WO2023243414A1

WO2023243414A1 - Resin composition, film, optical filter, solid-state imaging element, and image display device

Info

Publication number: WO2023243414A1
Application number: PCT/JP2023/020455
Authority: WO
Inventors: 俊佑柳; 憲晃佐藤
Original assignee: 富士フイルム株式会社
Priority date: 2022-06-13
Filing date: 2023-06-01
Publication date: 2023-12-21
Also published as: TW202400666A

Abstract

This resin composition contains: a pigment-containing colored material; a resin; and a compound represented by formula (1), wherein said compound has a maximum value of the molar extinction coefficient in the wavelength range of 400 to 700 nm of not more than 3000 L·mol^-1·cm^-1 and has a molecular weight of not more than 475. In formula (1), A¹ represents a group that contains an acid group or a basic group; X¹ represents a urea group, thiourea group, urethane group, thiourethane group, or amide group; L¹ represents an n-valent group; and n represents an integer from 1 to 4. Also provided are a film, an optical filter, a solid-state imaging element, and an image display device, each using the resin composition.

Description

Resin compositions, films, optical filters, solid-state imaging devices, and image display devices

The present invention relates to a resin composition containing a coloring material. The present invention also relates to a film, an optical filter, a solid-state image sensor, and an image display device using the resin composition.

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

JP2019-065210A

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

However, when a coloring material containing a pigment is used, increasing the concentration of the coloring material in the resin composition relatively reduces the proportion of the material that can be adsorbed to the pigment, such as the resin. For this reason, 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 with excellent storage stability. Further, an object of the present invention is to provide a film, an optical filter, a solid-state image sensor, and an image display device.

According to the studies of the present inventors, it has been found that the above object can be achieved by the resin composition described below, and the present invention has been completed. Accordingly, the present invention provides the following.

<1> A coloring material containing a pigment,
resin and
A compound represented by formula (1), which has a maximum molar extinction coefficient of 3000 L·mol ⁻¹ ·cm ⁻¹ or less in the wavelength range of 400 to 700 nm, and has a molecular weight of 475 or less. ,
A resin composition comprising;
In formula (1), A ¹ represents a group containing an acid group or a basic group,
X ¹ represents a urea group, thiourea group, urethane group, thiourethane group or amide group,
L ¹ represents an n-valent group,
n represents an integer from 1 to 4.
<2> The resin composition according to <1>, wherein X ¹ in the above formula (1) is a urea group.
<3> The resin composition according to <1> or <2>, wherein A ¹ in the above formula (1) is a group containing a basic group.
<4> The resin composition according to <1> or <2>, wherein A ¹ in formula (1) is a group represented by formula (A20);
^A20 - ^L20 -...(A20)
In formula (A20), A ²⁰ represents a basic group, and L ²⁰ represents an alkylene group.
<5> n in the above formula (1) is 1,
L ¹ is a polycyclic aromatic ring group, an aliphatic hydrocarbon group having 2 or more carbon atoms, or a monocyclic aromatic hydrocarbon group having an electron-withdrawing group or an electron-donating group as a substituent, < The resin composition according to any one of 1> to 4>.
<6> The resin composition according to any one of <1> to <4>, wherein n in the above formula (1) is an integer of 2 to 4.
<7> The pigment is any one of <1> to <6>, including at least one selected from the group consisting of diketopyrrolopyrrole pigments, isoindoline pigments, pteridine pigments, quinophthalone pigments, and azo pigments. The resin composition described in .
<8> A film obtained using the resin composition according to any one of <1> to <7>.
<9> An optical filter comprising the film according to <8>.
<10> A solid-state imaging device comprising the film according to <8>.
<11> An image display device including the film according to <8>.

According to the present invention, a resin composition with excellent storage stability can be provided. Furthermore, a film, an optical filter, a solid-state image sensor, and an image display device can be provided.

The content of the present invention will be explained in detail below.
In this specification, "~" is used to include the numerical values described before and after it as a lower limit and an upper limit.
In the description of a group (atomic group) in this specification, the description that does not indicate substituted or unsubstituted includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the term "alkyl group" includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
In the present specification, "(meth)acrylate" represents acrylate and/or methacrylate, "(meth)acrylic" represents both acrylic and/or methacrylic, and "(meth)acrylate" represents acrylic and/or methacrylate. ) "Acryloyl" refers to acryloyl and/or methacryloyl.
In this specification, Me in the structural formula 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 polystyrene equivalent values measured by GPC (gel permeation chromatography).
In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent.
In this specification, pigment means a coloring material that is difficult to dissolve in a solvent.
In this specification, the term "process" is used not only to refer to an independent process, but also to include a process in which the intended effect of the process is achieved even if the process cannot be clearly distinguished from other processes. .

<Resin composition>
The resin composition of the present invention is
A coloring material containing a pigment,
resin and
A compound represented by formula (1), which has a maximum molar extinction coefficient of 3000 L·mol ⁻¹ ·cm ⁻¹ or less in the wavelength range of 400 to 700 nm, and has a molecular weight of 475 or less ( (hereinafter also referred to as a specific compound),
It is characterized by including.

By containing the above-mentioned specific compound, the resin composition of the present invention can improve the dispersibility of the pigment in the resin composition and suppress the increase in viscosity of the resin composition over time. Therefore, the resin composition of the present invention has excellent storage stability. It is presumed that the reason why such an effect is obtained is as follows. The above-mentioned specific compound contains a functional group selected from a urea group, a thiourea group, a urethane group, a thiourethane group, and an amide group, so this functional group and the pigment interact through hydrogen bonding, and the specific compound is formed on the surface of the pigment. It is assumed that the specific compound is strongly adsorbed and exists near the pigment in the resin composition. Moreover, since the specific compound further has a group containing an acid group or a basic group, it is assumed that these groups included in the specific compound interact with the resin. Therefore, a strong network structure between the pigment, the specific compound, and the resin is formed in the resin composition, which suppresses aggregation of the pigment, and as a result, increases in the viscosity of the resin composition over time. It is presumed that this is because it was able to be suppressed.

Since the resin composition of the present invention can suppress pigment aggregation with the above-mentioned specific compound, it also has excellent pigment dispersibility and can also suppress the generation of coarse particles.

When a pattern is formed by photolithography using the resin composition of the present invention, generation of development residues can also be suppressed. The reason for this effect is that the above-mentioned specific compounds are strongly adsorbed on the surface of the pigment through hydrogen bonding, which enhances the emulsifying effect of the pigment during development and efficiently removes the resin composition in the unexposed areas. It is assumed that this is because it could not be removed by development. For these reasons, the resin composition of the present invention can also suppress the generation of development residues.
In addition, the resin composition of the present invention has excellent developability, and furthermore, since the above-mentioned specific compound contained in the resin composition has excellent transparency, the resin composition of the present invention can be used on a support on which pixels are formed. When forming pixels by patterning using the resin composition of the invention using a photolithography method, residues derived from the resin composition of the invention are unlikely to remain on the surfaces of the pixels that have been formed in advance. Even if it remains on the pixel, the influence of this residue on the spectral characteristics of the pixel is small, so it is possible to suppress fluctuations in the spectral characteristics of the pixel that have been formed in advance.

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

Examples of color filters include filters that have colored pixels that transmit light of a specific wavelength. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow pixels, etc., and red pixels are more preferable. The colored pixels of the color filter can be formed using a resin composition containing a chromatic coloring material.

The maximum absorption wavelength of the near-infrared cut filter preferably exists in a wavelength range of 700 to 1800 nm, more preferably exists in a wavelength range of 700 to 1300 nm, and even more preferably exists in a wavelength range of 700 to 1000 nm. . Further, 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. Further, the transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less. Further, the ratio of the absorbance Amax at the maximum absorption wavelength of the near-infrared cut filter to the absorbance A550 at a wavelength of 550 nm (absorbance Amax/absorbance A550) is preferably 20 to 500, more preferably 50 to 500. , more preferably from 70 to 450, particularly preferably from 100 to 400. The near-infrared cut filter can be formed using a resin composition containing a near-infrared absorbing coloring material.

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

The resin composition of the present invention can also be used for light-shielding films and the like.

The solid content 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, 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.

Each component used in the resin composition of the present invention will be explained below.

＜＜Color material＞＞
The resin composition of the present invention contains a coloring material. Examples of coloring materials include white coloring materials, black coloring materials, chromatic coloring materials, and near-infrared absorbing coloring materials. Note that, in the present invention, the white coloring material includes not only pure white but also a light gray coloring material close to white (for example, grayish white, light gray, etc.).

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

The average primary particle diameter of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. When the average primary particle diameter of the pigment is within the above range, the dispersion stability of the pigment in the resin composition is good. In the present invention, the primary particle diameter of the pigment can be determined from a photograph obtained by observing the primary particles of the pigment using a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is determined, and the corresponding circular equivalent diameter is calculated as the primary particle diameter of the pigment. Further, the average primary particle diameter in the present invention is the arithmetic mean value of the primary particle diameters of 400 pigment primary particles. Moreover, the primary particles of pigment refer to independent particles without agglomeration.

The crystallite size determined from the half-value width of the peak derived from any crystal plane in the X-ray diffraction spectrum when the CuKα ray of the pigment is used as the X-ray source is preferably 0.1 to 100 nm, and preferably 0.1 to 100 nm. It is more preferably from 5 to 50 nm, even more preferably from 1 to 30 nm, and particularly preferably from 5 to 25 nm.

The specific surface area of the pigment 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 is determined according to DIN 66131: determination of the specific surface area of solids by gas adsorption according to the BET (Brunauer, Emmett and Teller) method. (Measurement of specific surface area of solids).

The colorant is selected from the group consisting of phthalocyanine pigments, dioxazine pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments, pyrrolopyrrole pigments, isoindoline pigments, pteridine pigments, quinophthalone pigments, azo pigments and azomethine pigments. It preferably contains at least one kind, and more preferably contains at least one kind selected from the group consisting of diketopyrrolopyrrole pigments, isoindoline pigments, pteridine pigments, quinophthalone pigments, and azo pigments.

The coloring material contained in the resin composition of the present invention may further contain a dye. When a dye is included, the content of the dye is preferably 10 to 100 parts by weight per 100 parts by weight of the pigment. The upper limit is preferably 80 parts by mass or less, 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.
Further, 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 aspect, a film with excellent light resistance and heat resistance can be formed. "Substantially free of dye" means that the content of dye in the coloring material is 0.1% by mass or less, preferably 0.01% by mass or less, and more preferably no content. .

(Chromatic color materials)
Examples of the chromatic coloring materials include coloring materials having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. Examples include yellow coloring material, orange coloring material, red coloring material, green coloring material, purple coloring material, blue coloring material, and the like. From the viewpoint of heat resistance, the chromatic color material is preferably a pigment (chromatic pigment), more preferably a red pigment, a yellow pigment, and a blue pigment, and still more preferably a red pigment and a blue pigment. Specific examples of chromatic pigments include those shown below.

Examples of red colorants include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, thioindigo compounds, etc. It is preferably a compound, and more preferably a diketopyrrolopyrrole compound. Moreover, it is preferable that the red coloring material is a pigment.

Specific examples of red coloring materials 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, 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, Examples include red pigments such as 279, 291, 294, 295, 296, 297, and the like. Further, as a red coloring material, a compound described in paragraph number 0034 of International Publication No. 2022/085485 and a brominated diketopyrrolopyrrole compound described in JP-A No. 2020-085947 can also be used.

As a red coloring material, C. I. Pigment Red 122, 177, 254, 255, 264, 269, 272 are preferred, and C.I. I. Pigment Red 254, 264, and 272 are more preferred, and C.I. I. Pigment Red 254 and 272 are more preferred.

Examples of the green coloring material include phthalocyanine compounds and squarylium compounds, preferably phthalocyanine compounds, and more preferably phthalocyanine pigments. Moreover, it is preferable that the green coloring material is a pigment.

A specific example of the green coloring material is C. I. Examples include green pigments such as Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66. In addition, as a green coloring material, halogenated zinc phthalocyanine has an average number 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. Pigments can also be used. Specific examples include compounds described in International Publication No. 2015/118720. Further, as the green coloring material, the compound described in paragraph number 0029 of International Publication No. 2022/085485, the aluminum phthalocyanine compound described in JP 2020-070426, etc. can also be used.

As a green coloring material, C. I. Pigment Green 7, 36, 58, 62, 63 are preferred; I. Pigment Green 36 and 58 are more preferred.
used.

A specific example of the orange coloring material is C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. orange pigments.

Examples of yellow colorants include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds, and perylene compounds. Specific examples of yellow colorants include C.I. 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, Examples include yellow pigments such as 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232, 233, 234, 235, 236.

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

As a yellow coloring material, compounds described in paragraph numbers 0031 to 0033 of International Publication No. 2022/085485, methine dyes described in JP 2019-073695, methine dyes described in JP 2019-073696, and The methine dye described in JP-A No. 2019-073697, the methine dye described in JP-A No. 2019-073698, and the azo compound described in JP-A No. 2020-093994 can be used.

A specific example of the purple coloring material is C. I. Examples include purple pigments such as Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.

As a specific example of the blue coloring material, 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, 88, etc. Examples include pigments. Moreover, an aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue coloring material. Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A No. 2012-247591 and paragraph number 0047 of JP-A No. 2011-157478.

Diarylmethane compounds described in Japanese Patent Publication No. 2020-504758 can also be used as the green coloring material or the blue coloring material.

