WO2023120387A1

WO2023120387A1 - Resin composition, film, optical filter, solid imaging element, and image display device

Info

Publication number: WO2023120387A1
Application number: PCT/JP2022/046296
Authority: WO
Inventors: 憲晃佐藤; 俊佑柳
Original assignee: 富士フイルム株式会社
Priority date: 2021-12-24
Filing date: 2022-12-16
Publication date: 2023-06-29
Also published as: TW202330802A

Abstract

A resin composition comprising a colorant A and a resin B, wherein the colorant A comprises a pigment and the resin B comprises a random copolymer b1 comprising a repeating unit b-1 containing an acid group, a repeating unit b-2 containing a basic group, and a repeating unit b-3 including a polyalkyleneoxy structure; a film; an optical filter; a solid imaging element; and an image display device.

Description

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

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 imaging device, and an image display device using the resin composition.

Optical filters such as color filters are manufactured using resin compositions containing colorants.

Further, Patent Document 1 discloses a pigment colorant composition which is an oily pigment dispersion containing a pigment, a liquid medium and a polymer dispersant,
(1) The polymeric dispersant is an anionic cationic AB block copolymer composed of 90% by mass or more of a methacrylate-based monomer and composed of an anionic A block and a cationic B block,
(2) A block is composed of at least methacrylic acid, has an acid value of 10 to 150 mgKOH/g, and has a number average molecular weight of 3000 to 20000,
(3) The B block is composed of at least a methacrylate-based monomer having an amino group, has an amine value of 50 to 400 mgKOH/g, and an average molecular weight of the B polymer block of 500 to 8000, and the AB block. The content of the B block in the copolymer is 5 to 50% by mass,
(4) The invention relates to a pigment colorant composition in which the dispersity (weight average content/number average molecular weight) indicating the molecular weight distribution of the AB block copolymer is 1.6 or less.

JP 2013-203887 A

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

However, when a material containing a pigment is used as a coloring material, increasing the concentration of the coloring material in the resin composition relatively decreases the ratio of materials such as resins that can be adsorbed to the pigment. Pigments tend to aggregate during storage. For this reason, defects due to aggregates of pigments and the like may occur in the film obtained using the resin composition.

Further, according to the studies of the present inventors, a block polymer containing an anionic A block and a cationic B block as disclosed in Patent Document 1 tends to aggregate during storage of the resin composition, It was found that defects tend to occur in the resulting film. In such a block polymer, the ionic sites are biased due to acid-base interaction, and due to the occurrence of such ionic site biases, aggregates are easily aggregated and the block polymers are strongly aggregated. It is presumed that defects are likely to occur in the resulting film because of the occurrence of

Accordingly, an object of the present invention is to provide a resin composition capable of forming a film in which the occurrence of defects is suppressed. Another object of the present invention is to provide a film, an optical filter, a solid-state imaging device, and an image display device.

According to the studies of the present inventors, the inventors have found that the above-mentioned objects can be achieved with the resin composition described later, and have completed the present invention. Accordingly, the present invention provides the following.

<1> A resin composition containing a coloring material A and a resin B,
The coloring material A contains a pigment,
The resin B includes a repeating unit b-1 containing an acid group, a repeating unit b-2 containing a basic group, and a random copolymer b1 containing a repeating unit b-3 containing a polyalkyleneoxy structure. Composition.
<2> The resin composition according to <1>, wherein the random copolymer b1 has an acid value to base value ratio of 0.2 to 20.
<3> The resin composition according to <1> or <2>, wherein the repeating unit b-3 has a molecular weight of 350 to 1,500.
<4> The resin composition according to any one of <1> to <3>, wherein the polyalkyleneoxy structure is a polyethyleneoxy structure.
<5> The resin composition according to any one of <1> to <4>, wherein the random copolymer b1 has an acid value of 40 to 120 mgKOH/g.
<6> The resin composition according to any one of <1> to <5>, wherein the random copolymer b1 has a base value of 40 to 120 mgKOH/g.
<7> The resin composition according to any one of <1> to <6>, wherein the repeating unit b-2 is a repeating unit derived from a compound having a conjugate acid with a pKa of 9.5 or higher.
<8> The random copolymer b1 further includes a repeating unit b-4 having a functional group X selected from a group containing two or more aromatic rings, a group containing a heterocyclic group, and a group containing a condensed ring. The resin composition according to any one of <1> to <7>.
<9> The resin composition according to any one of <1> to <8>, wherein the content of the random copolymer b1 in the resin B is 1 to 30% by mass.
<10> The resin composition according to any one of <1> to <9>, wherein the content of the random copolymer b1 in the total solid content of the resin composition is 1 to 10% by mass.
<11> The resin composition according to any one of <1> to <10>, wherein the coloring material A contains a pigment derivative.
<12> The resin composition according to any one of <1> to <11>, further comprising a polymerizable compound and a photopolymerization initiator.
<13> A film obtained from the resin composition according to any one of <1> to <12>.
<14> An optical filter comprising the film according to <13>.
<15> A solid-state imaging device having the film according to <13>.
<16> An image display device comprising the film according to <13>.

According to the present invention, it is possible to provide a resin composition capable of forming a film in which the occurrence of defects is suppressed. Also, films, optical filters, solid-state imaging devices, and image display devices can be provided.

The contents of the present invention will be described in detail below.
In the present specification, the term "~" is used to include the numerical values before and after it as lower and upper limits.
In the description of a group (atomic group) in the present specification, a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
In this specification, "(meth)acrylate" represents both or either acrylate and methacrylate, "(meth)acryl" represents both or either acrylic and methacrylic, and "(meth) ) acryloyl” refers to acryloyl and/or methacryloyl.
In the present specification, Me in the structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
As used herein, the weight average molecular weight and number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).
As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent.
As used herein, the term "pigment" means a coloring material that is difficult to dissolve in a solvent.
As used herein, the term "process" includes not only an independent process, but also when the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. .

<Resin composition>
The resin composition of the present invention is a resin composition containing a coloring material A and a resin B,
The coloring material A contains a pigment,
The resin B contains a repeating unit b-1 containing an acid group, a repeating unit b-2 containing a basic group, and a random copolymer b1 containing a repeating unit b-3 containing a polyalkyleneoxy structure. Characterized by

According to the resin composition of the present invention, by containing the random copolymer b1 described above, it is possible to form a film in which the occurrence of defects is suppressed. The reason why such effects are obtained is presumed to be as follows.
The random copolymer b1 contains the repeating unit b-1 containing an acid group and the repeating unit b-2 containing a basic group. It is speculated that they interact and adsorb to the pigment. In addition, since the random copolymer b1 further includes a repeating unit b-3 containing a polyalkyleneoxy structure, the polyalkyleneoxy structure acts as a steric repulsion group to inhibit adsorption between pigments. It is speculated that defects can be suppressed.
The random copolymer b1 is a random copolymer containing a repeating unit b-1 containing an acid group, a repeating unit b-2 containing a basic group, and a repeating unit b-3 containing a polyalkyleneoxy structure. Therefore, in the resin composition, the acid-base interaction between the random copolymer b1 and between the random copolymer b1 and another resin is likely to occur reversibly, and it is assumed that the soft aggregation state is easily maintained. . For this reason, it is presumed that during storage of the resin composition, aggregation of the resin component can be suppressed, and the occurrence of microprecipitation can be suppressed. Furthermore, the random copolymer b1 contains the repeating unit b-3 containing a polyalkyleneoxy structure, so that the solubility in solvents can be increased and the softening point can be lowered, so that the resin composition Even if a microprecipitate originating from the random copolymer b1 occurs in it, it is presumed that it softens or dissolves due to heating during film formation, etc., and fits into the film.
For these reasons, it is presumed that the use of the resin composition of the present invention enables formation of a film in which the occurrence of defects is suppressed.

In addition, when a pattern is formed by photolithography using the resin composition of the present invention, it is possible to suppress the generation of development residues. Although the detailed reason why such an effect is obtained is unknown, since the random copolymer b1 contains an acid group and a basic group, it tends to be unevenly distributed on the substrate side of the film during film formation, and the coloring material It is presumed that the adsorption of development residue components, such as, to the substrate can be suppressed. Further, since the random copolymer b1 contains the repeating unit b-3 containing a polyalkyleneoxy structure, it has good compatibility with the developer and is easily removed during development. For these reasons, the resin composition of the present invention can also suppress the generation of development residues.

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

Examples of color filters include filters having colored pixels that transmit light of specific wavelengths. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels, and red pixels are preferred. 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 the wavelength range of 700 to 1800 nm, more preferably in the wavelength range of 700 to 1300 nm, and even more preferably in the wavelength range of 700 to 1000 nm. . The transmittance of the near-infrared cut filter over the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. Also, the transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less. 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 70-450, and particularly preferably 100-400. A near-infrared cut filter can be formed using a resin composition containing a near-infrared absorbing colorant.

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

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

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 described below.

<<coloring material A>>
The resin composition of the present invention contains coloring material A (hereinafter referred to as coloring material). Examples of colorants include white colorants, black colorants, chromatic colorants, and near-infrared absorption colorants. A pigment derivative can also be used as the coloring material. In the present invention, the white colorant includes not only a pure white colorant but also a light gray colorant close to white (for example, grayish white, light gray, etc.).

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

The average primary particle size of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. When the average primary particle size 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 size of the pigment can be determined from the photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is obtained, and the corresponding circle equivalent diameter is calculated as the primary particle diameter of the pigment. Further, the average primary particle size in the present invention is the arithmetic mean value of the primary particle sizes of 400 primary particles of the pigment. Further, the primary particles of the pigment refer to independent particles without agglomeration.

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

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

The coloring material contained in the resin composition of the present invention preferably contains a pigment and a pigment derivative. Pigment derivatives include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton. Details of the pigment derivative will be described later. The content of the pigment derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the pigment. The lower limit is preferably 2 parts by mass or more, more preferably 3 parts by mass or more. The upper limit is preferably 30 parts by mass or less, more preferably 20 parts by mass or less. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.

The coloring material contained in the resin composition of the present invention may further contain a dye. When a dye is included, the content of the dye is preferably 10 to 100 parts by mass with respect to 100 parts by mass 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 dye may be used, or two or more dyes may be used in combination.
Moreover, it is also preferable that the coloring material contained in the resin composition of the present invention substantially does not contain a dye. According to this aspect, a film having 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 dye. .

(chromatic colorant)
Examples of chromatic coloring materials include coloring materials having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. Examples thereof include yellow colorants, orange colorants, red colorants, green colorants, purple colorants, and blue colorants. From the viewpoint of heat resistance, the chromatic colorant is preferably a pigment (chromatic pigment), more preferably a red pigment, a yellow pigment, 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, and diketopyrrolopyrrole compounds, anthraquinone compounds, azo It is preferably a compound, more preferably a diketopyrrolopyrrole compound. Also, the red colorant is preferably a pigment.

Specific examples of the red colorant include C.I. 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, 279, 291, 294, 295, 296, 297 and other red pigments. Further, as a red colorant, a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, a diketopyrrolopyrrole described in paragraph numbers 0016 to 0022 of Japanese Patent No. 6248838 Pyrrole compounds, diketopyrrolopyrrole compounds described in WO 2012/102399, diketopyrrolopyrrole compounds described in WO 2012/117965, brominated diketopyrrolo described in JP 2020-085947 Pyrrole compound, naphthol azo compound described in JP-A-2012-229344, red colorant described in JP-A-6516119, red colorant described in JP-A-6525101, paragraph of JP-A-2020-090632 Brominated diketopyrrolopyrrole compounds described in No. 0229, anthraquinone compounds described in Korean Patent Publication No. 10-2019-0140741, anthraquinone compounds described in Korean Patent Publication No. 10-2019-0140744, JP 2020 A perylene compound described in JP-A-079396, a diketopyrrolopyrrole compound described in paragraphs 0025 to 0041 of JP-A-2020-066702, and the like can also be used. In addition, as a red colorant, a compound having a structure in which an aromatic ring group in which a group having an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton is used. can also

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

Examples of green colorants include phthalocyanine compounds, squarylium compounds, etc., preferably phthalocyanine compounds, and more preferably phthalocyanine pigments. Also, the green colorant is preferably a pigment.

Specific examples of green colorants include C.I. I. Green pigments such as Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65 and 66 are included. Further, as a green colorant, a halogenated zinc phthalocyanine having an average number of halogen atoms in one molecule of 10 to 14, an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5 Pigments can also be used. Specific examples include compounds described in International Publication No. 2015/118720. In addition, as a green colorant, the compound described in Chinese Patent Application No. 106909027, the phthalocyanine compound having a phosphoric acid ester as a ligand described in WO 2012/102395, described in JP 2019-008014. The phthalocyanine compound, the phthalocyanine compound described in JP-A-2018-180023, the compound described in JP-A-2019-038958, the aluminum phthalocyanine compound described in JP-A-2020-070426, JP-A-2020-076995 The core-shell type dyes described in can also be used.

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

Specific examples of orange colorants include C.I. 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. of orange pigments.

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

As the yellow colorant, a nickel azobarbiturate complex having the following structure can also be used.

