkyl group having 3 to 8 carbon atoms, a monocyclic aromatic hydrocarbon group having an electron-withdrawing group or an electron-donating group as a substituent, or a monocyclic aromatic heterocyclic group which may have an electron-withdrawing group or an electron-donating group as a substituent.

The number of carbon atoms in the alkyl group represented by R ^b11 is preferably 1 to 10, more preferably 1 to 3, and even more preferably 1. R ^b11 is preferably a hydrogen atom or a methyl group.

The polycyclic aromatic ring group represented by R ^b12 may be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group. A polycyclic aromatic hydrocarbon group is preferable because it can further improve the storage stability of the resin composition.
The number of ring structures contained in the polycyclic aromatic ring group is preferably 2 to 10. The upper limit is preferably 8 or less, and more preferably 5 or less. The lower limit is preferably 3 or more, and more preferably 4 or more, for the reason that the storage stability of the resin composition can be further improved.
Specific examples of the polycyclic aromatic ring group include a naphthalene ring group, an anthracene ring group, an acenaphthene ring group, an acenaphthylene ring group, a phenalene ring group, a phenanthrene ring group, a fluorene ring group, a pyrene ring group, a quinoline ring group, an isoquinoline ring group, a quinoxaline ring group, a pentacene ring group, a benzopyrene ring group, a chrysene group, a triphenylene group, a corannulene ring group, a coronene group, and an ovalene ring group.
The polycyclic aromatic ring group may or may not have a substituent. The substituent may be a substituent T described later. The substituent may be an electron-withdrawing group or an electron-donating group. Here, the electron-withdrawing group is a substituent that is more likely to attract electrons to the atom to which it is bonded compared to a hydrogen atom, and the electron-donating group is a substituent that is more likely to donate electrons to the atom to which it is bonded compared to a hydrogen atom. Specific examples of the electron-withdrawing group include a halogen atom, a halogenated alkyl group, an alkoxycarbonyl group, a cyano group, a nitro group, a carboxy group, and a sulfonyl group, and it is preferably a cyano group, a halogen atom, or a halogenated alkyl group. Specific examples of the electron-donating group include an alkyl group, an alkoxy group, a hydroxy group, and an amino group, and it is preferably an alkoxy group, a hydroxy group, or an amino group.

The number of carbon atoms in the unsubstituted alkyl group represented by R ^b12 is 3 to 8, and from the viewpoint of further improving the storage stability of the resin composition, it is preferably 4 to 8, and more preferably 5 to 8. The unsubstituted alkyl group represented by R ^b12 may be linear, branched, or cyclic, but from the viewpoint of further improving the storage stability of the resin composition, it is preferably linear or branched, and more preferably linear.

The monocyclic aromatic hydrocarbon group represented by R ^b12 may be a benzene ring group.
The heteroatoms constituting the ring of the monocyclic aromatic heterocyclic group represented by R ^b12 preferably contain at least one selected from a nitrogen atom, an oxygen atom and a sulfur atom, and more preferably contain a nitrogen atom. The number of heteroatoms constituting the ring of the aromatic heterocyclic group is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2. The monocyclic aromatic heterocyclic group is preferably a 5-membered or 6-membered ring, and more preferably a 6-membered ring.

Examples of the electron-withdrawing group which the monocyclic aromatic hydrocarbon group represented by R ^12b has and the electron-withdrawing group which the monocyclic aromatic heterocyclic group represented by R ^12b may have include the electron-withdrawing groups described above.

The monocyclic aromatic hydrocarbon group preferably has an electron-withdrawing group at the para position of the aromatic hydrocarbon group. According to this embodiment, the storage stability of the resin composition can be further improved. The monocyclic aromatic hydrocarbon group and the monocyclic aromatic heterocyclic group may have two or more electron-withdrawing groups.

Examples of the electron donating group contained in the monocyclic aromatic hydrocarbon group represented by R ^b12 and the electron donating group that may be contained in the monocyclic aromatic heterocyclic group represented by R ^b12 include the electron donating groups described above. The monocyclic aromatic hydrocarbon group and the monocyclic aromatic heterocyclic group may have two or more electron donating groups.

R ^b12 in formula (b1-1) is preferably a monocyclic aromatic hydrocarbon group having an electron-withdrawing group or an electron-donating group as a substituent, or a monocyclic aromatic heterocyclic group which may have an electron-withdrawing group or an electron-donating group as a substituent, and more preferably a monocyclic aromatic ring group having an electron-withdrawing group. According to this embodiment, the storage stability of the resin composition can be further improved. Although the detailed reason is unclear, it is speculated that because R ^b12 is such a functional group, the electronic state of the amide group (-NHCO-) bonded to R ^b12 can be changed, thereby further improving the adsorptivity to the pigment.

Examples of the above-mentioned substituent T include the following groups: halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms), alkenyl groups (preferably alkenyl groups having 2 to 30 carbon atoms), alkynyl groups (preferably alkynyl groups having 2 to 30 carbon atoms), aryl groups (preferably aryl groups having 6 to 30 carbon atoms), heterocyclic groups (preferably heterocyclic groups having 1 to 30 carbon atoms), amino groups (preferably amino groups having 0 to 30 carbon atoms), alkoxy groups (preferably alkoxy groups having 1 to 30 carbon atoms), aryloxy groups (preferably aryloxy groups having 6 to 30 carbon atoms), heterocyclic oxy groups (preferably heterocyclic oxy groups having 1 to 30 carbon atoms), acyl groups (preferably acyl groups having 2 to 30 carbon atoms), alkoxycarbonyl groups (preferably aryloxy groups having 2 to 30 carbon atoms), 0 alkoxycarbonyl group), aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms), heterocyclic oxycarbonyl group (preferably a heterocyclic oxycarbonyl group having 2 to 30 carbon atoms), acyloxy group (preferably an acyloxy group having 2 to 30 carbon atoms), acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), aminocarbonylamino group (preferably an aminocarbonylamino group having 2 to 30 carbon atoms), alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms), sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms), sulfamoylamino a sulfamoylamino group (preferably a sulfamoylamino 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 heterocyclic thio group (preferably a heterocyclic thio group having 1 to 30 carbon atoms), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 30 carbon atoms), an alkylsulfonylamino group (preferably an alkylsulfonylamino group having 1 to 30 carbon atoms), an arylsulfonyl group (preferably an arylsulfonylamino group having 6 to 30 carbon atoms), an arylsulfonylamino group (preferably an arylsulfonylamino group having 6 to 30 carbon atoms), a heterocyclic sulfonyl group (preferably a heterocyclic sulfonyl group having 1 to 30 carbon atoms), ring sulfonyl group), heterocyclic sulfonylamino group (preferably a heterocyclic sulfonylamino group having 1 to 30 carbon atoms), alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 30 carbon atoms), arylsulfinyl group (preferably an arylsulfinyl group having 6 to 30 carbon atoms), heterocyclic sulfinyl group (preferably a heterocyclic sulfinyl group having 1 to 30 carbon atoms), ureido group (preferably a ureido group having 1 to 30 carbon atoms), hydroxy group, nitro group, carboxylic acid amide group, sulfonic acid amide group, imido group, phosphino group, mercapto group, cyano group, alkylsulfino group, arylsulfino group, arylazo group, heterocyclic azo group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, hydrazino group, imino group. When these groups are further substitutable groups, they may further have a substituent.

Specific examples of repeating unit b1 include repeating units A-1 to A-33 described in the examples below.

The content of the repeating unit b1 in the specific resin is preferably 1 to 95% by mass. The lower limit is preferably 2.5% by mass or more, and more preferably 5% by mass or more. The upper limit is preferably 80% by mass or less, and more preferably 60% by mass or less.
The content of the repeating unit b1 in the specific resin is preferably 5 to 90 mol%, more preferably 5 to 75 mol%, and even more preferably 5 to 60 mol%, and is particularly preferably 5 to 55 mol% because it can more effectively suppress pigment aggregation and further improve the storage stability of the resin composition. The lower limit is preferably 7.5 mol% or more, more preferably 10 mol% or more, and even more preferably 12.5 mol% or more. The upper limit is preferably 53.5 mol% or less, more preferably 52 mol% or less, and even more preferably 50.5 mol% or less.
In the specific resin, the content of the repeating unit b1 in the total molar amount of the repeating unit b1 and the repeating unit b2 is preferably 10 to 90 mol%, and more preferably 20 to 70 mol% because storage stability can be further improved. The lower limit is preferably 22.5 mol% or more, and more preferably 25 mol% or more. The upper limit is preferably 67.5 mol% or less, more preferably 65 mol% or less, and even more preferably 62.5 mol% or less.

[Repeating unit b2]
The specific resin contains a repeating unit b2 having an acid group (hereinafter, also referred to as repeating unit b2).

The acid group contained in the repeating unit b2 includes a carboxy group, a phosphate group, a sulfo group, and a phenolic hydroxy group, and is preferably a carboxy group.

The number of acid groups contained in the repeating unit b2 may be 1 or 2 or more. The number of acid groups contained in the repeating unit b2 is preferably 1 to 4, and more preferably 1 or 2.

An example of the repeating unit b2 is a repeating unit represented by the following formula (b2-1).

In formula (b2-1), R ^b21 to R ^b23 each independently represent a hydrogen atom or an alkyl group. The alkyl group represented by R ^b21 to R ^b23 preferably has 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 1.

In formula (b2-1), L ^b21 represents a single bond or an (n2+1) valent linking group, provided that when n2 is 2 or greater, L ^b21 is an (n2+1) valent linking group.
Examples of the n2+1-valent linking group represented by L ^b21 include a hydrocarbon group, -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, and a group consisting of two or more of these. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 12 carbon atoms. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group and a halogen atom.

In formula (b2-1), A ^b21 represents an acid group. Examples of the acid group represented by A ^b21 include a carboxy group, a phosphate group, a sulfo group, and a phenolic hydroxy group, and is preferably a carboxy group.

In formula (b2-1), n2 represents an integer of 1 or more, preferably an integer of 1 to 4, and more preferably 1 or 2.

Specific examples of the repeating unit b2 include repeating units having the structures shown below.