Regarding the diffraction angles that various pigments preferably have, see the descriptions in Japanese Patent No. 6561862, Japanese Patent No. 6413872, Japanese Patent No. 6281345, Japanese Patent Application Publication No. 2020-026503, and Japanese Patent Application Publication No. 2020-033526. , the contents of which are incorporated herein. Pyrrolopyrrole pigments include those whose crystallite size in the plane direction corresponding to the maximum peak in the X-ray diffraction pattern among the eight (±1±1±1) crystal lattice planes is 140 Å or less. It is also preferable to use Further, the physical properties of the pyrrolopyrrole pigment are also preferably set as described in paragraph numbers 0028 to 0073 of JP-A-2020-097744.

As the pigment, it is also preferable to use a halogenated zinc phthalocyanine pigment having a Raman spectrum described in Japanese Patent No. 6744002 from the viewpoint of improving spectral characteristics. Further, as the pigment, it is also preferable to use a dioxazine pigment with a controlled contact angle described in International Publication No. 2019/107166 from the viewpoint of viscosity adjustment.

Dyes can also be used as chromatic coloring materials. There are no particular restrictions on the dye, and known dyes can be used. For example, pyrazole azo series, anilinoazo series, triarylmethane series, anthraquinone series, anthrapyridone series, benzylidene series, oxonol series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole azomethine series, xanthene series, Examples include phthalocyanine-based, benzopyran-based, indigo-based, and pyrromethene-based dyes.

A pigment multimer can also be used as a chromatic coloring material. The dye multimer is preferably a dye that is dissolved in a solvent. Further, the dye multimer may form particles. When the dye multimer is in the form of particles, it is usually used in a state of being dispersed in a solvent. The dye multimer in a particle state can be obtained, for example, by emulsion polymerization, and specific examples include the compound and manufacturing method described in JP-A No. 2015-214682. The dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less. The plurality of dye structures contained in one molecule may be the same dye structure or may be different dye structures. The weight average molecular weight (Mw) of the dye multimer 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. Dye multimers are described in JP 2011-213925, JP 2013-041097, JP 2015-028144, JP 2015-030742, WO 2016/031442, etc. Compounds can also be used.

In addition, as chromatic coloring materials, triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, xanthene compounds described in JP 2020-117638, and International Publication No. 2020/174991 are also used. The phthalocyanine compound described in JP-A No. 2020-160279 or a salt thereof, the compound represented by formula 1 described in Korean Published Patent No. 10-2020-0069442, Korean Published Patent No. 10 Compounds represented by formula 1 described in -2020-0069730, compounds represented by formula 1 described in Korean published patent No. 10-2020-0069070, Korean published patent No. 10-2020-0069067 Compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069062, halogenated zinc phthalocyanine pigments described in Patent No. 6809649, JP-A-2020- Isoindoline compounds described in JP 180176, phenothiazine compounds described in JP 2021-187913, halogenated zinc phthalocyanine described in WO 2022/004261, halogens described in WO 2021/250883 Zinc phthalocyanine can be used. The chromatic coloring material may be a rotaxane, and the dye skeleton may be used in the cyclic structure of the rotaxane, the rod-like structure, or both structures. As a chromatic coloring agent, a quinophthalone compound represented by formula 1 of Korean Patent Publication No. 10-2020-0030759, a polymer dye described in Korean Publication Patent No. 10-2020-0061793, and Japanese Patent Application Publication No. 2022-029701. You may use the coloring agent described in WO 2022/014635, the isoindoline compound described in WO 2022/024926, and the aluminum phthalocyanine compound described in WO 2022/024926.

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

(white coloring material)
White coloring materials include 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, Examples include hollow resin particles and inorganic pigments (white pigments) such as zinc sulfide. The white pigment is preferably particles containing titanium atoms, and more preferably titanium oxide. Moreover, it is preferable that the white pigment is a particle having a refractive index of 2.10 or more with respect to light with a wavelength of 589 nm. The above-mentioned refractive index is preferably 2.10 to 3.00, more preferably 2.50 to 2.75.

As the white pigment, titanium oxide described in "Titanium oxide physical properties and applied technology, Manabu Seino, pages 13-45, published June 25, 1991, published by Gihodo Publishing" can also be used.

The white pigment is not only made of a single inorganic substance, but also particles made of a composite with other materials may be used. For example, particles with pores or other materials inside, particles with a core particle attached to a large number of inorganic particles, and core/shell composite particles with a core particle made of polymer particles and a shell layer made of inorganic nanoparticles are used. It is preferable. For the core and shell composite particles consisting of a core particle consisting of a polymer particle and a shell layer consisting of an inorganic nanoparticle, for example, the description in paragraphs 0012 to 0042 of JP 2015-047520A can be referred to, This content is incorporated herein.

Hollow inorganic particles can also be used as the white pigment. A hollow inorganic particle is an inorganic particle having a structure that has a cavity inside, and is an inorganic particle having a cavity surrounded by an outer shell. Examples of hollow inorganic particles include hollow inorganic particles described in JP2011-075786A, WO2013/061621A, JP2015-164881A, etc., the contents of which are not incorporated herein. It will be done.

(black color material)
The black coloring material is not particularly limited, and any known material can be used. For example, examples of the inorganic black coloring material include inorganic pigments (black pigments) such as carbon black, titanium black, and graphite, with carbon black and titanium black being preferred, and titanium black being more preferred. Titanium black is black particles containing titanium atoms, and lower titanium oxide and titanium oxynitride are preferable. The surface of titanium black can be modified as necessary for the purpose of improving dispersibility, suppressing agglomeration, and the like. For example, it is possible to coat the surface of titanium black with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Furthermore, treatment with a water-repellent substance as disclosed in JP-A No. 2007-302836 is also possible. As a black pigment, C. I. Pigment Black 1, 7, etc. can be mentioned. It is preferable that the titanium black has a small primary particle size and an average primary particle size of each particle. Specifically, it is preferable that the average primary particle diameter is 10 to 45 nm. Titanium black can also be used as a dispersion. For example, there may be mentioned a dispersion containing titanium black particles and silica particles, in which the content ratio of Si atoms to Ti atoms in the dispersion is adjusted to a range of 0.20 to 0.50. Regarding the above-mentioned dispersion, the descriptions in paragraphs 0020 to 0105 of JP-A-2012-169556 can be referred to, the contents of which are incorporated herein. Examples of commercially available titanium blacks include Titanium Black 10S, 12S, 13R, 13M, 13MC, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilac D ( Product name: Ako Kasei Co., Ltd.).

Examples of organic black coloring materials include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds. Examples of bisbenzofuranone compounds include compounds described in Japanese Patent Application Publication No. 2010-534726, Japanese Patent Application Publication No. 2012-515233, and Japanese Patent Application Publication No. 2012-515234, and for example, as "Irgaphor Black" manufactured by BASF. available. Examples of perylene compounds include compounds described in paragraph numbers 0016 to 0020 of JP-A No. 2017-226821, C.I. I. Pigment Black 31, 32 and the like. Examples of the azomethine compound include compounds described in JP-A-01-170601 and JP-A-02-034664, and are available as "Chromofine Black A1103" manufactured by Dainichiseika Kaisha, Ltd., for example. Further, as a black coloring material, a black organic pigment described in Japanese Patent No. 6985715, Lumogen Black FK4280, Paliogen Black S0084 (manufactured by BASF) may be used.

The coloring material used in the resin composition of the present invention may be only the above-mentioned black coloring material, or may further include a chromatic coloring material. According to this aspect, it is easy to obtain a resin composition that can form a film with excellent light-shielding properties in the visible region. When a black coloring material and a chromatic coloring material are used together as a coloring material, the mass ratio of both is preferably black coloring material: chromatic coloring material = 100:10 to 300, and 100:20 to 200. It is more preferable.

Preferred combinations of black coloring materials and chromatic coloring materials include, for example, the following.
(A-1) Embodiment containing an organic black coloring material and a blue coloring material.
(A-2) Embodiment containing an organic black coloring material, a blue coloring material, and a yellow coloring material.
(A-3) Embodiment containing an organic black coloring material, a blue coloring material, a yellow coloring material, and a red coloring material.
(A-4) Embodiment containing an organic black coloring material, a blue coloring material, a yellow coloring material, and a purple coloring material.

In the embodiment (A-1) above, the mass ratio of the organic black coloring material to the blue coloring material is preferably organic black coloring material: blue coloring material = 100:1 to 70, and preferably 100:5 to 60. More preferably, the ratio is 100:10 to 50.
In the embodiment (A-2) above, the mass ratio of the organic black coloring material, blue coloring material, and yellow coloring material is organic black coloring material: blue coloring material: yellow coloring material = 100:10 to 90:10 to 90. The ratio is preferably 100:15 to 85:15 to 80, even more preferably 100:20 to 80:20 to 70.
In the embodiment (A-3) above, the mass ratio of the organic black coloring material, the blue coloring material, the yellow coloring material, and the red coloring material is: organic black coloring material: blue coloring material: yellow coloring material: red coloring material = 100 :20-150:1-60:10-100, more preferably 100:30-130:5-50:20-90, 100:40-120:10-40:30- More preferably, it is 80.
In the embodiment (A-4) above, the mass ratio of the organic black coloring material, the blue coloring material, the yellow coloring material, and the purple coloring material is: organic black coloring material: blue coloring material: yellow coloring material: purple coloring material = 100 :20-150:1-60:10-100, more preferably 100:30-130:5-50:20-90, 100:40-120:10-40:30- More preferably, it is 80.

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

Near-infrared absorbing coloring materials include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, and pyrromethene compounds. , azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, metal borides, and the like. Specific examples of these include compounds described in paragraph number 0114 of International Publication No. 2022/065215. In addition, as the near-infrared absorbing coloring material, the compound described in paragraph number 0121 of International Publication No. 2022/065215, the squarylium compound described in JP 2020-075959, Korean Published Patent No. 10-2019-0135217 Copper complexes described in the publication, croconic acid compounds described in JP 2021-195515, and near-infrared absorbing dyes described in JP 2022-022070 can also be used.

The content of the coloring material in the total solid content of the resin composition is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and 50% by mass. It is particularly preferable that it is above. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less.

The content of pigment 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. According to the resin composition of the present invention, even when the pigment content is high, the storage stability is excellent, so that the effects of the present invention are more prominently exhibited when the pigment content is high.

The content of 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.

<<Resin>>
The resin composition of the present invention contains a resin. The resin is blended, for example, for dispersing pigments in a resin composition or for use as a binder. Note that a resin used mainly for dispersing pigments and the like in a resin composition is also referred to as a dispersant. However, this use of the resin is just an example, and the resin can also be used for purposes other than this use.

Examples of the resin include (meth)acrylic resin, epoxy resin, (meth)acrylamide resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, and polyarylene. Examples include ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, and siloxane resin. In addition, the resins include the resin described in the examples of International Publication No. 2016/088645, the resin described in JP 2017-057265, the resin described in JP 2017-032685, and the resin described in JP 2017-032685. The resin described in JP 2017-075248, the resin described in JP 2017-066240, the resin described in JP 2017-167513, the resin described in JP 2017-173787, Resins described in paragraph numbers 0041 to 0060 of JP 2017-206689, resins described in paragraph numbers 0022 to 0071 of JP 2018-010856, and blocks described in JP 2016-222891. Polyisocyanate resin, resin described in JP 2020-122052, resin described in JP 2020-111656, resin described in JP 2020-139021, JP 2017-138503 Resin containing a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain described in JP-A-2020-186373, resin described in paragraphs 0199 to 0233 of JP-A No. 2020-186325 Alkali-soluble resins described in the publication, resins represented by formula 1 described in Korean Patent Publication No. 10-2020-0078339, copolymers containing epoxy groups and acid groups described in International Publication No. 2022/030445 You can also use

The weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 4000 or more, more preferably 5000 or more.

As the resin, it is preferable to use a resin having acid groups. Examples of the acid group include a carboxy group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group. When a compound in which A ¹ in formula (1) is a group containing a basic group is used as the specific compound described later, it is preferable to use a resin having an acid group as the resin. According to this aspect, the storage stability of the resin composition can be further improved.

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, 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, more preferably 5,000 to 50,000. Further, 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 in its side chain, and more preferably contains 5 to 70 mol% of repeating units having an acid group in its side chain based on the total repeating units of the resin. The upper limit of the content of repeating units having acid groups in their side chains is preferably 50 mol% or less, more preferably 30 mol% or less. The lower limit of the content of repeating units having acid groups in their side chains is preferably 10 mol% or more, more preferably 20 mol% or more.

Regarding resins having acid groups, the descriptions in paragraph numbers 0558 to 0571 of JP 2012-208494 (corresponding paragraph numbers 0685 to 0700 of US Patent Application Publication No. 2012/0235099), JP 2012-198408 The descriptions in paragraph numbers 0076 to 0099 of the publication can be referred to, and the contents thereof are incorporated into the present specification. Furthermore, commercially available resins having acid groups can also be used. Furthermore, there are no particular limitations on the method for introducing acid groups into the resin, but examples include the method described in Japanese Patent No. 6,349,629. Furthermore, as a method for introducing acid groups into the resin, there is also a method of reacting an acid anhydride with a hydroxy group generated by a ring-opening reaction of an epoxy group to introduce an acid group.

As the resin, a resin having a basic group can also be used. When using a compound in which A ¹ in formula (1) is a group containing an acid group as the specific compound described later, it is preferable to use a resin having a basic group as the resin. According to this aspect, the storage stability of the resin composition can be further improved.