Further, as the yellow colorant, compounds described in JP-A-2017-201003, compounds described in JP-A-2017-197719, paragraph numbers 0011-0062, 0137-0276 of JP-A-2017-171912 Compounds described in paragraph numbers 0010 to 0062 and 0138 to 0295 of JP-A-2017-171913, compounds described in paragraph numbers 0011-0062 and 0139-0190 of JP-A-2017-171914, JP 2017 -Compounds described in paragraph numbers 0010 to 0065 and 0142 to 0222 of JP-A-171915, quinophthalone compounds described in paragraph numbers 0011-0034 of JP-A-2013-054339, paragraph numbers 0013- of JP-A-2014-026228 0058, the isoindoline compound described in JP-A-2018-062644, the quinophthalone compound described in JP-A-2018-203798, the quinophthalone compound described in JP-A-2018-062578, and the patent No. 6432076. Quinophthalone compounds described in JP-A-2018-155881, quinophthalone compounds described in JP-A-2018-111757, quinophthalone compounds described in JP-A-2018-040835, JP-A-2017 -Quinophthalone compounds described in JP-A-197640, quinophthalone compounds described in JP-A-2016-145282, quinophthalone compounds described in JP-A-2014-085565, quinophthalone compounds described in JP-A-2014-021139, in particular Quinophthalone compounds described in JP-A-2013-209614, quinophthalone compounds described in JP-A-2013-209435, quinophthalone compounds described in JP-A-2013-181015, quinophthalone compounds described in JP-A-2013-061622 , the quinophthalone compound described in JP-A-2013-032486, the quinophthalone compound described in JP-A-2012-226110, the quinophthalone compound described in JP-A-2008-074987, the JP-A-2008-081565. Quinophthalone compounds, quinophthalone compounds described in JP-A-2008-074986, quinophthalone compounds described in JP-A-2008-074985, quinophthalone compounds described in JP-A-2008-050420, JP-A-2008-031281 The quinophthalone compound described, the quinophthalone compound described in JP-B-48-032765, the quinophthalone compound described in JP-A-2019-008014, the quinophthalone compound described in JP-A-6607427, and JP-A-2019-073695. The methine dye described, the methine dye described in JP-A-2019-073696, the methine dye described in JP-A-2019-073697, the methine dye described in JP-A-2019-073698, Korean Patent No. 10- Compounds described in 2014-0034963, compounds described in JP 2017-095706, compounds described in Taiwan Patent Application Publication No. 201920495, compounds described in Patent No. 6607427, JP 2020-033525 Compounds described in JP-A-2020-033524, compounds described in JP-A-2020-033523, compounds described in JP-A-2020-033522, JP-A-2020-033521 Compounds described in, compounds described in WO 2020/045200, compounds described in WO 2020/045199, compounds described in WO 2020/045197, described in JP 2020-093994 The azo compound, the perylene compound described in JP-A-2020-083982, the perylene compound described in International Publication No. 2020/105346, the quinophthalone compound described in JP-A-2020-517791, represented by the following formula (QP1) A compound represented by the following formula (QP2) can also be used. Moreover, those obtained by polymerizing these compounds are also preferably used from the viewpoint of improving the color value.

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

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

Specific examples of purple coloring materials include C.I. I. Purple pigments such as Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, 61 are included.

Specific examples of blue colorants include C.I. 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. pigments. An aluminum phthalocyanine compound having a phosphorus atom can also be used as the blue colorant. Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A-2012-247591 and paragraph number 0047 of JP-A-2011-157478.

Regarding the diffraction angle that various pigments preferably have, Japanese Patent No. 6561862, Japanese Patent No. 6413872, Japanese Patent No. 6281345, JP-A-2020-026503, JP-A-2020-033526. , the contents of which are incorporated herein. Also, the pyrrolopyrrole pigment has a crystallite size of 140 Å or less in the plane direction corresponding to the maximum peak in the X-ray diffraction pattern among the eight planes (±1±1±1) of the crystal lattice planes. is also preferred. Further, the physical properties of the pyrrolopyrrole pigment are preferably set as described in paragraphs 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 enhancing spectral characteristics. As the pigment, it is also preferable to use a dioxazine pigment with a controlled contact angle described in WO 2019/107166 from the viewpoint of viscosity adjustment.

Dyes can also be used as chromatic colorants. The dye is not particularly limited, and known dyes can be used. For example, pyrazole azo, anilinoazo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, Phthalocyanine-based, benzopyran-based, indigo-based, and pyrromethene-based dyes can be used.

A pigment multimer can also be used as a chromatic colorant. The dye multimer is preferably a dye dissolved in a solvent and used. Further, the dye multimer may form particles. When the dye multimer is particles, it is usually used in a state of being dispersed in a solvent. The particulate dye multimer can be obtained, for example, by emulsion polymerization, and specific examples include the compounds and production methods described in JP-A-2015-214682. A 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. A plurality of dye structures in one molecule may be the same dye structure or 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 3000 or more, and even more preferably 6000 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-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, WO 2016/031442, etc. Compounds can also be used.

In addition, as a chromatic colorant, a diarylmethane compound described in JP-A-2020-504758, a triarylmethane dye polymer described in Korean Patent Publication No. 10-2020-0028160, and JP-A-2020-117638. The xanthene compound described in, the phthalocyanine compound described in WO2020/174991, the isoindoline compound described in JP-A-2020-160279 or a salt thereof, described in Korean Patent Publication No. 10-2020-0069442 The compound represented by Formula 1 of, the compound represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069730, the compound represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069070 compounds, compounds represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069067, compounds represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069062, Patent No. 6809649 and the isoindoline compound described in JP-A-2020-180176. The chromatic colorant may be a rotaxane, and the dye skeleton may be used in the cyclic structure of the rotaxane, may be used in the rod-like structure, or may be used in both structures. As a chromatic colorant, a quinophthalone compound represented by Formula 1 in Korean Patent Publication No. 10-2020-0030759, a polymer dye described in Korean Patent Publication No. 10-2020-0061793, and JP-A-2022-029701. No. 2022/014635, the isoindoline compound described in WO 2022/014635, the aluminum phthalocyanine compound described in WO 2022/024926, the compound described in JP 2022-045895, the international publication Compounds described in 2022/050051 can also be used.

Two or more chromatic colorants may be used in combination. When two or more chromatic colorants are used in combination, the combination of two or more chromatic colorants may form a black color. Examples of such combinations include the following aspects (1) to (7). When the resin composition contains two or more chromatic colorants and the combination of the two or more chromatic colorants exhibits a black color, the resin composition of the present invention forms a near-infrared transmission filter. It can be preferably used as a resin composition for
(1) A mode containing a red colorant and a blue colorant.
(2) A mode containing a red colorant, a blue colorant, and a yellow colorant.
(3) A mode containing a red colorant, a blue colorant, a yellow colorant, and a purple colorant.
(4) A mode containing a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant.
(5) A mode containing a red colorant, a blue colorant, a yellow colorant, and a green colorant.
(6) A mode containing a red colorant, a blue colorant, and a green colorant.
(7) A mode containing a yellow colorant and a purple colorant.

(white colorant)
White colorants 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, more preferably titanium oxide. Further, the white pigment is preferably particles having a refractive index of 2.10 or more for light with a wavelength of 589 nm. The aforementioned refractive index is preferably 2.10 to 3.00, more preferably 2.50 to 2.75.

In addition, as the white pigment, the titanium oxide described in "Titanium Oxide Physical Properties and Applied Technology Manabu Seino, Pages 13-45, 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 combined with other materials may be used. For example, particles having voids or other materials inside, particles having a core particle to which a large number of inorganic particles are attached, and core-shell composite particles consisting of a core particle made of polymer particles and a shell layer made of inorganic nanoparticles are used. is preferred. For the core and shell composite particles composed of the core particles composed of the polymer particles and the shell layer composed of the inorganic nanoparticles, for example, the description of paragraphs 0012 to 0042 of JP-A-2015-047520 can be referred to, The contents of which are incorporated herein.

Hollow inorganic particles can also be used as the white pigment. A hollow inorganic particle is an inorganic particle having a structure having a cavity inside, and refers to an inorganic particle having a cavity surrounded by an outer shell. Examples of hollow inorganic particles include hollow inorganic particles described in JP 2011-075786, WO 2013/061621, JP 2015-164881, etc., the contents of which are incorporated herein. be

(black colorant)
The black colorant is not particularly limited, and known ones can be used. For example, inorganic black colorants include inorganic pigments (black pigments) such as carbon black, titanium black, and graphite. Carbon black and titanium black are preferred, and titanium black is more preferred.

Titanium black is black particles containing titanium atoms, preferably low order titanium oxide or titanium oxynitride. Titanium black can be surface-modified as necessary for the purpose of improving dispersibility, suppressing cohesion, 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. Further, treatment with a water-repellent substance as disclosed in Japanese Patent Laid-Open No. 2007-302836 is also possible. Titanium black preferably has a small primary particle size and an average primary particle size of individual particles. Specifically, the average primary particle size is preferably 10 to 45 nm. Titanium black can also be used as a dispersion. For example, a dispersion containing titanium black particles and silica particles, in which the content ratio of Si atoms and Ti atoms in the dispersion is adjusted to the range of 0.20 to 0.50, may be mentioned. Regarding the dispersion, the description in paragraphs 0020 to 0105 of JP-A-2012-169556 can be referred to, and the contents thereof are incorporated herein. Commercially available examples of titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilac D ( Trade name: manufactured by Ako Kasei Co., Ltd.) and the like.

Examples of carbon black include furnace black, channel black, thermal black, acetylene black and lamp black. As the carbon black, carbon black produced by a known method such as an oil furnace method or a gas black method may be used, or a commercially available product may be used. Commercially available products of carbon black include, for example, C.I. I. Pigment Black 7, Color Black S170 (manufactured by Degussa), and the like.

As the carbon black, surface-treated carbon black may be used. The surface treatment can modify the surface state of the carbon black particles and improve the dispersion stability in the composition. Examples of the surface treatment include coating treatment with a resin, surface treatment by introducing an acid group, and surface treatment with a silane coupling agent. Carbon black coated with a resin is preferable as the surface-treated carbon black. By coating the surface of the carbon black particles with a resin, the light-shielding properties and insulating properties of the film can be improved. In addition, the reliability of the image display device can be improved by reducing leakage current. Therefore, it is suitable for use in applications where the film is required to have light shielding properties and insulating properties. Coating resins include epoxy resins, polyamide resins, polyamideimide resins, novolac resins, phenolic resins, urea resins, melamine resins, polyurethane resins, diallyl phthalate resins, alkylbenzene resins, polystyrene resins, polycarbonate resins, polybutylene terephthalate, and modified polyphenylene. oxides. The content of the coating resin is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, with respect to the total of carbon black and coating resin, from the viewpoint of better light shielding and insulating properties of the film. preferable.

Also, examples of organic black colorants include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds. Examples of bisbenzofuranone compounds include compounds described in Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, Japanese Patent Publication No. 2012-515234, etc. For example, "Irgaphor Black" manufactured by BASF Corporation. Available. Examples of perylene compounds include compounds described in paragraphs 0016 to 0020 of JP-A-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, JP-A-02-034664, and the like.

The coloring material used in the resin composition of the present invention may be the above-described black coloring material only, or may further include a chromatic coloring material. By using a black colorant and a chromatic colorant together, it is easy to obtain a resin composition capable of forming a film having excellent light-shielding properties in the visible region. When a black colorant and a chromatic colorant are used together, the mass ratio of the two is preferably black colorant: chromatic colorant = 100:10 to 300, more preferably 100:20 to 200. preferable.

Preferred combinations of black colorants and chromatic colorants include, for example, the following.
(A-1) An embodiment containing an organic black colorant and a blue colorant.
(A-2) An embodiment containing an organic black colorant, a blue colorant and a yellow colorant.
(A-3) An embodiment containing an organic black colorant, a blue colorant, a yellow colorant and a red colorant.
(A-4) An embodiment containing an organic black colorant, a blue colorant, a yellow colorant and a purple colorant.

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

(Near-infrared absorption colorant)
The near-infrared absorbing colorant is preferably a compound having a maximum absorption wavelength on the longer wavelength side than the wavelength of 700 nm. The infrared absorbing agent is preferably a compound having a maximum absorption wavelength in the range of 700 nm and 1800 nm or less, more preferably a compound having a maximum absorption wavelength in the range of 700 nm and 1400 nm or less. A compound having a maximum absorption wavelength in the range of more than 1200 nm or less is more preferable, and a compound having a maximum absorption wavelength in the 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 colorant is preferably 0.08 or less, more preferably 0.04 or less. preferable. Also, the near-infrared absorbing colorant is preferably a pigment, more preferably an organic pigment.