The content of the repeating unit b2 in the specific resin is preferably 1 to 80% by mass. The lower limit is preferably 2.5% by mass or more, and more preferably 5% by mass or more. The upper limit is preferably 70% by mass or less, and more preferably 60% by mass or less.
The content of the repeating unit b2 in the specific resin is preferably 1 to 80 mol %. The lower limit is preferably 5 mol % or more, and more preferably 10 mol % or more. The upper limit is preferably 70 mol % or less, and more preferably 60 mol % or less.

[Repeating unit b3]
In addition to the repeating unit b1 and the repeating unit b2, the specific resin preferably further contains a repeating unit b3 having a graft chain (hereinafter, also referred to as repeating unit b3). When the specific resin contains the repeating unit b3, the storage stability of the resin composition can be further improved. Furthermore, the dispersibility of the pigment can be further improved, and the generation of coarse particles can be suppressed.

The graft chain of the repeating unit b3 may be a polymer chain containing at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure, and a poly(meth)acrylic structure, and is preferably a polymer chain containing a repeating unit of a structure selected from a polyether structure and a polyester structure, and more preferably a polymer chain of a polyether structure. In addition, the polymer chain of the polyether structure is preferably a polymer chain containing a polyalkyleneoxy structure. In other words, the graft chain is preferably a polymer chain containing a polyalkyleneoxy structure.

Here, the polyalkyleneoxy structure refers to a structure composed of two or more alkyleneoxy groups, with the alkyleneoxy group being the repeating unit. The polyalkyleneoxy structure may be composed of one type of alkyleneoxy group, or may be composed of two types of alkyleneoxy groups. The number of carbon atoms in the alkyleneoxy group constituting the polyalkyleneoxy structure is preferably 1 to 5, more preferably 1 to 3, even more preferably 2 or 3, and particularly preferably 2. The number of alkyleneoxy groups constituting the polyalkyleneoxy structure is preferably 4 to 40. The lower limit is preferably 5 or more, and more preferably 8 or more. The upper limit is preferably 35 or less, and more preferably 30 or less.

The polyalkyleneoxy structure is preferably a polytetramethyleneoxy structure, a polypropyleneoxy structure, a polyethyleneoxy structure, a polytetramethyleneoxy-polyethyleneoxy copolymer structure, or a polypropyleneoxy-polyethyleneoxy copolymer structure, more preferably a polyethyleneoxy structure, a polytetramethyleneoxy-polyethyleneoxy copolymer structure, or a polypropyleneoxy-polyethyleneoxy copolymer structure, and even more preferably a polyethyleneoxy structure.

The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkoxy group, an aryl group, and an aryloxy group.
The number of carbon atoms in the alkyl group and alkoxy group is preferably 1 to 30, and more preferably 1 to 20. The alkyl group and alkoxy group are preferably linear or branched. The alkyl group and alkoxy group may have a substituent. Examples of the substituent include a halogen atom and an aryl group. The alkyl group and alkoxy group are preferably unsubstituted alkyl groups.
The number of carbon atoms in the aryl group and the aryloxy group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12. The aryl group and the aryloxy group may have a substituent. Examples of the substituent include a halogen atom and an alkyl group.

When the graft chain is a polymer chain containing a polyalkyleneoxy structure, the terminal structure is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group.

Note that a graft chain refers to a molecular chain that branches off from a main chain. Also, a main chain refers to a molecular chain that has the most branch points.

The weight average molecular weight of the graft chain is preferably 500 to 30,000, more preferably 1,000 to 10,000, and even more preferably 1,000 to 10,000.

An example of the repeating unit b3 is a repeating unit represented by the following formula (b3-1).

In formula (b3-1), R ^b31 to R ^b33 each independently represent a hydrogen atom or an alkyl group. The alkyl group represented by R ^b31 to R ^b33 preferably has 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 1.

L ^b31 in formula (b3-1) represents a single bond or a divalent linking group. Examples of the divalent linking group represented by L ^b31 include a hydrocarbon group, -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, and a group combining two or more of these. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The number of carbon atoms in the hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 12. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group and a halogen atom.

In formula (b3-1), A ^b31 represents a graft chain. The preferred range of the graft chain represented by A ^b31 is the same as that described above.

Specific examples of repeating unit b3 include repeating units D-1 to D-7 described in the examples below.

The content of the repeating unit b3 in the specific resin is preferably 1 to 80% by mass. The lower limit is preferably 15% by mass or more, and more preferably 30% by mass or more. The upper limit is preferably 75% by mass or less, and more preferably 70% by mass or less.
The content of the repeating unit b3 in the specific resin is preferably 1 to 50 mol %. The lower limit is preferably 1.5 mol % or more, and more preferably 2.0 mol % or more. The upper limit is preferably 40 mol % or less, and more preferably 30 mol % or less.

[Repeating unit b4]
The specific resin may further include a repeating unit b4 having a crosslinkable group (hereinafter, also referred to as repeating unit b4).

The crosslinkable group contained in the repeating unit b4 includes an ethylenically unsaturated bond-containing group and a cyclic ether group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a styrene group, a (meth)allyl group, and a (meth)acryloyl group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group, and the epoxy group is preferred. The epoxy group may be an alicyclic epoxy group. The alicyclic epoxy group refers to a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.

An example of the repeating unit b4 is a repeating unit represented by the following formula (b4-1).

In formula (b4-1), R ^b41 to R ^b43 each independently represent a hydrogen atom or an alkyl group. The alkyl group represented by R ^b41 to R ^b43 preferably has 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 1.

L ^b41 in formula (b4-1) represents a single bond or a divalent linking group. Examples of the divalent linking group represented by L ^b41 include a hydrocarbon group, -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, and a group combining two or more of these. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The number of carbon atoms in the hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 12. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group and a halogen atom.

A ^b41 in formula (b4-1) represents a crosslinkable group.

Specific examples of the repeating unit b4 include repeating units having the structures shown below.

The content of the repeating unit b4 in the specific resin is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less. The lower limit may be 2.5% by mass or more, or 5% by mass or more.
The content of the repeating unit b4 in the specific resin is preferably 50 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less. The lower limit can be 1 mol% or more, 2.5 mol% or more, or 5 mol% or more.

[Repeating unit b5]
The specific resin may further contain a repeating unit b5 (hereinafter also referred to as repeating unit b5) other than the repeating units b1 to b4 described above.

Examples of the repeating unit b5 include repeating units having a functional group such as an alkyl group, a phenyl group, a hydroxyl group, an amino group, a cyano group, etc. Specific examples of the repeating unit b5 include repeating units having the structures shown below.

The content of the repeating unit b5 in the specific resin is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. The lower limit may be 2.5% by mass or more, or 5.0% by mass or more.
The content of the repeating unit b4 in the specific resin is preferably 50 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less. The lower limit can be 1 mol% or more, 2.5 mol% or more, or 5 mol% or more.

[Specific examples of specific resins]
Specific examples of the specific resin include resins P1 to P98 shown in the examples described below.

[Physical properties of specific resin]
The acid value of the specific resin is preferably 10 to 300 mgKOH/g. The upper limit is preferably 250 mgKOH/g or less, more preferably 200 mgKOH/g or less, and even more preferably 150 mgKOH/g or less. The lower limit is preferably 20 mgKOH/g or more, and more preferably 40 mgKOH/g or more. If the acid value of the specific resin is within the above range, the storage stability of the resin composition is excellent. Furthermore, the dispersibility of the pigment in the resin composition is good, and the generation of coarse particles in the resin composition can be more effectively suppressed. Furthermore, when a pattern is formed by a photolithography method, the generation of development residues can also be more effectively suppressed.

The weight average molecular weight of the specific resin is preferably 3,000 to 100,000. The lower limit is preferably 5,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more. The upper limit is preferably 80,000 or less, more preferably 60,000 or less, and even more preferably 50,000 or less. If the weight average molecular weight of the specific resin is within the above range, the storage stability of the resin composition is excellent. Furthermore, the dispersibility of the pigment in the resin composition is good, and the generation of coarse particles in the resin composition can be more effectively suppressed. Furthermore, the generation of development residues can be more effectively suppressed when a pattern is formed by photolithography.

The specific absorbance of the specific resin, represented by the following formula (A _λ ), is preferably 3 or less, more preferably 2 or less, and even more preferably 1 or less.
E=A/(c×l) ...(A _λ )
In the formula (A _λ ), E represents the specific absorbance of a specific resin at a maximum absorption wavelength in the wavelength range of 400 to 800 nm,
A represents the absorbance of a specific resin at the maximum absorption wavelength in the wavelength range of 400 to 800 nm,
l represents the cell length in cm,
c represents the concentration of the particular resin in the solution, expressed in mg/ml.

When the specific resin has crosslinkable groups, the amount of crosslinkable groups in the specific resin is preferably 0.01 to 2.5 mmol/g. The lower limit is preferably 0.2 mmol/g or more, and more preferably 0.5 mmol/g or more. The upper limit is preferably 2 mmol/g or less, and more preferably 1.5 mmol/g or less. If the amount of crosslinkable groups in the specific resin is within the above range, the dispersibility of the pigment in the resin composition and the curability of the resin composition are good. The amount of crosslinkable groups in the specific resin is a numerical value that represents the molar amount of crosslinkable groups per gram of solid content of the specific resin.

(Other resins)
The resin composition of the present invention may contain a resin (hereinafter, also referred to as "other resin") different from the specific resin described above.

Other resins include, for example, (meth)acrylic resins, epoxy resins, (meth)acrylamide resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and siloxane resins. Other resins include the resins described in paragraphs 0091 to 0099 of WO 2022/065215, the blocked polyisocyanate resins described in JP 2016-222891 A, the resins described in JP 2020-122052 A, the resins described in JP 2020-111656 A, the resins described in JP 2020-139021 A, and the resins described in JP 2017-138503 A having a ring structure in the main chain and a side chain Resins containing structural units having a biphenyl group in the chain, resins described in paragraphs 0199 to 0233 of JP 2020-186373 A, alkali-soluble resins described in JP 2020-186325 A, resins represented by formula 1 described in Korean Patent Publication No. 10-2020-0078339 A, copolymers containing epoxy groups and acid groups described in WO 2022/030445 A, and compounds described in JP 2018-135514 A can also be used.

The weight average molecular weight (Mw) of the other resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 4,000 or more, and more preferably 5,000 or more.

As the other resin, it is preferable to use a resin having an acid group. Examples of the acid group include a carboxy group, a phosphate group, a sulfo group, and a phenolic hydroxy group.