The resin having a basic group is preferably a resin containing a repeating unit having a basic group in its side chain, and a resin having a repeating unit having a basic group in its side chain and a repeating unit not containing a basic group. A polymer is more preferable, and a block copolymer having a repeating unit having a basic group in its side chain and a repeating unit not containing a basic group is even more preferable. A 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, more preferably 20 mgKOH/g or more. The upper limit is preferably 200 mgKOH/g or less, more preferably 100 mgKOH/g or less.

Commercially available resins having basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 (manufactured by BYK Chemie), Solsperse 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 385 00, 39000, 53095, 56000, 7100 (all manufactured by Japan Lubrizol), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), and the like. In addition, the resin having a basic group is the block copolymer (B) described in paragraph numbers 0063 to 0112 of JP2014-219665A, and the block copolymer (B) described in paragraphs 0046 to 0076 of JP2018-156021A. It is also possible to use block copolymer A1, a vinyl resin having a basic group described in paragraphs 0150 to 0153 of JP-A No. 2019-184763, the contents of which are incorporated herein.

It is also preferable to use a resin having an acid group and a resin having a basic group as the resin. According to this aspect, 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 together, the content of the resin having a basic group is preferably 20 to 500 parts by mass per 100 parts by mass of the resin having an acid group. The amount is preferably 30 to 300 parts by weight, more preferably 50 to 200 parts by weight.

The resin is derived from a monomer component containing a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer"). It is also preferable to use a resin containing repeating units.

In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For details of formula (ED2), the description in JP-A No. 2010-168539 can be referred to, the contents of which are incorporated herein.

As a specific example of the ether dimer, for example, the description in paragraph number 0317 of JP-A-2013-029760 can be referred to, the contents of which are incorporated herein.

As the resin, it is also preferable to use a resin containing a repeating unit derived from a compound represented by formula (X).
In the formula, R ¹ represents a hydrogen atom or a methyl group, R ²¹ and R ²² each independently represent an alkylene group, and n represents an integer of 0 to 15. The alkylene group represented by R ²¹ and R ²² preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly 2 or 3 carbon atoms. preferable. n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, even more preferably an integer of 0 to 3.

Examples of the compound represented by formula (X) include ethylene oxide- or propylene oxide-modified (meth)acrylate of paracumylphenol. Commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).

As the resin, it is also preferable to use a resin having a crosslinkable group. Examples of the crosslinkable group include ethylenically unsaturated bond-containing groups and cyclic ether groups. 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, with an epoxy group being preferred. The epoxy group may be a cycloaliphatic epoxy group. Note that 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.

As the resin, it is also preferable to use a resin having an aromatic carboxy group (hereinafter also referred to as resin Ac). In the resin Ac, the aromatic carboxy group may be included in the main chain of the repeating unit, or may be included in the side chain of the repeating unit. The aromatic carboxy group is preferably contained in the main chain of the repeating unit. In addition, 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 the aromatic carboxy group, the number of carboxy groups bonded to the aromatic ring is preferably 1 to 4, more preferably 1 to 2.

The resin Ac is preferably a resin containing at least one type of repeating unit selected from a repeating unit represented by formula (Ac-1) and a repeating unit represented by formula (Ac-2).
In formula (Ac-1), Ar ¹ represents a group containing an aromatic carboxy group, L ¹ represents -COO- or -CONH-, and L ² represents a divalent linking group.
In formula (Ac-2), Ar ¹⁰ represents a group containing an aromatic carboxy group, L ¹¹ represents -COO- or -CONH-, L ¹² represents a trivalent linking group, and P ¹⁰ represents a polymer Represents a chain.

Examples of the group containing an aromatic carboxy group represented by Ar ¹ in formula (Ac-1) include a structure derived from an aromatic tricarboxylic acid anhydride, a structure derived from an aromatic tetracarboxylic acid anhydride, and the like. Examples of the aromatic tricarboxylic anhydride and aromatic tetracarboxylic anhydride include compounds having the following structures.

In the above formula, Q ¹ is a single bond, -O-, -CO-, -COOCH ₂ CH ₂ OCO-, -SO ₂ -, -C(CF ₃ ) ₂ -, represented by the following formula (Q-1) or a group represented by the following formula (Q-2).

The aromatic carboxy group-containing group represented by Ar ¹ may have a crosslinkable group. The crosslinkable group is preferably an ethylenically unsaturated bond-containing group and a cyclic ether group, and more preferably an ethylenically unsaturated bond-containing group. Specific examples of the group containing an aromatic carboxy group represented by Ar ¹ include a group represented by formula (Ar-11), a group represented by formula (Ar-12), and a group represented by formula (Ar-13). Examples include groups such as

In formula (Ar-11), n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2.
In formula (Ar-12), n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 2.
In formula (Ar-13), n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2, and preferably 1. More preferred. However, at least one of n3 and n4 is an integer of 1 or more.
In formula (Ar-13), Q ¹ is a single bond, -O-, -CO-, -COOCH ₂ CH ₂ OCO-, -SO ₂ -, -C(CF ₃ ) ₂ -, the above formula (Q- Represents a group represented by 1) or a group represented by the above formula (Q-2).
In formulas (Ar-11) to (Ar-13), *1 represents the bonding position with L ¹ .

In formula (Ac-1), L ¹ represents -COO- or -CONH-, and preferably represents -COO-.

In formula (Ac-1), the divalent linking group represented by L ² includes an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and these. Examples include groups combining two or more of the following. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 15 carbon atoms. The alkylene group may be linear, branched, or cyclic. The number of carbon atoms in the arylene group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10. The alkylene group and arylene group may have a substituent. Examples of the substituent include a hydroxy group. The divalent linking group represented by L ² is preferably a group represented by -L ^2a -O-. L ^2a is an alkylene group; an arylene group; a group combining an alkylene group and an arylene group; at least one selected from an alkylene group and an arylene group, and -O-, -CO-, -COO-, -OCO-, Examples include a group combining at least one selected from -NH- and -S-, and an alkylene group is preferred. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 15 carbon atoms. The alkylene group may be linear, branched, or cyclic. The alkylene group and arylene group may have a substituent. Examples of the substituent include a hydroxy group.

The aromatic carboxy group-containing group represented by Ar ¹⁰ in formula (Ac-2) has the same meaning as Ar ¹ in formula (Ac-1), and the preferred range is also the same.

In formula (Ac-2), L ¹¹ represents -COO- or -CONH-, preferably -COO-.

In formula (Ac-2), the trivalent linking group represented by L ¹² includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and these two groups. Examples include groups that combine more than one species. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group. The trivalent linking group represented by L ¹² is preferably a group represented by formula (L12-1), and more preferably a group represented by formula (L12-2).

In formula (L12-1), L ^12b represents a trivalent linking group, X ¹ represents S, *1 represents the bonding position with L ¹¹ of formula (Ac-2), and *2 represents formula ( It represents the bonding position of Ac-2) with ^P10 . The trivalent linking group represented by L ^12b is a hydrocarbon group; a hydrocarbon group, and at least one kind selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-. A hydrocarbon group or a group consisting of a hydrocarbon group and -O- is preferable.

In formula (L12-2), L ^12c represents a trivalent linking group, X ¹ represents S, *1 represents the bonding position with L ¹¹ of formula (Ac-2), and *2 represents formula ( It represents the bonding position of Ac-2) with ^P10 . The trivalent linking group represented by L ^12c is a hydrocarbon group; a hydrocarbon group and at least one kind selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. A hydrocarbon group is preferable.

In formula (Ac-2), P ¹⁰ represents a polymer chain. The polymer chain represented by P ¹⁰ preferably has at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure, and a poly(meth)acrylic structure. The weight average molecular weight of the polymer chain P ¹⁰ is preferably 500 to 20,000. The lower limit is preferably 1000 or more. The upper limit is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less. If the weight average molecular weight of P ¹⁰ is within the above range, the pigment will have good dispersibility in the composition. When the resin having an aromatic carboxyl group is a resin having a repeating unit represented by formula (Ac-2), this resin is preferably used as a dispersant.

The polymer chain represented by P ¹⁰ may contain a crosslinkable group. Examples of the crosslinkable group include ethylenically unsaturated bond-containing groups and cyclic ether groups.

It is preferable to use at least one type of resin selected from graft polymers, star polymers, block copolymers, and resins in which at least one end of a polymer chain is capped with an acid group. Such resins are preferably used as dispersants.

Examples of the graft polymer include a resin having a repeating unit having a graft chain and a resin having a repeating unit represented by the above-mentioned formula (Ac-2). Examples of the graft chain include a graft chain containing at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure, and a poly(meth)acrylic 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 alkylthioether group, and the like. Among these, from the viewpoint of improving the dispersibility of the pigment, groups having a steric repulsion effect are preferred, and alkyl groups or alkoxy groups having 5 to 30 carbon atoms are preferred. The alkyl group and the alkoxy group may be linear, branched, or cyclic, and preferably linear or branched.

Specific examples of graft polymers include paragraph numbers 0025 to 0094 of JP2012-255128A, paragraphs 0022 to 0097 of JP2009-203462A, and paragraphs 0102 to 0166 of JP2012-255128A. Mention may be made of the resins mentioned.

Examples of star-shaped polymers include resins with a structure in which a plurality of polymer chains are bonded to a core portion. Specific examples of star-shaped polymers include polymer compounds C-1 to C-31 described in paragraph numbers 0196 to 0209 of JP-A No. 2013-043962.

The block copolymers include a polymer block having a repeating unit containing an acid group or a basic group (hereinafter also referred to as block A), and a polymer block having a repeating unit not containing an acid group or a basic group. (hereinafter also referred to as block B) is preferably a block copolymer. The block copolymers include block copolymers (B) described in paragraph numbers 0063 to 0112 of JP2014-219665A, and blocks described in paragraph numbers 0046 to 0076 of JP2018-156021A. Copolymers A1 can also be used, the contents of which are incorporated herein.

The resin in which at least one end of the polymer chain is capped with an acid group is a resin in which at least one end of the polymer chain contains at least one type of structure selected from a polyester structure, a polyether structure, and a poly(meth)acrylic structure. Examples include resins with a structure sealed with acid groups. Examples of acid groups that block the ends of polymer chains include carboxy groups, sulfo groups, and phosphoric acid groups.

As the resin, a resin as a dispersant can also be used. Examples of the dispersant include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol % or more when the total amount of acid groups and basic groups is 100 mol %. The acid group that the acidic dispersant (acidic resin) has is preferably a carboxy group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g. Moreover, the basic dispersant (basic resin) refers to a resin in which the amount of basic groups is greater than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is 100 mol%. The basic group that the basic dispersant has is preferably an amino group.

Dispersants are also available as commercial products, and specific examples include the Disperbyk series manufactured by Byk Chemie (for example, Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajisper series manufactured by Ajinomoto Fine Techno Co., Ltd., A208F (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), H-3606 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Sandet Examples include ET (manufactured by Sanyo Chemical Industries, Ltd.). Further, the product described in paragraph number 0129 of JP 2012-137564A and the product described in paragraph number 0235 of JP 2017-194662A can also be used as a dispersant.

The content of the resin in the total solid content of the resin composition is preferably 1 to 50% by mass. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more.
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 included, the total amount thereof is preferably within the above range.

<<Specific compound>>
The resin composition of the present invention is a compound represented by formula (1), and has a maximum molar extinction coefficient of 3000 L·mol ⁻¹ ·cm ⁻¹ or less in the wavelength range of 400 to 700 nm, and Includes compounds with a molecular weight of 475 or less (hereinafter also referred to as specific compounds). Certain compounds are used as dispersion aids. A dispersion aid is a material for improving the dispersibility of pigments in a coloring composition.
In formula (1), A ¹ represents a group containing an acid group or a basic group,
X ¹ represents a urea group, thiourea group, urethane group, thiourethane group or amide group,
L ¹ represents an n-valent group,
n represents an integer from 1 to 4.

A ¹ in formula (1) represents a group containing an acid group or a basic group, and is preferably a group containing a basic group.

Examples of the acid group contained in the group represented by ^A1 include a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group, and a phenolic hydroxy group. Preferably, a carboxy group or a sulfo group is more preferable.

When A ¹ is a group containing an acid group, the number of acid groups contained in A ¹ is preferably 1 to 4, more preferably 1 or 2, and 1. is even more preferable. Furthermore, when A ¹ is a group containing an acid group, the group represented by A ¹ preferably does not contain a basic group.

Examples of the basic group contained in the group represented by A ¹ include an amino group, a pyridinyl group and its salt, a salt of an ammonium group, and a phthalimidomethyl group, and an amino group is preferable. Examples of the atoms or atomic groups constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.

Examples of the amino group include a group represented by -NR ^x11 R ^x12 and a cyclic amino group.

In the group represented by -NR ^x11 R ^x12 , R ^x11 and R ^x12 each independently represent a hydrogen atom, an alkyl group, or an aryl group. Preferably, R ^x11 and R ^x12 are each independently an alkyl group or an aryl group. Among these, it is preferable that one of R ^x11 and R ^x12 is an alkyl group and the other is an alkyl group or an aryl group, and it is more preferable that R ^x11 and R ^x12 are each independently an alkyl group.
The alkyl group may be straight chain, branched, or ring, but is preferably straight chain or branched, and more preferably straight chain. The alkyl group may have a substituent. Examples of the substituent include a hydroxy group, an acyl group, a nitro group, an alkoxy group, an aryloxy group, an aryloxycarbonyl group, an alkoxycarbonyl group, an acyloxy group, an alkyl group, an aryl group, a halogen atom, and a polymerizable group. Examples of the polymerizable group include a vinyl group, a styrene group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group.
The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. The aryl group may have a substituent. Examples of substituents include hydroxy group, aldehyde group, carbonyl group, acyl group, nitro group, alkoxy group, aryloxy group, aryloxycarbonyl group, alkoxycarbonyl group, acyloxy group, ether group, ester group, alkyl group, aryl group, Examples include halogen atoms and polymerizable groups. Examples of the polymerizable group include a vinyl group, a styrene group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group.