Near-infrared absorbing colorants include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, and pyrromethene compounds. , azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, metal borides, and the like. As the pyrrolopyrrole compound, compounds described in paragraph numbers 0016 to 0058 of JP-A-2009-263614, compounds described in paragraph numbers 0037-0052 of JP-A-2011-068731, WO 2015/166873 Compounds described in Paragraph Nos. 0010 to 0033 and the like. Examples of the squarylium compound include compounds described in paragraph numbers 0044 to 0049 of JP-A-2011-208101, compounds described in paragraph numbers 0060 to 0061 of Japanese Patent No. 6065169, and paragraph number 0040 of WO 2016/181987. Compounds described in, compounds described in JP-A-2015-176046, compounds described in paragraph No. 0072 of WO 2016/190162, compounds described in paragraph Nos. 0196 to 0228 of JP-A-2016-074649 , the compound described in paragraph number 0124 of JP 2017-067963, the compound described in WO 2017/135359, the compound described in JP 2017-114956, the compound described in Patent 6197940, Examples include compounds described in International Publication No. 2016/120166. As the cyanine compound, compounds described in paragraphs 0044 to 0045 of JP-A-2009-108267, compounds described in paragraphs 0026-0030 of JP-A-2002-194040, and JP-A-2015-172004. The compound, the compound described in JP-A-2015-172102, the compound described in JP-A-2008-088426, the compound described in paragraph number 0090 of WO 2016/190162, JP-A-2017-031394 and the like compounds described in. Examples of croconium compounds include compounds described in JP-A-2017-082029. As the iminium compound, for example, compounds described in JP-A-2008-528706, compounds described in JP-A-2012-012399, compounds described in JP-A-2007-092060, International Publication No. 2018/043564 and the compounds described in paragraphs 0048 to 0063 of. Examples of the phthalocyanine compound include compounds described in paragraph number 0093 of JP-A-2012-077153, oxytitanium phthalocyanine described in JP-A-2006-343631, and paragraph numbers 0013 to 0029 of JP-A-2013-195480. compounds, vanadium phthalocyanine compounds described in Japanese Patent No. 6081771, vanadium phthalocyanine compounds described in International Publication No. 2020/071486, and phthalocyanine compounds described in International Publication No. 2020/071470. Examples of naphthalocyanine compounds include compounds described in paragraph number 0093 of JP-A-2012-077153. Dithiolene metal complexes include compounds described in Japanese Patent No. 5733804. Examples of metal oxides include indium tin oxide, antimony tin oxide, zinc oxide, Al-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, and tungsten oxide. For details of tungsten oxide, paragraph 0080 of JP-A-2016-006476 can be referred to, the content of which is incorporated herein. Examples of metal borides include lanthanum boride. Commercially available lanthanum boride products include LaB ₆ -F (manufactured by Nippon New Metal Co., Ltd.). Moreover, as a metal boride, the compound as described in international publication 2017/119394 can also be used. Commercially available products of indium tin oxide include F-ITO (manufactured by DOWA Hitech Co., Ltd.).

Further, as the near-infrared absorbing colorant, the squarylium compound described in JP-A-2017-197437, the squarylium compound described in JP-A-2017-025311, the squarylium compound described in International Publication No. 2016/154782, the patent Squarylium compounds described in Japanese Patent No. 5884953, squarylium compounds described in Japanese Patent No. 6036689, squarylium compounds described in Japanese Patent No. 5810604, squarylium compounds described in paragraph numbers 0090 to 0107 of International Publication No. 2017/213047 , Pyrrole ring-containing compounds described in paragraph numbers 0019 to 0075 of JP-A-2018-054760, pyrrole ring-containing compounds described in paragraph numbers 0078-0082 of JP-A-2018-040955, JP-A-2018-002773 A pyrrole ring-containing compound described in paragraph numbers 0043 to 0069 of JP-A-2018-041047, a squarylium compound having an aromatic ring at the amide α-position described in paragraph numbers 0024-0086 of JP-A-2017-179131. amide-linked squarylium compounds, compounds having a pyrrole bis-type squarylium skeleton or croconium skeleton described in JP-A-2017-141215, dihydrocarbazole bis-type squarylium compounds described in JP-A-2017-082029, JP-A-2017 -Asymmetric compounds described in paragraph numbers 0027 to 0114 of JP-A-068120, pyrrole ring-containing compounds (carbazole type) described in JP-A-2017-067963, phthalocyanine compounds described in Japanese Patent No. 6251530, etc. can also be used.

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

Dye skeletons constituting pigment derivatives include a quinoline dye skeleton, a benzimidazolone dye skeleton, a benzoisoindole dye skeleton, a benzothiazole dye skeleton, an iminium dye skeleton, a squarylium dye skeleton, a croconium dye skeleton, an oxonol dye skeleton, and a pyrrolopyrrole dye. skeleton, diketopyrrolopyrrole dye skeleton, azo dye skeleton, azomethine dye skeleton, phthalocyanine dye skeleton, naphthalocyanine dye skeleton, anthraquinone dye skeleton, quinacridone dye skeleton, dioxazine dye skeleton, perinone dye skeleton, perylene dye skeleton, thioindigo dye skeleton, Isoindoline dye skeletons, isoindolinone dye skeletons, quinophthalone dye skeletons, dithiol dye skeletons, triarylmethane dye skeletons, pyrromethene dye skeletons, and the like can be mentioned.

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

Basic groups include amino groups, pyridinyl groups and salts thereof, salts of ammonium groups, and phthalimidomethyl groups. Atoms or atomic groups constituting salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.

The pigment derivative is preferably a compound having a structure in which a basic group is bonded to the pigment skeleton. Also, the pigment derivative is preferably a compound having a urea structure, an amide structure or a urethane structure.

Specific examples of the pigment derivative include the compounds described in Examples below, the compounds described in JP-A-56-118462, the compounds described in JP-A-63-264674, and JP-A-01-217077. Compounds described in, compounds described in JP-A-03-009961, compounds described in JP-A-03-026767, compounds described in JP-A-03-153780, described in JP-A-03-045662 The compound, the compound described in JP-A-04-285669, the compound described in JP-A-06-145546, the compound described in JP-A-06-212088, the compound described in JP-A-06-240158 , the compound described in JP-A-10-030063, the compound described in JP-A-10-195326, the compound described in paragraph numbers 0086 to 0098 of WO 2011/024896, WO 2012/102399 The compound described in paragraph numbers 0063 to 0094 of, the compound described in paragraph number 0082 of WO 2017/038252, the compound described in paragraph number 0171 of JP 2015-151530, JP 2011-252065 Compounds described in paragraph numbers 0162 to 0183 of, compounds described in JP-A-2003-081972, compounds described in Patent No. 5299151, compounds described in JP-A-2015-172732, JP-A-2014-199308 Compounds described in JP-A-2014-085562, compounds described in JP-A-2014-035351, compounds described in JP-A-2008-081565, JP-A-2019-109512 Compounds described in, compounds described in JP-A-2019-133154, diketopyrrolopyrrole compounds having a thiol linking group described in WO 2020/002106, benzimidazo described in JP-A-2018-168244 ron compounds or salts thereof.

The content of the coloring material in the total solid content of the resin composition is preferably 30 to 80% by mass. The lower limit is preferably 40% by mass or more, more preferably 50% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 65% by mass or less.

The content of the pigment in the total solid content of the resin composition is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 45% by mass or more, and 50% by mass. More preferably, it is 55% by mass or more, and particularly 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 content of the pigment is high, it is possible to form a film in which the generation of defects is suppressed by containing the above-described random copolymer b1. Furthermore, generation of development residue can be suppressed. Therefore, the effect of the present invention is remarkably exhibited in the resin composition of the present invention when the pigment content is high.

The content of the pigment in the colorant is preferably 20-100% by mass, more preferably 50-100% by mass, and even more preferably 70-100% by mass. Further, the total content of the pigment and the pigment derivative in the colorant is preferably 25 to 100% by mass, more preferably 55 to 100% by mass, and further preferably 75 to 100% by mass. preferable.

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

(specific resin)
The resin contained in the resin composition of the present invention is a random copolymer containing a repeating unit b-1 containing an acid group, a repeating unit b-2 containing a basic group, and a repeating unit b-3 containing a polyalkyleneoxy structure. It contains a polymer b1 (hereinafter also referred to as a specific resin). Here, a random copolymer means a copolymer in which two or more repeating units are randomly arranged. On the other hand, a block copolymer is a copolymer composed of two or more types of monomers, in which polymer chains each composed of the same type of monomers are bound in one chain. It means a copolymer with

[Repeating unit b-1]
The specific resin contains a repeating unit b-1 having an acid group (hereinafter also referred to as repeating unit b-1). The acid group includes a carboxy group, a phosphoric acid group, a sulfo group and a phenolic hydroxy group, preferably a carboxy group.

The number of acid groups contained in the repeating unit b-1 may be one, or two or more. The number of acid groups contained in the repeating unit b-1 is preferably 1 to 4, more preferably 1 or 2.

Examples of the repeating unit b-1 include repeating units represented by the following formula (bb-1).

R ^b11 to R ^b13 in formula (bb-1) each independently represent a hydrogen atom or an alkyl group. The number of carbon atoms in the alkyl group represented by R ^b11 to R ^b13 is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1.

^Lb11 in formula (bb-1) represents a single bond or an n1+1-valent linking group. However, when n1 is 2 or more, L ^b11 is an n1+1-valent linking group.
The n1+1-valent linking group represented by L ^b11 includes an aliphatic hydrocarbon group, an aromatic hydrocarbon group, -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, - OCO-, -S- and groups formed by combinations of two or more of these may be mentioned. The aliphatic hydrocarbon group and aromatic hydrocarbon group may have a substituent. A hydroxy group, a halogen atom, etc. are mentioned as a substituent.

A ^b11 in formula (bb-1) represents an acid group. The acid group represented by A ^b11 includes a carboxy group, a phosphoric acid group, a sulfo group and a phenolic hydroxy group, preferably a carboxy group.

n1 in formula (bb-1) represents an integer of 1 or more, preferably an integer of 1 to 4, more preferably 1 or 2.

Specific examples of the repeating unit b-1 include repeating units derived from compounds having the structures shown below.

The content of the repeating unit b-1 in the specific resin is preferably 0.1 to 50% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less.

[Repeating unit b-2]
The specific resin contains a repeating unit b-2 containing a basic group (hereinafter also referred to as repeating unit b-2). Preferably, the basic group is an amino group. The amino group includes a group represented by -NR ^am1 R ^am2 and a cyclic amino group, preferably a group represented by -NR ^am1 R ^am2 .

In the group represented by -NR ^am1 R ^am2 , R ^am1 and R ^am2 each independently represent a hydrogen atom, an alkyl group or an aryl group, preferably an alkyl group. The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-5, even more preferably 1-3, and particularly preferably 1 or 2. The alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
The number of carbon atoms in the aryl group is preferably 6-30, more preferably 6-20, even more preferably 6-12.

The cyclic amino group includes a pyrrolidine group, a piperidine group, a piperazine group, a morpholine group and the like. These groups may further have a substituent. Substituents include alkyl groups and aryl groups.

The number of basic groups contained in the repeating unit b-2 may be 1, or may be 2 or more. The number of basic groups contained in the repeating unit b-2 is preferably 1 to 4, more preferably 1 or 2.

The repeating unit b-2 is preferably a repeating unit derived from a compound having a conjugate acid pKa of 9.5 or higher. According to this aspect, it is possible to form a film in which the occurrence of defects is suppressed. The pKa of the conjugate acid of the compound is preferably 6 or more, more preferably 9 or more. The upper limit of the pKa of the conjugate acid of the above compound is preferably 12 or less, more preferably 10 or less. The pKa of the conjugate acid of the compound can be measured by a neutralization titration method. As a measurement method, a mixed solution of 50 mM sulfuric acid and dimethyl sulfoxide is added to 20 mL of a dimethyl sulfoxide solution having a concentration of 1 mM of the measurement sample, and the pKa of the conjugate acid is calculated from the neutralization titration curve. . The pH during neutralization titration can be measured using an ISFET (Ion Sensitive Field Effect Transistor) electrode.

Examples of the repeating unit b-2 include repeating units represented by the following formula (bb-2).

R ^b21 to R ^b23 in formula (bb-2) each independently represent a hydrogen atom or an alkyl group. The number of carbon atoms in the alkyl group represented by R ^b21 to R ^b23 is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1.

^Lb21 in formula (bb-2) represents a single bond or an n2+1-valent linking group. However, when n2 is 2 or more, L ^b21 is an n2+1-valent linking group.
The n2+1-valent linking group represented by L ^b21 includes an aliphatic hydrocarbon group, an aromatic hydrocarbon group, —NH—, —SO—, —SO ₂ —, —CO—, —O—, —COO—, OCO -, -S- and groups formed by combinations of two or more thereof. The aliphatic hydrocarbon group and aromatic hydrocarbon group may have a substituent. A hydroxy group, a halogen atom, etc. are mentioned as a substituent. The n2+1-valent linking group represented by L ^b21 may contain a urea bond (--NH--CO--NH--) or a urethane bond (--NH--COO-- or --OCO--NH--).

A ^b21 in formula (bb-2) represents a basic group. The basic group represented by A ^b21 is preferably an amino group.

n2 in formula (bb-2) represents an integer of 1 or more, preferably an integer of 1 to 4, more preferably 1 or 2.

Specific examples of the repeating unit b-2 include repeating units derived from compounds b-2-1 to b-2-22 described in Examples described later.

The content of the repeating unit b-2 in the specific resin is preferably 0.1 to 50% by mass. The lower limit is preferably 1% by mass or more, more preferably 5% by mass or more. The upper limit is preferably 45% by mass or less, more preferably 35% by mass or less.

[Repeating unit b-3]
The specific resin contains a repeating unit b-3 containing a polyalkyleneoxy structure (hereinafter also referred to as repeating unit b-3).

The molecular weight of the repeating unit b1-3 is preferably 350-1500. If the molecular weight is within the above range, it is possible to form a film in which the occurrence of defects is further suppressed. Furthermore, the generation of development residues can be suppressed more effectively. Furthermore, the increase in the viscosity of the resin composition over time can be suppressed, and the stability over time can be further improved. The upper limit of the molecular weight of the repeating unit b1-3 is preferably 1400 or less, more preferably 1200 or less. The lower limit is preferably 400 or more. In this specification, the molecular weight of the repeating unit b-3 is a value calculated from the molecular weight of the raw material monomer used for polymerization of the same repeating unit. When the molecular weight of the starting monomer can be calculated from the structural formula, the molecular weight of the starting monomer calculated from the structural formula is used as the molecular weight of the repeating unit b-3. When the molecular weight of the raw material monomer cannot be calculated from the structural formula, the value of the weight average molecular weight of the raw material monomer is used as the value of the molecular weight of the repeating unit b-3.