The acid value of the resin having acid groups is preferably 30 to 500 mgKOH/g. The lower limit is more preferably 40 mgKOH/g or more, and particularly preferably 50 mgKOH/g or more. The upper limit is more preferably 400 mgKOH/g or less, even more preferably 300 mgKOH/g or less, and particularly preferably 200 mgKOH/g or less. The weight average molecular weight (Mw) of the resin having acid groups is preferably 5,000 to 100,000, and more preferably 5,000 to 50,000. The number average molecular weight (Mn) of the resin having acid groups is preferably 1,000 to 20,000.

The resin having an acid group preferably contains a repeating unit having an acid group on the side chain, and more preferably contains 5 to 70 mol% of the repeating units having an acid group on the side chain out of all the repeating units of the resin. The upper limit of the content of repeating units having an acid group on the side chain is preferably 50 mol% or less, and more preferably 30 mol% or less. The lower limit of the content of repeating units having an acid group on the side chain is preferably 10 mol% or more, and more preferably 20 mol% or more.

For the resin having an acid group, the description in paragraphs 0558 to 0571 of JP 2012-208494 A (corresponding paragraphs 0685 to 0700 of the specification of US Patent Application Publication No. 2012/0235099) and the description in paragraphs 0076 to 0099 of JP 2012-198408 A can be referred to, and the contents of these are incorporated herein. In addition, a commercially available product can also be used as the resin having an acid group. In addition, there is no particular restriction on the method of introducing an acid group into the resin, but an example of the method is the method described in Japanese Patent No. 6349629 A. Furthermore, as a method of introducing an acid group into a resin, a method of reacting an acid anhydride with a hydroxyl group generated by a ring-opening reaction of an epoxy group to introduce an acid group can also be used.

As another resin, a resin having a basic group can be used. The resin having a basic group is preferably a resin containing a repeating unit having a basic group in the side chain, more preferably a copolymer having a repeating unit having a basic group in the side chain and a repeating unit not having a basic group, and even more preferably a block copolymer having a repeating unit having a basic group in the side chain and a repeating unit not having a basic group. The resin having a basic group can also be used as a dispersant. The amine value of the resin having a basic group is preferably 5 to 300 mgKOH/g. The lower limit is preferably 10 mgKOH/g or more, and more preferably 20 mgKOH/g or more. The upper limit is preferably 200 mgKOH/g or less, and more preferably 100 mgKOH/g or less.

Commercially available resins with basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 (all manufactured by BYK-Chemie), Solsperse 11200, 13240, 13650, 13940, 24 000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100 (all manufactured by Lubrizol Japan), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), and the like. In addition, the resin having a basic group may be a block copolymer (B) described in paragraphs 0063 to 0112 of JP 2014-219665 A, a block copolymer A1 described in paragraphs 0046 to 0076 of JP 2018-156021 A, or a vinyl resin having a basic group described in paragraphs 0150 to 0153 of JP 2019-184763 A, the contents of which are incorporated herein by reference.

As the other resin, it is also preferable to use a resin having an acid group and a resin having a basic group. According to this embodiment, the storage stability of the resin composition can be further improved. When a resin having an acid group and a resin having a basic group are used in combination, the content of the resin having a basic group is preferably 20 to 500 parts by mass, more preferably 30 to 300 parts by mass, and even more preferably 50 to 200 parts by mass per 100 parts by mass of the resin having an acid group.

As another resin, it is also preferable to use a resin having an aromatic carboxy group. In a resin having an aromatic carboxy group, the aromatic carboxy group may be included in the main chain of a repeating unit, or may be included in a side chain of the repeating unit. It is preferable that the aromatic carboxy group is included in the main chain of a repeating unit. In this specification, an aromatic carboxy group refers to a group having a structure in which one or more carboxy groups are bonded to an aromatic ring. In an aromatic carboxy group, the number of carboxy groups bonded to an aromatic ring is preferably 1 to 4, and more preferably 1 to 2. Examples of resins having an aromatic carboxy group include the resins described in paragraphs 0082 to 0107 of WO 2021/166858.

As the other resin, it is preferable to use at least one selected from graft polymers, star polymers, block copolymers, and resins in which at least one end of the polymer chain is blocked with an acid group. Such resins are preferably used as dispersants.

Examples of the graft polymer include resins having repeating units with graft chains. Examples of the graft chain include graft chains containing at least one structure selected from polyester structures, polyether structures, polystyrene structures, and poly(meth)acrylic structures. The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkoxy group, and an alkylthioether group. Of these, from the viewpoint of improving the dispersibility of the pigment, a group having a steric repulsion effect is preferred, and an alkyl group or an alkoxy group having 5 to 30 carbon atoms is preferred. The alkyl group and the alkoxy group may be linear, branched, or cyclic, and linear or branched groups are preferred.

Specific examples of graft polymers include the resins described in paragraphs 0025 to 0094 of JP 2012-255128 A, paragraphs 0022 to 0097 of JP 2009-203462 A, and paragraphs 0102 to 0166 of JP 2012-255128 A.

Star polymers include resins with a structure in which multiple polymer chains are bonded to a core. Specific examples of star polymers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP2013-043962A.

The block copolymer is preferably a block copolymer of a block of a polymer having a repeating unit containing an acid group or a basic group (hereinafter also referred to as block A) and a block of a polymer having a repeating unit not containing an acid group or a basic group (hereinafter also referred to as block B). As the block copolymer, the block copolymer (B) described in paragraphs 0063 to 0112 of JP 2014-219665 A and the block copolymer A1 described in paragraphs 0046 to 0076 of JP 2018-156021 A can also be used, the contents of which are incorporated herein by reference.

Examples of resins in which at least one end of a polymer chain is blocked with an acid group include resins in which at least one end of a polymer chain containing at least one structure selected from a polyester structure, a polyether structure, and a poly(meth)acrylic structure is blocked with an acid group. Examples of acid groups that block the ends of polymer chains include carboxy groups, sulfo groups, and phosphate groups.

Other resins can also be used as dispersants. Examples of dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the term "acidic dispersant (acidic resin)" refers to a resin in which the amount of acid groups is greater than the amount of basic groups. As the acidic dispersant (acidic resin), a resin in which the amount of acid groups is 70 mol% or more is preferable when the total amount of the acid groups and the basic groups is 100 mol%. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxy group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g. Furthermore, the term "basic dispersant (basic resin)" refers to a resin in which the amount of basic groups is greater than the amount of acid groups. As the basic dispersant (basic resin), a resin in which the amount of basic groups is greater than the amount of acid groups is preferable when the total amount of the acid groups and the basic groups is 100 mol% is preferable when the total amount of the acid groups and the basic groups is 100 mol%. The basic group possessed by the basic dispersant is preferably an amino group.

Dispersants are also available as commercially available products. Specific examples include the Disperbyk series manufactured by BYK-Chemie (e.g., Disperbyk-111, 161, 2001, etc.), the Solsperse series manufactured by Lubrizol Japan (e.g., Solsperse 20000, 76500, etc.), the Ajisper series manufactured by Ajinomoto Fine-Techno Co., Ltd., A208F (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), H-3606 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and Sandet ET (manufactured by Sanyo Chemical Industries, Ltd.). In addition, the products described in paragraph 0129 of JP 2012-137564 A and the products described in paragraph 0235 of JP 2017-194662 A can also be used as dispersants.

The resin content in the total solid content of the resin composition is preferably 1 to 50 mass%. The upper limit is preferably 40 mass% or less, and more preferably 30 mass% or less. The lower limit is preferably 5 mass% or more, and more preferably 10 mass% or more.

The content of the specific resin in the total solid content of the resin composition is preferably 1 to 50 mass%. The upper limit is preferably 40 mass% or less, and more preferably 30 mass% or less. The lower limit is preferably 5 mass% or more, and more preferably 10 mass% or more.

The content of the specific resin in the resin contained in the resin composition is preferably 10 to 100% by mass, more preferably 25 to 100% by mass, and even more preferably 45 to 100% by mass.

The resin composition of the present invention may contain only one type of resin, or may contain two or more types of resin. When two or more types of resin are contained, it is preferable that the total amount of the resins is within the above range.

<<Polymerizable compound>>
The resin composition of the present invention preferably contains a polymerizable compound. Examples of the polymerizable compound include compounds having an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include vinyl A group, a (meth)allyl group, a (meth)acryloyl group, etc. The polymerizable compound used in the present invention is preferably a radical polymerizable compound.

The polymerizable compound may be in any chemical form, such as a monomer, prepolymer, or oligomer, but is preferably a monomer. The molecular weight of the polymerizable compound is preferably 100 to 2500. The upper limit is preferably 2000 or less, more preferably 1500 or less. The lower limit is preferably 150 or more, more preferably 250 or more.

The ethylenically unsaturated bond-containing group value (hereinafter referred to as the C=C value) of the polymerizable compound is preferably 2 to 14 mmol/g from the viewpoint of storage stability of the resin composition. The lower limit is preferably 3 mmol/g or more, more preferably 4 mmol/g or more, and even more preferably 5 mmol/g or more. The upper limit is preferably 12 mmol/g or less, more preferably 10 mmol/g or less, and even more preferably 8 mmol/g or less. The C=C value of the polymerizable compound is a value calculated by dividing the number of ethylenically unsaturated bond-containing groups contained in one molecule of the polymerizable compound by the molecular weight of the polymerizable compound.

The polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated bond-containing groups, 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. The polymerizable compound is preferably a 3-15 functional (meth)acrylate compound, and more preferably a 3-6 functional (meth)acrylate compound. Specific examples of the polymerizable compound include the compounds described in paragraphs 0075 to 0083 of WO 2022/065215.

Preferred polymerizable compounds include dipentaerythritol tri(meth)acrylate (commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available products are KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., and NK Ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and compounds in which the (meth)acryloyl groups are bonded via ethylene glycol and/or propylene glycol residues (e.g., SR454, SR499, commercially available from Sartomer Corporation). Examples of the polymerizable compound include diglycerol EO (ethylene oxide) modified (meth)acrylate (commercially available product is M-460; manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate (NK Ester A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (KAYARAD HDDA, manufactured by Nippon Kayaku Co., Ltd.), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.). ), NK Oligo UA-7200 (Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINC-202UA (Kyoeisha Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (all manufactured by Taisei Fine Chemical Co., Ltd.), Light Acrylate POB-A0 (Kyoeisha Chemical Co., Ltd.), etc. can also be used.