Examples of the cyclic amino group include a pyrrolidine ring group, a piperidine ring group, a morpholine ring group, a pyrrole ring group, an imidazole ring group, a pyrazole ring group, a pyrazolidine group, an imidazolin(di)ine ring group, a succinimide group, a 2-oxazolidone ring group, Examples include hydantoin ring group, phenothiazine ring group, phenoxazine ring group, and tetrazole ring group.

When A ¹ is a group containing a basic group, the number of basic groups contained in A ¹ is preferably 1 to 4, more preferably 1 or 2, and more preferably 1 or 2. It is even more preferable that there be. Moreover, when A ¹ is a group containing a basic group, it is preferable that the group represented by A ¹ does not contain an acid group.

A ¹ in formula (1) is preferably a group represented by formula (A10).
(A ¹⁰ ) _p -L ¹⁰ - (A10)
In formula (A10), A ¹⁰ represents an acid group or a basic group, L ¹⁰ represents a single bond or an aliphatic hydrocarbon group, and p represents an integer of 1 to 4.

Examples of the acid group and basic group represented by A ¹⁰ include the above-mentioned acid groups and basic groups. A ¹⁰ is preferably a basic group, more preferably a group represented by -NR ^x11 R ^x12 or a cyclic amino group.
The aliphatic hydrocarbon group represented by L ¹⁰ preferably has 1 to 15 carbon atoms. The upper limit is preferably 10 or less, more preferably 8 or less. The lower limit is preferably 2 or more, more preferably 3 or more. The aliphatic hydrocarbon group may be linear, branched, or cyclic, and preferably linear or branched. The aliphatic hydrocarbon group may have a substituent. Examples of substituents include hydroxy group, aldehyde group, carbonyl group, acyl group, nitro group, alkoxy group, aryloxy group, aryloxycarbonyl group, alkoxycarbonyl group, acyloxy group, ether group, ester group, alkyl group, aryl group, Examples include halogen atoms and polymerizable groups. Examples of the polymerizable group include a vinyl group, a styrene group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group.
Preferably, L ¹⁰ is an aliphatic hydrocarbon group.
p represents an integer of 1 to 4, preferably 1 or 2, more preferably 1.

A ¹ in formula (1) is preferably a group represented by formula (A20). According to this aspect, the storage stability of the resin composition can be further improved.
^A20 - ^L20 -...(A20)
In formula (A20), A ²⁰ represents a basic group, and L ²⁰ represents an alkylene group.

The acid group and basic group represented by A ¹⁰ include the above-mentioned basic groups, and are preferably a group represented by -NR ^x11 R ^x12 or a cyclic amino group.
The alkylene group represented by L ¹⁰ preferably has 1 to 15 carbon atoms. The upper limit is preferably 10 or less, more preferably 8 or less. The lower limit is preferably 2 or more, more preferably 3 or more. The alkylene group may be linear, branched, or cyclic, and preferably linear or branched. The alkylene group may have a substituent. Examples of substituents include hydroxy group, aldehyde group, carbonyl group, acyl group, nitro group, alkoxy group, aryloxy group, aryloxycarbonyl group, alkoxycarbonyl group, acyloxy group, ether group, ester group, alkyl group, aryl group, Examples include halogen atoms and polymerizable groups. Examples of the polymerizable group include a vinyl group, a styrene group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group.

Specific examples of the group represented by A ¹ include the groups shown below.

X ¹ in formula (1) represents a urea group, a thiourea group, a urethane group, a thiourethane group, or an amide group, preferably a urea group, a thiourea group, a urethane group, or a thiourethane group; It is more preferably a urethane group, even more preferably a urea group or a thiourea group, and particularly preferably a urea group.

L ¹ in formula (1) represents an n-valent group. Examples of the n-valent group represented by L ¹ include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aromatic heterocyclic group, and a combination of two or more of these groups.

The number of carbon atoms in the aliphatic hydrocarbon group is 1 or more, and is 2 or more because it can further improve the pigment adsorption property through hydrophobic interaction and further improve the storage stability of the resin composition. It is preferably 3 or more, more preferably 5 or more, even more preferably 8 or more. The upper limit is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. The aliphatic hydrocarbon group may be linear, branched, or cyclic, but is preferably linear or branched because it can further improve the storage stability of the resin composition. It is more preferable that there be. The aliphatic hydrocarbon group may have a substituent. Examples of substituents include hydroxy group, aldehyde group, carbonyl group, acyl group, nitro group, alkoxy group, aryloxy group, aryloxycarbonyl group, alkoxycarbonyl group, acyloxy group, ether group, ester group, alkyl group, aryl group, Examples include halogen atoms and polymerizable groups. Examples of the polymerizable group include a vinyl group, a styrene group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group. Moreover, it is also preferable that the aliphatic hydrocarbon group has no substituent.

The aromatic hydrocarbon group and the aromatic heterocyclic group may be monocyclic or polycyclic. The heteroatom constituting the ring of the aromatic heterocyclic group preferably contains at least one selected from a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably 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 still more preferably 1 or 2.
When the aromatic hydrocarbon group is polycyclic, the number of ring structures contained in the aromatic hydrocarbon group is preferably 2 to 10, more preferably 2 to 8, and 2 to 5. It is even more preferable.
When the aromatic heterocyclic group is polycyclic, the number of ring structures contained in the aromatic heterocyclic group is preferably 2 to 10, more preferably 2 to 8, and 2 to 5. It is even more preferable.
The aromatic hydrocarbon group and the aromatic heterocyclic group may have a substituent. The substituent is preferably an electron-withdrawing group or an electron-donating group. Here, an electron-withdrawing group is a substituent that is more likely to attract electrons to the bonded atom compared to a hydrogen atom, and an electron-donating group is a substituent that is more likely to attract electrons to the bonded atom than a hydrogen atom. A substituent that tends to donate electrons to the side of the atom that is present. Specific examples of electron-withdrawing groups include halogen atoms, halogenated alkyl groups, alkoxycarbonyl groups, cyano groups, nitro groups, carboxy groups, and sulfonyl groups. It is preferable that there be. Specific examples of the electron-donating group include an alkyl group, an alkoxy group, a hydroxy group, an amino group, etc., and preferably an alkoxy group, a hydroxy group, or an amino group.

When the aromatic hydrocarbon group and the aromatic heterocyclic group are polycyclic, the pigment adsorption property can be further improved by the π-π interaction, and the storage stability of the resin composition can be further improved. can.
When the aromatic hydrocarbon group has an electron-withdrawing group or an electron-donating group as a substituent, it is possible to further improve pigment adsorption by changing the electronic state of the X ¹ part in formula (1). Therefore, the storage stability of the resin composition can be further improved.

n in formula (1) represents an integer from 1 to 4.

A preferred embodiment of n in formula (1) is an embodiment in which n is 1.
Another preferred embodiment of n in formula (1) includes an embodiment in which n is an integer of 2 to 4. In this embodiment, n is preferably 2 or 3, more preferably 2.

When n in formula (1) is 1, L ¹ is a polycyclic aromatic ring group, an aliphatic hydrocarbon group having 2 or more carbon atoms, or an electron-withdrawing group or an electron-donating group substituted. A monocyclic aromatic hydrocarbon group is preferable.

The polycyclic aromatic ring group may be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group. A polycyclic aromatic hydrocarbon group is preferred 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, more preferably 2 to 8, and even more preferably 2 to 5.
Specific examples of the polycyclic aromatic ring group include naphthalene ring group, anthracene ring group, acenaphthene ring group, acenaphthylene ring group, phenalene ring group, phenanthrene ring group, fluorene ring group, pyrene ring group, quinoline ring group, and isoquinoline ring group. Examples include ring groups, quinoxaline ring groups, pentacene ring groups, benzopyrene ring groups, chrysene groups, triphenylene groups, corannulene ring groups, coronene groups, and obalene ring groups.
The polycyclic aromatic ring group may have a substituent or not have a substituent. Examples of the substituent include electron-withdrawing groups and electron-donating groups.

The number of carbon atoms in the aliphatic hydrocarbon group is preferably 3 or more, more preferably 5 or more, and even more preferably 8 or more. The upper limit is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. The aliphatic hydrocarbon group may be linear, branched, or cyclic, but is preferably linear or branched because it can further improve the storage stability of the resin composition. It is more preferable that Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, etc., and an alkyl group is preferable, and a straight-chain alkyl group is more preferable. The aliphatic hydrocarbon group may have a substituent or not have a substituent. Examples of substituents include hydroxy group, aldehyde group, carbonyl group, acyl group, nitro group, alkoxy group, aryloxy group, aryloxycarbonyl group, alkoxycarbonyl group, acyloxy group, ether group, ester group, alkyl group, aryl group, Examples include halogen atoms and polymerizable groups. Examples of the polymerizable group include a vinyl group, a styrene group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group. Moreover, it is also preferable that the aliphatic hydrocarbon group has no substituent.

Examples of the monocyclic aromatic hydrocarbon group include a benzene ring group.

Examples of the electron-withdrawing group possessed by the monocyclic aromatic hydrocarbon group include the above-mentioned electron-withdrawing groups. The monocyclic aromatic hydrocarbon group preferably has an electron-withdrawing group at the para position of the aromatic hydrocarbon group. According to this aspect, 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 possessed by the monocyclic aromatic hydrocarbon group include the electron-donating groups described above. The monocyclic aromatic hydrocarbon group may have two or more electron-donating groups.

When n in formula (1) is an integer of 2 to 4, L ¹ is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aromatic heterocyclic group, or a combination of two or more of these groups. An aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of two or more of these groups is preferred. The preferred ranges of the aliphatic hydrocarbon group, aromatic hydrocarbon group, and aromatic heterocyclic group are the same as described above.

Specific examples of the group represented by L ¹ include the groups shown below.

The maximum value of the molar extinction coefficient of the specific compound in the wavelength range of 400 to 700 nm is 3000 L·mol ⁻¹ ·cm ⁻¹ or less, preferably 1000 L·mol ⁻¹ ·cm ⁻¹ or less, and 100 L·mol It is more preferably ^-1 ·cm ^-1 or less, and even more preferably 10 L·mol ^-1 ·cm ^-1 or less.

The molecular weight of the specific compound is 475 or less, preferably 465 or less, and more preferably 460 or less. The lower limit is preferably 150 or more, more preferably 200 or more, and even more preferably 250 or more.

Specific examples of the specific compound include compounds having the structures shown in the dispersion aids M-1 to M-53 described in Examples below.

The content of the specific compound in the total solid content of the resin composition is preferably 0.01 to 15% by mass. The upper limit is preferably 12% by mass or less, more preferably 10% by mass or less. The lower limit is preferably 0.05% by mass or more, more preferably 1% by mass or more.
The total content with the specific compound is preferably 1 to 30 parts by weight per 100 parts by weight of the pigment. The lower limit is preferably 2 parts by mass or more, more preferably 4 parts by mass or more. The upper limit is preferably 15 parts by mass or less, more preferably 10 parts by mass or less.
The resin composition of the present invention may contain only one type of specific compound, or may contain two or more types of specific compounds. When two or more types of resin are included, the total amount thereof is preferably within the above range.

<<Pigment derivative>>
The resin composition of the present invention can contain a pigment derivative. Pigment derivatives are used, for example, as dispersion aids. Examples of the pigment derivative include compounds having at least one structure selected from the group consisting of a pigment structure and a triazine structure, and an acid group or a basic group.

The above dye structures include quinoline dye structure, benzimidazolone dye structure, benzisoindole dye structure, benzothiazole dye structure, iminium dye structure, squarylium dye structure, croconium dye structure, oxonol dye structure, pyrrolopyrrole dye structure, diketo Pyrrolopyrrole dye structure, azo dye structure, azomethine dye structure, phthalocyanine dye structure, naphthalocyanine dye structure, anthraquinone dye structure, quinacridone dye structure, dioxazine dye structure, perinone dye structure, perylene dye structure, thiazine indigo dye structure, thioindigo dye structure, isoindoline dye structure, isoindolinone dye structure, quinophthalone dye structure, dithiol dye structure, triarylmethane dye structure, pyrromethene dye structure, etc.

Examples of acid groups possessed by pigment derivatives include carboxy groups, sulfo groups, phosphoric acid groups, phosphonic acids, and phenolic hydroxy groups.

Examples of the basic group that the pigment derivative has include an amino group, a pyridinyl group and its salts, an ammonium group salt, and a phthalimidomethyl group. Examples of atoms or atomic groups constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.