A polyalkyleneoxy structure is a structure composed of two or more alkyleneoxy groups, each of which has an alkyleneoxy group as a repeating unit. The polyalkyleneoxy structure may be composed of one type of alkyleneoxy group, or may be composed of two types of alkyleneoxy groups. The number of carbon atoms in the alkyleneoxy group constituting the polyalkyleneoxy structure is preferably 1 to 5, more preferably 1 to 3, still more preferably 2 or 3, and particularly preferably 2.
The number of alkyleneoxy groups constituting the polyalkyleneoxy structure is preferably 4-40. The lower limit is preferably 5 or more, more preferably 8 or more. The upper limit is preferably 35 or less, more preferably 30 or less.

The above polyalkyleneoxy structure is preferably a polytetramethyleneoxy structure, a polypropyleneoxy structure, a polyethyleneoxy structure, a polytetramethyleneoxy-polyethyleneoxy copolymer structure and a polypropyleneoxy-polyethyleneoxy copolymer structure, and a polyethyleneoxy structure and a polytetramethyleneoxy-polyethylene An oxy copolymer structure and a polypropyleneoxy-polyethyleneoxy copolymer structure are more preferred, and a polyethyleneoxy structure is even more preferred.

The terminal structure of the polyoxyalkylene structure is not particularly limited. It may be a hydrogen atom or a substituent. Examples of substituents include alkyl groups and aryl groups. Alkyl groups are
The number of carbon atoms in the alkyl group is preferably 1-30, more preferably 1-20. Alkyl groups are preferably straight or branched. The alkyl group may have a substituent. A halogen atom, an aryl group, etc. are mentioned as a substituent. The alkyl group is preferably an unsubstituted alkyl group.
The number of carbon atoms in the aryl group is preferably 6-30, more preferably 6-20, even more preferably 6-12. The aryl group may have a substituent. A halogen atom, an alkyl group, etc. are mentioned as a substituent.
The terminal structure of the polyoxyalkylene structure is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group.

Examples of the repeating unit b-3 include repeating units represented by the following formula (bb-3).

R ^b31 to R ^b33 in formula (bb-3) each independently represent a hydrogen atom or an alkyl group. The number of carbon atoms in the alkyl group represented by R ^b31 to R ^b33 is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1.

L ^b31 in formula (bb-3) represents a single bond or a divalent linking group.
The divalent linking group represented by L ^b31 includes an aliphatic hydrocarbon group, an aromatic hydrocarbon group, —NH—, —SO—, —SO _{2 —} , —CO—, —O—, —COO—, and OCO -, -S- and groups formed by combinations of two or more thereof. The aliphatic hydrocarbon group and aromatic hydrocarbon group may have a substituent. A hydroxy group, a halogen atom, etc. are mentioned as a substituent.

A ^b31 in formula (bb-3) represents a polyalkyleneoxy structure. Examples of the polyalkyleneoxy structure represented by A ^b31 include those described above.

A ^b32 in formula (bb-3) represents a hydrogen atom or a substituent. Examples of substituents include alkyl groups and aryl groups. The number of carbon atoms in the alkyl group is preferably 1-30, more preferably 1-20. Alkyl groups are preferably straight or branched. The alkyl group may have a substituent. A halogen atom, an aryl group, etc. are mentioned as a substituent. The alkyl group is preferably an unsubstituted alkyl group. The number of carbon atoms in the aryl group is preferably 6-30, more preferably 6-20, even more preferably 6-12. The aryl group may have a substituent. A halogen atom, an alkyl group, etc. are mentioned as a substituent.
^Ab32 is preferably a hydrogen atom or an alkyl group.

Specific examples of the repeating unit b-3 include repeating units derived from the compounds shown below.

The content of the repeating unit b-3 in the specific resin is preferably 20-90% by mass. The lower limit is preferably 25% by mass or more, more preferably 30% by mass or more. The upper limit is preferably 85% by mass or less, more preferably 75% by mass or less.

[Repeating unit b-4]
The specific resin further comprises a repeating unit b-4 having a functional group X selected from a group containing two or more aromatic rings, a group containing a heterocyclic group and a group containing a condensed ring (hereinafter also referred to as repeating unit b-4 ) is preferably included. According to this aspect, it is possible to form a film in which the occurrence of defects is further suppressed. Furthermore, the generation of development residues can be suppressed more effectively. Furthermore, the increase in the viscosity of the resin composition over time can be suppressed, and the stability over time can be further improved.

The functional group X of the repeating unit b-4 is preferably a group containing a ketone structure.
The functional group X is also preferably a group having 2 to 4 ring structures. In this aspect, the number of ring structures contained in the functional group X is preferably 2-3.
The functional group X is also preferably a group containing 2 to 5 heteroatoms. In this aspect, the number of heteroatoms contained in the functional group X is preferably 2-4.

The functional group X is preferably a group having 2 to 4 ring structures and containing 2 to 5 heteroatoms, and preferably has 2 to 3 ring structures and 2 heteroatoms. Groups containing up to 4 groups are more preferred. In particular, the functional group X is a group containing a ketone structure, has 2 to 4 ring structures (preferably 2 to 3 ring structures), and has 2 to 5 heteroatoms (preferably 2 to 4) are preferred. By using a group having such a structure as the functional group X, it is possible to form a film in which the occurrence of defects is further suppressed.

The functional group X has a naphthalimide structure, an acridone structure, a thioxanthone structure, a xanthone structure, anthrone structure, a benzimidazole structure, a benzothiazole structure, a benzoxazole structure, a benzotriazole structure, a benzoxadiazole structure, a benzothiadiazole structure, a benzothiazine structure, Benzoxazine structure, benzolein urea structure, isothiazolinone structure, phenoxazine structure, phenothiazine structure, dihydroacridine structure, phenoxathiin structure, dibenzopyran structure, fluorene structure, carbazole structure, carboline structure, dibenzothiophene structure, dibenzofuran structure, pyrimidine structure , pyrazine structure, quinazoline structure, quinoxaline structure, quinoline structure, imidazole structure, thiazole structure, indole structure, benzothiophene structure, benzopyran structure, quinolinone structure, thiochromanone structure, chroman structure, benzimidazolone structure, phthalimide structure, naphthalene-2, 3-dicarboximide structure, pyrazole structure, pyrazolone structure, isoindoline structure, isoindolinone structure, anthraquinone structure, tetrazole structure, benzophenone structure, triazine structure, azobenzene structure, benzalaniline structure, phenazine structure, barbituric acid structure, perylene structure, a perinone structure, a quinophthalone structure, a caprolactam structure, a saccharin structure, a biphenyl structure, a triarylbenzene structure, a triarylamine structure, a benzothiazolone structure or a benzoxazolinone structure.
naphthalimide structure, acridone structure, xanthone structure, anthrone structure, benzimidazole structure, benzothiazole structure, benzoxazole structure, benzotriazole structure, benzoxodiazole structure, benzothiadiazole structure, phenoxazine structure, phenothiazine structure, dihydroacridine structure, phenoxathiin structure, dibenzopyran structure, carbazole structure, carboline structure, dibenzothiophene structure, dibenzofuran structure, pyrimidine structure, pyrazine structure, quinazoline structure, quinoxaline structure, imidazole structure, thiazole structure, indole structure, benzothiophene structure, benzopyran structure, quinolinone structure, thiochromanone structure, chroman structure, phthalimide structure, naphthalene-2,3-dicarboximide structure, pyrazole structure, pyrazolone structure, isoindoline structure, isoindolinone structure, anthraquinone structure, tetrazole structure, benzophenone structure, triazine structure, A group containing an azobenzene structure, benzalaniline structure, phenazine structure, barbituric acid structure, perylene structure, perinone structure, saccharin structure, biphenyl structure, triarylbenzene structure, triarylamine structure, benzothiazolone structure or benzoxazolinone structure is more preferable,
naphthalimide structure, acridone structure, xanthone structure, anthrone structure, benzimidazole structure, benzothiazole structure, benzoxazole structure, benzotriazole structure, benzoxodiazole structure, benzothiadiazole structure, phenoxazine structure, phenothiazine structure, dihydroacridine structure, Phenoxathiin structure, dibenzopyran structure, carboline structure, dibenzothiophene structure, dibenzofuran structure, pyrimidine structure, pyrazine structure, quinazoline structure, quinoxaline structure, thiochromanone structure, chroman structure, phthalimide structure, pyrazolone structure, isoindolinone structure, tetrazole structure , a group containing a benzalaniline structure, a benzothiazolone structure or a benzoxazolinone structure,
naphthalimide structure, acridone structure, xanthone structure, benzimidazole structure, benzothiazole structure, benzoxazole structure, benzotriazole structure, benzoxadiazole structure, benzothiadiazole structure, phenoxazine structure, phenothiazine structure, phenoxathiin structure, phthalimide structure , a group containing a pyrazolone structure, a tetrazole structure, a benzothiazolone structure or a benzoxazolinone structure,
A group containing a naphthalimide structure, an acridone structure, a benzimidazole structure, a benzothiazole structure, a benzoxazole structure, a phenoxazine structure, a phenothiazine structure, a phenoxathiin structure, a phthalimide structure, a pyrazolone structure or a tetrazole structure is even more preferred. ,
A group containing a naphthalimide structure or an acridone structure is particularly preferred because it facilitates the formation of a film in which the occurrence of defects is more suppressed.

Specific examples of the functional group X include groups having the structures shown below and groups having a structure in which a substituent is bonded to these groups. Examples of the substituent include the groups exemplified for the substituent T described later. In the following formulas, * represents a linking hand, and R represents a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.

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

Examples of the repeating unit b-4 include repeating units represented by the following formula (bb-4).

R ^b41 to R ^b43 in formula (bb-4) each independently represent a hydrogen atom or an alkyl group. The number of carbon atoms in the alkyl group represented by R ^b41 to R ^b43 is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1.

L ^b41 in formula (bb-4) represents a single bond or a divalent linking group. The divalent linking group represented by L ^b41 includes an aliphatic hydrocarbon group, an aromatic hydrocarbon group, -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, OCO -, -S-, and groups formed by combining two or more of these. The aliphatic hydrocarbon group and aromatic hydrocarbon group may have a substituent. A hydroxy group, a halogen atom, etc. are mentioned as a substituent.

A ^b41 in formula (bb-4) represents the functional group X described above.

Specific examples of the repeating unit b-4 include repeating units derived from compounds b-4-1 to b-4-6 described later in Examples.

The content of the repeating unit b-4 in the specific resin is preferably 1 to 40% by mass. The lower limit is preferably 3% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 35% by mass or less, more preferably 30% by mass or less.

[Repeating unit b-5]
The specific resin may further contain a repeating unit (hereinafter referred to as repeating unit b-5) other than repeating units b-1 to b-4 described above.

Examples of the repeating unit b-5 include repeating units having functional groups such as alkyl groups, phenyl groups, and hydroxy groups.

The content of the repeating unit b-5 in the specific resin is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.

[Specific examples of specific resins]
Specific examples of the specific resin include resins P1 to P65 shown in Examples described later.

[Physical properties of specific resin]
The acid value of the specific resin is preferably 10-200 mgKOH/g. The upper limit is
It is preferably 180 mgKOH/g or less, more preferably 140 mgKOH/g or less, and even more preferably 120 mgKOH/g or less. The lower limit is preferably 20 mgKOH/g or more, more preferably 30 mgKOH/g or more, and even more preferably 40 mgKOH/g or more. If the acid value of the specific resin is within the above range, it is possible to form a film in which defective color unevenness is suppressed. Furthermore, when the pattern is formed by photolithography, the generation of development residue can be more effectively suppressed. It is particularly preferable that the specific resin has an acid value of 40 to 120 mgKOH/g.

The base number of the specific resin is preferably 10-200 mgKOH/g. The upper limit is preferably 180 mgKOH/g or less, more preferably 140 mgKOH/g or less, and even more preferably 120 mgKOH/g or less. The lower limit is preferably 20 mgKOH/g or more, more preferably 30 mgKOH/g or more, and even more preferably 40 mgKOH/g or more. If the base number of the specific resin is within the above range, it is possible to form a film in which defective color unevenness is suppressed. Furthermore, when the pattern is formed by photolithography, the generation of development residue can be more effectively suppressed. It is particularly preferable that the specific resin has an acid value of 40 to 120 mgKOH/g.

The ratio of the acid value to the base value of the specific resin (acid value/base value) is preferably 0.1 to 30, so that a film can be formed in which the occurrence of defects is further suppressed, and further development residue It is more preferably 0.2 to 20 because the occurrence of is also suppressed. The lower limit is preferably 0.3 or more, more preferably 0.4 or more. The upper limit is preferably 10 or less, more preferably 8 or less, and even more preferably 4 or less.

The weight average molecular weight of the specific resin is preferably 3,000 to 100,000. If the weight average molecular weight of the specific resin is within the above range, it is possible to form a film in which the occurrence of defects is further suppressed. The lower limit is preferably 4,000 or more, more preferably 5,000 or more, because the generation of development residue can be more effectively suppressed when a pattern is formed by photolithography. The upper limit is preferably 50,000 or less, more preferably 30,000 or less, for the reason that the increase in viscosity of the resin composition over time can be suppressed and the stability over time can be further improved.

(other resin)
The resin composition of the present invention can contain a resin different from the specific resin described above (hereinafter also referred to as other resin).