The content of the polymerizable compound in the total solid content of the resin composition is preferably 1 to 35 mass%. The upper limit is preferably 30 mass% or less, more preferably 25 mass% or less, even more preferably 20 mass% or less, and particularly preferably 10 mass% or less. The lower limit is preferably 2 mass% or more, and more preferably 5 mass% or more. The resin composition of the present invention may contain only one type of polymerizable compound, or may contain two or more types. When two or more types of polymerizable compounds are contained, it is preferable that the total amount thereof is within the above range.

<<Photopolymerization initiator>>
The resin composition of the present invention may contain a photopolymerization initiator. When the resin composition of the present invention contains a polymerizable compound, it is preferable that the resin composition of the present invention further contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays in the ultraviolet to visible regions is preferable. The photopolymerization initiator is preferably a photoradical polymerization initiator.

Photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, 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 benzyl dimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a hexaarylbiimidazole compound, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, or a 3-aryl substituted coumarin compound, more preferably a compound selected from an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound. In addition, examples of the photopolymerization initiator include the compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A, the compounds described in Japanese Patent No. 6301489 A, and the compounds described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3,2019, a photopolymerization initiator described in WO 2018/221177, a photopolymerization initiator described in WO 2018/110179, a photopolymerization initiator described in JP 2019-043864 A, a photopolymerization initiator described in JP 2019-044030 A, a peroxide-based initiator described in JP 2019-167313 A, an aminoacetophenone-based initiator having an oxazolidine group described in JP 2020-055992 A, an oxime-based photopolymerization initiator described in JP 2013-190459 A, a polymer described in JP 2020-172619 A, a compound represented by formula 1 described in WO 2020/152120 A, JP 2021-181406 Compounds described in JP 2022-013379 A, photopolymerization initiators described in JP 2022-015747 A, compounds represented by formula (1) described in JP 2022-015747 A, fluorine-containing fluorene oxime ester photoinitiators described in JP 2021-507058 A, initiators described in China Patent Application Publication No. 110764367, initiators described in JP 2022-518535 A, initiators described in WO 2021/175855, compounds described in Taiwan Patent Application Publication No. 202200534, compounds described in JP 2022-078550 A, compounds described in Korean Patent Publication No. 10-2017-0087330, compounds described in WO 2022/075452, and the like.

Specific examples of hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole.

Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (all manufactured by BASF), etc. Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (all manufactured by BASF), etc. Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (all manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (all manufactured by BASF), etc.

Examples of oxime compounds include the compound described in paragraph 0142 of WO 2022/085485, the compound described in Japanese Patent No. 5,430,746, the compound described in Japanese Patent No. 5,647,738, the compound represented by general formula (1) and the compounds described in paragraphs 0022 to 0024 of JP 2021-173858 A, the compound represented by general formula (1) and the compounds described in paragraphs 0117 to 0120 of JP 2021-170089 A, 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, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), and the like. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, and Irgacure OXE04 (all manufactured by BASF), TR-PBG-301, TR-PBG-304, and TR-PBG-327 (manufactured by TRONLY), and Adeka Optomer N-1919 (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in JP 2012-014052 A). In addition, it is also preferable to use a compound that is not colorable or a compound that is highly transparent and does not easily discolor as the oxime compound. Commercially available products include Adeka Arcles NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA Corporation).

As the photopolymerization initiator, an oxime compound having a fluorene ring, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, an oxime compound having a fluorine atom, an oxime compound having a nitro group, an oxime compound having a benzofuran skeleton, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton, or a compound described in paragraphs 0143 to 0149 of WO 2022/085485 can be used.

Specific examples of oxime compounds that are preferably used in the present invention are shown below, but the present invention is not limited to these.

The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably 1000 to 300,000, even more preferably 2000 to 300,000, and particularly preferably 5000 to 200,000. The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure using a spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g/L using ethyl acetate as a solvent.

As a photopolymerization initiator, it is also preferable to use a combination of Irgacure OXE01 (manufactured by BASF) and/or Irgacure OXE02 (manufactured by BASF) and Omnirad 2959 (manufactured by IGM Resins B.V.).

As the photopolymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, crystallinity is reduced and solubility in solvents is improved, making it less likely to precipitate over time, and the stability over time of the coloring composition can be improved. Specific examples of bifunctional or trifunctional or higher functional photoradical polymerization initiators include the compounds described in paragraph 0148 of WO 2022/065215.

The content of the photopolymerization initiator in the total solid content of the resin composition is preferably 0.1 to 20 mass%. The lower limit is preferably 0.5 mass% or more, and more preferably 1 mass% or more. The upper limit is preferably 15 mass% or less, and more preferably 10 mass% or less. In the resin composition of the present invention, only one type of photopolymerization initiator may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.

<<Solvent>>
The resin composition of the present invention preferably contains a solvent. Examples of the solvent include organic solvents. The type of solvent is not particularly limited as long as the solubility of each component and the coatability of the composition are satisfied. Examples of the organic solvent include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. For details of these, refer to paragraph 0223 of International Publication No. 2015/166779, the contents of which are incorporated herein by reference. In addition, ester-based solvents substituted with a cyclic alkyl group and ketone-based solvents substituted with a cyclic alkyl group can also be preferably used. Specific examples of organic solvents 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, 2-pentanone, 3-pentanone, 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 dimethyl ether, butyl acetate ... Examples of the ethylene glycol monomethyl ether acetate include 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as diacetone alcohol and 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol. However, there are cases where it is better to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents for environmental reasons, etc. (for example, the amount can be 50 ppm (parts per million) by mass or less, 10 ppm by mass or less, or 1 ppm by mass or less, relative to the total amount of organic solvents).

In the present invention, it is preferable to use an organic solvent with a low metal content. The metal content of the organic solvent is preferably, for example, 10 parts per billion (ppb) by mass or less. If necessary, an organic solvent with a mass ppt (parts per trillion) level may be used, and such an organic solvent is provided, for example, by Toyo Gosei Co., Ltd. (The Chemical Daily, November 13, 2015).

Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin-film distillation, etc.) and filtration using a filter. The filter used for filtration preferably has a pore size of 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.

The organic solvent may contain isomers (compounds with the same number of atoms but different structures). In addition, the organic solvent may contain only one type of isomer, or multiple types of isomers.

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

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.

Furthermore, from the viewpoint of environmental regulations, it is preferable that the resin composition of the present invention is substantially free of environmentally restricted substances. In the present invention, substantially free of environmentally restricted substances means that the content of environmentally restricted substances in the resin composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, more preferably 10 ppm by mass or less, and particularly preferably 1 ppm by mass or less. Examples of environmentally restricted substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These substances are registered as environmentally regulated substances under the REACH (Registration Evaluation Authorization and Restriction of Chemicals) regulations, the PRTR (Pollutant Release and Transfer Register) Act, the VOC (Volatile Organic Compounds) regulations, etc., and their usage and handling methods are strictly regulated. These compounds may be used as solvents when producing each component used in the resin composition, and may be mixed into the resin composition as a residual solvent. From the viewpoint of human safety and environmental consideration, it is preferable to reduce these substances as much as possible. As a method for reducing environmentally regulated substances, a method of reducing them by heating or reducing pressure in the system to a temperature above the boiling point of the environmentally regulated substance and distilling off the environmentally regulated substance from the system can be mentioned. In addition, when distilling off a small amount of environmentally regulated substances, it is useful to perform azeotropy with a solvent having a boiling point equivalent to that of the solvent in question in order to increase efficiency. In addition, when a radically polymerizable compound is contained, a polymerization inhibitor or the like may be added and then distilled off under reduced pressure in order to suppress the radical polymerization reaction from proceeding during the distillation under reduced pressure and causing crosslinking between molecules. These distillation methods can be used at any stage, such as the stage of the raw materials, the stage of the product obtained by reacting the raw materials (for example, a resin solution or a polyfunctional monomer solution after polymerization), or the stage of the resin composition prepared by mixing these compounds.

<<Thermal crosslinking agent>>
The resin composition of the present invention may contain a thermal crosslinking agent as a component other than the above-mentioned resin and polymerizable compound. Examples of the thermal crosslinking agent include a compound having a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. The epoxy group may be an alicyclic epoxy group. The alicyclic epoxy group means a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed. The compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter also referred to as an epoxy compound). Examples of the epoxy compound include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferred. The epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule. The upper limit of the epoxy groups contained in the epoxy compound can be, for example, 10 or less, or 5 or less. The lower limit of the epoxy groups contained in the epoxy compound is preferably 2 or more. As the epoxy compound, the compounds described in paragraphs 0034 to 0036 of JP-A-2013-011869, paragraphs 0147 to 0156 of JP-A-2014-043556, and paragraphs 0085 to 0092 of JP-A-2014-089408, and the compounds described in JP-A-2017-179172 can also be used.

The compound having a cyclic ether group may be a low molecular weight compound (e.g., a molecular weight of less than 2000, or even less than 1000) or a high molecular weight compound (macromolecule) (e.g., a molecular weight of 1000 or more, or in the case of a polymer, a weight average molecular weight of 1000 or more). The weight average molecular weight of the compound having a cyclic ether group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is more preferably 10,000 or less, particularly preferably 5,000 or less, and even more preferably 3,000 or less.

Commercially available compounds having a cyclic ether group include, for example, EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (all manufactured by NOF Corporation, epoxy group-containing polymers). In addition, the compounds described in the examples below can also be used as compounds having a cyclic ether group.

The content of the thermal crosslinking agent in the total solid content of the resin composition is preferably 0.1 to 20 mass%. The lower limit is, for example, more preferably 0.5 mass% or more, and even more preferably 1 mass% or more. The upper limit is, for example, more preferably 15 mass% or less, and even more preferably 10 mass% or less. Only one type of thermal crosslinking agent may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.

<<Polyalkyleneimine>>
The resin composition of the present invention may also contain polyalkyleneimine. Polyalkyleneimine is used, for example, as a dispersing aid for pigments. A dispersing aid is a material for enhancing the dispersibility of coloring materials such as pigments in a resin composition. Polyalkyleneimine is a polymer obtained by ring-opening polymerization of alkyleneimine. The polyalkyleneimine is preferably a polymer having a branched structure containing a primary amino group, a secondary amino group, and a tertiary amino group. The number of carbon atoms in the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2.