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

Specific examples of pigment derivatives include compounds described in JP-A-56-118462, compounds described in JP-A-63-264674, compounds described in JP-A-01-217077, and JP-A-03-1999. Compounds described in JP-A-03-026767, compounds described in JP-A-03-153780, compounds described in JP-A-03-045662, JP-A-04-285669 Compounds described in JP-A No. 06-145546, compounds described in JP-A No. 06-212088, compounds described in JP-A No. 06-240158, compounds described in JP-A No. 10-030063 Compounds described in JP-A-10-195326, compounds described in paragraph numbers 0086 to 0098 of International Publication No. 2011/024896, compounds described in paragraph numbers 0063 to 0094 of International Publication No. 2012/102399. Compounds, compounds described in paragraph number 0082 of International Publication No. 2017/038252, compounds described in paragraph number 0171 of JP 2015-151530, paragraphs 0162 to 0183 of JP 2011-252065, Compounds, compounds described in JP 2003-081972, compounds described in JP 5299151, compounds described in JP 2015-172732, compounds described in JP 2014-199308, JP Compounds described in JP 2014-085562, compounds described in JP 2014-035351, compounds described in JP 2008-081565, compounds described in JP 2019-109512, JP 2019- Compounds described in No. 133154, diketopyrrolopyrrole compounds having a thiol linking group described in International Publication No. 2020/002106, benzimidazolone compounds or salts thereof described in JP 2018-168244, etc. It will be done. As the pigment derivative, a compound having an isoindoline skeleton described in the general formula (1) of Japanese Patent No. 6996282 may be used.

The total content of the pigment derivative and the above-mentioned specific compound is preferably 1 to 30 parts by weight based on 100 parts by weight of the pigment. The lower limit is preferably 2 parts by mass or more, more preferably 4 parts by mass or more. The upper limit is preferably 15 parts by mass or less, more preferably 10 parts by mass or less.
The content of the pigment derivative is preferably 10 to 90 parts by weight, more preferably 15 to 85 parts by weight, and even more preferably 20 to 80 parts by weight based on 100 parts by weight of the above-mentioned specific compound.
Only one type of pigment derivative may be used, or two or more types may be used in combination. When two or more types are used in combination, it is preferable that the total amount is within the above range.

It is also preferable that the resin composition of the present invention does not substantially contain a pigment derivative. When the resin composition of the present invention does not substantially contain a pigment derivative, it means that the content of the pigment derivative in the total solid content of the resin composition is 0.1% by mass or less, and 0.05% by mass. It is more preferable that it is at most % by mass, and even more preferably that it does not contain a pigment derivative.

<<Polymerizable compound>>
It is preferable that the resin composition of the present invention 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 a vinyl group, (meth)allyl group, and (meth)acryloyl group. The polymerizable compound used in the present invention is preferably a radically polymerizable compound.

The polymerizable compound may be in any chemical form such as a monomer, prepolymer, or oligomer, but monomers are preferred. The molecular weight of the polymerizable compound is preferably 100 to 2,500. 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 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 a 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 three or more ethylenically unsaturated bond-containing groups, and more preferably a compound containing four or more ethylenically unsaturated bond-containing groups. The upper limit of the ethylenically unsaturated bond-containing groups is preferably 15 or less, more preferably 10 or less, and even more preferably 6 or less from the viewpoint of storage stability of the resin composition. Further, the polymerizable compound is preferably a trifunctional or higher functional (meth)acrylate compound, more preferably a trifunctional to 15 functional (meth)acrylate compound, and a trifunctional to 10 functional (meth)acrylate compound. More preferably, it is a tri- to hexa-functional (meth)acrylate compound. Specific examples of polymerizable compounds include paragraph numbers 0095 to 0108 of JP 2009-288705, paragraph 0227 of JP 2013-029760, paragraph 0254 to 0257 of JP 2008-292970, and The compounds described in paragraph numbers 0034 to 0038 of JP 2013-253224, paragraph 0477 of JP 2012-208494, JP 2017-048367, JP 6057891, and JP 6031807 are , the contents of which are incorporated herein.

Examples of polymerizable compounds include dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and modified products of these compounds. Can be mentioned. Examples of the modified product include compounds having a structure in which the (meth)acryloyl groups of the above compounds are bonded via an alkyleneoxy group, such as ethoxylated dipentaerythritol hexa(meth)acrylate. Specific examples include compounds represented by formula (Z-4) and compounds represented by formula (Z-5).

In formulas (Z-4) and (Z-5), E is each independently -((CH ₂ ) _y CH ₂ O)-, or -((CH ₂ ) _y CH(CH ₃ )O)- , each y independently represents an integer of 0 to 10, and each X independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxy group. In formula (Z-4), the total number of (meth)acryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. In formula (Z-5), the total number of (meth)acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.

In formula (Z-4), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the sum of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
In formula (Z-5), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
E in formula (Z-4) or formula (Z-5), that is, -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)- is an oxygen atom A form in which the side end is bonded to X is preferable.

As the polymerizable compound, polypentaerythritol poly(meth)acrylate as shown in the following formula (Z-6) can also be used.
In formula (Z-6), X ¹ to X ⁶ each independently represent a hydrogen atom or a (meth)acryloyl group, and n represents an integer of 1 to 10. However, at least one of X ¹ to X ⁶ is a (meth)acryloyl group.

The polymerizable compound used in the present invention is at least one selected from the group consisting of dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, polypentaerythritol poly(meth)acrylate, and modified products thereof. Preferably it is a seed. Commercially available products include KAYARAD D-310, DPHA, DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.), NK Ester A-DPH-12E, and TPOA-50 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). Can be mentioned.

Examples of polymerizable compounds include diglycerin EO (ethylene oxide) modified (meth)acrylate (commercial product: M-460; manufactured by Toagosei), pentaerythritol tetra(meth)acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester) A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Toagosei Co., Ltd.) ), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), Light Acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), EBECRYL80 ( Amine-containing tetrafunctional acrylate (manufactured by Daicel Allnex) can also be used.

Polymerizable compounds include trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide modified tri(meth)acrylate, trimethylolpropane ethylene oxide modified tri(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, and pentaerythritol. It is also preferable to use trifunctional (meth)acrylate compounds such as tri(meth)acrylate. Commercially available trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) Examples include.

As the polymerizable compound, a compound having an acid group such as a carboxy group, a sulfo group, or a phosphoric acid group can also be used. Commercially available products of such compounds include Aronix M-305, M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), and the like.

As the polymerizable compound, a compound having a caprolactone structure can also be used. Regarding the compound having a caprolactone structure, the description in paragraphs 0042 to 0045 of JP-A No. 2013-253224 can be referred to, the contents of which are incorporated herein. Examples of compounds having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, and DPCA-120, which are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series.

As the polymerizable compound, a polymerizable compound having a fluorene skeleton can also be used. Commercially available products include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., (meth)acrylate monomer having a fluorene skeleton).

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

Examples of the polymerizable compound include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765; Urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable. It is also preferable to use polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238. In addition, the polymerizable compounds include UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, Commercially available products such as T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.

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

<<Photopolymerization initiator>>
The resin composition of the present invention can 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, compounds having photosensitivity to light in the ultraviolet to visible range are preferred. The photopolymerization initiator is preferably a radical photopolymerization initiator.

Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with 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, and the like. From the viewpoint of exposure sensitivity, photopolymerization initiators include trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and hexaarylbylene compounds. Preferred are imidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl substituted coumarin compounds, oxime compounds, α-hydroxyketones The compound is more preferably a compound selected from a compound, an α-aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound. In addition, as photopolymerization initiators, compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60p, vol. 19, No. 3,2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, JP 2019-043864 The photopolymerization initiator described in JP-A No. 2019-044030, the peroxide-based initiator described in JP-A No. 2019-167313, the photopolymerization initiator described in JP-A No. 2020-055992 The aminoacetophenone initiator having an oxazolidine group as described, the oxime photopolymerization initiator described in JP 2013-190459, the polymer described in JP 2020-172619, the WO 2020/152120 The compound represented by the formula 1 described in JP-A No. 2021-181406, the photopolymerization initiator described in JP-A No. 2022-013379, the formula (1) described in JP-A No. 2022-015747 ), the fluorine-containing fluorene oxime ester photoinitiator described in Japanese Patent Publication No. 2021-507058, and the contents thereof are incorporated herein.

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

Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, and Irgacure 117. 3, Irgacure 2959, Irgacure 127 (all BASF (manufactured by a company). Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, and Irgacure 36. 9, Irgacure 369E, Irgacure 379EG (all manufactured by BASF) (manufactured by). Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (manufactured by BASF), and the like.

Examples of oxime compounds include the compounds described in JP-A No. 2001-233842, the compounds described in JP-A No. 2000-080068, the compounds described in JP-A No. 2006-342166, and the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660); C. S. Compounds described in Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP-A-2000-0 Compounds described in Publication No. 66385, Compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2006-342166, compounds described in Japanese Patent Application Publication No. 2017-019766, compounds described in Japanese Patent No. 6065596, International Publication No. 2015 /152153, the compound described in International Publication No. 2017/051680, the compound described in JP 2017-198865, the compound described in paragraph numbers 0025 to 0038 of International Publication No. 2017/164127, Compounds described in International Publication No. 2013/167515, compounds represented by general formula (1) in JP-A No. 2021-173858, compounds described in paragraphs 0022 to 0024, general formula in JP-A No. 2021-170089 Examples include the compound represented by (1) and the compounds described in paragraphs 0117 to 0120. Specific examples of oxime compounds 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, Irgacure OXE04 (manufactured by BASF), TR-PBG-301, TR-PBG-304, TR-PBG-327 (manufactured by TRONLY). ), Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., photopolymerization initiator 2) described in JP-A-2012-014052 can be mentioned. Further, as the oxime compound, it is also preferable to use a compound without coloring property or a compound with high transparency and resistance to discoloration. Commercially available products include ADEKA Arkles NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA Co., Ltd.).

As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of oxime compounds having a fluorene ring include compounds described in JP-A No. 2014-137466, compounds described in Japanese Patent No. 6636081, compounds described in Korean Patent Publication No. 10-2016-0109444, Examples include fluorenylaminoketone photoinitiators described in Japanese Patent Publication No. 2020-507664 and oxime ester compounds described in International Publication No. 2021/023144.

As the photopolymerization initiator, it is also possible to use an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring. Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505.

As a photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of oxime compounds having a fluorine atom include compounds described in JP-A No. 2010-262028, compounds 24, 36 to 40 described in Japanese Patent Application Publication No. 2014-500852, and compounds described in JP-A No. 2013-164471. Examples include compound (C-3).

As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable that the oxime compound having a nitro group is in the form of a dimer. Specific examples of oxime compounds having a nitro group include compounds described in paragraph numbers 0031 to 0047 of JP 2013-114249, paragraphs 0008 to 0012, and 0070 to 0079 of JP 2014-137466, Examples include compounds described in paragraph numbers 0007 to 0025 of Japanese Patent No. 4223071, and Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).

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

As a photopolymerization initiator, it is also possible to use an oxime compound in which a substituent having a hydroxy group is bonded to a carbazole skeleton. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019/088055.

As the photopolymerization initiator, it is also possible to use an oxime compound having an aromatic ring group Ar ^OX1 (hereinafter also referred to as oxime compound OX) in which an electron-withdrawing group is introduced into the aromatic ring. Examples of the electron-withdrawing group possessed by the aromatic ring group Ar ^OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group, An acyl group and a nitro group are preferred, an acyl group is more preferred, and a benzoyl group is even more preferred. The benzoyl group may have a substituent. Examples of substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, It is preferably an acyl group or an amino group, and more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group. More preferably, it is a sulfanyl group or an amino group.

Specific examples of the oxime compound OX include compounds described in paragraph numbers 0083 to 0105 of Japanese Patent No. 4,600,600.

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

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

As the 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 difunctional, trifunctional or more functional photoradical polymerization initiator may be used. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so that good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, the crystallinity decreases and the solubility in solvents improves, making it difficult to precipitate over time and improving the storage stability of the resin composition. . Specific examples of bifunctional or trifunctional or more functional photoradical polymerization initiators include those listed in Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Application Publication No. 2016-532675. Dimers of oxime compounds described in paragraph numbers 0407 to 0412, paragraph numbers 0039 to 0055 of International Publication No. 2017/033680, compound (E) and compound ( G), Cmpd1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiators described in paragraph number 0007 of Japanese Patent Publication No. 2017-523465, Photoinitiators described in paragraph numbers 0020 to 0033, photoinitiators (A) described in paragraph numbers 0017 to 0026 of JP2017-151342A, and photoinitiators (A) described in Japanese Patent No. 6469669. Examples include oxime ester photoinitiators.

The content of the photopolymerization initiator in the total solid content of the resin composition is preferably 0.1 to 20% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 10% by 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 their total amount falls within the above range.

<<Solvent>>
It is preferable that the resin composition of the present invention contains a solvent. Examples of the solvent include organic solvents. The type of solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition. Examples of the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For these details, paragraph number 0223 of International Publication No. 2015/166779 can be referred to, the contents of which are incorporated herein. Ester solvents substituted with a cyclic alkyl group and ketone 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 monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxy Butanol, 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 Examples include diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol. However, it may be better to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents for environmental reasons (for example, 50 mass ppm (parts) based on the total amount of organic solvents). per million), 10 mass ppm or less, and 1 mass ppm or less).

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

Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon.