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

The weight average molecular weight (Mw) of other resins 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 other resin, it is preferable to use a resin having an acid group. Examples of acid groups include carboxy groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups.

The acid value of the resin having acid groups is preferably 30-500 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, still more preferably 300 mgKOH/g or less, and particularly preferably 200 mgKOH/g or less. The weight average molecular weight (Mw) of the acid group-containing resin is preferably 5,000 to 100,000, more preferably 5,000 to 50,000. Moreover, the number average molecular weight (Mn) of the resin having an acid group is preferably 1,000 to 20,000.

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

For the resin having an acid group, JP 2012-208494, paragraph numbers 0558 to 0571 (corresponding US Patent Application Publication No. 2012/0235099, paragraph numbers 0685 to 0700), JP 2012-198408 The descriptions in paragraphs 0076 to 0099 of the publication can be referred to, and the contents thereof are incorporated herein. Moreover, resin which has an acid group can also use a commercial item. Moreover, the method for introducing the acid group into the resin is not particularly limited, but includes, for example, the method described in Japanese Patent No. 6349629 . Furthermore, as a method for introducing an acid group into a resin, 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 can also be mentioned.

As other resins, resins having basic groups can also be used. Resins having basic groups can also be used as dispersants. The amine value of the resin having basic groups is preferably 5-300 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, 38 500, 39000, 53095, 56000, 7100 (manufactured by Nippon Lubrizol), Efka PX 4300, 4330, 4046, 4060, 4080 (manufactured by BASF) and the like. Further, the resin having a basic group is a block copolymer (B) described in paragraph numbers 0063 to 0112 of JP-A-2014-219665, and described in paragraph numbers 0046-0076 of JP-A-2018-156021. It is also possible to use the block copolymer A1 described above and vinyl resins having basic groups described in paragraphs 0150 to 0153 of JP-A-2019-184763.

Other resins include 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 dimers"). It is also preferable to use a resin containing a repeating unit derived from.

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 the formula (ED2), the description in JP-A-2010-168539 can be referred to, the content of which is 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 another resin, it is also preferable to use a resin containing a repeating unit derived from the 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 0-15. The number of carbon atoms in the alkylene group represented by R ²¹ and R ²² is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, particularly 2 or 3. preferable. n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and 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 another resin, it is also preferable to use a resin having a crosslinkable group. Crosslinkable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, styrene groups, (meth)allyl groups, and (meth)acryloyl groups. Examples of the cyclic ether group include an epoxy group and an oxetanyl group, with the epoxy group being preferred. The epoxy group may be a cycloaliphatic epoxy group. The alicyclic epoxy group means a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.

As another resin, it is also preferable to use a resin having an aromatic carboxy group (hereinafter also referred to as resin Ac). In Resin Ac, the aromatic carboxy group may be contained in the main chain of the repeating unit or may be contained in the side chain of the repeating unit. The aromatic carboxy group is preferably contained in the main chain of the repeating unit. In this specification, an aromatic carboxy group is 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 1-4, more preferably 1-2.

Resin Ac is preferably a resin containing at least one repeating unit selected from repeating units represented by formula (Ac-1) and repeating units represented by formula (Ac-2).

In formula (Ac-1), Ar ¹ represents a group containing an aromatic carboxyl 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 carboxyl group, L ¹¹ represents -COO- or -CONH-, L ¹² represents a trivalent linking group, P ¹⁰ represents a polymer represents a chain.

Examples of the aromatic carboxy group-containing group represented by Ar ¹ in formula (Ac-1) include structures derived from aromatic tricarboxylic acid anhydrides, structures derived from aromatic tetracarboxylic acid anhydrides, and the like. Examples of aromatic tricarboxylic anhydrides and aromatic tetracarboxylic anhydrides 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 group containing an aromatic carboxyl 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, 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). and the like.

In formula (Ar-11), n1 represents an integer of 1 to 4, preferably 1 or 2, 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 still 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, 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- 1) or a group represented by the above formula (Q-2).
In formulas (Ar-11) to (Ar-13), *1 represents the bonding position with ^L1 .

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

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

The group containing an aromatic carboxyl 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-.

The trivalent linking group represented by L ¹² in formula (Ac-2) includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and 2 of these Groups in which more than one species are combined are included. Hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1-30, more preferably 1-20, even more preferably 1-15. The aliphatic hydrocarbon group may be linear, branched or cyclic. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-30, more preferably 6-20, even more preferably 6-10. The hydrocarbon group may have a substituent. A hydroxy group etc. are mentioned as a substituent. The trivalent linking group represented by L ¹² is preferably a group represented by formula (L12-1), 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), *2 represents formula ( The binding position of Ac-2) with ^P10 is shown. The trivalent linking group represented by L ^12b includes a hydrocarbon group; and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S- is preferably a hydrocarbon group or a group of a combination of a hydrocarbon group and —O—.

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), *2 represents formula ( The binding position of Ac-2) with ^P10 is shown. The trivalent linking group represented by L ^12c includes a hydrocarbon group; and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S- and the like, preferably a hydrocarbon group.

P ¹⁰ in formula (Ac-2) represents a polymer chain. The polymer chain represented by ^P10 preferably has at least one structure selected from polyester structure, polyether structure, polystyrene structure and poly(meth)acrylic structure. The weight average molecular weight of the polymer chain ^P10 is preferably 500-20,000. 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 ^P10 is within the above range, the dispersibility of the pigment in the composition is good. When the resin having an aromatic carboxyl group is a resin having repeating units represented by formula (Ac-2), this resin is preferably used as a dispersant.

The polymer chain represented by ^P10 may contain crosslinkable groups. Crosslinkable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups.

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

Examples of the graft polymer include a resin having a repeating unit having a graft chain and a resin having a repeating unit represented by the above formula (Ac-2). Examples of graft chains include graft chains 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 substituents include alkyl groups, alkoxy groups, alkylthioether groups, and the like. Among them, from the viewpoint of improving the dispersibility of the pigment, a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 30 carbon atoms is preferable. The alkyl group and alkoxy group may be linear, branched or cyclic, preferably linear or branched.

Specific examples of the graft polymer include paragraph numbers 0025 to 0094 of JP-A-2012-255128, paragraph numbers 0022-0097 of JP-A-2009-203462, and paragraph numbers 0102-0166 of JP-A-2012-255128. Mention may be made of the resins mentioned.

Star-shaped polymers include resins with a structure in which multiple polymer chains are bonded to the core. Specific examples of the star polymer include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A-2013-043962.

As the resin in which at least one end of the polymer chain is blocked with an acid group, at least one end of the polymer chain containing at least one structure selected from a polyester structure, a polyether structure and a poly(meth)acrylic structure is A resin having a structure sealed with an acid group can be mentioned. A carboxy group, a sulfo group, and a phosphoric acid group are examples of the acid group that seals the end of the polymer chain.

Other resins can also be used as dispersants. Dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is greater than the amount of basic groups. As the acidic dispersant (acidic resin), a resin having an acid group content of 70 mol % or more is preferable when the total amount of the acid group and the basic group is 100 mol %. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxy group. The acid value of the acidic dispersant (acidic resin) is preferably 10-105 mgKOH/g. Further, a basic dispersant (basic resin) represents a resin in which the amount of basic groups is greater than the amount of acid groups. As the basic dispersant (basic resin), a resin containing more than 50 mol % of basic groups is preferable when the total amount of acid groups and basic groups is 100 mol %. The basic group possessed by the basic dispersant is preferably an amino group.

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

The resin content 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 content of the specific resin in the total solid content of the resin composition is preferably 1 to 10% by mass. The upper limit is preferably 9% by mass or less, more preferably 7.5% by mass or less. The lower limit is preferably 1.5% by mass or more, more preferably 3% by mass or more.

The content of the specific resin in the resin contained in the resin composition is preferably 1 to 30% by mass. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less. The lower limit is preferably 3% by mass or more, more preferably 5% 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. When two or more resins are included, the total amount thereof is preferably within the above range.

<<polymerizable compound>>
The resin composition of the present invention preferably contains a polymerizable compound. Examples of the polymerizable compound include compounds having an ethylenically unsaturated bond-containing group. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups. 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 monomer, prepolymer, oligomer, etc., but monomer is preferred. The molecular weight of the polymerizable compound is preferably 100-2500. The upper limit is preferably 2000 or less, more preferably 1500 or less. The lower limit is preferably 150 or more, more preferably 250 or more.

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

The polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated bond-containing groups, more preferably a compound containing 4 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, even more preferably 6 or less, from the viewpoint of the stability of the resin composition over time. Further, the polymerizable compound is preferably a tri- or more functional (meth) acrylate compound, more preferably a 3- to 15-functional (meth) acrylate compound, and a 3- to 10-functional (meth) acrylate compound. is more preferred, and tri- to hexa-functional (meth)acrylate compounds are particularly preferred. Specific examples of the polymerizable compound include paragraph numbers 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-029760, paragraph numbers 0254-0257 of JP-A-2008-292970, and JP-A-2008-292970. 2013-253224, paragraphs 0034 to 0038, JP 2012-208494, paragraph 0477, JP 2017-048367, JP 6057891, the compound described in JP 6031807 , 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. mentioned. Modified compounds include compounds having a structure in which the (meth)acryloyl groups of the above compounds are bonded through 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)- , y each 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 sum of 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 0-10, and the sum of each n is an integer of 0-60.

In formula (Z-4), m is preferably an integer of 0-6, more preferably an integer of 0-4. The sum of 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 0-6, more preferably an integer of 0-4. The sum of n is preferably an integer of 3-60, more preferably an integer of 3-24, and particularly preferably an integer of 6-12.
Further, 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 A form in which the end on the oxygen atom side is bonded to X is preferred.

Polypentaerythritol poly(meth)acrylates represented by the following formula (Z-6) can also be used as the polymerizable compound.

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 1-10. 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. Seeds are preferred. Commercially available products include KAYARAD D-310, DPHA, DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.), NK Ester A-DPH-12E, TPOA-50 (manufactured by Shin-Nakamura Chemical Co., Ltd.), etc. mentioned.

Further, as the polymerizable compound, diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available 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 (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 (manufactured by Daicel Allnex, amine-containing tetrafunctional acrylate) and the like can also be used.

Further, as the polymerizable compound, trimethylolpropane tri(meth)acrylate, trimethylolpropane propyleneoxy-modified tri(meth)acrylate, trimethylolpropane ethyleneoxy-modified tri(meth)acrylate, ethyleneoxy isocyanurate-modified tri(meth) It is also preferable to use trifunctional (meth)acrylate compounds such as acrylates and pentaerythritol tri(meth)acrylates. Commercial products of trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306 and 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.) etc.

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

A compound having a caprolactone structure can also be used as the polymerizable compound. For compounds having a caprolactone structure, the descriptions in paragraphs 0042 to 0045 of JP-A-2013-253224 can be referred to, the contents of which are incorporated herein. Compounds having a caprolactone structure include, for example, DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available as KAYARAD DPCA series from Nippon Kayaku Co., Ltd.

In addition, 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 Chemicals Co., Ltd., (meth)acrylate monomer having a fluorene skeleton).

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

Further, as the polymerizable compound, urethane acrylates such as those described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765 Also suitable are urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418. It is also preferable to use a polymerizable compound 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. Further, the polymerizable compound includes UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, 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 30% by mass. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less. The lower limit is preferably 2% by mass or more. The resin composition of the present invention may contain only one polymerizable compound, or may contain two or more polymerizable compounds. When two or more polymerizable compounds are included, the total amount thereof is preferably within the above range.

<<Photoinitiator>>
The resin composition of the present invention can contain a photopolymerization initiator. When the resin composition of the present invention contains a polymerizable compound, the resin composition of the present invention preferably 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 range to the visible range are preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds and the like. From the viewpoint of exposure sensitivity, photopolymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, hexaarylbi 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 compounds, α-aminoketone compounds, and acylphosphine compounds, more preferably oxime compounds. Further, as the photopolymerization initiator, compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37-60p, vol. 19, No. 3, the peroxide photopolymerization initiator described in 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-2019-044030, the photopolymerization initiator described in JP-A-2019-167313, the peroxide-based initiator described in JP-A-2020-055992. An aminoacetophenone-based initiator having an oxazolidine group described, an oxime-based photopolymerization initiator described in JP-A-2013-190459, a polymer described in JP-A-2020-172619, and International Publication No. 2020/152120. The compound represented by Formula 1 described, the compound described in JP-A-2021-181406, the photopolymerization initiator described in JP-A-2022-013379, the formula (1) described in JP-A-2022-015747 ), a fluorine-containing fluorene oxime ester photopolymerization initiator described in JP-A-2021-507058, a photopolymerization initiator described in Chinese Patent Application Publication No. 110764367, JP-A-2022-518535 No. 2021/175855, the contents of which 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. is mentioned.

Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (above, BASF company) and the like. Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 3. 79EG (above, BASF made), etc. Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819 and Irgacure TPO (manufactured by BASF).

Examples of oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in 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), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, compounds described in Patent No. 6065596, International Publication No. 2015 / 152153, compounds described in WO 2017/051680, compounds described in JP 2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017/164127, Examples include compounds described in International Publication No. 2013/167515. Specific examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino -1-phenylpropane-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-304, TR-PBG-327 (manufactured by TRONLY), Adeka Optomer N-1919 (manufactured by ) manufactured by ADEKA, photopolymerization initiator 2) described in JP-A-2012-014052. As the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and resistance to discoloration. Commercially available products include ADEKA Arkles NCI-730, NCI-831 and NCI-930 (manufactured by ADEKA Corporation).