The molecular weight of the polyalkyleneimine is preferably 200 or more, more preferably 250 or more. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less. In addition, when the molecular weight value of the polyalkyleneimine can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula. On the other hand, when the molecular weight of the specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the number average molecular weight value measured by the boiling point elevation method is used. In addition, when the molecular weight cannot be measured by the boiling point elevation method or is difficult to measure, the number average molecular weight value measured by the viscosity method is used. In addition, when the molecular weight cannot be measured by the viscosity method or is difficult to measure by the viscosity method, the number average molecular weight value measured in polystyrene equivalent value by GPC (gel permeation chromatography) method is used.

The amine value of the polyalkyleneimine is preferably 5 mmol/g or more, more preferably 10 mmol/g or more, and even more preferably 15 mmol/g or more.

Specific examples of alkyleneimines include ethyleneimine, propyleneimine, 1,2-butyleneimine, and 2,3-butyleneimine, with ethyleneimine or propyleneimine being preferred, and ethyleneimine being more preferred. The polyalkyleneimine is particularly preferably polyethyleneimine. Furthermore, the polyethyleneimine preferably contains primary amino groups in an amount of 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total of the primary amino groups, secondary amino groups, and tertiary amino groups. Commercially available polyethyleneimines include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by Nippon Shokubai Co., Ltd.).

The content of polyalkyleneimine in the total solid content of the resin composition is preferably 0.1 to 5 mass%. The lower limit is preferably 0.2 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1 mass% or more. The upper limit is preferably 4.5 mass% or less, more preferably 4 mass% or less, and even more preferably 3 mass% or less. The content of polyalkyleneimine is preferably 0.5 to 20 mass parts per 100 mass parts of pigment. The lower limit is preferably 0.6 mass% or more, more preferably 1 mass% or more, and even more preferably 2 mass% or more. The upper limit is preferably 10 mass% or less, and even more preferably 8 mass% or less. Only one type of polyalkyleneimine may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

<<Curing accelerator>>
The resin composition of the present invention may contain a curing accelerator. Examples of the curing accelerator include a thiol compound, a methylol compound, an amine compound, a phosphonium salt compound, an amidine salt compound, an amide compound, a base generator, an isocyanate compound, an alkoxysilane compound, and an onium salt compound. Specific examples of the curing accelerator include the compound described in paragraph 0164 of International Publication No. 2022/085485 and the compound described in JP-A-2021-181406. The content of the curing accelerator in the total solid content of the resin composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.

<<Ultraviolet absorbing agent>>
The resin composition of the present invention may contain an ultraviolet absorber. Examples of ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, and dibenzoyl compounds. Specific examples of such compounds include the compounds described in paragraph 0179 of International Publication No. 2022/085485, the reactive triazine ultraviolet absorbers described in JP-A-2021-178918, the ultraviolet absorbers described in JP-A-2022-007884, and the compounds described in Korean Patent Publication No. 10-2022-0014454. 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. In the present invention, only one type of ultraviolet absorber may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

<<Polymerization inhibitor>>
The resin composition of the present invention may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine salt (ammonium salt, cerium salt, etc.). Among these, 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 mass%. The polymerization inhibitor may be one type or two or more types. In the case of two or more types, the total amount is preferably within the above range.

<<Silane coupling agents>>
The resin composition of the present invention may contain a silane coupling agent. Examples of the silane coupling agent include silane compounds having a hydrolyzable group, and it is preferable that the silane coupling agent is a silane compound having a hydrolyzable group and other functional groups. The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate 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, and an acyloxy group, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. In addition, examples of functional groups other than the hydrolyzable group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group, and a phenyl group, 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 0177 of International Publication No. 2022/085485 and the compounds described in JP-A-2019-183020. The content of the silane coupling agent in the total solid content of the resin composition is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass. The silane coupling agent may be one type or two or more types. In the case of two or more types, it is preferable that the total amount is within the above range.

<<Surfactants>>
The resin composition of the present invention may contain a surfactant. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. The surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant, and more preferably a silicone-based surfactant. For the surfactant, the surfactants described in paragraphs 0238 to 0245 of WO 2015/166779 can be referred to, the contents of which are incorporated herein.

As fluorosurfactants, the compounds described in paragraphs 0167 to 0173 of WO 2022/085485 can be used.

Nonionic surfactants include the compounds described in paragraph 0174 of WO 2022/085485.

Silicone surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, and SF 8419. OIL (all manufactured by Dow Toray Co., Ltd.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials, Inc.), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (all manufactured by BYK-Chemie), etc. In addition, a compound having the following structure can also be used as the silicone surfactant.

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% by mass to 3.0% by mass. There may be only one type of surfactant, or two or more types. When there are two or more types, it is preferable that the total amount is within the above range.

<<Antioxidants>>
The resin composition of the present invention may contain an antioxidant. Examples of the antioxidant include phenolic compounds, phosphite compounds, and thioether compounds. As the phenolic compound, any phenolic compound known as a phenolic antioxidant may be used. As a preferred phenolic compound, a hindered phenolic compound may be used. A compound having a substituent at the site (ortho position) adjacent to the phenolic hydroxy group is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. In addition, as the antioxidant, a compound having a phenolic group and a phosphite ester group in the same molecule is also preferred. In addition, as the antioxidant, a phosphorus-based antioxidant may also be suitably used. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, and ethylbis(2,4-di-tert-butyl-6-methylphenyl)phosphite. Commercially available antioxidants include, for example, Adeka STAB AO-20, Adeka STAB AO-30, Adeka STAB AO-40, Adeka STAB AO-50, Adeka STAB AO-50F, Adeka STAB AO-60, Adeka STAB AO-60G, Adeka STAB AO-80, and Adeka STAB AO-330 (manufactured by ADEKA Corporation). In addition, the antioxidant may be a compound described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, a compound described in International Publication No. WO 2017/006600, a compound described in International Publication No. WO 2017/164024, or a compound described in Korean Patent Publication No. 10-2019-0059371. The content of the antioxidant in the total solid content of the resin composition is preferably 0.01 to 20 mass%, more preferably 0.3 to 15 mass%. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is in the above range.

<<Other ingredients>>
The resin composition of the present invention may contain, as necessary, a sensitizer, a plasticizer, and other auxiliaries (for example, conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling promoters, fragrances, surface tension regulators, chain transfer agents, etc.). By appropriately incorporating these components, properties such as film properties can be adjusted. As these components, the compounds described in paragraph 0182 of WO 2022/085485 can be used.

The resin composition of the present invention may contain a metal oxide in order to adjust the refractive index of the resulting film. Examples of the metal oxide include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , and SiO _2. The primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, and even more preferably 5 to 50 nm. The metal oxide may have a core-shell structure. In this case, the core may be hollow.

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 0183 of WO 2022/085485.

It is also preferable that the resin composition of the present invention is substantially free of terephthalic acid esters. Here, "substantially free" means that the content of terephthalic acid esters in the total amount of the resin composition is 1000 ppb by mass or less, more preferably 100 ppb by mass or less, and particularly preferably zero.

In view of environmental regulations, it is preferable that the resin composition of the present invention has a melamine content of 10,000 ppm by mass or less.

The resin composition of the present invention preferably has a free metal content of 100 ppm or less, more preferably 50 ppm or less. The free halogen content is preferably 100 ppm or less, more preferably 50 ppm or less. Methods for reducing free metals and halogens in the resin composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with ion-exchange resins.

From the viewpoint of environmental regulations, the use of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts may be restricted. When the content of the above-mentioned compounds is reduced in the resin composition of the present invention, the content of perfluoroalkylsulfonic acid (particularly perfluoroalkylsulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts, and perfluoroalkylcarboxylic acid (particularly perfluoroalkylcarboxylic acid having 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 be substantially free of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts. For example, a resin composition that is substantially free of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts, may be selected by using a compound that can be a substitute for perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts. Examples of compounds that can be a substitute for regulated compounds include compounds that are excluded from regulation due to the difference in the number of carbon atoms in the perfluoroalkyl group. However, the above content does not prevent the use of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts. The resin composition of the present invention may contain perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts, within the maximum allowable range.

The water content of the resin composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably in the range of 0.1 to 1.0% by mass. The water content can be measured by the Karl Fischer method.

The resin composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface state (flatness, etc.) and film thickness. The viscosity value can be selected appropriately as needed, but for example, a value of 0.3 mPa·s to 50 mPa·s at 25°C is preferable, and 0.5 mPa·s to 20 mPa·s is more preferable. The viscosity can be measured, for example, using a cone-plate type viscometer with the temperature adjusted to 25°C.

<<Storage container>>
The container for storing the resin composition is not particularly limited, and a known container can be used. In addition, the container described in paragraph 0187 of WO 2022/085485 can be used as the container.

<Method for preparing resin composition>
The resin composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the resin composition, all the components may be simultaneously dissolved and/or dispersed in a solvent to prepare the resin composition, or, if necessary, each component may be appropriately prepared as two or more solutions or dispersions, which are mixed at the time of use (at the time of application) to prepare the resin composition.

In addition, when preparing the resin composition, it is preferable to include a process for dispersing the pigment. In the process for dispersing the pigment, mechanical forces used to disperse the pigment include compression, squeezing, impact, shear, and cavitation. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, and ultrasonic dispersion. In addition, when grinding the pigment in a sand mill (bead mill), it is preferable to use beads with a small diameter and increase the bead packing rate, thereby increasing the grinding efficiency. In addition, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the grinding process. In addition, the process and dispersing machine for dispersing the pigment may be suitably used as described in "Dispersion Technology Encyclopedia, published by Information Technology Co., Ltd., July 15, 2005" or "Dispersion Technology and Industrial Application Practice Focused on Suspension (Solid/Liquid Dispersion System) - Comprehensive Data Collection, published by Management Development Center Publishing Department, October 10, 1978", and in paragraph number 0022 of JP 2015-157893 A. In addition, in the process for dispersing the pigment, a salt milling process may be performed to refine the particles. For the materials, equipment, processing conditions, etc. used in the salt milling process, the descriptions in, for example, JP 2015-194521 A and JP 2012-046629 A may be referred to. Examples of materials for the beads used for dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, and glass. The beads may also be made of inorganic compounds with a Mohs hardness of 2 or more. The resin composition may contain 1 to 10,000 ppm of the beads.