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

It is preferable that the content of peroxide in the organic solvent is 0.8 mmol/L or less, and it is more preferable that the organic solvent contains substantially no 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 does not substantially contain environmentally regulated substances. In the present invention, "not substantially containing environmentally controlled substances" means that the content of environmentally controlled substances in the resin composition is 50 mass ppm or less, preferably 30 mass ppm or less. , more preferably 10 mass ppm or less, particularly preferably 1 mass ppm or less. Examples of environmentally controlled substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These are REACH (Registration Evaluation Authorization and Restriction of CHemicals) rules, PRTR (Pollutant Release and It is registered as an environmentally regulated substance under the Transfer Register Act, VOC (Volatile Organic Compounds) regulations, etc., and its usage and handling are The method is strictly regulated. These compounds are sometimes 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 considerations, it is preferable to reduce the amount of these substances as much as possible. Examples of methods for reducing environmentally controlled substances include a method of heating or reducing pressure in the system to raise the temperature above the boiling point of the environmentally controlled substance to distill off the environmentally controlled substances from the system. Furthermore, when distilling off a small amount of environmentally regulated substances, it is also useful to carry out azeotropy with a solvent having the same boiling point as the relevant solvent in order to increase efficiency. In addition, if a compound that has radical polymerizability is contained, a polymerization inhibitor or the like may be added to prevent the radical polymerization reaction from proceeding during vacuum distillation and crosslinking between molecules. It's okay. These distillation methods can be used at the stage of raw materials, at the stage of products obtained by reacting raw materials (for example, resin solution or polyfunctional monomer solution after polymerization), or at the stage of resin compositions prepared by mixing these compounds. This is possible at any stage.

<<Thermal crosslinking agent>>
The resin composition of the present invention can contain a thermal crosslinking agent as a component other than the above-mentioned resin and polymerizable compound. Examples of the thermal crosslinking agent include compounds having a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. The epoxy group may be a cycloaliphatic epoxy group. Note that 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 preferably compounds having two or more epoxy groups. 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 two or more. Examples of epoxy compounds include those described in paragraph numbers 0034 to 0036 of JP2013-011869, paragraphs 0147 to 0156 of JP2014-043556, and paragraphs 0085 to 0092 of JP2014-089408. Compounds, compounds described in JP 2017-179172, xanthene type epoxy resins described in JP 2021-195421, and xanthene epoxy resins described in JP 2021-195422 can also be used.

The compound having a cyclic ether group may be a low-molecular compound (e.g., molecular weight less than 2,000, further, molecular weight less than 1,000), or a macromolecule (e.g., molecular weight 1,000 or more, in the case of a polymer, a weight average molecular weight may be 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, and G-0130SP. -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (all of which are epoxy group-containing polymers manufactured by NOF Corporation). Further, as a compound having a cyclic ether group, compounds described in Examples described later can also be used.

The content of the thermal crosslinking agent in the total solid content of the resin composition is preferably 0.1 to 20% by mass. The lower limit is, for example, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is, for example, more preferably 15% by mass or less, and even more preferably 10% by 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 their total amount falls within the above range.

<<Curing accelerator>>
The resin composition of the present invention may also contain a curing accelerator. Examples of the curing accelerator include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, onium salt compounds, and the like. Specific examples of the curing accelerator include compounds described in paragraph numbers 0094 to 0097 of International Publication No. 2018/056189, compounds described in paragraph numbers 0246 to 0253 of JP 2015-034963, and JP 2013-041165. Compounds described in paragraph numbers 0186 to 0251 of JP-A No. 2014-055114, compounds described in paragraph numbers 0071 to 0080 of JP-A-2012-150180, JP-A-2011-253054 Alkoxysilane compounds having epoxy groups as described in Japanese Patent Publication No. 5765059, compounds described in paragraph numbers 0085 to 0092 of Japanese Patent No. 5765059, carboxyl group-containing epoxy curing agents described in Japanese Patent Application Publication No. 2017-036379, Japanese Patent Publication No. 2021- Examples include compounds described in JP 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 absorber>>
The resin composition of the present invention can contain an ultraviolet absorber. Examples of the ultraviolet absorber include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, and the like. Specific examples of such compounds include the compound described in paragraph number 0179 of International Publication No. 2022/085485, the reactive triazine ultraviolet absorber described in JP 2021-178918, and JP 2022-007884. It is also possible to use the ultraviolet absorbers described in .

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 falls within the above range.

<<Polymerization inhibitor>>
The resin composition of the present invention can contain a polymerization inhibitor. Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), Examples include 2,2'-methylenebis(4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the resin composition is preferably 0.0001 to 5% by mass. The number of polymerization inhibitors may be one, or two or more. In the case of two or more types, it is preferable that the total amount falls within the above range.

<<Silane coupling agent>>
The resin composition of the present invention can contain a silane coupling agent. In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Furthermore, the term "hydrolyzable group" refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkoxy group is preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, and isocyanate groups. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferable. Specific examples of silane coupling agents include N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N-β-aminoethyl-γ-amino Propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N-β-aminoethyl-γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), γ-Aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-903), 3-methacryloxy Examples include propylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-502), 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-503), and the like. Specific examples of the silane coupling agent include compounds described in paragraph numbers 0018 to 0036 of JP-A No. 2009-288703 and compounds described in paragraph numbers 0056 to 0066 of JP-A-2009-242604. , the contents of which are incorporated herein. 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. Only one type of silane coupling agent may be used, or two or more types may be used. In the case of two or more types, it is preferable that the total amount falls within the above range.

<<Surfactant>>
The resin composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. The surfactant is preferably a silicone surfactant or a fluorine surfactant. Regarding the surfactant, reference can be made to the surfactants described in paragraph numbers 0238 to 0245 of International Publication No. 2015/166779, the contents of which are incorporated herein.

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

As the fluorine-based surfactant, compounds described in paragraph numbers 0167 to 0169 of International Publication No. 2022/085485 can be used.

A block polymer can also be used as the fluorosurfactant. The fluorine-based surfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy group, propyleneoxy group) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. Further, the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A No. 2010-032698 and the following compounds are also exemplified as the fluorine-containing surfactant used in the present invention.
The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example 14,000. In the above compounds, % indicating the proportion of repeating units is mol%.

Further, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in its side chain can also be used. Specific examples include compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A No. 2010-164965, Megafac RS-101, RS-102, RS-718K manufactured by DIC Corporation, Examples include RS-72-K. Further, as the fluorine-based surfactant, compounds described in paragraph numbers 0015 to 0158 of JP-A No. 2015-117327 and fluorine-containing copolymers described in JP-A No. 2022-000494 can also be used.

Furthermore, it is also preferable from the viewpoint of environmental regulations to use the surfactant described in International Publication No. 2020/084854 as a substitute for a surfactant having a perfluoroalkyl group having 6 or more carbon atoms.

It is also preferable to use a fluorine-containing imide salt compound represented by formula (fi-1) as a surfactant.
In formula (fi-1), m represents 1 or 2, n represents an integer of 1 to 4, a represents 1 or 2, and X ^a+ represents an a-valent metal ion, a primary ammonium ion, a Represents a secondary ammonium ion, a tertiary ammonium ion, a quaternary ammonium ion, or NH ₄ ⁺ .

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Japan Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Fujifilm Wa (manufactured by Hikari Junyaku Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Olfin E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) ), etc.

Examples of silicone surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Industries, Inc.), and TSF- 4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.) , BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (manufactured by BYK Chemie), and the like.

Moreover, 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, more preferably 0.005% to 3.0% by mass. The number of surfactants may be one, or two or more. In the case of two or more types, it is preferable that the total amount falls within the above range.

<<Antioxidant>>
The resin composition of the present invention can contain an antioxidant. Examples of antioxidants include phenol compounds, phosphite compounds, thioether compounds, and the like. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferred phenol compounds include hindered phenol compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. The above-mentioned substituents are preferably substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms. Further, as the antioxidant, a compound having a phenol group and a phosphorous acid ester group in the same molecule is also preferable. Further, as the antioxidant, phosphorus-based antioxidants can also be suitably used. As a phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepine-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, ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like. Commercially available antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Co., Ltd.). In addition, antioxidants include compounds described in paragraph numbers 0023 to 0048 of Patent No. 6268967, compounds described in International Publication No. 2017/006600, compounds described in International Publication No. 2017/164024, Compounds described in Korean Patent Publication No. 10-2019-0059371 can also be used. The content of the antioxidant in the total solid content of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by 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 falls within the above range.

<<Other ingredients>>
The resin composition of the present invention may contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers, and other auxiliary agents (for example, conductive particles, antifoaming agents, flame retardants, (leveling agents, peeling accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.) may also be included. By appropriately containing these components, properties such as film physical properties can be adjusted. These components are described, for example, in paragraphs 0183 and after of JP-A-2012-003225 (corresponding paragraph 0237 of U.S. Patent Application Publication No. 2013/0034812), and in paragraphs of JP-A-2008-250074. The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated into the present specification. Furthermore, the resin composition of the present invention may contain a latent antioxidant, if necessary. A latent antioxidant is a compound whose moiety that functions as an antioxidant is protected with a protecting group, and is heated at 100 to 250°C or heated at 80 to 200°C in the presence of an acid/base catalyst. Examples include compounds that function as antioxidants by removing protective groups. Examples of the latent antioxidant include compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219. Commercially available latent antioxidants include Adeka Arcles GPA-5001 (manufactured by ADEKA Co., Ltd.).

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 metal oxides include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , and SiO ₂ . The primary particle diameter of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, even more preferably 5 to 50 nm. The metal oxide may have a core-shell structure. Further, in this case, the core portion may be hollow.

The resin composition of the present invention may also contain a light resistance improver. Examples of the light resistance improver include compounds described in paragraph number 0183 of International Publication No. 2022/085485.

It is also preferable that the resin composition of the present invention does not substantially contain terephthalic acid ester. Here, "substantially not containing" means that the content of terephthalic acid ester is 1000 mass ppb or less in the total amount of the resin composition, more preferably 100 mass ppb or less, Particularly preferred is zero.
The resin composition of the present invention preferably has a free metal content of 100 ppm or less, more preferably 50 ppm or less. Further, the free halogen content is preferably 100 ppm or less, more preferably 50 ppm or less. Examples of methods for reducing free metals and halogens in the resin composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification using ion-exchange resins.

From the perspective of environmental regulations, the use of perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts may be regulated. In the resin composition of the present invention, when reducing the content of the above-mentioned compounds, perfluoroalkylsulfonic acids (particularly perfluoroalkylsulfonic acids whose perfluoroalkyl group has 6 to 8 carbon atoms), salts thereof, and perfluoroalkylsulfonic acids, The content of fluoroalkylcarboxylic acid (particularly perfluoroalkylcarboxylic acid whose perfluoroalkyl group has 6 to 8 carbon atoms) and its salt is 0.01 ppb to 1,000 ppb based on the total solid content of the resin composition. It is preferably in the range of , more preferably in the range of 0.05 ppb to 500 ppb, even more preferably in the range of 0.1 ppb to 300 ppb. The resin composition of the present invention may be substantially free of perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and its salt. For example, by using a compound that can be substituted for perfluoroalkylsulfonic acid and its salt, and a compound that can be substituted for perfluoroalkylcarboxylic acid and its salt, perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid You may also select a resin composition that is substantially free of and salts thereof. Compounds that can be substituted for regulated compounds include, for example, compounds that are excluded from regulated targets due to differences in the number of carbon atoms in perfluoroalkyl groups. However, the above content does not preclude the use of perfluoroalkylsulfonic acids and salts thereof, and perfluoroalkylcarboxylic acids and salts thereof. The resin composition of the present invention may contain perfluoroalkyl sulfonic acids and salts thereof, and perfluoroalkyl carboxylic acids and salts thereof, within the maximum allowable range.

The water content of the resin composition of the present invention is usually 3% by mass or less, preferably from 0.01 to 1.5% by mass, and more preferably from 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 condition (flatness, etc.), adjusting the film thickness, etc. The value of viscosity can be appropriately selected as required, but for example, at 25° C., 0.3 mPa·s to 50 mPa·s is preferable, and 0.5 mPa·s to 20 mPa·s is more preferable. The viscosity can be measured using, for example, 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 any known container can be used. In addition, for the purpose of suppressing impurities from entering raw materials and resin compositions, we have used multilayer bottles with container inner walls made of 6 types of 6 layers of resin, and bottles with 7 layers of 6 types of resin as storage containers. It is also preferable to use Examples of such a container include the container described in JP-A No. 2015-123351. Further, the inner wall of the container is preferably made of glass, stainless steel, etc. for the purpose of preventing metal elution from the inner wall of the container, increasing the storage stability of the resin composition, and suppressing component deterioration.

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

Furthermore, it is preferable to include a process of dispersing the pigment when preparing the resin composition. In the process of dispersing pigments, mechanical forces used for dispersing pigments include compression, squeezing, impact, shearing, cavitation, and the like. 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, ultrasonic dispersion, and the like. In addition, when pulverizing pigments in a sand mill (bead mill), it is preferable to use small-diameter beads or increase the filling rate of the beads, thereby increasing the pulverizing efficiency. Further, it is preferable to remove coarse particles by filtration, centrifugation, etc. after the pulverization treatment. In addition, the process and dispersion machine for dispersing pigments are described in ``Complete Works of Dispersion Technology, Published by Information Technology Corporation, July 15, 2005'' and ``Dispersion technology centered on suspension (solid/liquid dispersion system) and industrial The process and dispersion machine described in Paragraph No. 0022 of JP 2015-157893 A, "Practical Application Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be suitably used. Further, in the process of dispersing the pigment, the particles may be made finer in a salt milling step. For the materials, equipment, processing conditions, etc. used in the salt milling process, the descriptions in JP-A No. 2015-194521 and JP-A No. 2012-046629 can be referred to, for example. Bead materials used for dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, and glass. Moreover, an inorganic compound having a Mohs hardness of 2 or more can also be used for the beads. The resin composition may contain 1 to 10,000 ppm of the beads.