An oxime compound having a fluorene ring can also be used as the photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466, compounds described in Japanese Patent No. 6636081, and compounds described in Korean Patent Publication No. 10-2016-0109444. mentioned.

As the photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in WO2013/083505.

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

An oxime compound having a nitro group can be used as the photopolymerization initiator. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 and ADEKA Arkles NCI-831 (manufactured by ADEKA Corporation) can be mentioned.

An oxime compound having a benzofuran skeleton can also be used as the photopolymerization initiator. Specific examples include OE-01 to OE-75 described in WO 2015/036910.

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

As the photopolymerization initiator, an oxime compound having an aromatic ring group Ar ^{2 OX1} in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX) can be used. Examples of the electron-withdrawing group of 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. A 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, heterocyclicoxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, It is preferably an acyl group or an amino group, 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. A sulfanyl group or an amino group is more preferred.

The oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), more preferably the compound represented by the formula (OX2). preferable.

In the formula, R ^X1 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl a group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group,
R ^X2 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, aryl represents a sulfonyl group, an acyloxy group or an amino group,
R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent;
However, at least one of R ^X10 to R ^X14 is an electron-withdrawing group.

The electron-withdrawing group includes 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, preferably an acyl group and a nitro group. is more preferably a group, more preferably a benzoyl group.

In the above formula, R ^X12 is an electron-withdrawing group, and R ^X10 , R ^X11 , R ^X13 and R ^X14 are preferably hydrogen atoms.

Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600.

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

The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. Further, the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high from the viewpoint of sensitivity, more preferably 1000 to 300000, further preferably 2000 to 300000, even more preferably 5000 to 200000. It is particularly preferred to have The molar extinction coefficient of a compound can be measured using known methods. For example, it is preferably measured at a concentration of 0.01 g/L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

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 bifunctional or trifunctional or higher 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 good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, the crystallinity is lowered, the solubility in a solvent or the like is improved, and precipitation becomes difficult over time, and the stability over time of the resin composition can be improved. . Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Publication No. 2016-532675. Paragraph numbers 0407 to 0412, dimers of oxime compounds described in paragraph numbers 0039 to 0055 of International Publication No. 2017/033680, compound (E) and compounds described in JP-A-2013-522445 ( G), Cmpd1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiators described in paragraph number 0007 of JP 2017-523465, JP 2017-167399 Photoinitiators described in paragraph numbers 0020 to 0033, photoinitiators (A) described in paragraph numbers 0017 to 0026 of JP-A-2017-151342, described in Japanese Patent No. 6469669 and 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 kinds are used, it is preferable that the total amount thereof is within the above range.

<<Solvent>>
The resin composition of the present invention preferably contains a solvent. An organic solvent is mentioned as a solvent. 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. Organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. For these details, reference can be made to paragraph number 0223 of WO2015/166779, the content of which is incorporated herein. Ester-based solvents substituted with cyclic alkyl groups and ketone-based solvents substituted with cyclic alkyl groups 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, ethylcarbitol 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 diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, isopropyl alcohol and the like. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may be better reduced for environmental reasons (e.g., 50 mass ppm (parts per million), 10 ppm by mass or less, or 1 ppm by mass or less).

In the present invention, it is preferable to use an organic solvent with a low metal content. The metal content of the organic solvent is preferably, for example, 10 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, for example, by Toyo Gosei Co., Ltd. (Chemical Daily, 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 size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The 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 isomer may be contained, or a plurality of isomers may be contained.

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

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

In addition, it is preferable that the resin composition of the present invention does not substantially contain environmentally regulated substances from the viewpoint of environmental regulations. In the present invention, "substantially free of environmental regulation substances" means that the content of environmental regulation substances in the resin composition is 50 mass ppm or less, preferably 30 mass ppm or less. , is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less. Environmental control substances include, for example, benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These comply with environmental regulations such as the REACH (Registration Evaluation Authorization and Restriction of Chemicals) Regulations, the PRTR (Pollutant Release and Transfer Register) Law, and the VOC (Volatile Organic Compounds) Regulations. It is registered as a substance, and the amount used and handling methods are strictly regulated. These compounds may be used as solvents in the production of components used in the resin composition, and may be mixed into the resin composition as residual solvents. From the viewpoint of safety to humans and consideration for the environment, it is preferable to reduce these substances as much as possible. As a method for reducing the amount of environmentally regulated substances, there is a method in which the system is heated or decompressed to raise the temperature to the boiling point of the environmentally regulated substances or higher, and the environmentally regulated substances are distilled off from the system. In the case of distilling off a small amount of environmentally regulated substances, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in order to increase the efficiency. In addition, when a compound having radical polymerizability is contained, a polymerization inhibitor or the like is added and distilled off under reduced pressure in order to suppress the radical polymerization reaction from progressing during the vacuum distillation and the intermolecular cross-linking. may These distillation methods are at the stage of raw materials, the stage of reaction products of raw materials (for example, resin solutions and polyfunctional monomer solutions after polymerization), or the stages of resin compositions prepared by mixing these compounds. It is possible at any stage such as

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

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

Examples of commercially available compounds having a cyclic ether group include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (these are epoxy group-containing polymers manufactured by NOF Corporation) and the like. Further, as the compound having a cyclic ether group, the compounds described in the examples described later can also be used.

The content of the thermosetting 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 thermosetting agent may be used, or two or more types may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.

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

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

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

Specific examples of alkyleneimine include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine and the like, preferably ethyleneimine or propyleneimine, more preferably ethyleneimine. preferable. It is particularly preferred that the polyalkyleneimine is polyethyleneimine. In addition, the polyethyleneimine preferably contains 10 mol% or more, more preferably 20 mol% or more, of the primary amino group with respect to the total of the primary amino group, the secondary amino group and the tertiary amino group. , more preferably 30 mol % or more. Commercial products of polyethyleneimine include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, P-1000 (manufactured by Nippon Shokubai Co., Ltd.).

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

<<Curing accelerator>>
The resin composition of the present invention may contain a curing accelerator. Curing accelerators 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 WO 2018/056189, compounds described in paragraph numbers 0246 to 0253 of JP 2015-034963, JP 2013-041165 Compounds described in paragraphs 0186 to 0251 of the publication, ionic compounds described in JP 2014-055114, compounds described in paragraphs 0071 to 0080 of JP 2012-150180, JP 2011-253054 Alkoxysilane compounds having an epoxy group described in JP-A-2005-200157, compounds described in paragraphs 0085 to 0092 of Japanese Patent No. 5765059, and carboxy group-containing epoxy curing agents described in JP-A-2017-036379. 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 ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, and dibenzoyl compounds. Specific examples of such compounds include paragraph numbers 0038 to 0052 of JP-A-2009-217221, paragraph numbers 0052-0072 of JP-A-2012-208374, and paragraph numbers 0317-0317 of JP-A-2013-068814. 0334, and compounds described in paragraphs 0061 to 0080 of JP-A-2016-162946, the contents of which are incorporated herein. Specific examples of the ultraviolet absorber include compounds having the following structures. Examples of commercially available UV absorbers include UV-503 (manufactured by Daito Chemical Co., Ltd.), Tinuvin series and Uvinul series manufactured by BASF, and Sumisorb series manufactured by Sumika Chemtex Co., Ltd. . Benzotriazole compounds include the MYUA series manufactured by Miyoshi Oil (Kagaku Kogyo Nippo, February 1, 2016). In addition, the ultraviolet absorber is a compound described in paragraph numbers 0049 to 0059 of Japanese Patent No. 6268967, a compound described in paragraph numbers 0059 to 0076 of WO 2016/181987, and WO 2020/137819. A thioaryl group-substituted benzotriazole-type ultraviolet absorber described in can also be used.

The content of the ultraviolet absorber in the total solid content of the resin composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. Only one type of ultraviolet absorber may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

<<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), 2,2′-methylenebis(4-methyl-6-t-butylphenol), 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. Only one kind of polymerization inhibitor may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount is preferably within the above range.

<<Silane coupling agent>>
The resin composition of the present invention can contain a silane coupling agent. As used herein, a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Further, the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and capable of forming a siloxane bond by at least one of hydrolysis reaction and condensation reaction. Hydrolyzable groups include, for example, halogen atoms, alkoxy groups, acyloxy groups and the like, with alkoxy groups being 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 group, (meth)allyl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group and isocyanate group. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferred. Specific examples of the silane coupling agent 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 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. Further, specific examples of the silane coupling agent include compounds described in paragraph numbers 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraph numbers 0056-0066 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% by mass, more preferably 0.05 to 10% by mass. Only one kind of silane coupling agent may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount is preferably 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-based surfactant or a fluorine-based surfactant. For surfactants, reference can be made to surfactants described in paragraphs 0238-0245 of WO2015/166779, the contents of which are incorporated herein.

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

As the fluorine-based surfactant, JP 2014-041318 Paragraph Nos. 0060 to 0064 (corresponding International Publication No. 2014/017669 Paragraph Nos. 0060 to 0064) surfactants described in, JP 2011- Examples include surfactants described in paragraphs 0117 to 0132 of JP-A-132503 and surfactants described in JP-A-2020-008634, the contents of which are incorporated herein. Commercially available fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, and F-144. , F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560 , F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-01, R-40, R-40-LM, R-41, R -41-LM, RS-43, R-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH- 40 (manufactured by AGC), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), Futergent 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 710 FS , FTX-218 (manufactured by NEOS Corporation) and the like.

The fluorosurfactant has a molecular structure with a functional group containing a fluorine atom, and an acrylic compound in which the functional group containing a fluorine atom is cleaved and the fluorine atom volatilizes when heat is applied is also suitable. Available. Examples of such fluorine-based surfactants include Megafac DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Mega Fac DS-21.

It is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorosurfactant. Such fluorosurfactants include fluorosurfactants described in JP-A-2016-216602, the contents of which are incorporated herein.

A block polymer can also be used as the fluorosurfactant. The fluorosurfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meta) 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-2010-032698 and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.

The weight average molecular weight of the above compound is preferably 3000-50000, for example 14000. In the above compounds, % indicating the ratio of repeating units is mol %.

A fluoropolymer having an ethylenically unsaturated bond-containing group in a side chain can also be used as the fluorosurfactant. Specific examples include compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A-2010-164965, MEGAFACE RS-101, RS-102 and RS-718K manufactured by DIC Corporation, and RS-72-K. Further, as the fluorosurfactant, compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.

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 the surfactant having a perfluoroalkyl group with 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 the formula (fi-1), m represents 1 or 2, n represents an integer of 1 to 4, a represents 1 or 2, X ^a+ is an a-valent metal ion, primary ammonium ion, Represents secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ion or NH ₄ ⁺ .

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 company), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Fujifilm Wa Kojunyaku Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (Takemoto Oil Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (Nissin Chemical Industry Co., Ltd.) ) and the like.

Silicone surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Industries, Inc.), 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.

A compound having the following structure can also be used as the silicone-based surfactant.

The content of the surfactant in the total solid content of the resin composition is preferably 0.001% by mass to 5% by mass, more preferably 0.005% by mass to 3% by mass. Only one type of surfactant may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

<<Antioxidant>>
The resin composition of the present invention can contain an antioxidant. Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. The antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Phosphorus-based antioxidants can also be suitably used as antioxidants. As a phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, ethyl bis(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 Corporation) and the like. In addition, antioxidants are compounds described in paragraph numbers 0023 to 0048 of Japanese Patent No. 6268967, compounds described in WO 2017/006600, compounds described in WO 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 kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more kinds are used, the total amount is preferably within the above range.

<<Other Ingredients>>
The resin composition of the present invention may optionally contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliaries (e.g., conductive particles, antifoaming agents, flame retardants, leveling agents, release accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). Properties such as film physical properties can be adjusted by appropriately containing these components. These components are, for example, described in JP 2012-003225, paragraph number 0183 and later (corresponding US Patent Application Publication No. 2013/0034812, paragraph number 0237), JP 2008-250074 paragraph The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated herein. Moreover, the resin composition of the present invention may contain a latent antioxidant, if necessary. The latent antioxidant is a compound in which the site functioning 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. A compound that functions as an antioxidant by removing the protective group by the reaction is exemplified. Examples of latent antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219. Commercially available latent antioxidants include ADEKA Arkles 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 size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, even more preferably 5 to 50 nm. Metal oxides may have a core-shell structure. Moreover, in this case, the core portion may be hollow.

The resin composition of the present invention may contain a light resistance improver. As the light resistance improver, compounds described in paragraph numbers 0036 to 0037 of JP-A-2017-198787, compounds described in paragraph numbers 0029-0034 of JP-A-2017-146350, JP-A-2017-129774 Compounds described in paragraph numbers 0036 to 0037, 0049 to 0052 of JP 2017-129674 JP 2017-129674 paragraph numbers 0031 to 0034, 0058 to 0059 compounds described in JP 2017-122803 paragraph numbers 0036 to 0037 , compounds described in 0051 to 0054, compounds described in paragraph numbers 0025 to 0039 of WO 2017/164127, compounds described in paragraph numbers 0034 to 0047 of JP 2017-186546, JP 2015-025116 Compounds described in paragraph numbers 0019 to 0041 of JP-A-2012-145604, compounds described in paragraph numbers 0101-0125 of JP-A-2012-103475, compounds described in paragraph numbers 0018-0021 of JP-A-2012-103475, in particular Compounds described in paragraphs 0015 to 0018 of JP 2011-257591, compounds described in paragraphs 0017 to 0021 of JP 2011-191483, described in paragraphs 0108 to 0116 of JP 2011-145668 and compounds described in paragraph numbers 0103 to 0153 of JP-A-2011-253174.