When preparing the resin composition, it is preferable to filter the resin composition with a filter for the purpose of removing foreign matter and reducing defects. Examples of the types of filters and filtration methods used for filtration include the filters and filtration methods described in paragraphs 0196 to 0199 of WO 2022/085485.

<Membrane>
The film of the present invention is a film obtained from the above-mentioned resin composition of the present invention. 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.

The thickness of the film of the present invention can be adjusted appropriately depending on the purpose. For example, the 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.

When the film of the present invention is used as a color filter, the film of the present invention preferably has a green, red, blue, cyan, magenta or yellow hue, and more preferably has a red hue. The film of the present invention can also be preferably used as a colored pixel of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels, and more preferably, red pixels.

<Membrane manufacturing method>
Next, the method for producing the film of the present invention will be described. The film of the present invention can be produced through a step of applying the resin composition of the present invention. The film production method preferably further includes 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. By forming a pattern by the photolithography method using the resin composition of the present invention, the generation of development residues can be further suppressed.

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 parts of the resin composition layer to form a pattern (pixels). If necessary, a step of baking the resin composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided.

In the step of forming the resin composition layer, the resin composition of the present invention is used to form a resin composition layer on a support. The support is not particularly limited and can be appropriately selected depending on the application. For example, a glass substrate, a silicon substrate, etc. can be mentioned, and a silicon substrate is preferable. A charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. may be formed on the silicon substrate. A black matrix that isolates each pixel may be formed on the silicon substrate. A base layer may be provided on the silicon substrate to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the substrate surface. The surface contact angle of the base layer is preferably 20 to 70° when measured with diiodomethane. It is also preferable that the surface contact angle is 30 to 80° when measured with water.

　A known method can be used as a method for applying the resin composition. For example, a dropping method (drop casting); a slit coating method; a spray method; a roll coating method; a rotary coating method (spin coating); a casting coating method; a slit and spin method; a pre-wetting method (for example, a method described in JP 2009-145395 A); various printing methods such as inkjet (for example, on-demand method, piezo method, thermal method), ejection printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, and metal mask printing; a transfer method using a mold or the like; and a nanoimprint method. In addition, the application method described in paragraph 0207 of WO 2022/085485 can also be used.

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

Next, the resin composition layer is exposed to light in a pattern (exposure process). For example, the resin composition layer can be exposed to light in a pattern by using a stepper exposure machine or a scanner exposure machine through a mask having a predetermined mask pattern. This allows the exposed parts to be cured.

Radiation (light) that can be used for exposure includes g-line and i-line. Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light with a wavelength of 300 nm or less include KrF line (wavelength 248 nm) and ArF line (wavelength 193 nm), with KrF line (wavelength 248 nm) being preferred. Long-wavelength light sources of 300 nm or more can also be used.

In addition, during exposure, light may be applied continuously or in pulses (pulse exposure). Pulse exposure is an exposure method in which light is applied and paused repeatedly in short cycles (e.g., milliseconds or less).

The irradiation amount (exposure amount) is, for example, preferably 0.03 to 2.5 J/cm ² , more preferably 0.05 to 1.0 J/cm ^2. The oxygen concentration during exposure can be appropriately selected, and in addition to being performed under air, for example, exposure may be performed under a low-oxygen atmosphere with an oxygen concentration of 19 volume% or less (e.g., 15 volume%, 5 volume%, or substantially oxygen-free), or exposure may be performed under a high-oxygen atmosphere with an oxygen concentration of more than 21 volume% (e.g., 22 volume%, 30 volume%, or 50 volume%). The exposure illuminance can be appropriately set, and can usually be selected from the range of 1000 W/m ² to 100,000 W/m ² (e.g., 5,000 W/m ² , 15,000 W/m ² , or 35,000 W/m ² ). The oxygen concentration and exposure illuminance may be appropriately combined. For example, an oxygen concentration of 10% by volume and an illuminance of 10,000 W/m ² , and an oxygen concentration of 35% by volume and an illuminance of 20,000 W/m ² , can be used.

Next, the unexposed parts of the resin composition layer are developed and removed to form a pattern (pixels). The unexposed parts of the resin composition layer can be developed and removed using a developer. As a result, the resin composition layer in the unexposed parts during the exposure process dissolves into the developer, leaving only the photocured parts. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. In order to improve residue removal, the process of shaking off the developer every 60 seconds and then supplying new developer may be repeated several times.

The developer may be an organic solvent or an alkaline developer, with an alkaline developer being preferred. The developer and the washing (rinsing) method after development may be as described in paragraph 0214 of WO 2022/085485.

After development and drying, it is preferable to perform additional exposure processing or heating processing (post-baking). Additional exposure processing and post-baking are curing processing after development to complete curing. The heating temperature in post-baking is, for example, preferably 100 to 300°C, more preferably 200 to 270°C. Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater to achieve the above conditions for the developed film. When additional exposure processing is performed, it is preferable that the light used for exposure has a wavelength of 400 nm or less. In addition, additional exposure processing may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.

The pattern formation by the dry etching method preferably includes the steps of forming a resin composition layer on a support using the resin composition of the present invention, curing the entire resin composition layer to form a cured layer, forming a photoresist layer on the cured layer, exposing the photoresist layer to light in a pattern and developing it to form a resist pattern, and dry etching the cured layer using an etching gas as a mask with the resist pattern. In forming the photoresist layer, it is preferable to further perform a pre-bake treatment. In particular, the process of forming the photoresist layer is preferably a form in which a heat treatment after exposure and a heat treatment after development (post-bake treatment) are performed. For the pattern formation by the dry etching method, the description in paragraphs 0010 to 0067 of JP 2013-064993 A can be referred to, and the contents of this specification are incorporated herein.

<Optical filter>
The optical filter of the present invention has the above-mentioned film of the present invention. The types of optical filters include color filters, near-infrared cut filters, and near-infrared transmission filters, and are preferably color filters. The color filter preferably has the film of the present invention as its pixel, more preferably has the film of the present invention as its color pixel, and even more preferably has the film of the present invention as its red pixel.

The optical filter may have a protective layer on the surface of the film of the present invention. By providing a protective layer, various functions such as oxygen blocking, low reflection, hydrophilicity/hydrophobicity, and shielding of light of a specific wavelength (ultraviolet rays, near infrared rays, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm. Methods for forming the protective layer include a method of forming the protective layer by applying a resin composition for forming the protective layer, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive. 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, fluorine resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al ₂ O ₃ , Mo, SiO ₂ , and Si ₂ N ₄ , and may contain two or more of these components. For example, in the case of a protective layer intended for oxygen blocking, the protective layer preferably contains a polyol resin, SiO ₂ , and Si ₂ N _4. In addition, in the case of a protective layer intended for low reflection, the protective layer preferably contains a (meth)acrylic resin and a fluorine resin.

When forming a protective layer by applying a resin composition, known methods such as spin coating, casting, screen printing, and inkjet can be used as a method for applying the resin composition. Known organic solvents (e.g., propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used as the organic solvent contained in the resin composition. When forming the protective layer by chemical vapor deposition, known chemical vapor deposition methods (thermal chemical vapor deposition, plasma chemical vapor deposition, photochemical vapor deposition) can be used as the chemical vapor deposition method.

The protective layer may contain additives such as organic or inorganic fine particles, absorbents for light of specific wavelengths (e.g., ultraviolet light, near infrared light, etc.), refractive index adjusters, antioxidants, adhesion agents, and surfactants, as necessary. Examples of organic or inorganic fine particles include 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, titanium oxynitride, magnesium fluoride, hollow silica, silica, calcium carbonate, and barium sulfate. Known absorbents can be used as absorbents for light of specific wavelengths. The content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by mass, and more preferably 1 to 60% by mass, based on the total mass of the protective layer.

The protective layer may be the one described in paragraphs 0073 to 0092 of JP2017-151176A.

The optical filter may have a structure in which each pixel is embedded in a space partitioned by partitions, for example in a grid pattern.

<Solid-state imaging element>
The solid-state imaging device of the present invention has the above-mentioned film of the present invention. The configuration of the solid-state imaging device is not particularly limited as long as it has the film of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.

The substrate has a plurality of photodiodes constituting the light receiving area of a solid-state imaging element (such as a CCD (charge-coupled device) image sensor or a CMOS (complementary metal-oxide semiconductor) image sensor) and a transfer electrode made of polysilicon or the like, a light-shielding film that opens only the light receiving portion of the photodiode on the photodiode and the transfer electrode, a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the light receiving portion of the photodiode, and a color filter on the device protection film. Furthermore, the device protection film may have a light-collecting means (e.g., a microlens, etc.; the same applies below) on the device protection film and below the color filter (the side closer to the substrate), or a light-collecting means on the color filter. The color filter may have a structure in which each colored pixel is embedded in a space partitioned by partitions, for example in a lattice shape. In this case, it is preferable that the partitions have a lower refractive index than each colored pixel. Examples of imaging devices having such a structure include those described in JP 2012-227478 A, JP 2014-179577 A, and WO 2018/043654 A. In addition, as shown in JP 2019-211559 A, an ultraviolet absorbing layer may be provided in the structure of the solid-state imaging element to improve light resistance. The imaging device equipped with the solid-state imaging element of the present invention can be used for digital cameras, electronic devices with imaging functions (such as mobile phones), as well as in-vehicle cameras and surveillance cameras.

<Image display device>
The image display device of the present invention has the above-mentioned film of the present invention. Examples of the image display device include liquid crystal display devices and organic electroluminescence display devices. The definition of the image display device and details of each image display device are described, for example, in "Electronic Display Devices" (written by Akio Sasaki, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (written by Junsho Ibuki, published by Sangyo Tosho Co., Ltd. in 1989). The liquid crystal display device is described, for example, in "Next Generation Liquid Crystal Display Technology" (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994). There is no particular limitation on the liquid crystal display device to which the present invention can be applied, and the present invention can be applied to various types of liquid crystal display devices described in the above "Next Generation Liquid Crystal Display Technology".