In preparing the resin composition, it is preferable to filter the resin composition with a filter for the purpose of removing foreign substances and reducing defects. Examples of the type of filter and filtration method used for filtration include the filters and filtration methods described in paragraph numbers 0196 to 0199 of International Publication No. 2022/085485.

<Membrane>
The membrane of the present invention is a membrane obtained from the resin composition of the present invention described above. The film of the present invention can be used for optical filters such as color filters, near-infrared transmission filters, and near-infrared cut filters.

The film thickness of the film of the present invention can be adjusted as appropriate depending on the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

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 a red hue. Further, the film of the present invention can 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, yellow pixels, etc., and red pixels are more preferable.

<Membrane manufacturing method>
Next, a method for manufacturing the membrane of the present invention will be explained. The film of the present invention can be manufactured through a step of applying the resin composition of the present invention. The film manufacturing method preferably further includes a step of forming a pattern (pixel). Examples of methods for forming patterns (pixels) include photolithography and dry etching, with photolithography being preferred. By forming a pattern using the resin composition of the present invention by photolithography, the generation of development residues can be further suppressed.

Pattern formation by the photolithography method 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 to light in a pattern, and a step of exposing the resin composition layer to light. It is preferable to include a step of developing and removing the exposed portion to form a pattern (pixel). If necessary, a step of baking the resin composition layer (pre-bake step) and a step of baking the developed pattern (pixel) (post-bake step) may be provided.

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

As a method for applying the resin composition, a known method can be used. For example, the coating method described in paragraph number 0207 of International Publication No. 2022/085485 can be used.

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

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

Radiation (light) that can be used during exposure includes g-line, i-line, etc. Furthermore, 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 rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm). Furthermore, a long-wave light source of 300 nm or more can also be used. As a light source, an electrodeless ultraviolet lamp system, a hybrid ultraviolet and infrared curing can be used.

Furthermore, during exposure, light may be exposed by continuous irradiation, or exposure may be performed by irradiation in pulses (pulse exposure). Note that pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and pauses in short cycles (for example, on the millisecond level 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 carried out in the atmosphere, for example, in a low oxygen atmosphere with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially The exposure may be performed in an oxygen-free atmosphere (without oxygen), or in a high oxygen atmosphere where the oxygen concentration exceeds 21 volume % (for example, 22 volume %, 30 volume %, or 50 volume %). Further, the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000W/m ² to 100000W/m ² (for example, 5000W/m ² , 15000W/m ² , or 35000W/m ² ). Can be done. The oxygen concentration and the exposure illuminance may be appropriately combined. For example, the illuminance may be 10,000 W/m ² when the oxygen concentration is 10% by volume, and 20,000 W/m ² when the oxygen concentration is 35% by volume.

Next, the unexposed areas of the resin composition layer are developed and removed to form a pattern (pixel). The unexposed areas of the resin composition layer can be removed by development using a developer. As a result, the unexposed portions of the resin composition layer in the exposure step are eluted into the developer, leaving only the photocured portions. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. Furthermore, in order to improve the ability to remove residues, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.

Examples of the developer include organic solvents, alkaline developers, and alkaline developers are preferably used. Regarding the developer and the cleaning (rinsing) method after development, the developer and cleaning method described in paragraph number 0214 of International Publication No. 2022/085485 can be used.

After development, it is preferable to perform additional exposure treatment or heat treatment (post-bake) after drying. Additional exposure processing and post-bake are post-development curing processing to complete curing. The heating temperature in post-baking is, for example, preferably 100 to 240°C, more preferably 200 to 240°C. Post-baking can be carried out in a continuous or batch manner using a heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to maintain the developed film under the above conditions. . When performing additional exposure processing, the light used for exposure is preferably light with a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.

Pattern formation by the dry etching method includes the steps of forming a resin composition layer on a support using the resin composition of the present invention, and curing the entire resin composition layer to form a cured product layer; A step of forming a photoresist layer on this cured material layer, a step of exposing the photoresist layer in a pattern and then developing it to form a resist pattern, and etching the cured material layer using this resist pattern as a mask. It is preferable to include a step of dry etching using gas. In forming the photoresist layer, it is preferable to further perform a prebaking process. In particular, as a process for forming the photoresist layer, it is desirable to perform a heat treatment after exposure and a heat treatment after development (post-bake treatment). Regarding pattern formation by the dry etching method, the descriptions in paragraphs 0010 to 0067 of JP-A No. 2013-064993 can be referred to, and the contents thereof are incorporated into the present specification.

<Optical filter>
The optical filter of the present invention has the film of the present invention described above. Types of optical filters include color filters, near-infrared cut filters, near-infrared transmission filters, etc., and color filters are preferred. The color filter preferably has the film of the invention as its pixels, more preferably the film of the invention as colored pixels, and still more preferably the film of the invention as red pixels.

The optical filter may be provided with 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, hydrophilic and hydrophobic properties, and shielding of light of a specific wavelength (ultraviolet rays, near infrared rays, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm. Examples of the method for forming the protective layer include a method of applying a resin composition for forming the protective layer, a chemical vapor deposition method, and a method of pasting a molded resin with an adhesive. 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 Examples include resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al ₂ O ₃ , Mo, SiO ₂ , Si ₂ N ₄ and the like, and two or more of these components may be contained. 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 . Furthermore, in the case of a protective layer intended for low reflection, the protective layer preferably contains a (meth)acrylic resin and a fluororesin.

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

The protective layer may contain organic/inorganic fine particles, absorbers for light of specific wavelengths (e.g., ultraviolet rays, near-infrared rays, etc.), refractive index adjusters, antioxidants, adhesives, surfactants, and other additives, as necessary. It may contain. Examples of organic/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, barium sulfate, and the like. As the absorber for light of a specific wavelength, a known absorber can be used. The content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by weight, more preferably 1 to 60% by weight, based on the total weight of the protective layer.

Furthermore, as the protective layer, the protective layers described in paragraph numbers 0073 to 0092 of JP-A No. 2017-151176 can also be used.

The optical filter may have a structure in which each pixel is embedded in a space partitioned into a lattice shape by partition walls, for example.

<Solid-state image sensor>
The solid-state imaging device of the present invention has the film of the present invention described above. The structure of the solid-state image sensor is not particularly limited as long as it includes the film of the present invention and functions as a solid-state image sensor, but examples include the following structure.

The substrate has a plurality of photodiodes that constitute the light receiving area of a solid-state image sensor (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and a transfer electrode made of polysilicon or the like. A device protective film made of silicon nitride or the like is formed on the light-shielding film to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode. It has a configuration in which a color filter is provided on the device protective film. Furthermore, a configuration in which a light condensing means (for example, a microlens, etc., the same applies hereinafter) is provided on the device protective film and below the color filter (on the side closer to the substrate), or a configuration in which the condensing means is provided on the color filter, etc. There may be. Further, the color filter may have a structure in which each colored pixel is embedded in a space partitioned into, for example, a lattice shape by partition walls. In this case, the partition wall preferably has a lower refractive index than each colored pixel. Examples of imaging devices having such a structure include devices described in Japanese Patent Application Publication No. 2012-227478, Japanese Patent Application Publication No. 2014-179577, and International Publication No. 2018/043654. Further, as shown in Japanese Patent Application Laid-open No. 2019-211559, an ultraviolet absorbing layer may be provided within the structure of the solid-state image sensor to improve light resistance. An imaging device equipped with the solid-state imaging device of the present invention can be used not only as a digital camera or an electronic device having an imaging function (such as a mobile phone), but also as a vehicle-mounted camera or a surveillance camera.

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

The present invention will be explained in more detail with reference to Examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed 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.

<Production of pigment dispersion>
A mixture of the materials listed 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 mixed and dispersed using a high-pressure dispersion machine with a pressure reduction mechanism, NANO-3000-10 (Japan BEE). Co., Ltd.) under a pressure of 2000 MPa and a flow rate of 500 g/min. This dispersion treatment was repeated 10 times to obtain each pigment dispersion. The numerical values listed in the table below are in parts by mass.
The average particle diameter (nm) of the pigment in each pigment dispersion and the viscosity value (mPa·s) of each pigment dispersion are also shown in the table below. The average particle diameter of the pigment was measured by a dynamic light scattering method using a particle diameter measuring device (nanoSAQLA, manufactured by Otsuka Electronics Co., Ltd.). The viscosity of the pigment dispersion was measured using a viscometer (RE-85L, manufactured by Toki Sangyo Co., Ltd.) while adjusting the temperature of the pigment dispersion to 25°C.

Details of the materials listed by abbreviations in the table above are as follows.
(color material)
PR122: C. I. Pigment Red 122 (quinacridone pigment, red pigment)
PR224: C. I. Pigment Red 224 (perylene pigment, red pigment)
PR254: C. I. Pigment Red 254 (diketopyrrolopyrrole pigment, red pigment)
PR272: C. I. Pigment Red 272 (diketopyrrolopyrrole pigment, red pigment)
PY138: C. I. Pigment Yellow 138 (quinophthalone pigment, yellow pigment)
PY139: C. I. Pigment Yellow 139 (isoindoline pigment, yellow pigment)
PY150: C. I. Pigment Yellow 150 (azo pigment, yellow pigment)
PY185:C. I. Pigment Yellow 185 (isoindoline pigment, yellow pigment)
PG36: C. I. Pigment Green 36 (phthalocyanine pigment, green pigment)
PB15:6: C. I. Pigment Blue 15:6 (phthalocyanine pigment, blue pigment)
PV23: C. I. Pigment Violet 23 (dioxazine pigment, purple pigment)
PBk32: C. I. Pigment Black 32 (perylene pigment, organic black pigment)
IR coloring material 1: Compound with the following structure (pyrrolopyrrole pigment, near-infrared absorbing pigment)

(Dispersion aid)
M-1 to M-53: Compounds with the following structure

The molecular weights and maximum molar absorption coefficients (ε ^max ) in the wavelength range of 400 to 700 nm of the dispersion aids M-1 to M-53 are as follows.

MC-1: Compound with the following structure (molecular weight: 255, ε ^max : 10 L・mol ⁻¹・cm ⁻¹ or less)
MC-2: Compound with the following structure (molecular weight: 785, ε ^max : more than 3000 L・mol ⁻¹・cm ⁻¹ )
Derivative A: Compound with the following structure (molecular weight: 768, ε ^max : more than 3000 L・mol ⁻¹・cm ⁻¹ )
Derivative B: Compound with the following structure (molecular weight: 403, ε ^max : more than 3000 L・mol ⁻¹・cm ⁻¹ )

(resin)
P-1: Resin with the following structure. The numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight: 7000.

P-2: Resin synthesized by the following method 50 parts by mass of methyl methacrylate, 50 parts by mass of n-butyl methacrylate, and 45.4 parts by mass of PGMEA (propylene glycol monomethyl ether acetate) were charged into a reaction vessel, and the atmosphere was replaced with nitrogen gas. Replaced. The inside of the reaction vessel was heated to 70°C, 6 parts by mass of 3-mercapto-1,2-propanediol was added, and further 0.12 parts by mass of AIBN (azobisisobutyronitrile) was added, followed by reaction for 12 hours. I let it happen. It was confirmed by solid content measurement that 95% had reacted. Next, 9.7 parts by mass of pyromellitic anhydride, 70.3 parts by mass of PGMEA, and 0.20 parts by mass of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) were added as a catalyst. , and reacted at 120°C for 7 hours. After measuring the acid value, it was confirmed that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated to obtain resin P-2 having an acid value of 43 mgKOH/g and a weight average molecular weight of 9,000.

P-3: Resin synthesized by the following method 50 parts by mass of methyl methacrylate, 30 parts by mass of n-butyl methacrylate, 20 parts by mass of t-butyl methacrylate, and 45.4 parts by mass of PGMEA were charged into a reaction vessel, and the atmosphere was replaced with nitrogen gas. Replaced. The inside of the reaction vessel was heated to 70°C, 6 parts by mass of 3-mercapto-1,2-propanediol was added, and further 0.12 parts by mass of AIBN (azobisisobutyronitrile) was added, followed by reaction for 12 hours. I let it happen. It was confirmed by solid content measurement that 95% had reacted. Next, 9.7 parts by mass of pyromellitic anhydride, 70.3 parts by mass of PGMEA, and 0.20 parts by mass of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst were added. , and reacted at 120°C for 7 hours. After measuring the acid value, it was confirmed that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated to obtain a resin P-3 having an acid value of 43 mgKOH/g and a weight average molecular weight of 9,000.

P-4: Resin synthesized by the following method In the synthesis of resin P-3, acid Resin P-4 having a value of 43 mgKOH/g and a weight average molecular weight of 9,000 was obtained.

P-5: Resin synthesized by the following method Resin P-3 was synthesized in the same manner except that 20 parts by mass of t-butyl methacrylate was changed to "Karens MOI-BM" manufactured by Showa Denko, and the acid value was 43 mgKOH/ Resin P-5 having a weight average molecular weight of 9,000 was obtained.

P-6: Resin synthesized by the following method 6.0 parts by mass of 3-mercapto-1,2-propanediol, 9.5 parts by mass of pyromellitic anhydride, 62 parts by mass of PGMEA, 1,8-diazabicyclo-[5 .4.0]-7-undecene was charged into a reaction vessel, and the atmospheric gas was replaced with nitrogen gas. The inside of the reaction vessel was heated to 100° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70°C, and 65 parts by mass of methyl methacrylate, 5.0 parts by mass of ethyl acrylate, and t - Add 53.5 parts by mass of a PGMEA solution in which 15 parts by mass of butyl acrylate, 5.0 parts by mass of methacrylic acid, 10 parts by mass of hydroxyethyl methacrylate, and 0.1 part by mass of 2,2'-azobisisobutyronitrile are dissolved. The mixture was reacted for 10 hours. After confirming that 95% of the polymerization had progressed by solid content measurement, the reaction was terminated to obtain resin P-6 having an acid value of 70.5 mgKOH/g and a weight average molecular weight of 10,000.