The resin composition of the present invention preferably does not substantially contain terephthalic acid ester. Here, "substantially free" means that the content of the terephthalic acid ester is 1000 mass ppb or less, more preferably 100 mass ppb or less, in the total amount of the resin composition. Zero is particularly preferred.

The resin composition of the present invention preferably has a free metal content of 100 ppm or less, more preferably 50 ppm or less. The type of metal is not particularly limited, but examples include alkali metals, alkaline earth metals, transition metals, Al, Sn, Pb, and Bi. Also, the free halogen content is preferably 100 ppm or less, more preferably 50 ppm or less. Methods for reducing free metals and halogens in the resin composition include methods such as washing with ion-exchanged water, filtration, ultrafiltration, and purification by emphasizing ion exchange.

From the perspective of environmental regulations, the use of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts may be regulated. In the resin composition of the present invention, when the content of the above compounds is reduced, perfluoroalkylsulfonic acid (especially perfluoroalkylsulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and salts thereof, and perfluoroalkylsulfonic acid The content of fluoroalkylcarboxylic acid (especially perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt is 0.01ppb to 1,000ppb with respect to the total solid content of the resin composition. 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 salts and perfluoroalkylcarboxylic acid and its salts. For example, by using a compound that can substitute for perfluoroalkylsulfonic acid and its salt, and a compound that can substitute for perfluoroalkylcarboxylic acid and its salt, perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and salts thereof may be selected. Compounds that can substitute for the regulated compounds include, for example, compounds excluded from the regulation due to the difference in the number of carbon atoms in the perfluoroalkyl group. However, the above contents do not prevent the use of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts. The resin composition of the present invention may contain perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts within the maximum permissible range.

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

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

<<Container>>
The storage container for the resin composition is not particularly limited, and known storage containers can be used. In addition, as a storage container, a multi-layer bottle whose inner wall is composed of 6 types and 6 layers of resins and a bottle with a 7-layer structure of 6 types of resins are used for the purpose of suppressing contamination of raw materials and resin compositions. It is also preferred to use Examples of such a container include the container described in JP-A-2015-123351. In addition, the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, enhancing the stability of the resin composition over time, and suppressing deterioration of components.

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

In addition, 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 pulverizing the pigment in a sand mill (bead mill), it is preferable to use beads with a small diameter or to increase the filling rate of the beads so as to increase the pulverization efficiency. Moreover, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. In addition, the process and dispersing machine for dispersing pigments are described in "Dispersion Technology Complete Works, Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology centered on suspension (solid / liquid dispersion system) and industrial Practical Application General Documents, Published by Management Development Center Publishing Department, October 10, 1978", the process and dispersing machine described in paragraph number 0022 of JP-A-2015-157893 can be suitably used. In the process of dispersing the pigment, the particles may be made finer in the salt milling process. Materials, equipment, processing conditions, etc. used in the salt milling step can be referred to, for example, Japanese Patent Application Laid-Open Nos. 2015-194521 and 2012-046629. Bead materials used for dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel and glass. An inorganic compound having a Mohs hardness of 2 or more can also be used for the beads. The composition may contain 1 to 10000 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. As the filter, any filter that has been conventionally used for filtration or the like can be used without particular limitation. For example, fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) (including high-density, ultra-high-molecular-weight polyolefin resin) and other materials. Among these materials, polypropylene (including high density polypropylene) and nylon are preferred.

The pore size of the filter is preferably 0.01-7.0 μm, more preferably 0.01-3.0 μm, and even more preferably 0.05-0.5 μm. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. For the pore size value of the filter, reference can be made to the filter manufacturer's nominal value. Various filters provided by Nippon Pall Co., Ltd. (DFA4201NXEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Nihon Entegris Co., Ltd. (former Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can be used as filters. .

It is also preferable to use a fiber-like filter medium as the filter. Examples of fibrous filter media include polypropylene fibers, nylon fibers, and glass fibers. Commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by Roki Techno.

When using filters, different filters (eg, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed twice or more. Also, filters with different pore sizes within the range described above may be combined. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration with the second filter may be performed. In addition, the filter can be appropriately selected according to the hydrophilicity/hydrophobicity of the composition.

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

The film thickness of the film of the present invention can be appropriately adjusted according to the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, 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 hue of green, red, blue, cyan, magenta or yellow, and may have a hue of green, blue or cyan. More preferably, it has a green hue. Moreover, 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, and yellow pixels, and red pixels are more preferable.

<Method for producing membrane>
Next, the method for producing the film of the present invention will be described. The film of the present invention can be produced through the step of applying the resin composition of the present invention. Preferably, the film manufacturing method further includes a step of forming a pattern (pixels). A method for forming the pattern (pixels) includes a photolithography method and a dry etching method, and the photolithography method is preferable. By forming a pattern by photolithography using the resin composition of the present invention, generation of development residue can be further suppressed.

Pattern formation by photolithography includes the steps of forming a resin composition layer on a support using the resin composition of the present invention, exposing the resin composition layer in a pattern, and exposing the resin composition layer to light. forming a pattern (pixels) by developing and removing the exposed portion. If necessary, a step of baking the resin composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided.

In the step of forming a resin composition layer, the resin composition of the present invention is used to form a resin composition layer on a support. The support is not particularly limited and can be appropriately selected depending on the application. Examples thereof include glass substrates and silicon substrates, and silicon substrates are preferred. Also, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate. In some cases, the silicon substrate is formed with a black matrix that isolates each pixel. In addition, the silicon substrate may be provided with an underlying layer for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface. The surface contact angle of the underlayer is preferably 20 to 70° when measured with diiodomethane. Further, it is preferably 30 to 80° when measured with water.

A known method can be used as a method for applying the resin composition. For example, dropping method (drop cast); slit coating method; spray method; roll coating method; spin coating method (spin coating); methods described in publications); inkjet (e.g., on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc. Examples include various printing methods; transfer methods using molds and the like; nanoimprinting methods and the like. The application method for inkjet is not particularly limited. 133 page), and methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, etc. mentioned. In addition, regarding the coating method of the resin composition, the descriptions of WO2017/030174 and WO2017/018419 can be referred to, and the contents thereof are incorporated herein.

The resin composition layer formed on the support may be dried (pre-baked). Pre-baking may not be performed when the film is manufactured by a low-temperature process. When pre-baking is performed, the pre-baking 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, and can also be 80° C. or higher. The pre-bake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, even more preferably 80 to 220 seconds. Pre-baking can be performed using a hot plate, an 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 through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. Thereby, the exposed portion can be cured.

Radiation (light) that can be used for exposure includes g-line, i-line, and the like. Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Light having a wavelength of 300 nm or less includes KrF rays (wavelength: 248 nm), ArF rays (wavelength: 193 nm), etc., and KrF rays (wavelength: 248 nm) are preferred. A long-wave light source of 300 nm or more can also be used. As a light source, an electrodeless UV lamp system, a hybrid curing of UV and IR can be used.

In addition, when exposing, the light may be continuously irradiated and exposed, or may be irradiated and exposed in pulses (pulse exposure). Note that the pulse exposure is an exposure method in which light irradiation and pause are repeated in a cycle of short time (for example, less than millisecond level).

The dose (exposure dose) 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 at the time of exposure can be appropriately selected. The exposure may be in an oxygen-free atmosphere, or in a high-oxygen atmosphere with an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume). In addition, the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W/m ² to 100000 W/m ² (eg, 5000 W/m ² , 15000 W/m ² or 35000 W/m ² ). can be done. Oxygen concentration and exposure illuminance may be appropriately combined. For example, illuminance of 10000 W/m ² at oxygen concentration of 10% by volume and illuminance of 20000 W/m ² at oxygen concentration of 35% by volume.

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

The developer includes an organic solvent, an alkaline developer, etc., and an alkaline developer is preferably used. As the alkaline developer, an alkaline aqueous solution (alkali developer) obtained by diluting an alkaline agent with pure water is preferable. Examples of alkaline agents include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. , ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene, etc. Examples include organic alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate and sodium metasilicate. A compound having a large molecular weight is preferable for the alkaline agent from the standpoint of environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. Moreover, the developer may further contain a surfactant. From the viewpoint of transportation and storage convenience, the developer may be produced once as a concentrated solution and then diluted to the required concentration when used. Although the dilution ratio is not particularly limited, it can be set, for example, in the range of 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Rinsing is preferably carried out by supplying a rinse liquid to the resin composition layer after development while rotating the support on which the resin composition layer after development is formed. It is also preferable to move the nozzle for discharging the rinsing liquid from the central portion of the support to the peripheral portion of the support. At this time, when moving the nozzle from the center of the support to the periphery, the moving speed of the nozzle may be gradually decreased. By performing rinsing in this manner, in-plane variations in rinsing can be suppressed. A similar effect can be obtained by gradually decreasing the rotation speed of the support while moving the nozzle from the center of the support to the periphery.

After development, it is preferable to perform additional exposure processing and heat processing (post-baking) after drying. Additional exposure processing and post-baking are post-development curing treatments for complete curing. The heating temperature in post-baking is, for example, preferably 100 to 300.degree. C., more preferably 200 to 270.degree. Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulating dryer), or a high-frequency heater so that the developed film satisfies the above conditions. . When the additional exposure process is performed, the light used for exposure preferably has 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 a 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 the cured layer; a step of patternwise exposing the photoresist layer and then developing it to form a resist pattern; and etching the cured layer using the resist pattern as a mask. and dry etching using a gas. In forming the photoresist layer, it is preferable to further perform a pre-baking process. In particular, as the formation process of the photoresist layer, a mode in which heat treatment after exposure and heat treatment (post-baking treatment) after development are performed is desirable. Regarding pattern formation by a dry etching method, descriptions in paragraphs 0010 to 0067 of JP-A-2013-064993 can be referred to, and the contents thereof are incorporated herein.

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

The optical filter may have a protective layer on the surface of the film of the present invention. By providing the protective layer, it is possible to impart various functions such as blocking oxygen, reducing reflection, making the film hydrophilic and hydrophobic, and blocking light of a specific wavelength (ultraviolet rays, near-infrared rays, etc.). The thickness of the protective layer is preferably 0.01-10 μm, more preferably 0.1-5 μm. Examples of the method of forming the protective layer include a method of applying a protective layer-forming resin composition, a chemical vapor deposition method, and a method of bonding a molded resin with an adhesive. Components constituting the protective layer include (meth)acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, and polyimides. Resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, polyol resins, polyvinylidene chloride resins, melamine resins, urethane resins, aramid resins, polyamide resins, alkyd resins, epoxy resins, modified silicone resins, fluorine Resins, polycarbonate resins, polyacrylonitrile resins, cellulose resins, 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 to block oxygen, the protective layer preferably contains a polyol resin, SiO ₂ and Si ₂ N ₄ . In the case of a protective layer intended to reduce reflection, the protective layer preferably contains a (meth)acrylic resin and a fluororesin.

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

If necessary, the protective layer contains organic/inorganic fine particles, absorbers for light of specific wavelengths (e.g., ultraviolet rays, near-infrared rays, etc.), refractive index modifiers, antioxidants, adhesion agents, additives such as surfactants. may contain. Examples of organic/inorganic fine particles include polymeric fine particles (eg, silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, and titanium oxynitride. , magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, and the like. A known absorber can be used as the absorber for light of a specific wavelength. The content of these additives can be appropriately adjusted, but is preferably 0.1 to 70% by mass, more preferably 1 to 60% by mass, based on the total mass of the protective layer.

Further, as the protective layer, the protective layers described in paragraphs 0073 to 0092 of JP-A-2017-151176 can also be used.

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

<Solid-state image sensor>
The solid-state imaging device of the present invention has the film of the present invention described above. The configuration of the solid-state imaging device is not particularly limited as long as it has the film of the present invention and functions as a solid-state imaging device.

A plurality of photodiodes and transfer electrodes made of polysilicon or the like are provided on the substrate, forming the light-receiving area of a solid-state imaging device (CCD (charge-coupled device) image sensor, CMOS (complementary metal-oxide semiconductor) image sensor, etc.). and a device protective film made of silicon nitride or the like formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving portion. and a color filter on the device protective film. Furthermore, a configuration having a condensing means (for example, a microlens or the like; the same shall apply hereinafter) on the device protective film and below the color filter (on the side close to the substrate), or a configuration having a condensing means on the color filter, etc. There may be. Moreover, the color filter may have a structure in which each color pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern. In this case, the partition wall preferably has a lower refractive index than each color pixel. Examples of imaging devices having such a structure include devices described in JP-A-2012-227478, JP-A-2014-179577, and International Publication No. 2018/043654. Further, as disclosed in Japanese Patent Application Laid-Open No. 2019-211559, an ultraviolet absorption layer may be provided in the structure of the solid-state imaging device to improve light resistance. An imaging device equipped with the solid-state imaging device of the present invention can be used not only for digital cameras and electronic devices having an imaging function (mobile phones, etc.), but also for vehicle-mounted cameras and monitoring cameras.

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

The present invention will be described more specifically below with reference to examples. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below.