The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing contents, processing procedures, etc. shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, in the structural formulas shown below, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

<Synthesis Example>
(Synthesis of Monomer A-1a)
Into a three-neck flask, 6.4 g (119 mmol) of n-propylamine, 12.0 g (119 mmol) of triethylamine, and 500 ml of dehydrated dichloromethane were added and cooled to 0° C. Then, 10.8 g (119 mmol) of acrylic acid chloride was added dropwise, and the mixture was stirred at 0° C. for 1.5 hours. After removing the by-product triethylammonium chloride by filtration, dichloromethane was distilled off under reduced pressure to obtain 15.0 g of Monomer A-1.

(Synthesis of Monomers A-2a to A-33a)
Monomers A-2a to A-33a were synthesized in the same manner as for monomer A-1a.

(Synthesis of resin P1)
A three-neck flask was charged with 2.5 g (0.029 mol) of monomer B-2a, 7.5 g (0.059 mol) of monomer A-1a, 15.0 g (0.150 mol) of monomer C-1a, and 58.3 g of 1-methoxy-2-propanol to obtain a mixture. Next, the mixture was stirred while blowing in nitrogen, and the mixture was heated to 75 ° C. Next, 0.95 g of dodecyl mercaptan and then 0.24 g of 2,2'-azobis (methyl 2-methylpropionate) (hereinafter referred to as V-601) were added to the mixture to initiate a polymerization reaction. After heating the mixture at 75 ° C. for 3 hours, 0.24 g of V-601 was further added to the mixture. After 2 hours, 0.24 g of V-601 was further added to the mixture, and the temperature was raised to 90 ° C. The mixture was stirred for 3 hours to obtain resin P1.

(Synthesis of resins P2 to P6, P81 to P92)
Resins P2 to P6 and P81 to P92 were synthesized in the same manner as for resin P1.

(Synthesis of resin P7)
A three-neck flask was charged with 13.0 g (0.151 mol) of monomer B-2a, 29.9 g (0.235 mol) of monomer A-1a, 50.0 g (0.050 mol) of monomer D-5a, and 210 g of 1-methoxy-2-propanol to obtain a mixture. Next, the mixture was stirred while blowing in nitrogen, and the mixture was heated to 75°C. Next, 1.46 g of dodecyl mercaptan and then 0.37 g of 2,2'-azobis(methyl 2-methylpropionate) (hereinafter referred to as V-601) were added to the mixture to initiate the polymerization reaction. After heating the mixture at 75°C for 3 hours, 0.37 g of V-601 was further added to the mixture. After 2 hours, 0.37 g of V-601 was further added to the mixture, and the temperature was raised to 90°C. The mixture was stirred for 3 hours to obtain a precursor polymer.
To a 1000 mL three-neck flask that had been thoroughly purged with air, 305.5 g of the precursor polymer, 7.00 g (0.035 mol) of 4-HBAGE (4-hydroxybutyl acrylate glycidyl ether), 2.42 g (0.011 mol) of N,N-dimethyldodecylamine, 0.25 g (0.0016 mol) of 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), and 34.7 g of 1-methoxy-2-propanol were added and stirred for 48 hours to obtain a 30 mass % solution of resin P7.

(Synthesis of resins P8 to P80, P93 to P98)
Resins P8 to P80 and P93 to P98 were synthesized in the same manner as for Resin P7.

<About resins P1 to P98 and CP1>
Resins P1 to P98 and CP1 are resins containing the repeating units shown in the table below, which also show the acid value, weight average molecular weight, content of repeating unit 1 in the resin (content 1), and molar content of repeating unit 1 in the total molar amount of repeating unit 1 and repeating unit 2 (content 2).

[Repeating unit 1]
A-1 to A-33: Repeating units having the following structure

[Repeating unit 2]
B-2, B-3, B-4, B-6, B-9, B-11, and B-14: repeating units having the following structures (repeating units having an acid group)

[Repeating unit 3]
C-1, C-3, C-9, C-17: repeating units having the following structure

[Repeating unit 4]
D-1 to D-7: Repeating units having the following structures (repeating units having graft chains)

[Repeating unit 5]
E-2, E-3, E-6: repeating units having the following structures

<Production of Pigment Dispersion>
A mixture of the materials shown in the table below was mixed and dispersed for 3 hours using a bead mill (using zirconia beads with a diameter of 0.1 mm), and then further dispersed using a high-pressure disperser with a pressure reducing mechanism, NANO-3000-10 (manufactured by Japan BEE Co., Ltd.), at a pressure of 2000 MPa and a flow rate of 500 g/min. This dispersion process was repeated 10 times to obtain each pigment dispersion. The values shown in the table below are in parts by mass.
The average particle size (nm) of the pigment in each pigment dispersion and the viscosity value (mPa·s) are also shown. The average particle size of the pigment was measured by dynamic light scattering using a particle size measuring device (nanoSAQLA, manufactured by Otsuka Electronics Co., Ltd.). The viscosity of the pigment dispersion was measured by adjusting the temperature of the pigment dispersion to 25° C. using a viscometer (RE-85L, manufactured by Toki Sangyo Co., Ltd.).

Details of the materials listed with the abbreviations in the table above are as follows:
(Coloring material)
PR254: C.I. Pigment Red 254 (diketopyrrolopyrrole compound, red pigment)
PR272: C.I. Pigment Red 272 (diketopyrrolopyrrole compound, red pigment)
PR224: C.I. Pigment Red 224 (perylene compound, red pigment)
PY139: C.I. Pigment Yellow 139 (isoindoline compound, yellow pigment)
PY150: C.I. Pigment Yellow 150 (azobarbituric acid compound, yellow pigment)
PY185: C.I. Pigment Yellow 150 (isoindoline compound, yellow pigment)
PG36: C.I. Pigment Green 36 (phthalocyanine compound, green pigment)
PG58: C.I. Pigment Green 58 (phthalocyanine compound, green pigment)
PB15:6: C.I. Pigment Blue 15:6 (phthalocyanine compound, blue pigment)
PV23: C.I. Pigment Violet 23 (dioxazine compound, purple pigment)
PBk32: C.I. Pigment Black 32 (perylene compound, organic black pigment)
IR colorant 1: Compound having the following structure (near infrared absorbing pigment)

Derivative 1: Compound having the following structure
Derivative 2: Compound having the following structure
Derivative 3: Compound having the following structure
Derivative 4: Compound having the following structure
Derivative 5: Compound having the following structure
Derivative 6: Compound having the following structure
Derivative 7: Compound of the following structure

(resin)
P1 to P98, CP1: the above-mentioned resin CP12: Plysurf H-3606 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., resin having a carboxy group (pKa = about 4.5), terminal acid group type)
CP13: Resin having the following structure (resin having a sulfo group (pKa = approx. 2), terminal acid group type)

(solvent)
Solvent 1: Propylene glycol monomethyl ether acetate Solvent 2: Cyclopentanone Solvent 3: 1-methoxy-2-propanol

<Production of Colored Composition>
Each material was mixed in the ratio of formulations 1 to 13 shown below, and filtered through a nylon filter with a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to produce each resin composition. In the table below, the content of the coloring material in the total solid content of the resin composition is shown in the column "Coloring material content".

(Formulation 1)
Pigment dispersion liquid described in the table below: 66.30 parts by weight Polymerizable compound 1: 0.64 parts by weight Photopolymerization initiator 1: 0.54 parts by weight Surfactant 1: 0.02 parts by weight Polymerization inhibitor 1: 0.0345 parts by weight Solvent 1: 26.00 parts by weight Solvent 2: 3.20 parts by weight Solvent 3: 3.20 parts by weight

(Formulation 2)
Pigment dispersion liquid shown in the table below: 64.80 parts by weight Polymerizable compound 1: 2.14 parts by weight Photopolymerization initiator 1: 0.54 parts by weight Surfactant 1: 0.02 parts by weight Polymerization inhibitor 1: 0.0345 parts by weight Solvent 1: 26.00 parts by weight Solvent 2: 3.20
Solvent 3...3.20

(Formulation 3)
Pigment dispersion liquid described in the table below: 65.10 parts by weight Polymerizable compound 1: 1.84 parts by weight Photopolymerization initiator 1: 0.54 parts by weight Surfactant 1: 0.02 parts by weight Polymerization inhibitor 1: 0.0345 parts by weight Solvent 1: 26.00 parts by weight Solvent 2: 3.20 parts by weight Solvent 3: 3.20 parts by weight

(Formulation 4)
Pigment dispersion liquid described in the table below: 65.40 parts by weight Polymerizable compound 1: 1.54 parts by weight Photopolymerization initiator 1: 0.54 parts by weight Surfactant 1: 0.02 parts by weight Polymerization inhibitor 1: 0.0345 parts by weight Solvent 1: 26.00 parts by weight Solvent 2: 3.20 parts by weight Solvent 3: 3.20 parts by weight

(Formulation 5)
Pigment dispersion liquid described in the table below: 65.80 parts by weight Polymerizable compound 1: 1.14 parts by weight Photopolymerization initiator 1: 0.54 parts by weight Surfactant 1: 0.02 parts by weight Polymerization inhibitor 1: 0.0345 parts by weight Solvent 1: 26.00 parts by weight Solvent 2: 3.20 parts by weight Solvent 3: 3.20 parts by weight

(Formulation 6)
Pigment dispersion liquid described in the table below: 66.10 parts by weight Polymerizable compound 1: 0.84 parts by weight Photopolymerization initiator 1: 0.54 parts by weight Surfactant 1: 0.02 parts by weight Polymerization inhibitor 1: 0.0345 parts by weight Solvent 1: 26.00 parts by weight Solvent 2: 3.20 parts by weight Solvent 3: 3.20 parts by weight

(Formulation 7)
Pigment dispersion liquid described in the table below: 66.40 parts by weight Polymerizable compound 1: 0.54 parts by weight Photopolymerization initiator 1: 0.54 parts by weight Surfactant 1: 0.02 parts by weight Polymerization inhibitor 1: 0.0345 parts by weight Solvent 1: 26.00 parts by weight Solvent 2: 3.20 parts by weight Solvent 3: 3.20 parts by weight

(Formulation 8)
Pigment dispersion liquid shown in the table below: 165.75 parts by weight Polymerizable compound 1: 0.64 parts by weight Photopolymerization initiator 1: 0.54 parts by weight Surfactant 1: 0.02 parts by weight Polymerization inhibitor 1: 0.0345 parts by weight Solvent 1: 64.90 parts by weight Solvent 2: 8.10 parts by weight Solvent 3: 8.10 parts by weight