P-7: Resin synthesized by the following method 108 parts by mass of 1-thioglycerol, 174 parts by mass of pyromellitic anhydride, 650 parts by mass of methoxypropyl acetate, and 0.2 parts by mass of monobutyltin oxide as a catalyst were charged into a reaction vessel. After replacing the atmospheric gas with nitrogen gas, the reaction was carried out at 120° C. for 5 hours (first step). Acid value measurement confirmed that 95% or more of the acid anhydride was half-esterified. Next, 160 parts by mass of the compound obtained in the first step in terms of solid content, 200 parts by mass of 2-hydroxypropyl methacrylate, 200 parts by mass of ethyl acrylate, 150 parts by mass of t-butyl acrylate, and 200 parts by mass of 2-methoxyethyl acrylate. 1 part, 200 parts by mass of methyl acrylate, 50 parts by mass of methacrylic acid, and 663 parts by mass of PGMEA were charged into a reaction vessel, and the inside of the reaction vessel was heated to 80°C to produce 1 part of 2,2'-azobis(2,4-dimethylvaleronitrile). .2 parts by mass was added and reacted for 12 hours (second step). It was confirmed by solid content measurement that 95% had reacted. Finally, 500 parts by mass of a 50% by mass PGMEA solution of the compound obtained in the second step, 27.0 parts by mass of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 part by mass of hydroquinone were charged into a reaction vessel to form an isocyanate group. The reaction was carried out until the disappearance of the peak at 2270 cm ⁻¹ based on the above was confirmed (third step). After confirming that the peak had disappeared, the reaction solution was cooled to obtain resin P-7 having an acid value of 68 mgKOH/g, an unsaturated double bond value of 0.62 mmol/g, and a weight average molecular weight of 13,000.
P-8: Resin with the following structure. The numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 20,000.
P-9: Resin with the following structure. The numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 18,000.
P-10: Resin with the following structure. The numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 22,000.

P-11: Resin with the following structure. The numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 22,900.
P-12: Resin with the following structure. The numerical value appended to the main chain is the mass ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 18000
P-13: Resin with the following structure. The numerical value appended to the main chain is the mass ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 18000
P-14: Resin with the following structure. The numerical value appended to the main chain is the mass ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 18000
P-15: Resin with the following structure. The numerical value appended to the main chain is the mass ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 20000
P-16: Resin with the following structure. The numerical value appended to the main chain is the mass ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 23000
P-17: Resin with the following structure. The numerical value appended to the main chain is the mass ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 25000

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

<Manufacture of resin composition>
Each material was mixed in the proportions of formulations 1 to 12 shown below and filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) with a pore size of 0.45 μm to produce each resin composition.

Pigment dispersion: Pigment dispersion of the type listed in the table below Polymerizable compound 1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
Photoinitiator 1: Irgacure OXE02 (manufactured by BASF, oxime compound)
Surfactant 1: KF6000 (manufactured by Shin-Etsu Chemical Co., Ltd., polydimethylsiloxane modified with carbinol at both ends, hydroxyl value 120 mgKOH/g, silicone surfactant)
Polymerization inhibitor 1: p-methoxyphenol Solvent 1: Propylene glycol monomethyl ether acetate Solvent 2: cyclopentanone Solvent 3: Propylene glycol monomethyl ether

<Performance evaluation>
(Storage stability)
The viscosity (mPa·s) of the resin compositions of Examples 1 to 175 and Comparative Examples 1 and 2 was measured using a viscometer (RE-85L, manufactured by Toki Sangyo Co., Ltd.). After the above measurement, the resin composition was allowed to stand at 45° C. and shielded from light for 5 days, and the viscosity (mPa·s) was measured again. The storage stability was evaluated based on the viscosity difference (ΔVis) before and after the above-mentioned standing in accordance with the following evaluation criteria. It can be said that the smaller the value of the viscosity difference (ΔVis), the better the storage stability of the resin composition. The above viscosity measurements were all performed in a laboratory where the temperature and humidity were controlled at 22±5°C and 60±20%, with the temperature of the resin composition adjusted to 25°C. All measurements were performed three times and the average value was used.
A: ΔVis was 0.2 mPa・s or less B: ΔVis exceeded 0.2 mPa・s and was 0.3 mPa・s or less C: ΔVis exceeded 0.3 mPa・s and was 0.5 mPa・s D: ΔVis exceeded 0.5 mPa・s

(coarse particles)
A base layer forming composition (CT-4000, manufactured by Fujifilm Electronics Materials Co., Ltd.) was coated on a glass substrate using a spin coater to a thickness of 0.1 μm after post-baking, and coated on a hot plate. was heated at 220° C. for 300 seconds to form a base layer, thereby obtaining a glass substrate (support) with a base layer. The resin compositions of Examples 1 to 175 and Comparative Examples 1 and 2 were applied on the glass substrate with the base layer by spin coating, and then heated at 100°C for 2 minutes using a hot plate to form a film. A film with a thickness of 0.5 μm was formed. Foreign matter contained in this film is detected using a foreign matter evaluation device (Complas III, manufactured by Applied Materials), and foreign matter (coarse particles) with a maximum width of 1.0 μm or more are visually checked from all detected foreign matter. The particles were classified, and the number of classified coarse particles having a maximum width of 1.0 μm or more (number of coarse particles per 1 cm ² ) was counted.
A: The number of coarse particles per 1 cm ² of the membrane is less than 10. B: The number of coarse particles per 1 cm ² of the membrane is 10 or more and less than 30. C: The number of coarse particles per 1 cm ² of the membrane is 30. D: The number of coarse particles is 100 or more per ^1cm2 of the membrane.

(spectral variation)
A base layer forming composition (CT-4000, manufactured by Fujifilm Electronics Materials Co., Ltd.) was applied to a glass wafer using a spin coater to a thickness of 0.1 μm after post-baking, and then using a hot plate. A base layer was formed by heating at 220° C. for 300 seconds to obtain a glass wafer (support) with a base layer.
Next, the resin composition described in the first type column of the table below was applied by spin coating so that the film thickness after post-baking was 1.0 μm. Then, using a hot plate, it was heated at 100° C. for 2 minutes. Next, using an i-line stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), the film was exposed to light with a wavelength of 365 nm at an exposure dose of 1000 mJ/cm ² through a mask with a 2 μm square dot pattern. Next, the glass wafer on which the exposed coating film has been formed is placed on the horizontal rotary table of a spin shower developing machine (Model DW-30, manufactured by Chemitronics Co., Ltd.), After puddle development was performed at 23°C for 60 seconds using a 60% diluted solution (manufactured by Materials Co., Ltd.), the glass wafer was fixed on a horizontal rotating table using a vacuum chuck method, and the glass wafer was rotated at a rotation speed of 50 rpm using a rotating device. While rotating, pure water was supplied in a shower form from a jet nozzle above the center of rotation for rinsing treatment, followed by spray drying. Furthermore, heat treatment (post-bake) was performed for 480 seconds using a 200° C. hot plate to form a first type of pattern (pixel).
Next, the resin compositions of Examples 1 to 175 and Comparative Examples 1 and 2 were coated on the glass wafer on which the first type of pixels were formed using a spin coater so that the film thickness after post-baking was 1.0 μm. Then, heat treatment (prebaking) was performed for 120 seconds using a 100°C hot plate, and the first type of pixel was coated with
A laminated filter was obtained in which a resin composition layer (a second type of resin composition layer) was formed using the resin compositions of Examples 1 to 175 and Comparative Examples 1 and 2. Next, the obtained multilayer filter is developed, rinsed, and dried in the same manner as the formation of the first layer of pixels, and the second type of resin composition layer formed on the first type of pixel is removed by development. did. The transmittance of the first type of pixel before forming the second type of resin composition layer and the first type of pixel after developing and removing the second type of resin composition layer was measured using MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.). ) to determine the maximum value of transmittance variation (ΔT%max), and the spectral variation was evaluated based on the following criteria.
Amount of variation in transmittance = |Transmittance of the first type of pixel before forming the second type of resin composition layer - Transmittance of the first type of pixel after developing and removing the second type of resin composition layer |
The smaller ΔT%max means that the spectral fluctuation of the first type of pixel is less likely to occur.
A: ΔT%max is 1.5% or less B: ΔT%max is greater than 1.5% and less than 2.0% C: ΔT%max is greater than 2.0% and less than 2.5% Yes D: ΔT%max is greater than 2.5%

(Developability)
A base layer forming composition (CT-4000, manufactured by Fujifilm Electronics Materials Co., Ltd.) was applied to an 8-inch (20.32 cm) silicon wafer using a spin coater so that the thickness became 0.1 μm after post-baking. The base layer was formed by coating the base layer and heating it for 300 seconds at 220° C. using a hot plate to obtain a silicon wafer (support) with the base layer. Next, each resin composition was applied by spin coating so that the film thickness after post-baking was 0.62 μm. Then, using a hot plate, it was heated at 100° C. for 2 minutes. Next, using an i-line stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), light with a wavelength of 365 nm was exposed at an exposure dose of 1000 mJ/cm ² through a mask with a 1.0 μm square dot pattern. Next, the silicon wafer on which the exposed coating film has been formed is placed on the horizontal rotary table of a spin shower developer (Model DW-30, manufactured by Chemitronics Co., Ltd.), After puddle development was performed at 23°C for 60 seconds using a 60% diluted solution (manufactured by Materials Co., Ltd.), the silicon wafer was fixed on a horizontal rotating table using a vacuum chuck method, and the silicon wafer was rotated at a rotation speed of 50 rpm using a rotating device. While rotating, pure water was supplied in a shower form from a jet nozzle above the center of rotation for rinsing treatment, followed by spray drying. Further, a heat treatment (post-bake) was performed for 300 seconds using a 200° C. hot plate to form a pattern (pixel).
The silicon wafer on which pixels were formed was observed with a scanning electron microscope (magnification: 10,000 times), and the developability was evaluated according to the following evaluation criteria.
A: No residue was observed outside the pixel formation area (unexposed area) B: A very small amount of residue was observed outside the pixel formation area (unexposed area), but this is not a practical problem. C: A slight amount of residue was observed outside the pixel formation area (unexposed area), but it was enough to cause no practical problems D: Outside the pixel formation area (unexposed area) , significant residue was observed.

The table below shows each evaluation result. In addition, in the table below, the value of the content of the coloring material in the total solid content of the resin composition is described in the column of "Content of coloring material".

As shown in the table above, the resin compositions of Examples had excellent storage stability. Furthermore, the evaluation of spectral fluctuation and developability was also excellent.

Films obtained from the resin compositions described in Examples can be suitably used for optical filters, solid-state imaging devices, and image display devices.

In Example 6, similar effects were obtained even when polymerizable compound 1 was changed to compound M-2 or M-3 having the structure shown below.

In Example 6, similar effects were obtained even when the photopolymerization initiator 1 was changed to compounds I-2 to I-5 having the structures shown below.

In Example 6, the surfactant 1 was a compound having the structure shown below (a fluorine-based surfactant with a weight average molecular weight of 14,000, and the numerical value of % indicating the proportion of repeating units is mol%) or PolyFox PF6320 (OMNOVA Co., Ltd.). Similar effects were obtained even when the fluorine-based surfactant was used.

In Example 6, similar effects were obtained even when the polymerization inhibitor 1 was changed to compound H-2 or H-3 having the structure shown below.

Claims

A coloring material containing a pigment,
resin and
A compound represented by formula (1), which has a maximum molar extinction coefficient of 3000 L·mol −1 ·cm −1 or less in the wavelength range of 400 to 700 nm, and has a molecular weight of 475 or less. ,
A resin composition comprising;
In formula (1), A 1 represents a group containing an acid group or a basic group,
X 1 represents a urea group, thiourea group, urethane group, thiourethane group or amide group,
L 1 represents an n-valent group,
n represents an integer from 1 to 4.
The resin composition according to claim 1, wherein X1 in the formula (1) is a urea group.
The resin composition according to claim 1 or 2, wherein A 1 in the formula (1) is a group containing a basic group.
The resin composition according to claim 1 or 2, wherein A 1 in the formula (1) is a group represented by the formula (A20);
A20 - L20 -...(A20)
In formula (A20), A 20 represents a basic group, and L 20 represents an alkylene group.
n in the formula (1) is 1,
A claim in which L 1 is a polycyclic aromatic ring group, an aliphatic hydrocarbon group having 2 or more carbon atoms, or a monocyclic aromatic hydrocarbon group having an electron-withdrawing group or an electron-donating group as a substituent. Item 2. The resin composition according to item 1 or 2.
The resin composition according to claim 1 or 2, wherein n in the formula (1) is an integer of 2 to 4.
The resin composition according to claim 1 or 2, wherein the pigment includes at least one selected from the group consisting of diketopyrrolopyrrole pigments, isoindoline pigments, pteridine pigments, quinophthalone pigments, and azo pigments.
A film obtained using the resin composition according to claim 1 or 2.
An optical filter comprising the film according to claim 8.
A solid-state imaging device comprising the film according to claim 8.
An image display device comprising the film according to claim 8.