<Resins P1 to P65, CP1 and CP2>
Resins P1 to P65, CP1, and CP2 are the compounds described in the column of compound b-1, the compounds described in the column of compound b-2, the compounds described in the column of compound b-3, and the compound b- in the table below. It is a random copolymer with the compound described in column 4. That is, the resins P1 to P65, CP1, and CP2 are composed of a repeating unit derived from the compound described in compound b-1, a repeating unit derived from the compound described in compound b-2, and a repeating unit derived from the compound described in compound b-3. It is a random copolymer having repeating units and repeating units derived from the compound described in compound b-4. Incidentally, the repeating unit derived from the compound described in compound b-1 is a repeating unit containing an acid group, the repeating unit derived from the compound described in compound b-2 is a repeating unit b-2 containing a basic group, The repeating unit derived from the compound described in compound b-3 is a repeating unit containing a polyalkyleneoxy structure.

(Compound b-1)
b-1-2, b-1-3, b-1-6, b-1-14: compounds having the following structures

(Compound b-2)
b-2-1 to b-2-22: compounds having the following structures

(Compound b-3)
b-3-2, b-3-3, b-3-5, b-3-6, b-3-9, b-3-11, b-3-13, b-3-17, b- 3-18, b-3-19: compounds having the following structures

(Compound b-4)
b-4-1 to b-4-6: compounds having the following structures

The acid value, base value, ratio of acid value to base value (acid value/base value), and weight average molecular weight of resins P1 to P65, CP1, and CP2 are as follows.

<Resin CP3>
Resin CP3 is a block copolymer synthesized by the following method.
303 parts by mass of propylene glycol monomethyl ether, 3.6 parts by mass of iodine, 2,2'-azobis(4-methoxy-2, 4-dimethylvaleronitrile) 17.7 parts by mass, methyl methacrylate 77.7 parts by mass, butyl methacrylate 77.7 parts by mass, 2-ethylhexyl methacrylate 38.8 parts by mass, methoxypolyethylene glycol methacrylate 38.8 parts 19.4 parts by weight of benzyl methacrylate, 50.0 parts by weight of methacrylic acid and 1.0 parts by weight of 3,5-di-t-butyl-4-hydroxytoluene were charged. Then, polymerization was carried out at 40° C. for 7 hours while flowing nitrogen to obtain a solution of A polymer block. The polymerization rate of the A polymer block calculated from the solid content was 90.4%. The number average molecular weight of the A polymer block was 7400, the molecular weight distribution (PDI) was 1.35, the peak top molecular weight was 10200, and the acid value was 107.5 mgKOH/g.
Next, while the resulting A block polymer solution was kept at 40° C., 62.8 parts by mass of 2-dimethylaminoethyl methacrylate and 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) were added. A mixture of 1.3 parts by mass and 62.8 parts by mass of propylene glycol monomethyl ether was added and polymerized at the same temperature for 4 hours to form a B polymer block. Then, after stopping the flow of nitrogen, the mixture was heated to 80° C. to release the iodine bound to the ends of the polymer chains, thereby obtaining a polymer solution containing resin CP3, which is an AB block copolymer. The liberation of iodine was determined by the fact that the polymer solution became a brown transparent liquid. The resulting AB block copolymer solution had a solid content of 48.9% by mass, and the polymerization rate of the B polymer block calculated from the solid content was almost 100%. The AB block copolymer (resin CP3) has a number average molecular weight of 9500, a PDI of 1.40, a peak top molecular weight of 13500, an acid value of 88.8 mgKOH/g, and an amine value of 61.2 mgKOH/g. Met. Also, the number average molecular weight of the B polymer block was 2,100.

<Production of pigment dispersion>
After mixing and dispersing the mixed liquid obtained by mixing the materials listed in the table below for 3 hours using a bead mill (using zirconia beads with a diameter of 0.1 mm), a high-pressure disperser with a pressure reduction mechanism (NANO-3000-10, (manufactured by Nippon BEE Co., Ltd.), the dispersion treatment was performed under a pressure of 2000 MPa and a flow rate of 500 g/min. This dispersion treatment was repeated 10 times to produce each pigment dispersion. The numerical values shown in the table below are the values in parts by mass. In addition, the average particle diameter (nm) and the viscosity value (mPa·s) of the pigment in each pigment dispersion are also described. The average particle size of the pigment is measured by a dynamic light scattering method using a multi-analyte nanoparticle size measurement system (nanoSAQLA, manufactured by Otsuka Electronics Co., Ltd.), and the viscosity of the pigment dispersion is measured at a temperature of 25°C. ℃ and measured.

The details of the materials described by abbreviations in the above table are as follows.
(dispersant)
Dispersant 1: Resin having the following structure (weight average molecular weight: 28,000, the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units.)

(pigment)
PR254: C.I. I. Pigment Red 254 (red pigment)
PR272: C.I. I. Pigment Red 272 (red pigment)
PY139: C.I. I. Pigment Yellow 139 (yellow pigment)
PY185: Color Index Pigment Yellow 185 (yellow pigment)
PG36: C.I. I. Pigment Green 36 (green pigment)
PG58: C.I. I. Pigment Green 58 (green pigment)
PB15:6: C.I. I. Pigment Blue 15:6 (blue pigment)
PV23: C.I. I. Pigment Violet 23 (purple pigment)
PBk32: C.I. I. Pigment Black 32 (organic black pigment)
IR colorant 1: compound having the following structure (near-infrared absorbing pigment)

Titanium Black 1:13M-T (manufactured by Mitsubishi Materials Corporation)
Carbon black 1: Color black S170 (manufactured by Degussa, average primary particle diameter 17 nm, BET specific surface area 200 m ² /g, carbon black produced by gas black method)

(derivative)
Derivatives 1 to 3: compounds having the following structures (pigment derivatives)

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

<Production of resin composition>
(Examples 1 to 93, Comparative Examples 1 to 3)
Each material was mixed at a ratio of Formula 1 shown below and filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to produce each resin composition.

(Prescription 1)
Pigment dispersion described in the table below...588.21 parts by mass Polymerizable compound 1...1.5 parts by mass Polymerizable compound 2...1.5 parts by mass Specific resins listed in the table below... Parts by mass listed in the table below Binder resin 1 Parts by mass listed in the table below Photoinitiator 1 2 parts by mass Surfactant 1 0.15 parts by mass Thermosetting agent 1 . 0.5 parts by mass Solvent 1: 200 parts by mass Solvent 2: 100 parts by mass Solvent 3: 21.96 parts by mass

(Examples 94-127, Comparative Examples 4-6)
Each material was mixed at the ratio of Formula 2 shown below, and filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to produce each resin composition.

(Prescription 2)
Pigment dispersion described in the table below...588.21 parts by mass Polymerizable compound 1...3.0 parts by mass Specified resin listed in the table below...Parts by mass listed in the table below Binder resin 1... Parts by mass listed in the table below Photoinitiator 2...5.05 parts by mass Surfactant 1...0.15 parts by mass Thermosetting agent 1...0.5 parts by mass Solvent 1... 102.3 parts by mass Solvent 2: 15 parts by mass Solvent 3: 15 parts by mass

Polymerizable compound 1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
Polymerizable compound 2: KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.)
Binder resin 1: resin having the following structure (weight average molecular weight: 25,000, the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units.)

Photoinitiator 1: Irgacure OXE02 (manufactured by BASF, oxime compound)
Photopolymerization initiator 2: Irgacure OXE03 (manufactured by BASF, oxime compound)
Surfactant 1: KF6001 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone-based surfactant)
Thermosetting agent 1: compound T-1 having the following structure

Solvent 1: propylene glycol monomethyl ether acetate (PGMEA)
Solvent 2: Cyclopentanone Solvent 3: 1-methoxy-2-propanol

<Performance evaluation>
(Defects over time)
The resin composition immediately after production was stored at 45°C for 7 days. Thereafter, the resin composition was applied onto the undercoat layer-attached glass substrate using a spin coater so that the film thickness after prebaking was 1.0 μm, and the film was prebaked using a hot plate at 100° C. for 120 seconds. formed. A 1 cm square portion of the resulting film was observed with an optical microscope, and the number of crystalline defects having a size of 0.5 μm or more was counted to evaluate defects over time according to the following evaluation criteria.
5: The number of defects is 0 4: The number of defects is 1 to 3 3: The number of defects is 4 to 6 2: The number of defects is 7 to 9 1: The number of defects is 10 or more

(Development residue)
On an 8-inch (20.32 cm) silicon wafer, a spin coater was applied so that the composition for forming the underlayer (CT-4000, manufactured by Fuji Film Electronic Materials Co., Ltd.) was post-baked to a thickness of 0.1 μm. and heated at 220° C. for 300 seconds using a hot plate to form a base layer, and then a silicon wafer (support) with a base layer was obtained. Then, each resin composition was applied by spin coating so that the film thickness after post-baking was 0.8 μm, and heated at 100° C. for 2 minutes using a hot plate. Then, through a 1.0 μm square dot pattern mask, using an i-line stepper exposure device (FPA-3000i5+, manufactured by Canon Inc.), light with a wavelength of 365 nm was irradiated at an exposure amount of 1000 mJ/cm ² . and exposed. Thereafter, the silicon wafer on which the exposed coating film is formed is placed on a horizontal rotating table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and a developing solution (CD-2000, A 60% diluted solution (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was used for puddle development at 23° C. for 60 seconds. After the development, the silicon wafer is fixed on a horizontal rotary table by a vacuum chuck method, and while the silicon wafer is rotated at a rotation speed of 50 rpm by a rotating device, deionized water is supplied in a shower form from a jet nozzle from above the rotation center to rinse. Treated and spray dried. Further, heat treatment (post-baking) was performed for 300 seconds using a hot plate at 200° C. to form pixels (patterns).
The silicon wafer on which the pixels were formed was observed with a scanning electron microscope (SEM, magnification: 10000), and development residues were evaluated according to the following evaluation criteria.
5: No residue was observed outside the pixel formation area (unexposed area). 4: A very small amount of residue was observed outside the pixel formation area (unexposed area). 3: A slight amount of residue was observed outside the pixel formation area (unexposed area), but it was not a problem in practice. 2: Outside the pixel formation area (unexposed area). 1: Remarkable residue was observed outside the pixel formation area (unexposed area)

(Stability over time)
The viscosity (mPa·s) of the resin composition immediately after production was measured with a viscometer (RE-85L, manufactured by Toki Sangyo Co., Ltd.). After that, the resin composition was allowed to stand under the conditions of 45° C. and light shielding for 5 days, and the viscosity (mPa·s) was measured again. Stability over time was evaluated from the viscosity difference (ΔVis) before and after standing according to the following evaluation criteria. It can be said that the smaller the numerical value of the viscosity difference (ΔVis), the better the stability over time of the resin composition. All of the above viscosity measurements were performed in a laboratory where the temperature and humidity were controlled at 22±5°C and 60±20%, and the temperature of the resin composition was adjusted to 25°C. Each measurement was performed three times and the average value was used.
5: ΔVis was 0.2 mPa s or less 4: ΔVis was more than 0.2 mPa s and was 0.3 mPa s or less 3: ΔVis was more than 0.3 mPa s and 0.5 mPa s s or less 2: ΔVis exceeded 0.5 mPa s and was 1.0 mPa s or less 1: ΔVis exceeded 1.0 mPa s

As shown in the table above, the examples were excellent in evaluation of defects over time, development residue, and stability over time.

The 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 43, similar effects were obtained even when polymerizable compound 2 was changed to compound M-2 or M-3 having the structure shown below.

In Example 43, 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 43, similar effects were obtained even when the thermosetting agent 1 was changed to compound T-2 or T-3 having the structure shown below.

In Example 43, surfactant 1 was a compound having the structure shown below (weight-average molecular weight of 14,000, percentage of repeating units is mol%, fluorosurfactant) or PolyFox PF6320 ( A similar effect was obtained even when the surfactant was changed to a fluorosurfactant manufactured by OMNOVA.

Claims

A resin composition containing a coloring material A and a resin B,
The coloring material A contains a pigment,
The resin B includes a repeating unit b-1 containing an acid group, a repeating unit b-2 containing a basic group, and a random copolymer b1 containing a repeating unit b-3 containing a polyalkyleneoxy structure. Composition.
The resin composition according to claim 1, wherein the random copolymer b1 has an acid value to base value ratio of 0.2 to 20.
The resin composition according to claim 1 or 2, wherein the repeating unit b-3 has a molecular weight of 350 to 1,500.
The resin composition according to claim 1 or 2, wherein the polyalkyleneoxy structure is a polyethyleneoxy structure.
The resin composition according to claim 1 or 2, wherein the random copolymer b1 has an acid value of 40 to 120 mgKOH/g.
The resin composition according to claim 1 or 2, wherein the random copolymer b1 has a base value of 40 to 120 mgKOH/g.
The resin composition according to claim 1 or 2, wherein the repeating unit b-2 is a repeating unit derived from a compound having a conjugate acid pKa of 9.5 or higher.
Claim 1, wherein the random copolymer b1 further comprises a repeating unit b-4 having a functional group X selected from a group containing two or more aromatic rings, a group containing a heterocyclic group, and a group containing a condensed ring. Or the resin composition according to 2.
The resin composition according to claim 1 or 2, wherein the content of the random copolymer b1 in the resin B is 1 to 30% by mass.
The resin composition according to claim 1 or 2, wherein the content of the random copolymer b1 in the total solid content of the resin composition is 1 to 10% by mass.
The resin composition according to claim 1 or 2, wherein the coloring material A contains a pigment derivative.
The resin composition according to claim 1 or 2, further comprising a polymerizable compound and a photopolymerization initiator.
A film obtained from the resin composition according to claim 1 or 2.
An optical filter having the film according to claim 13.
A solid-state imaging device having the film according to claim 13.
An image display device having the film according to claim 13.