(Formulation 9)
Pigment dispersion liquid shown in the table below: 33.15 parts by weight Polymerizable compound 1: 0.64 parts by weight Photopolymerization initiator 1: 0.54 parts by weight Surfactant 1: 0.02 parts by weight Polymerization inhibitor 1: 0.0345 parts by weight Solvent 1: 13.00 parts by weight Solvent 2: 1.60 parts by weight Solvent 3: 1.60 parts by weight

(Formulation 10)
Pigment dispersion liquid shown in the table below: 163.50 parts by weight Polymerizable compound 1: 0.64 parts by weight Photopolymerization initiator 1: 0.54 parts by weight Surfactant 1: 0.02 parts by weight Polymerization inhibitor 1: 0.0345 parts by weight Solvent 1: 64.90 parts by weight Solvent 2: 8.10 parts by weight Solvent 3: 8.10 parts by weight

(Formulation 11)
Pigment dispersion liquid described in the table below: 32.70 parts by weight Polymerizable compound 1: 0.64 parts by weight Photopolymerization initiator 1: 0.54 parts by weight Surfactant 1: 0.02 parts by weight Polymerization inhibitor 1: 0.0345 parts by weight Solvent 1: 13.00 parts by weight Solvent 2: 1.60 parts by weight Solvent 3: 1.60 parts by weight

(Formulation 12)
Pigment dispersion liquid described in the table below: 70.00 parts by weight Polymerizable compound 2: 0.84 parts by weight Photopolymerization initiator 1: 0.32 parts by weight Surfactant 1: 0.04 parts by weight Polymerization inhibitor 1: 0.0345 parts by weight Solvent 1: 23.00 parts by weight Solvent 2: 2.90 parts by weight Solvent 3: 2.90 parts by weight

(Formulation 13)
Pigment dispersion liquid described in the table below: 66.30 parts by weight Polymerizable compound 1: 0.32 parts by weight Thermal crosslinking agent 1: 0.32 parts by weight Photopolymerization initiator 1: 0.54 parts by weight Surfactant 1: 0.02 parts by weight Polymerization inhibitor 1: 0.0345 parts by weight Solvent 1: 26.00 parts by weight Solvent 2: 3.20 parts by weight Solvent 3: 3.20 parts by weight

Polymerizable compound 1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., compound having the following structure)
Polymerizable compound 2: KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd., compound having the following structure)
Photopolymerization initiator 1: Irgacure OXE02 (manufactured by BASF, oxime compound, compound having the following structure)
Surfactant 1: KF-6000 (Shin-Etsu Chemical Co., Ltd., silicone surfactant)
Polymerization inhibitor 1: Compound A-1 having the following structure
Thermal crosslinking agent 1: Compound T-1 having the following structure
Solvent 1: Propylene glycol monomethyl ether acetate (PGMEA)
Solvent 2: Cyclopentanone Solvent 3: 1-Methoxy-2-propanol (MFG)

<Performance evaluation>
(Stability over time)
The viscosity (mPa·s) of the resin compositions of the examples and comparative examples was measured using "RE-85L" manufactured by Toki Sangyo Co., Ltd. After the above measurement, the resin composition was left to stand at 45°C, shielded from light, for 5 days, and the viscosity (mPa·s) was measured again. The stability over time was evaluated according to the following evaluation criteria from the viscosity difference (ΔVis) before and after the above standing. The smaller the viscosity difference (ΔVis) value, the better the stability over time of the resin composition. The viscosity measurements were all performed in a laboratory where the temperature and humidity were controlled to 22±5°C and 60±20%, and the temperature of the resin composition was adjusted to 25°C. Each measurement was performed three times, and the average value was used.
-Evaluation criteria-
A: ΔVis was 0.2 mPa·s or less. B: ΔVis was greater than 0.2 mPa·s and less than 0.3 mPa·s. C: ΔVis was greater than 0.3 mPa·s and less than 0.5 mPa·s. D: ΔVis was greater than 0.5 mPa·s.

(coarse particles)
A composition for forming an undercoat layer (CT-4000, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied onto a glass substrate using a spin coater so that the thickness after post-baking was 0.1 μm, and the undercoat layer was formed by heating for 300 seconds at 220° C. using a hot plate, to obtain a glass substrate (support) with an undercoat layer. Each resin composition was applied onto the glass substrate with the undercoat layer by spin coating, and then heated for 2 minutes at 100° C. using a hot plate to form a film with a thickness of 0.5 μm. Foreign matter contained in this film was detected using a foreign matter evaluation device Complas III (manufactured by Applied Materials, Inc.), and foreign matter (coarse particles) with a maximum width of 1.0 μm or more was visually classified from all detected foreign matter, and the number of classified coarse particles with a maximum width of 1.0 μm or more (the number of coarse particles per 1 cm ² ) was counted.
-Evaluation criteria-
A: The number of coarse particles per ^{1 cm2} of the film is less than 10. B: The number of coarse particles per ^{1 cm2} of the film is 10 or more and less than 30. C: The number of coarse particles per ^{1 cm2} of the film is 30 or more and less than 100. D: The number of coarse particles per ^{1 cm2} of the film is 100 or more.

(Developability)
A composition for forming an undercoat layer (CT-4000, manufactured by Fujifilm Electronic Materials Co., Ltd.) was applied to an 8-inch (20.32 cm) silicon wafer using a spin coater so that the thickness after post-baking was 0.1 μm, and the undercoat layer was formed by heating at 220° C. for 300 seconds using a hot plate to obtain a silicon wafer with an undercoat layer (support). Next, each resin composition was applied by spin coating so that the film thickness after post-baking was 0.62 μm. Next, the wafer was heated at 100° C. for 2 minutes using a hot plate. Next, an i-line stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.) was used to expose the wafer to light having a wavelength of 365 nm at an exposure dose of 1000 mJ/cm ² through a mask with a dot pattern of 1.0 μm square. Next, the silicon wafer on which the exposed coating film was formed was placed on the horizontal rotating table of a spin-shower developer (DW-30 type, manufactured by Chemitronics Co., Ltd.), and paddle development was performed for 60 seconds at 23°C using a 60% diluted solution of CD-2000 (manufactured by Fujifilm Electronic Materials Co., Ltd.). The silicon wafer was then fixed to the horizontal rotating table by a vacuum chuck system, and while rotating the silicon wafer at a rotation speed of 50 rpm using a rotating device, pure water was supplied in the form of a shower from a spray nozzle from above the center of rotation to perform a rinse treatment, and then spray-dried. Furthermore, a heat treatment (post-bake) was performed for 300 seconds using a hot plate at 200°C to form a pattern (pixel).
The silicon wafer on which the pixels were formed was observed under a scanning electron microscope (SEM) (magnification: 10,000 times), and the developability was evaluated according to the following evaluation criteria.
-Evaluation criteria-
A: No residue was found outside the pixel formation area (unexposed area). B: Very slight residue was found outside the pixel formation area (unexposed area), but to a degree that did not pose any practical problems. C: Slight residue was found outside the pixel formation area (unexposed area), but to a degree that did not pose any practical problems. D: Significant residue was found outside the pixel formation area (unexposed area).

As shown in the table above, the resin compositions of the examples had excellent stability over time and were excellent in developability. In addition, the compositions of the examples were able to form films with little foreign matter.

The films obtained from the resin compositions described in the examples can be suitably used in optical filters, solid-state imaging devices, and image display devices.

In Example 1, even when the polymerizable compound 1 was changed to the compound M-2 or M-3 having the structure shown below, the same effect was obtained.

In Example 1, even when the photopolymerization initiator 1 was changed to compounds I-2 to I-9 having the structures shown below, the same effect was obtained.

In Example 1, even when the polymerization inhibitor 1 was changed to the compound A-2 or A-3 having the structure shown below, the same effect was obtained.

In Example 125, even when the thermal crosslinking agent 1 was changed to the compound T-2 or T-3 having the structure shown below, the same effect was obtained.

In Example 1, the same effect was obtained even when Surfactant 1 was changed to a compound having the structure shown below (Mw=14,000, the percentage indicating the proportion of repeating units is mol%, a fluorosurfactant) or PolyFox PF6320 (manufactured by OMNOVA, a fluorosurfactant).

Claims

A resin composition comprising a color material A containing a pigment and a resin B,
The content of the color material A in the total solid content of the resin composition is 50 mass% or more,
The resin B is a resin composition including a resin b having a repeating unit b1 represented by formula (b1-1) and a repeating unit b2 having an acid group;
In formula (b1-1), R b11 represents a hydrogen atom or an alkyl group.
R b12 represents a polycyclic aromatic ring group, an unsubstituted alkyl group having 3 to 8 carbon atoms, a monocyclic aromatic hydrocarbon group having an electron-withdrawing group or an electron-donating group as a substituent, or a monocyclic aromatic heterocyclic group which may have an electron-withdrawing group or an electron-donating group as a substituent.
The resin composition according to claim 1, wherein R b12 in the formula (b1-1) is a monocyclic aromatic hydrocarbon group having an electron-withdrawing group or an electron-donating group as a substituent, or a monocyclic aromatic heterocyclic group which may have an electron-withdrawing group or an electron-donating group as a substituent.
The resin composition according to claim 1 or 2, wherein the content of the repeating unit b1 in the resin b is 5 to 55 mol %.
The resin composition according to claim 1 or 2, wherein the content of the repeating unit b1 in the total molar amount of the repeating unit b1 and the repeating unit b2 is 20 to 70 mol %.
The resin composition according to claim 1 or 2, wherein the resin b further contains a repeating unit b3 having a graft chain.
The resin composition according to claim 5, wherein the graft chain is a polymer chain containing a polyalkyleneoxy structure.
The resin composition according to claim 1 or 2, wherein the pigment comprises at least one selected from the group consisting of diketopyrrolopyrrole pigments, isoindoline pigments, quinophthalone pigments, and azo pigments.
The resin composition according to claim 1 or 2, further comprising a polymerizable compound and a photopolymerization initiator.
A film obtained using the resin composition according to claim 1 or 2.
An optical filter comprising the film according to claim 9.
A solid-state imaging device including the film according to claim 9.
An image display device including the film according to claim 9.